EO / PO block copolymerized silicone oil and preparation method thereof

Abstract

The invention relates to the technical field of silicone oil, and discloses EO / PO block copolymerized silicone oil and a preparation method thereof. The EO / PO block copolymerized silicone oil prepared by the preparation method disclosed by the invention utilizes a copolymer structure of a polysiloxane main chain, an EO / PO block and a hyperbranched polyether side chain to realize multifunctional finishing of softness, hydrophilicity, durability and the like on fabrics, and the copolymerized silicone oil does not need to be emulsified, is good in stability, can be directly used, and is convenient and quick.

Description

Technical Field

[0001] This invention relates to the field of silicone oil technology, specifically to an EO / PO block copolymer silicone oil and its preparation method. Background Technology

[0002] In the textile printing and dyeing industry, fabric finishing is a key step in improving wearability, and the demand for softening and hydrophilic finishing agents is increasing. While traditional amino silicone oils can impart excellent softness to fabrics, they tend to cause hydrophobicity, yellowing, and poor compatibility with anionic systems. On the other hand, conventional polyether silicone oils, although they can improve hydrophilicity, often face limitations such as insufficient softness, poor wash resistance, and inability to be used in the same bath as dyeing.

[0003] EO / PO block copolymer silicone oils, as an important branch of polyether-modified silicone oils, achieve a preliminary balance between hydrophilicity and softening properties by grafting hydrophilic polyethylene oxide (EO) segments and hydrophobic polypropylene oxide (PO) segments onto the polysiloxane backbone in a block form. However, existing linear EO / PO block structures still have significant drawbacks: their hydrophilicity relies on ether-hydrogen bonding, which is easily diminished after high temperatures or repeated washing; while the hydrophobic properties of the PO segments help improve adsorption to fibers, they may result in a sticky feel; and conventional block copolymers have low end activity, making it difficult to improve durability through chemical bonding. Therefore, with the market's pursuit of multifunctional, high-efficiency, and green short-process technologies, developing finishing agents that combine excellent softening, long-lasting hydrophilicity, good compatibility, and adaptability to one-bath processing has become an important direction for technological innovation. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides an EO / PO block copolymer silicone oil and its preparation method.

[0005] The objective of this invention can be achieved through the following technical solutions: A method for preparing an EO / PO block copolymer silicone oil includes the following steps: Step S1: Add octamethylcyclotetrasiloxane to the reactor, then add 98wt% concentrated sulfuric acid and stir thoroughly. Then heat to 45-55℃, add tetramethyldihydrodisiloxane and stir for 5-7 hours. After post-treatment, the double-ended hydrogen-containing silicone oil is obtained. Further, the post-processing step in step S1 is to add sodium carbonate powder to neutralize sulfuric acid, adjust the pH of the system to neutral, filter, add anhydrous magnesium sulfate to the obtained filtrate to dry, filter again, and remove solids. Further, in step S1, the mass ratio of octamethylcyclotetrasiloxane to tetramethyldihydrodisiloxane is 5-10:1; Furthermore, in step S1, the amount of concentrated sulfuric acid used is 0.7%-1.0% of the total mass of the reactants; Furthermore, in step S1, the amount of sodium carbonate powder used is 1.8%-2.2% of the total mass of the reactants, and the amount of anhydrous magnesium sulfate is 2.1%-2.5% of the total mass of the reactants; Step S2: Under nitrogen conditions, add the hydrogen-containing silicone oil and allyl polyoxyalkyl epoxy ether to toluene and mix evenly. Then add 0.5 mg / mL isopropanol chloroplatinic acid solution and react in an oil bath at 90-100℃ for 2-4 hours. Distill under reduced pressure to obtain the epoxy PO / EO silicone oil. Furthermore, in step S2, the molar ratio of hydrogen content in the double-ended hydrogen-containing silicone oil to allyl groups in the allyl polyoxyalkyl epoxy ether is 1:1.1-1.3; Furthermore, in step S2, the amount of isopropanol chloroplatinic acid solution used is 2%-4% of the total amount of reactants; Step S3: Stir the terminal epoxy PO / EO silicone oil, 3-hydroxypropanesulfonic acid and tetrabutylammonium bromide in DMF until uniform, introduce nitrogen gas, heat to 90℃ and react for 5 hours, evaporate by rotary evaporation, and then treat to obtain terminal sulfonic acid PO / EO silicone oil. Further, the post-treatment steps in step S3 are as follows: dilute with ethyl acetate, wash with deionized water, dry with anhydrous sodium sulfate, and finally rotary evaporate. Furthermore, in step S3, the molar ratio of epoxy groups in the terminal epoxy PO / EO silicone oil, hydroxyl groups in 3-hydroxypropanesulfonic acid, and tetrabutylammonium bromide is 1:1-1.02:0.05-0.08; Step S4: Mix sulfonic acid-terminated PO / EO silicone oil, 1,3,5,7-tetramethylcyclotetrasiloxane and 98wt% concentrated sulfuric acid evenly, heat to 45℃ and stir for 1.5-2.5h, add sodium carbonate powder to adjust pH to 6-7, filter, collect filtrate, then add anhydrous magnesium sulfate to dry, filter to remove solid, and obtain sulfonic acid-terminated hydrogen-containing PO / EO silicone oil. Furthermore, in step S4, the mass ratio of terminal sulfonic acid PO / EO silicone oil to 1,3,5,7-tetramethylcyclotetrasiloxane is 20:0.5-1.5; Furthermore, in step S4, the amount of concentrated sulfuric acid used is 0.5%-0.8% of the total mass of the reactants; Furthermore, in step S4, the amount of sodium carbonate powder used is 1.5%-2% of the total mass of the reactants, and the amount of anhydrous magnesium sulfate is 2.1%-2.5% of the total mass of the reactants; Step S5: Under nitrogen conditions, add 0.5 mg / mL isopropanol chloroplatinic acid solution to the hydrogen-containing PO / EO silicone oil with terminal sulfonic acid groups obtained in step S4, heat to 80°C, then add the end-double-bond hyperbranched polyether and stir for 3-5 hours. Distill under reduced pressure to obtain EO / PO block copolymer silicone oil. Furthermore, in step S5, the molar ratio of hydrogen content in the hydrogen-containing PO / EO silicone oil with terminal sulfonic acid groups to the molar ratio of double bonds in the hyperbranched polyether with terminal double bonds is 1:1-1.1, and the amount of isopropanol chloroplatinic acid solution used is 2%-4% of the total amount of reactants; Further, the terminal double-bond hyperbranched polyether described in step S5 is prepared by the following steps: Under a nitrogen atmosphere, diethanolamine and methanol were added to a reactor, and allyl acrylate was slowly added at 0°C. The temperature was then raised to 35°C and reacted for 4 hours. The intermediate product was collected by vacuum distillation. Trimethylolpropane triglycidyl ether and tetrabutylammonium bromide were thoroughly mixed in DMF, and the above intermediate product was added. The mixture was stirred and reacted under nitrogen at 90°C for 1-2 hours. Then 2-hydroxymethyl-1,3-propanediol was added and reacted for 2-4 hours. Tetrahydrofuran was then added and stirred until homogeneous. The mixture was washed and dried to obtain the end-double-bond hyperbranched polyether. Furthermore, the molar ratio of diethanolamine to allyl acrylate in the above intermediate product is 1:1.5-2; Furthermore, in the above-mentioned hyperbranched polyether with terminal double bonds, the molar ratio of intermediate product, hydroxymethylpropane triglycidyl ether, and 2-hydroxymethyl-1,3-propanediol is 1:2-4:4-8, and the amount of tetrabutylammonium bromide is 4.5-5.5% of the amount of reactants.

[0006] On the other hand, the present invention also provides an EO / PO block copolymer silicone oil prepared by the above method.

[0007] The beneficial effects of this invention are: The EO / PO block copolymer silicone oil prepared by this invention utilizes the copolymer structure of polysiloxane backbone, EO / PO block and hyperbranched polyether side chain to achieve multifunctional finishing of fabrics such as softness, hydrophilicity and durability. Moreover, this copolymer silicone oil does not require emulsification, has good stability, can be used directly, and is convenient and quick.

[0008] The EO / PO block copolymer silicone oil of this invention uses polysiloxane as the main chain and introduces EO / PO blocks into the main chain through hydrosilylation reaction, while simultaneously introducing epoxy groups. The epoxy groups can react with 3-hydroxypropanesulfonic acid in subsequent processes to introduce terminal sulfonic acid groups. The terminal sulfonic acid groups are ionic hydrophilic groups that are more hydrophilic than polyether chains (relying on ether bonds and hydrogen bonds) and are less affected by temperature. They have extremely strong hydration capacity and can quickly adsorb moisture, enabling fabrics to achieve instant moisture absorption and improve the hydrophilicity of the fabric. Placing them at the end of the molecule greatly enhances the self-emulsification ability of the silicone oil, making it easy to emulsify into a fine-particle-size, uniformly distributed, and extremely stable microemulsion. The hyperbranched polyether structure with side-linked branches has a large number of terminal hydrophilic groups. Due to its three-dimensional rigidity, it tends to arrange itself strongly at the fabric-air interface, forming a permanent high-density hydrophilic surface. Furthermore, because the movement of the three-dimensional structure is hindered, it is not easy to migrate or flip due to thermal movement or washing, making the hydrophilic properties extremely durable and wash-resistant. The three-dimensional structure of the side chains prevents the excessively tight stacking of the siloxane backbone, allowing it to form a more uniform, thinner, and more elastic nanoscale film on the fiber surface. This results in a uniform hand feel after finishing, better maintaining the natural fluffiness and breathability of the fiber, and reducing the "silicone oil feel." It is especially suitable for applications such as high-count and high-density fabrics that require maintaining the original style of the fabric. Detailed Implementation

[0009] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0010] Example 1: End-double-bond hyperbranched polyether was prepared by the following steps: Under a nitrogen atmosphere, diethanolamine and methanol were added to a reactor, and allyl acrylate was slowly added at 0°C. The temperature was then raised to 35°C and reacted for 4 hours. The intermediate product was collected by vacuum distillation. Trimethylolpropane triglycidyl ether and tetrabutylammonium bromide were thoroughly mixed in DMF, and the above intermediate product was added. The mixture was stirred and reacted at 90°C under nitrogen for 1 hour. Then 2-hydroxymethyl-1,3-propanediol was added and reacted for 2 hours. Tetrahydrofuran was then added and stirred until homogeneous. The mixture was washed and dried to obtain the terminal double-bond hyperbranched polyether. The molar ratio of diethanolamine to allyl acrylate in the intermediate product was 1:1.5. The molar ratio of the intermediate product, methylolpropane triglycidyl ether, and 2-hydroxymethyl-1,3-propanediol in the terminal double-bond hyperbranched polyether was 1:2:4. The amount of tetrabutylammonium bromide was 4.5% of the reactants.

[0011] A method for preparing an EO / PO block copolymer silicone oil includes the following steps: Step S1: Add octamethylcyclotetrasiloxane to the reactor, then add 98wt% concentrated sulfuric acid and stir thoroughly. Heat to 45℃, then add tetramethyldihydrodisiloxane and stir for 5 hours. Add sodium carbonate powder to neutralize the sulfuric acid, adjust the pH of the system to neutral, filter, add anhydrous magnesium sulfate to the filtrate for drying, filter again, and remove the solid to obtain the double-ended hydrogen-containing silicone oil. The mass ratio of octamethylcyclotetrasiloxane to tetramethyldihydrodisiloxane is 5:1. The amounts of concentrated sulfuric acid, sodium carbonate powder, and anhydrous magnesium sulfate are 0.7%, 1.8%, and 2.1% of the total mass of the reactants, respectively. Step S2: Under nitrogen atmosphere, add the hydrogen-terminated silicone oil and allyl polyoxyalkyl epoxy ether to toluene and mix thoroughly. Then add 0.5 mg / mL isopropanol chloroplatinate solution and react in a 90°C oil bath for 2 hours. Distill under reduced pressure to obtain terminal epoxy PO / EO silicone oil. The molar ratio of hydrogen content in the hydrogen-terminated silicone oil to allyl groups in the allyl polyoxyalkyl epoxy ether is 1:1.1. The amount of isopropanol chloroplatinate solution used is 2% of the total reactants. Step S3: Stir the terminal epoxy PO / EO silicone oil, 3-hydroxypropanesulfonic acid and tetrabutylammonium bromide in DMF until homogeneous, purge with nitrogen, and heat to 90℃ for 5 hours. Rotary evaporate, dilute with ethyl acetate, wash with deionized water, dry with anhydrous sodium sulfate, and finally rotary evaporate to obtain terminal sulfonic acid PO / EO silicone oil. The molar ratio of epoxy groups in the terminal epoxy PO / EO silicone oil, hydroxyl groups in 3-hydroxypropanesulfonic acid and tetrabutylammonium bromide is 1:1:0.05. Step S4: Mix terminal sulfonic acid-based PO / EO silicone oil, 1,3,5,7-tetramethylcyclotetrasiloxane, and 98wt% concentrated sulfuric acid until homogeneous. Heat to 45℃ and stir for 1.5h. Add sodium carbonate powder to adjust the pH to 6. Filter and collect the filtrate. Then add anhydrous magnesium sulfate to dry. Filter again to remove the solid, thus obtaining terminal sulfonic acid-based hydrogen-containing PO / EO silicone oil. The mass ratio of terminal sulfonic acid-based PO / EO silicone oil to 1,3,5,7-tetramethylcyclotetrasiloxane is 20:0.5. The amounts of concentrated sulfuric acid, sodium carbonate powder, and anhydrous magnesium sulfate are 0.5%, 1.5%, and 2.1% of the total mass of the reactants, respectively. Step S5: Under nitrogen atmosphere, add 0.5 mg / mL isopropanol chloroplatinic acid solution to the hydrogen-containing PO / EO silicone oil with terminal sulfonic acid groups obtained in step S4, heat to 80°C, then add the hyperbranched polyether with terminal double bonds and stir for 3 hours. Distill under reduced pressure to obtain EO / PO block copolymer silicone oil. The molar ratio of hydrogen content in the hydrogen-containing PO / EO silicone oil with terminal sulfonic acid groups to the molar ratio of double bonds in the hyperbranched polyether with terminal double bonds is 1:1, and the amount of isopropanol chloroplatinic acid solution used is 2% of the total amount of reactants.

[0012] Example 2: End-double-bond hyperbranched polyether was prepared by the following steps: Under a nitrogen atmosphere, diethanolamine and methanol were added to a reactor, and allyl acrylate was slowly added at 0°C. The temperature was then raised to 35°C and reacted for 4 hours. The intermediate product was collected by vacuum distillation. Trimethylolpropane triglycidyl ether and tetrabutylammonium bromide were thoroughly mixed in DMF, and the above intermediate product was added. The mixture was stirred and reacted at 90°C under nitrogen for 1.5 hours. Then 2-hydroxymethyl-1,3-propanediol was added and reacted for 3 hours. Tetrahydrofuran was then added and stirred until homogeneous. The mixture was washed and dried to obtain the terminal double-bond hyperbranched polyether. The molar ratio of diethanolamine to allyl acrylate in the intermediate product was 1:1.8, and the molar ratio of the intermediate product, methylolpropane triglycidyl ether, and 2-hydroxymethyl-1,3-propanediol in the terminal double-bond hyperbranched polyether was 1:3:6. The amount of tetrabutylammonium bromide was 5% of the reactant amount.

[0013] A method for preparing an EO / PO block copolymer silicone oil includes the following steps: Step S1: Add octamethylcyclotetrasiloxane to the reactor, then add 98wt% concentrated sulfuric acid and stir thoroughly. Heat to 50℃, then add tetramethyldihydrodisiloxane and stir for 6 hours. Add sodium carbonate powder to neutralize the sulfuric acid, adjust the pH of the system to neutral, filter, add anhydrous magnesium sulfate to the filtrate for drying, filter again, remove the solid, and obtain the double-ended hydrogen-containing silicone oil. The mass ratio of octamethylcyclotetrasiloxane to tetramethyldihydrodisiloxane is 7.5:1. The amounts of concentrated sulfuric acid, sodium carbonate powder, and anhydrous magnesium sulfate are 0.85%, 2%, and 2.3% of the total mass of the reactants, respectively. Step S2: Under nitrogen atmosphere, add the hydrogen-terminated silicone oil and allyl polyoxyalkyl epoxy ether to toluene and mix thoroughly. Then add 0.5 mg / mL isopropanol chloroplatinate solution and react in a 95°C oil bath for 3 hours. Distill under reduced pressure to obtain terminal epoxy PO / EO silicone oil. The molar ratio of hydrogen content in the hydrogen-terminated silicone oil to allyl groups in the allyl polyoxyalkyl epoxy ether is 1:1.2. The amount of isopropanol chloroplatinate solution used is 3% of the total reactants. Step S3: Stir the terminal epoxy PO / EO silicone oil, 3-hydroxypropanesulfonic acid and tetrabutylammonium bromide in DMF until homogeneous, purge with nitrogen, and heat to 90℃ for 5 hours. Rotary evaporate, dilute with ethyl acetate, wash with deionized water, dry with anhydrous sodium sulfate, and finally rotary evaporate to obtain terminal sulfonic acid PO / EO silicone oil. The molar ratio of epoxy groups in the terminal epoxy PO / EO silicone oil, hydroxyl groups in 3-hydroxypropanesulfonic acid and tetrabutylammonium bromide is 1:1.01:0.07. Step S4: Mix terminal sulfonic acid-based PO / EO silicone oil, 1,3,5,7-tetramethylcyclotetrasiloxane, and 98wt% concentrated sulfuric acid until homogeneous. Heat to 45℃ and stir for 2 hours. Add sodium carbonate powder to adjust the pH to 6.5. Filter and collect the filtrate. Then add anhydrous magnesium sulfate to dry the filtrate. Filter again to remove the solid, thus obtaining terminal sulfonic acid-based hydrogen-containing PO / EO silicone oil. The mass ratio of terminal sulfonic acid-based PO / EO silicone oil to 1,3,5,7-tetramethylcyclotetrasiloxane is 20:1. The amounts of concentrated sulfuric acid, sodium carbonate powder, and anhydrous magnesium sulfate are 0.65%, 1.8%, and 2.3% of the total mass of the reactants, respectively. Step S5: Under nitrogen atmosphere, add 0.5 mg / mL isopropanol chloroplatinic acid solution to the hydrogen-containing PO / EO silicone oil with terminal sulfonic acid groups obtained in step S4, heat to 80°C, then add the hyperbranched polyether with terminal double bonds and stir for 4 hours. Distill under reduced pressure to obtain EO / PO block copolymer silicone oil. The molar ratio of hydrogen content in the hydrogen-containing PO / EO silicone oil with terminal sulfonic acid groups to the double bonds in the hyperbranched polyether with terminal double bonds is 1:1.05, and the amount of isopropanol chloroplatinic acid solution used is 3% of the total amount of reactants.

[0014] Example 3: End-double-bond hyperbranched polyether was prepared by the following steps: Under a nitrogen atmosphere, diethanolamine and methanol were added to a reactor, and allyl acrylate was slowly added at 0°C. The temperature was then raised to 35°C and reacted for 4 hours. The intermediate product was collected by vacuum distillation. Trimethylolpropane triglycidyl ether and tetrabutylammonium bromide were thoroughly mixed in DMF, and the above intermediate product was added. The mixture was stirred and reacted at 90°C under nitrogen for 2 hours. Then, 2-hydroxymethyl-1,3-propanediol was added and reacted for 4 hours. Tetrahydrofuran was then added and stirred until homogeneous. The mixture was washed and dried to obtain the terminal double-bond hyperbranched polyether. The molar ratio of diethanolamine to allyl acrylate in the intermediate product was 1:2. The molar ratio of the intermediate product, methylolpropane triglycidyl ether, and 2-hydroxymethyl-1,3-propanediol in the terminal double-bond hyperbranched polyether was 1:4:8. The amount of tetrabutylammonium bromide was 5.5% of the reactant amount.

[0015] A method for preparing an EO / PO block copolymer silicone oil includes the following steps: Step S1: Add octamethylcyclotetrasiloxane to the reactor, then add 98wt% concentrated sulfuric acid and stir thoroughly. Heat to 55℃, then add tetramethyldihydrodisiloxane and stir for 7 hours. Add sodium carbonate powder to neutralize the sulfuric acid, adjust the pH of the system to neutral, filter, add anhydrous magnesium sulfate to the filtrate for drying, filter again, and remove the solid to obtain the double-ended hydrogen-containing silicone oil. The mass ratio of octamethylcyclotetrasiloxane to tetramethyldihydrodisiloxane is 10:1. The amounts of concentrated sulfuric acid, sodium carbonate powder, and anhydrous magnesium sulfate are 1.0%, 2.2%, and 2.5% of the total mass of the reactants, respectively. Step S2: Under nitrogen atmosphere, add the hydrogen-terminated silicone oil and allyl polyoxyalkyl epoxy ether to toluene and mix thoroughly. Then add 0.5 mg / mL isopropanol chloroplatinate solution and react in an oil bath at 100°C for 4 hours. Distill under reduced pressure to obtain terminal epoxy PO / EO silicone oil. The molar ratio of hydrogen content in the hydrogen-terminated silicone oil to allyl groups in the allyl polyoxyalkyl epoxy ether is 1:1.3. The amount of isopropanol chloroplatinate solution used is 4% of the total reactants. Step S3: Stir the terminal epoxy PO / EO silicone oil, 3-hydroxypropanesulfonic acid and tetrabutylammonium bromide in DMF until homogeneous, purge with nitrogen, and heat to 90℃ for 5 hours. Rotary evaporate, dilute with ethyl acetate, wash with deionized water, dry with anhydrous sodium sulfate, and finally rotary evaporate to obtain terminal sulfonic acid PO / EO silicone oil. The molar ratio of epoxy groups in the terminal epoxy PO / EO silicone oil, hydroxyl groups in 3-hydroxypropanesulfonic acid and tetrabutylammonium bromide is 1:1.02:0.08. Step S4: Mix terminal sulfonic acid-based PO / EO silicone oil, 1,3,5,7-tetramethylcyclotetrasiloxane, and 98wt% concentrated sulfuric acid until homogeneous. Heat to 45℃ and stir for 2.5h. Add sodium carbonate powder to adjust the pH to 7. Filter and collect the filtrate. Then add anhydrous magnesium sulfate to dry. Filter again to remove the solid, thus obtaining terminal sulfonic acid-based hydrogen-containing PO / EO silicone oil. The mass ratio of terminal sulfonic acid-based PO / EO silicone oil to 1,3,5,7-tetramethylcyclotetrasiloxane is 20:1.5. The amounts of concentrated sulfuric acid, sodium carbonate powder, and anhydrous magnesium sulfate are 0.8%, 2%, and 2.5% of the total mass of the reactants, respectively. Step S5: Under nitrogen atmosphere, add 0.5 mg / mL isopropanol chloroplatinic acid solution to the hydrogen-containing PO / EO silicone oil with terminal sulfonic acid groups obtained in step S4, heat to 80°C, then add the hyperbranched polyether with terminal double bonds and stir for 5 hours. Distill under reduced pressure to obtain EO / PO block copolymer silicone oil. The molar ratio of hydrogen content in the hydrogen-containing PO / EO silicone oil with terminal sulfonic acid groups to the double bonds in the hyperbranched polyether with terminal double bonds is 1:1.1, and the amount of isopropanol chloroplatinic acid solution used is 4% of the total amount of reactants.

[0016] Comparative Example 1: This comparative example is a commercially available JF-2018 ternary copolymer silicone oil, purchased from Hubei Shuaiyan Ligao Biomedical Co., Ltd.

[0017] The EO / PO block copolymer silicone oil prepared in Examples 1-3 and the ternary copolymer silicone oil in Comparative Example 1 were used to fabrics (300D×300D polyester filament, width 160cm, weight 74g / m²). 2 The samples were prepared by cleaning and then subjected to performance testing. Hydrophilicity: The static water drop method is used. One drop of water is dropped from 1 cm away from the fabric using a standard dropper (25 drops / mL). The hydrophilicity is determined by the time it takes for the water droplet to be completely absorbed. The shorter the time, the better the hydrophilicity.

[0018] Hand feel assessment: The actual hand feel assessment method is adopted. After the fabric sample is cooled and re-moistened, it is comprehensively evaluated by several senior hand feel assessment professionals from aspects such as smoothness, softness, and fluffiness. The original fabric hand feel is assigned 1 point, and the best hand feel assessment is 5 points. The average value is taken.

[0019] Stability test: (1) Prepare acetic acid into a solution with a pH of about 3. Take 97 ml of this solution and mix it with 3 g of silicone oil emulsion with a solid content of 20%. After standing for 4 hours, observe whether there is oil floating, layering or flocculent matter in the solution. If not, it indicates that the emulsion has good acid resistance stability. (2) Prepare sodium carbonate into a solution with a pH of about 12. Take 97 ml of this solution and mix it with 3 g of silicone oil with a solid content of 20%. After standing for 4 hours, observe whether there is oil floating, layering or flocculent matter in the solution. If not, it indicates that the emulsion has good acid resistance stability.

[0020] Transmittance: The silicone oil was prepared into a 30 g / L solution sample, and its transmittance was measured in a spectrophotometer using distilled water as a reference.

[0021] The test results are shown in Table 1: Table 1: Performance Test Results

[0022] As can be seen from Table 1, the EO / PO block copolymer silicone oil prepared by this invention has good stability and permeability. After being used to finish fabrics, the fabrics exhibit excellent hydrophilicity and a soft, skin-friendly feel.

[0023] The above content is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the scope defined by the inventive concept, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing an EO / PO block copolymer silicone oil, characterized in that, Includes the following steps: Step S1: Add octamethylcyclotetrasiloxane to the reactor, then add 98wt% concentrated sulfuric acid and stir thoroughly. Then heat to 45-55℃, add tetramethyldihydrodisiloxane and stir for 5-7 hours. After post-treatment, the double-ended hydrogen-containing silicone oil is obtained. Step S2: Under nitrogen conditions, add the hydrogen-containing silicone oil and allyl polyoxyalkyl epoxy ether to toluene and mix evenly. Then add 0.5 mg / mL isopropanol chloroplatinic acid solution and react in an oil bath at 90-100℃ for 2-4 hours. Distill under reduced pressure to obtain the epoxy PO / EO silicone oil. Step S3: Stir the terminal epoxy PO / EO silicone oil, 3-hydroxypropanesulfonic acid and tetrabutylammonium bromide in DMF until uniform, introduce nitrogen gas, heat to 90℃ and react for 5 hours, evaporate by rotary evaporation, and then treat to obtain terminal sulfonic acid PO / EO silicone oil. Step S4: Mix sulfonic acid-terminated PO / EO silicone oil, 1,3,5,7-tetramethylcyclotetrasiloxane and 98wt% concentrated sulfuric acid evenly, heat to 45℃ and stir for 1.5-2.5h, add sodium carbonate powder to adjust pH to 6-7, filter, collect filtrate, then add anhydrous magnesium sulfate to dry, filter to remove solid, and obtain sulfonic acid-terminated hydrogen-containing PO / EO silicone oil. Step S5: Under nitrogen conditions, add 0.5 mg / mL isopropanol chloroplatinic acid solution to the hydrogen-containing PO / EO silicone oil with terminal sulfonic acid groups obtained in step S4, heat to 80°C, then add the end-double-bond hyperbranched polyether and stir for 3-5 hours. Distill under reduced pressure to obtain EO / PO block copolymer silicone oil.

2. The method for preparing an EO / PO block copolymer silicone oil according to claim 1, characterized in that, The post-processing steps in step S1 are as follows: add sodium carbonate powder to neutralize sulfuric acid, adjust the pH of the system to neutral, filter, add anhydrous magnesium sulfate to the obtained filtrate to dry, filter again, and remove solids.

3. The method for preparing an EO / PO block copolymer silicone oil according to claim 1, characterized in that, In step S1, the mass ratio of octamethylcyclotetrasiloxane to tetramethyldihydrodisiloxane is 5-10:1, and the amounts of concentrated sulfuric acid, sodium carbonate powder, and anhydrous magnesium sulfate are 0.7%-1.0%, 1.8%-2.2%, and 2.1%-2.5% of the total mass of the reactants, respectively.

4. The method for preparing an EO / PO block copolymer silicone oil according to claim 1, characterized in that, In step S2, the molar ratio of hydrogen content in the double-ended hydrogen-containing silicone oil to allyl groups in the allyl polyoxyalkyl epoxy ether is 1:1.1-1.3, and the amount of isopropanol chloroplatinate solution used is 2%-4% of the total amount of reactants.

5. The method for preparing an EO / PO block copolymer silicone oil according to claim 1, characterized in that, In step S3, the molar ratio of epoxy groups in the terminal epoxy PO / EO silicone oil, hydroxyl groups in 3-hydroxypropanesulfonic acid, and tetrabutylammonium bromide is 1:1-1.02:0.05-0.

08.

6. The method for preparing an EO / PO block copolymer silicone oil according to claim 1, characterized in that, In step S4, the mass ratio of terminal sulfonic acid PO / EO silicone oil to 1,3,5,7-tetramethylcyclotetrasiloxane is 20:0.5-1.5, and the amounts of concentrated sulfuric acid, sodium carbonate powder, and anhydrous magnesium sulfate are 0.5%-0.8%, 1.5%-2%, and 2.1%-2.5% of the total mass of the reactants, respectively.

7. The method for preparing an EO / PO block copolymer silicone oil according to claim 1, characterized in that, In step S5, the molar ratio of hydrogen content in the hydrogen-containing PO / EO silicone oil with terminal sulfonic acid groups to the molar ratio of double bonds in the hyperbranched polyether with terminal double bonds is 1:1-1.1, and the amount of isopropanol chloroplatinic acid solution used is 2%-4% of the total amount of reactants.

8. The method for preparing an EO / PO block copolymer silicone oil according to claim 1, characterized in that, The hyperbranched polyether with terminal double bonds described in step S5 is prepared by the following steps: Under a nitrogen atmosphere, diethanolamine and methanol were added to a reactor, and allyl acrylate was slowly added at 0°C. The temperature was then raised to 35°C and reacted for 4 hours. The intermediate product was collected by vacuum distillation. Trimethylolpropane triglycidyl ether and tetrabutylammonium bromide were thoroughly mixed in DMF, and the above intermediate product was added. The mixture was stirred and reacted under nitrogen at 90°C for 1-2 hours. Then 2-hydroxymethyl-1,3-propanediol was added and reacted for 2-4 hours. Tetrahydrofuran was then added and stirred until homogeneous. The mixture was washed and dried to obtain the end-double-bond hyperbranched polyether.

9. The method for preparing an EO / PO block copolymer silicone oil according to claim 8, characterized in that, The molar ratio of diethanolamine to allyl acrylate in the intermediate product is 1:1.5-2, the molar ratio of the intermediate product, hydroxymethylpropane triglycidyl ether, and 2-hydroxymethyl-1,3-propanediol in the terminal double-bond hyperbranched polyether is 1:2-4:4-8, and the amount of tetrabutylammonium bromide is 4.5-5.5% of the amount of reactants.

10. An EO / PO block copolymer silicone oil prepared by the preparation method according to any one of claims 1-9.

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