Acetylenic alcohol-modified fluorosilicone, method for preparing the same, and use thereof

Abstract

The application relates to the fine chemical field and discloses a kind of alkyne alcohol modified fluorine-containing polysiloxane and its preparation method and application, with hexamethyldisiloxane, octamethylcyclotetrasiloxane, hydrogen-containing tetramethylcyclotetrasiloxane and trifluoropropyl methyl cyclotrisiloxane as raw materials to prepare side chain fluorine-containing polysiloxane, then reacted with alkyne alcohol polyoxyethylene ether to obtain alkyne alcohol modified fluorine-containing polysiloxane.The above preparation method is simple, easy to control, short in preparation period, and suitable for industrial production;Meanwhile, as a silicone super low foam wetting agent, it has good substrate wettability, can solve the surface coating defects such as edge shrinkage, shrinkage and uneven coating of water-based paint on the surface of wood and industrial substrate during coating, and can cause the problem of decreased protection performance and decorative effect, without worrying about the adverse consequences of foaming.

Description

Technical Field

[0001] This invention relates to the field of fine chemicals, specifically to an alkynyl alcohol-modified fluorinated polysiloxane, its preparation method, and its application. Background Technology

[0002] In industrial production processes such as printing and dyeing, coatings, papermaking, bio-fermentation, food manufacturing, wastewater treatment, and petrochemicals, large amounts of foam are frequently generated due to operations such as stirring, vibration, and boiling. If not properly controlled, foam can cause numerous problems in production, such as affecting normal production operations, reducing equipment load capacity, and causing a decline in product quality and production capacity. Therefore, it is necessary to eliminate foam, and adding defoamers is a commonly used method.

[0003] Existing defoamers mainly include: (1) aliphatic defoamers; (2) polyether defoamers; (3) silicone defoamers; and (4) polyether-modified silicone defoamers. However, while defoamers eliminate foam, they can also affect the wetting properties of the system, and sometimes cause adverse effects such as pinholes. Therefore, finding a balance between defoaming and wetting has become an urgent problem to be solved. Developing an ultra-low foaming wetting agent that combines excellent substrate wetting properties with superior defoaming performance has become the key to solving this problem. Summary of the Invention

[0004] This invention provides an alkynyl alcohol-modified fluorinated polysiloxane, its preparation method, and its application, using hexamethyldisiloxane, octamethylcyclotetrasiloxane, and hydrogen-containing tetramethylcyclotetrasiloxane (D4). H Fluorinated polysiloxanes with side chains were prepared using trifluoropropylmethylcyclotrisiloxane as raw material, and then reacted with alkynyl alcohol polyoxyethylene ether to obtain alkynyl alcohol-modified fluorinated polysiloxanes. The above preparation method is simple, easy to control, and has a short preparation cycle, making it suitable for industrial production. Furthermore, as an organosilicon ultra-low foaming wetting agent, it exhibits excellent substrate wetting properties. This solves the problem of surface coating defects such as edge shrinkage, pinholes, and uneven coating caused by poor wetting effect in water-based coatings on wood and industrial substrates, which leads to a decrease in protective performance and decorative effect, without the concern about the adverse consequences of foaming.

[0005] The inventive concept of this application is as follows:

[0006] Fluorinated polysiloxanes exhibit very low surface activity due to the low surface energy of fluorine atoms, further reducing the compatibility between coatings and systems. They also combine the advantages of fluoropolymers and organosilicon polymers, possessing low surface tension, low dielectric constant, and excellent resistance to solvents, oils, acids, and alkalis. The alkynyl alcohol segments contain highly polar hydroxyl groups that can form hydrogen bonds with water, giving them hydrophilicity in aqueous systems. The siloxane bonds in the siloxane segments have high bond energy, providing a degree of stability. Furthermore, the inactive hydrocarbon groups on the siloxane backbone and the introduced vinyl segments also possess some hydrophobic properties. The combination of hydrophilic and hydrophobic segments effectively reduces surface tension in aqueous systems. Compared to traditional polysiloxanes, alkynyl alcohol-modified fluorinated polysiloxanes not only have a wider operating temperature range (-60~310 ℃) but also exhibit superior hydrophobicity and oil resistance, making them widely applicable in textile finishing, water and oil repellency, mold release, lubrication, and coating applications.

[0007] In view of this, the present invention provides an alkynyl alcohol-modified fluorinated polysiloxane, prepared by modifying the main chain of the polysiloxane. As an ultra-low foaming wetting agent, it not only possesses the advantages of broad spectrum and high efficiency, but also, by controlling the type, position, and number of related groups in the organosilicon molecular structure, its defoaming and foam-suppressing properties can be improved, and even additional properties can be imparted. When using this ultra-low foaming wetting agent, no additional defoamer is required, meeting specific market demands. Users can add it freely, reducing the surface tension of the entire system and giving it good substrate wettability. This avoids the problems of poor wetting effect in water-based coatings on wood and industrial substrates, which can lead to surface coating defects such as edge shrinkage, pinholes, and uneven coating, resulting in reduced protective and decorative effects. At the same time, there is no need to worry about the adverse consequences of foaming, such as bubbles and pinholes. Furthermore, this ultra-low foaming wetting agent also has the advantages of low volatile organic compound (VOC) content and low odor release, thus it can be widely used in downstream coatings, ink spraying, PVC board cleaning, and metal cutting.

[0008] Based on the above inventive concept, the specific technical solution of the present invention is as follows:

[0009] An alkynyl alcohol-modified fluorinated polysiloxane has the following chemical structural formula:

[0010] ;

[0011] Wherein, x and z are integers from 0 to 5, y is an integer from 1 to 5, m and n are integers from 0 to 10, and R is -OH, -OCH3, or .

[0012] Furthermore, the x value is 1 or 2, the y value is 1 or 2 or 3, the z value is 1 or 2, the m value is 1 or 2, and the n value is 1 or 2.

[0013] The preparation method of the alkynol-modified fluorinated polysiloxane is as follows:

[0014] Step 1), hexamethyldisiloxane, octamethylcyclotetrasiloxane, and hydrogen-containing tetramethylcyclotetrasiloxane (D4) H The mixture of 1,2-difluoropropylmethylcyclotrisiloxane and trifluoropropylmethylcyclotrisiloxane is homogeneous, and a catalyst is added to induce a ring-opening polymerization reaction, yielding an intermediate, namely a fluorinated polysiloxane with side chains. The reaction equation is as follows:

[0015] ;

[0016] The hexamethyldisiloxane, trifluoropropylmethylcyclotrisiloxane, and hydrogen-containing tetramethylcyclotetrasiloxane (D4) are mentioned. H The molar ratio of x to octamethylcyclotetrasiloxane is 1:x / 3:y / 4:z / 4; wherein the values ​​of x and z are integers from 0 to 5, and the value of y is an integer from 1 to 5; further, the value of x is 1 or 2, the value of y is 1 or 2 or 3, and the value of z is 1 or 2.

[0017] The catalyst mentioned in step 1) above is a solid acid catalyst, preferably an acidic resin, specifically Rohm and Haas UP150, and the dosage is hexamethyldisiloxane, octamethylcyclotetrasiloxane, and hydrogen-containing tetramethylcyclotetrasiloxane (D4). H The total mass of the 1%-10% of the total mass of trifluoropropylmethylcyclotrisiloxane is 1%-10%; the reaction temperature of step 1) is 40-100℃, more preferably 50-80℃, and the reaction time is 2-5 h.

[0018] Preferably, after the above ring-opening polymerization reaction, low-boiling substances can be removed under negative pressure and heating conditions to obtain a fluorinated polysiloxane with side chains; wherein the negative pressure is -0.094 to -0.099 MPa, the heating temperature is 80-100 ℃, and the time for removing low-boiling substances is 40-60 min.

[0019] Step 2) involves reacting the intermediate generated in Step 1) with alkynyl alcohol polyoxyethylene ether in the presence of a second catalyst to obtain alkynyl alcohol-modified fluorinated polysiloxane. The reaction equation is as follows:

[0020] ;

[0021] The second catalyst mentioned in step 2) is a nickel-based catalyst and / or a platinum-based catalyst, more preferably one or more of metallic platinum, chloroplatinic acid, or platinum chelates; the molar ratio of the alkynyl alcohol polyoxyethylene ether to the fluorinated polysiloxane is 1-2:1; preferably, the ratio of the total mass of the fluorinated polysiloxane and the alkynyl alcohol polyoxyethylene ether to the mass of nickel and / or platinum in the second catalyst is 1 g: 1-70 μg;

[0022] The reaction temperature in step 2) is 60-110℃, preferably 80-100℃, and the reaction time is 1-3 h.

[0023] The alkynyl alcohol-modified fluorinated polysiloxane obtained above can be used as an organosilicon ultra-low foam wetting agent.

[0024] Compared with the prior art, the alkynyl alcohol-modified fluorinated polysiloxane obtained in this invention has the following advantages as an ultra-low foaming wetting agent:

[0025] (1) The ultra-low foaming wetting agent of the present invention has low foaming and defoaming properties due to the introduction of alkynol modified polysiloxane side chain, which makes the system less foamy and easy to produce and use; at the same time, it can reduce the surface tension of the water system, making the system have a lower surface tension and good wetting performance; and it also has a certain emulsifying property, so the prepared suspension is dispersed in water in a mist and is evenly dispersed.

[0026] (2) The ultra-low foaming wetting agent of the present invention introduces trifluoropropylmethylcyclotrisiloxane. The very low surface energy of fluorine atoms makes the long-chain polysiloxane with fluorine side groups have very low surface activity, thus achieving the effect of further reducing surface tension and further improving wetting performance.

[0027] (3) The preparation method of the modified organosilicon defoamer of the present invention is simple to operate, easy to control, has high production efficiency and low production cost, and can be used for large-scale production;

[0028] (4) The ultra-low foaming wetting agent of the present invention can be widely used in the industrial production of water-based printing inks, water-based adhesives, water-based coatings, oil extraction, pesticide synergists, solvent-based tinplate inks, glass coatings and so on.

[0029] When the alkynyl alcohol-modified fluorinated polysiloxane prepared by this invention is used as an ultra-low foaming wetting agent, a 1000 mg / L solution can have a surface tension as low as 18.72 mN / m. In the application of water-based coatings, it has certain emulsifying properties and solves the problem of surface coating defects such as edge shrinkage, pinholes and uneven coating caused by poor wetting effect when water-based coatings are applied to wood and industrial substrates, which can lead to a decrease in protective performance and decorative effect. At the same time, there is no need to worry about the adverse consequences of foaming. Detailed Implementation

[0030] The embodiments of the present invention will be described in further detail below. It should be noted that the following embodiments are only for further illustrating the present invention, and the implementation of the present invention is not limited thereto. Some non-essential adjustments and improvements made by those skilled in the art based on the above-described inventive solutions still fall within the protection scope of the present invention.

[0031] The catalyst in step 2) of the following examples can be selected from nickel-based catalysts and / or platinum-based catalysts, especially metallic platinum or chloroplatinic acid or platinum chelates. For ease of comparison, chloroplatinic acid is used as an example below, but this does not mean that only chloroplatinic acid can be used.

[0032] Unless otherwise specified, the experimental methods used in the following examples are conventional methods; the materials and reagents used in the following examples are commercially available unless otherwise specified.

[0033] Example 1: A method for preparing alkynyl alcohol-modified fluorinated polysiloxane, the specific steps of which are as follows:

[0034] 1) Preparation of fluorinated polysiloxanes:

[0035] After thoroughly drying a 500 mL four-necked flask, purge it with nitrogen for 10 min. Then, add 49.3 g of octamethylcyclotetrasiloxane, 97.5 g of trifluoropropylmethylcyclotrisiloxane, 101.25 g of hexamethyldisiloxane, and 46.25 g of hydrogen-containing tetramethylcyclotetrasiloxane (D4). H The product was placed in a four-necked flask equipped with a thermometer and stirrer, and then 6.4 g of acidic resin (Rohm and Haas UP150) was added as a catalyst. The temperature was raised to 50 °C, and the reaction was carried out for 3 h to obtain a transparent product. Then, under negative pressure conditions (vacuum gauge pressure of -0.094 to -0.099 MPa), the low-boiling substances were removed at 80 °C for 60 min to obtain an intermediate product, fluorinated polysiloxane A1, with a molecular weight of 512. The structural formula is as follows:

[0036] .

[0037] 2) Preparation of alkynyl alcohol-modified fluorinated organosilicon:

[0038] The structural formula of the alkynyl alcohol polyoxyethylene ether (C1) used is as follows:

[0039] ;

[0040] In a reaction flask equipped with an N2 inlet, thermometer, and distillation apparatus, 75 g of fluorinated polysiloxane (A1) and 69.54 g of alkynyl alcohol polyoxyethylene ether (C1) were added. The mixture was slowly heated with N2, and when the temperature reached 50 °C, 13.17 mg of chloroplatinic acid was added as a catalyst. The mixture was then stirred and heated further. After adding the catalyst, when the temperature stabilized at 80–90 °C, 75 g of fluorinated polysiloxane (A1) was added dropwise. The temperature was maintained at 80–90 °C, and the addition polymerization reaction was carried out for 2 hours to obtain the target product, alkynyl alcohol-modified fluorinated polysiloxane B1, with the following structural formula:

[0041] .

[0042] Example 2: A method for preparing alkynyl alcohol-modified fluorinated polysiloxane, the specific steps of which are as follows:

[0043] 1) Preparation of fluorinated polysiloxanes:

[0044] After thoroughly drying a 500 mL four-necked flask, purge with nitrogen for 10 min. Add 74 g of octamethylcyclotetrasiloxane, 156 g of trifluoropropylmethylcyclotrisiloxane, 81 g of hexamethyldisiloxane, and 30 g of hydrogen-containing tetramethylcyclotetrasiloxane (D4). H The product was placed in a four-necked flask equipped with a thermometer and stirrer, and then 6.82 g of acidic resin (Rohm and Haas UP150) was added as a catalyst. The temperature was raised to 50 °C, and the reaction was carried out for 3 h to obtain a transparent product. Then, under negative pressure conditions (vacuum gauge pressure of -0.094 to -0.099 MPa), low-boiling substances were removed at 80 °C for 60 min to obtain an intermediate product, fluorinated polysiloxane A2, with a molecular weight of 682. The structural formula is as follows:

[0045] .

[0046] 2) Preparation of alkynyl alcohol-modified fluorinated organosilicon:

[0047] The structural formula of the alkynyl alcohol polyoxyethylene ether (C2) used is as follows:

[0048] ;

[0049] In a reaction flask equipped with an N2 conduit, thermometer, and distillation apparatus, 75 g of fluorinated polysiloxane (A2) and 84.56 g of alkynol polyoxyethylene ether (C2) were added. The mixture was slowly heated with N2, and when the temperature reached 50 °C, 14.08 mg of chloroplatinic acid was added as a catalyst. The mixture was then stirred and heated further. After adding the catalyst, when the temperature stabilized at 80-90 °C, 75 g of fluorinated polysiloxane (A2) was added dropwise, maintaining the temperature at 80-90 °C for 2 hours to complete the addition polymerization reaction. The target product, alkynol-modified fluorinated polysiloxane B2, was obtained, with the following structural formula:

[0050] .

[0051] Example 3: A method for preparing alkynyl alcohol-modified fluorinated polysiloxane, the specific steps of which are as follows:

[0052] 1) Preparation of fluorinated polysiloxanes:

[0053] After thoroughly drying a 500 mL four-necked flask, purge with nitrogen for 10 min. Add 37 g of octamethylcyclotetrasiloxane, 78 g of trifluoropropylmethylcyclotrisiloxane, 81 g of hexamethyldisiloxane, and 90 g of hydrogen-containing tetramethylcyclotetrasiloxane (D4). H The product was placed in a four-necked flask equipped with a thermometer and stirrer, and then 5.72 g of acidic resin (Rohm and Haas UP150) was added as a catalyst. The temperature was raised to 50 °C, and the reaction was carried out for 3 h to obtain a transparent product. Then, under negative pressure conditions (vacuum gauge pressure of -0.094 to -0.099 MPa), low-boiling substances were removed at 80 °C for 60 min to obtain an intermediate product, fluorinated polysiloxane A3, with a molecular weight of 572. The structural formula is as follows:

[0054] .

[0055] 2) Preparation of alkynyl alcohol-modified fluorinated organosilicon:

[0056] The structural formula of the alkynyl alcohol polyoxyethylene ether (C3) used is as follows:

[0057] ;

[0058] In a reaction flask equipped with an N2 inlet, thermometer, and distillation apparatus, 75 g of fluorinated polysiloxane (A3) and 74.66 g of alkynyl alcohol polyoxyethylene ether (C3) were added. The mixture was slowly heated with N2, and when the temperature reached 50 °C, 13.48 mg of chloroplatinic acid was added as a catalyst. The mixture was then stirred and heated further. After adding the catalyst, when the temperature stabilized at 80-90 °C, 75 g of fluorinated polysiloxane (A3) was added dropwise. The temperature was maintained at 80-90 °C, and the addition polymerization reaction was carried out for 2 hours to obtain the target product, alkynyl alcohol-modified fluorinated polysiloxane B3, with the following structural formula:

[0059] .

[0060] The preparation method of comparative allyl polyether modified organosilicon includes the following specific steps:

[0061] 1) Preparation of hydrogen-containing polysiloxanes:

[0062] After thoroughly drying a 500 mL four-necked flask, purge it with nitrogen for 10 min. Add 231 g of octamethylcyclotetrasiloxane and 38 g of hydrogen-containing tetramethylcyclotetrasiloxane (D4)H The product was placed in a four-necked flask equipped with a thermometer and stirrer, and then 5.38 g of acidic resin (Rohm and Haas UP150) was added as a catalyst. The temperature was raised to 50 °C, and the reaction was carried out for 3 h to obtain a transparent product. Then, under negative pressure conditions (vacuum gauge pressure of -0.094 to -0.099 MPa), the low-boiling substances were removed at 80 °C for 60 min to obtain the intermediate product hydrogen-containing polysiloxane A4.

[0063] 2) Preparation of allyl polyether modified organosilicon:

[0064] The allyl polyether structure used is as follows:

[0065] ;

[0066] 35 g of hydrogen-containing polysiloxane (A4) and 114.35 g of allyl polyether were added to a reaction flask equipped with an N2 conduit, thermometer, and distillation apparatus. The mixture was slowly heated with N2. When the temperature reached 50 °C, 16.59 mg of chloroplatinic acid was added as a catalyst. The mixture was stirred and heated until the temperature stabilized at 80-90 °C. Then, 35 g of hydrogen-containing polysiloxane (A4) was added dropwise. The temperature was maintained at 80-90 °C. The addition polymerization reaction was carried out for 2 hours to obtain allyl polyether-modified organosilicon B4.

[0067] Performance testing

[0068] Experimental Example 1: Surface Tension Test

[0069] The surface tension of the samples obtained from all the above embodiments and comparative examples was tested, and the specific steps are as follows:

[0070] First, prepare a 0.1 wt% aqueous solution of the sample to be tested using a volumetric flask, using purified water; stabilize the aqueous solution at 25±0.2 ℃; start the static surface tension instrument; use the platinum ring method; measure the corresponding values; repeat the test three times and take the average value. The test results are shown in Table 1.

[0071] Table 1 Surface tension test results

[0072] sample Surface tension (mN / m) B1 (Example 1) 18.72 B2 (Example 2) 18.97 B3 (Example 3) 18.74 B4 (Comparative Example) 22.16 .

[0073] Experimental Example 2: Water Dispersibility Test

[0074] The water dispersibility of the samples obtained from all the above examples and comparative examples was tested, and the specific steps are as follows:

[0075] Add the sample to a graduated cylinder containing water, shake, and observe the dispersion effect in the water. If it is difficult to disperse in water and white flocculent matter appears, the water dispersibility is poor; if it diffuses slowly in water and only a small amount of white flocculent matter appears, the water dispersibility is good; if it disperses rapidly and evenly in water, the water dispersibility is excellent. The test results are shown in Table 2.

[0076] Table 2 Results of water dispersibility test

[0077] sample Water dispersibility B1 (Example 1) excellent B2 (Example 2) excellent B3 (Example 3) excellent B4 (Comparative Example) good .

[0078] Experimental Example 3: Wetting Performance Test

[0079] The wetting properties of the samples obtained from all the above examples and comparative examples were tested, and the specific steps are as follows:

[0080] First, the sample to be tested was prepared into a 0.1 wt% aqueous solution using a volumetric flask. 10 μL was then pipetted onto a PVC board, and the spreading speed and area on the board were observed. The test results are shown in Table 3.

[0081] Table 3 Spreading performance test results

[0082] sample Spreading performance B1 (Example 1) The droplets spread and expand at a relatively fast speed B2 (Example 2) The droplets spread and expand at a relatively fast speed B3 (Example 3) The droplets spread and expand at a relatively fast speed B4 (Comparative Example) The droplets spread and expand at a relatively slow rate. .

[0083] Test Example 4: Foam Suppression Performance Test

[0084] The antifoaming performance of the samples obtained from all the above examples and comparative examples was tested, and the specific steps are as follows:

[0085] Add 100 mL of foaming solution (sodium dodecylbenzenesulfonate with a mass fraction of 1%) and 0.01 g of sample to a 500 mL graduated cylinder. Insert a glass tube connected to a nitrogen cylinder and control the nitrogen flow rate to 500 mL / min. Start a stopwatch at the same time and stop timing when the foam rises to the 500 mL mark. The obtained time is the foam suppression time. The test results are shown in Table 4.

[0086] Table 4. Results of foam suppression performance test

[0087] sample Defoaming time (s) B1 (Example 1) 22.3 B2 (Example 2) 20.5 B3 (Example 3) 21.6 B4 (Comparative Example) 23.2 .

[0088] Test Example 5: Defoaming Performance Test

[0089] The defoaming performance of the samples obtained from all the above examples and comparative examples was tested, and the specific steps are as follows:

[0090] Add 100 mL of foaming solution (1% sodium dodecylbenzenesulfonate by mass) and 0.01 g of sample to a 500 mL graduated cylinder. Insert a glass tube connected to a nitrogen cylinder and control the nitrogen flow rate at 500 mL / min. Stop the nitrogen flow when the foam reaches the 500 mL mark and remove the glass tube. Start a stopwatch when the foam drops to the 500 mL mark and stop timing when the foam is completely eliminated. The time obtained is the defoaming time. The test results are shown in Table 5.

[0091] Table 5 Defoaming performance test results

[0092] sample Defoaming time (s) B1 (Example 1) 23.8 B2 (Example 2) 25.2 B3 (Example 3) 25.4 B4 (Comparative Example) 25.9 .

[0093] Experimental Example 6 Centrifugation Stability Test

[0094] The centrifugal stability of the samples obtained from all the above examples and comparative examples was tested, and the specific steps are as follows:

[0095] Referring to GB / T 26527—2024 "Organic Silicone Defoamers", the stability of the defoamer is represented by the stratification time at a speed of 3000 r / min. The longer the stratification time, the better the stability of the sample. No stratification for 15 min is sufficient to meet the standard. The test results are shown in Table 6.

[0096] Table 6 Results of centrifugal stability test

[0097] sample Centrifugal stability B1 (Example 1) No layering B2 (Example 2) No layering B3 (Example 3) No layering B4 (Comparative Example) No layering .

[0098] Experimental Example 7 Thermal Stability Test

[0099] The thermal stability of the samples obtained from all the above embodiments and comparative examples was tested, and the specific steps are as follows:

[0100] Take 5 g of sample, place it in a test tube and seal it. Then place it in an oven set to 60 ℃ and let it stand for 48 h. After removing it and cooling it to room temperature, observe whether the defoamer separates into layers and floats oil. The test results are shown in Table 7.

[0101] Table 7 Thermal stability test results

[0102] sample thermal stability B1 (Example 1) No layering, no floating oil B2 (Example 2) No layering, no floating oil B3 (Example 3) No layering, no floating oil B4 (Comparative Example) No layering, a little oil floating on top .

[0103] Experimental Example 8: Performance Test of Ultra-Low Foaming Wetting Agent

[0104] The application performance of the samples obtained from all the above embodiments and comparative examples was tested, and the specific steps are as follows:

[0105] Waterborne acrylic paint was prepared using conventional processes. Then, the samples obtained from the examples and comparative examples of this application were added to the waterborne acrylic paint at a ratio of 0.25 wt%. An appropriate amount was dropped onto a tinplate sheet and immediately spread evenly with a wire-bar applicator. The pinholes in the paint film on the tinplate sheet were observed. (Per 100 cm²) 2 The number of pinholes with a diameter greater than 1 mm on the area coating film is used to measure the compatibility between the defoamer and the coating. The fewer the pinholes, the better the compatibility between the ultra-low foaming wetting agent and the coating. The test results are shown in Table 8.

[0106] Table 8 Application Test Results

[0107] sample Application B1 (Example 1) No orange peel, no shrinkage, no edge shrinkage B2 (Example 2) No orange peel texture, no shrinkage pores, no edge shrinkage B3 (Example 3) No orange peel, no shrinkage, no edge shrinkage B4 (Comparative Example) No orange peel texture, a few pinholes, a few edge shrinkages .

[0108] In summary, the alkynyl alcohol-modified fluorinated polysiloxane prepared in this invention exhibits excellent defoaming and foam-suppressing properties as an ultra-low foaming wetting agent. The introduction of fluorine atoms and the presence of alkynyl alcohol in the alkynyl alcohol-modified hydrogen-containing polysiloxane broaden its usable temperature range and reduce its surface tension in the system, thereby improving the wetting performance of the ultra-low foaming wetting agent. Performance testing results show that this ultra-low foaming wetting agent has excellent thermal stability, centrifugal stability, and water dispersibility, and application tests indicate that it also has good application prospects in practical applications.

[0109] The above embodiments are preferred embodiments of the present invention, mainly demonstrating and describing the main features and basic principles of the present invention. However, the implementation of the present invention is not limited to the above embodiments. Any modifications, alterations, substitutions, combinations, or simplifications made by those skilled in the art without departing from the spirit and scope of the present invention should be considered within the scope of the present invention.

Claims

1. An alkynyl alcohol-modified fluorinated polysiloxane, characterized in that, Its chemical structural formula is: Wherein, x is 1 or 2, y is an integer from 1 to 5, z is an integer from 0 to 5, m is 1 or 2, n is 1 or 2, and R is -OH or -OCH3.

2. The alkynyl alcohol-modified fluorinated polysiloxane according to claim 1, characterized in that, The value of y is 1, 2, or 3, and the value of z is 1 or 2.

3. The method for preparing the alkynyl alcohol-modified fluorinated polysiloxane according to claim 1, characterized in that, The specific steps are as follows: Step 1): Hexamethyldisiloxane, octamethylcyclotetrasiloxane, hydrogen-containing tetramethylcyclotetrasiloxane, and trifluoropropylmethylcyclotrisiloxane are mixed evenly, and a catalyst is added to induce a ring-opening polymerization reaction, yielding an intermediate, namely a side-chain fluorinated polysiloxane. The reaction equation is as follows: ； The molar ratio of hexamethyldisiloxane, trifluoropropylmethylcyclotrisiloxane, hydrogen-containing tetramethylcyclotetrasiloxane to octamethylcyclotetrasiloxane is 1:x / 3:y / 4:z / 4; Step 2) involves reacting the intermediate generated in Step 1) with alkynyl alcohol polyoxyethylene ether in the presence of a second catalyst to obtain alkynyl alcohol-modified fluorinated polysiloxane. The reaction equation is as follows: 。 4. The method for preparing alkynyl alcohol-modified fluorinated polysiloxane according to claim 3, characterized in that, In step 1), the x value is 1 or 2, the y value is 1 or 2 or 3, and the z value is 1 or 2.

5. The method for preparing alkynyl alcohol-modified fluorinated polysiloxane according to claim 3 or 4, characterized in that, The catalyst mentioned in step 1) is a solid acid catalyst, and the amount used is 1%-10% of the total mass of the added hexamethyldisiloxane, octamethylcyclotetrasiloxane, hydrogen-containing tetramethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane; the reaction temperature in step 1) is 40-100℃ and the reaction time is 2-5 h.

6. The method for preparing alkynyl alcohol-modified fluorinated polysiloxane according to claim 5, characterized in that, The catalyst mentioned in step 1) is an acidic resin, and the reaction temperature is 50-80 ℃.

7. The method for preparing alkynyl alcohol-modified fluorinated polysiloxane according to claim 3, characterized in that, Step 1) After the ring-opening polymerization reaction, the low-boiling substances are removed under negative pressure and heating conditions to obtain a fluorinated polysiloxane with side chains; wherein, the negative pressure is -0.094~-0.099 MPa, the heating temperature is 80-100 ℃, and the time for removing the low-boiling substances is 40-60 min.

8. The method for preparing alkynyl alcohol-modified fluorinated polysiloxane according to claim 3, characterized in that, The second catalyst mentioned in step 2) is selected from nickel-based catalysts or platinum-based catalysts; the reaction temperature is 60-110 ℃, and the reaction time is 1-3 h; the molar ratio of the alkynyl alcohol polyoxyethylene ether to the fluorinated polysiloxane is 1-2:1; the ratio of the total mass of the fluorinated polysiloxane and the alkynyl alcohol polyoxyethylene ether to the mass of nickel or platinum in the second catalyst is 1 g: 1-70 μg.

9. The method for preparing alkynyl alcohol-modified fluorinated polysiloxane according to claim 8, characterized in that, In step 2), the second catalyst is selected from platinum, chloroplatinic acid, or platinum chelate, and the reaction temperature is 80-100℃.

10. The application of the alkynyl alcohol-modified fluorinated polysiloxane of claim 1 as an ultra-low foaming wetting agent.

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