Alkynol modified fluorine-containing polysiloxane as well as preparation method and application thereof

Abstract

The invention relates to the field of fine chemical engineering, and provides alkynol modified fluorine-containing polysiloxane as well as a preparation method and application thereof, hexamethyldisiloxane, octamethylcyclotetrasiloxane, hydrogen-containing tetramethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane are used as raw materials to prepare side chain fluorine-containing polysiloxane, and the side chain fluorine-containing polysiloxane is prepared by using hexamethyldisiloxane, octamethylcyclotetrasiloxane, hydrogen-containing tetramethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane as raw materials. And reacting the fluorine-containing polysiloxane with alkynol polyoxyethylene ether to obtain alkynol modified fluorine-containing polysiloxane. The preparation method is simple in process, easy to control, short in preparation period and suitable for industrial production; meanwhile, as an organic silicon ultra-low-foam wetting agent, the organic silicon ultra-low-foam wetting agent has good base material wettability, so that the problem that the protective performance and the decorative effect are reduced due to surface coating defects such as edge shrinkage, hole shrinkage and uneven coating which are easily caused by poor wetting effect of a water-based coating in woodware and industrial base material surface coating can be solved; and bad consequences caused by bubbling do not need to be worried.

Description

Technical Field

[0001] The invention relates to the field of fine chemicals, and in particular to an acetylenol-modified fluorine-containing polysiloxane and a preparation method and application thereof. Background Art

[0002] In industrial production in printing and dyeing, coatings, papermaking, biological fermentation, food manufacturing, sewage treatment and petrochemical industries, a large amount of foam is often generated due to operations such as stirring, vibration and boiling. If it cannot be well controlled, the foam will bring many troubles to production, such as affecting the normal production, reducing the effective load of equipment, causing product quality and production capacity to decline, etc. Therefore, it is necessary to eliminate the foam, and adding a defoaming agent is a commonly used method.

[0003] The main types of existing defoamers are: (1) fat defoamers; (2) polyether defoamers; (3) silicone defoamers; (4) polyether modified silicone defoamers. However, the addition of defoamers will not only eliminate foam, but also affect the wetting properties of the system, and sometimes cause adverse effects such as shrinkage. Therefore, finding a balance between defoaming and wetting has become an urgent problem to be solved. Developing an ultra-low foaming wetting agent that has both excellent substrate wetting and excellent defoaming performance has become the key to solving this problem. Summary of the invention

[0004] The present invention provides an acetylenol-modified fluorinated polysiloxane and a preparation method and application thereof, wherein hexamethyldisiloxane, octamethylcyclotetrasiloxane, hydrogen-containing tetramethylcyclotetrasiloxane (D4 H ) and trifluoropropylmethylcyclotrisiloxane as raw materials to prepare side chain fluorinated polysiloxane, which is then reacted with acetylene alcohol polyoxyethylene ether to obtain acetylene alcohol modified fluorinated polysiloxane. The above preparation method is simple in process, easy to control, short in preparation cycle, and suitable for industrial production; at the same time, it has good substrate wettability as an organosilicon ultra-low foam wetting agent, which can solve the problem that water-based coatings are prone to shrinkage, shrinkage holes and uneven coating due to poor coating wetting effect in the surface coating of wood and industrial substrates, resulting in reduced protective performance and decorative effects, and there is no need to worry about the adverse consequences of foaming.

[0005] The inventive concept of this application is as follows: Fluorinated polysiloxane has very low surface activity due to the low surface energy of fluorine atoms, which can further reduce the compatibility of coatings with the system. At the same time, it also combines the advantages of fluorinated polymers and silicone polymers, and has low surface tension, small dielectric constant, and excellent solvent resistance, oil resistance, acid and alkali resistance and other properties. The acetylene alcohol segment contains alcohol hydroxyl groups with strong polarity, which can form hydrogen bonds with water, making it hydrophilic in aqueous systems. The siloxane bonds in the siloxane segment have a certain stability due to the high bond energy, and the inactive hydrocarbon groups on the siloxane main chain and the introduced vinyl segments also have certain hydrophobic properties. When the hydrophilic segment and the hydrophobic segment are combined together, the surface tension in the aqueous system can be effectively reduced. Compared with traditional polysiloxanes, acetylene alcohol-modified fluorinated polysiloxane not only has a wider temperature range (-60~310 ℃), but also has more outstanding hydrophobicity and oil resistance. It has a wide range of uses in textile finishing, water and oil repellency, demolding, lubrication, and coating.

[0006] In view of this, the present invention provides an acetylene alcohol modified fluorinated polysiloxane, which is prepared by modifying the main chain of polysiloxane. As an ultra-low foam wetting agent, it not only has the advantages of broad spectrum and high efficiency, but also can improve its defoaming and anti-foaming properties by regulating the types, positions and quantities of related groups in the molecular structure of organic silicon, and even give it more additional properties. When using this ultra-low foam wetting agent, there is no need to add an additional defoamer, which meets the specific needs of the market. Users can add it freely, reduce the surface tension of the entire system, make it have good substrate wettability, and avoid the problem that water-based coatings are prone to shrinkage, shrinkage and uneven coating due to poor coating wetting effect in the surface coating of wood and industrial substrates, resulting in reduced protective performance and decorative effects. At the same time, there is no need to worry about the adverse consequences of foaming, such as bubbles and pinholes. Not only that, the ultra-low foam wetting agent also has the advantages of low volatile organic compound (VOC) content and low odor release, and can be widely used in downstream coatings, ink spraying, PVC board cleaning and metal cutting and other fields.

[0007] Based on the above inventive concept, the specific technical solution of the present invention is as follows: An acetylenol-modified fluorinated polysiloxane, the chemical structure of which is: ; Wherein, the values ​​of x and z are integers of 0-5, the value of y is integer of 1-5, the values ​​of m and n are integers of 0-10, and R is -OH, -OCH3 or .

[0008] 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.

[0009] The preparation method of the acetylenol-modified fluorinated polysiloxane is as follows: Step 1), hexamethyldisiloxane, octamethylcyclotetrasiloxane, hydrogen-containing tetramethylcyclotetrasiloxane (D4 H ) and trifluoropropylmethylcyclotrisiloxane are uniformly mixed, a catalyst is added, and a ring-opening polymerization reaction occurs to obtain an intermediate, i.e., a side-chain fluorinated polysiloxane. The reaction equation is as follows: ; Wherein the hexamethyldisiloxane, trifluoropropylmethylcyclotrisiloxane, hydrogen-containing tetramethylcyclotetrasiloxane (D4 H ) and octamethylcyclotetrasiloxane in a molar ratio of 1:x / 3:y / 4:z / 4; wherein the x and z values ​​are both integers of 0-5, and the y value is an integer of 1-5; further, the x value is 1 or 2, the y value is 1 or 2 or 3, and the z value is 1 or 2.

[0010] The catalyst in step 1) is a solid acid catalyst, preferably an acidic resin, which can be selected from Rohm and Haas UP150, and the amount is added to hexamethyldisiloxane, octamethylcyclotetrasiloxane, hydrogen-containing tetramethylcyclotetrasiloxane (D4 H ) and trifluoropropylmethylcyclotrisiloxane by weight; the reaction temperature of step 1) is 40-100°C, more preferably 50-80°C, and the reaction time is 2-5 h.

[0011] Preferably, after the above-mentioned ring-opening polymerization reaction, low boiling substances can be removed under negative pressure and heating conditions to obtain side chain fluorinated polysiloxane; wherein the negative pressure is -0.094~-0.099 MPa, the heating temperature is 80-100°C, and the time for removing low boiling substances is 40-60 min.

[0012] Step 2), reacting the intermediate generated by the reaction in step 1) with acetylene alcohol polyoxyethylene ether in the presence of a second catalyst to obtain acetylene alcohol-modified fluorinated polysiloxane, the reaction equation of which is as follows: ; The second catalyst in step 2) is a nickel catalyst and / or a platinum catalyst, more preferably one or more of metal platinum, chloroplatinic acid or platinum chelate; the molar ratio of the acetylene alcohol polyoxyethylene ether to the fluorinated polysiloxane is 1-2:1; preferably, the total mass of the fluorinated polysiloxane and the acetylene alcohol polyoxyethylene ether to the mass ratio of the nickel element and / or the platinum element in the second catalyst is 1 g:1-70 μg; The reaction temperature of step 2) is 60-110°C, preferably 80-100°C, and the reaction time is 1-3 h.

[0013] The acetylene alcohol modified fluorinated polysiloxane obtained above can be used as an organosilicon ultra-low foam wetting agent.

[0014] Compared with the prior art, the acetylene alcohol modified fluorinated polysiloxane obtained in the present invention has the following advantages as an ultra-low foaming wetting agent: (1) The ultra-low foam wetting agent of the present invention has low foam and defoaming properties due to the introduction of acetylene alcohol modified polysiloxane side chains, 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, so that the system has a lower surface tension and good wetting performance; and it has a certain emulsification property, and the prepared suspension is dispersed in the form of mist when entering water and is evenly dispersed; (2) Since trifluoropropylmethylcyclotrisiloxane is introduced into the ultra-low foam wetting agent of the present invention, the low surface energy of the fluorine atom makes the long-chain fluorine-containing side group polysiloxane have very low surface activity, thereby further reducing the surface tension and further improving the wetting performance; (3) The preparation method of the modified organosilicon defoamer of the present invention is simple to operate, convenient to control, high in production efficiency, low in production cost, and can be used for large-scale production; (4) The ultra-low foam wetting agent of the present invention can be widely used in industrial production such as water-based printing inks, water-based adhesives, water-based coatings, oil production, pesticide synergists, solvent-based tinplate inks, and glass coatings.

[0015] When the acetylene alcohol modified fluorinated polysiloxane prepared by the present invention is used as an ultra-low foaming wetting agent and is prepared into a 1000 mg / L solution, its surface tension can be as low as 18.72 mN / m: in the application of water-based coatings, it has certain emulsification properties, and in the process of using a paint scraper, it can solve the problem that water-based coatings are prone to surface coating defects such as edge shrinkage, shrinkage holes and uneven coating due to poor coating wetting effect in the coating of wood and industrial substrates, resulting in reduced protective performance and decorative effects, and there is no need to worry about the adverse consequences of foaming. DETAILED DESCRIPTION

[0016] The embodiments of the present invention will be further described in detail by examples. It is necessary to point out that the following examples are only used to further illustrate the present invention, and the embodiments of the present invention are not limited thereto. Some non-essential adjustments and improvements made by people familiar with the relevant fields according to the above invention scheme still belong to the protection scope of the present invention.

[0017] The catalyst in step 2) of the following embodiment can be selected from nickel-based catalysts and / or platinum-based catalysts, in particular metal platinum or chloroplatinic acid or platinum chelate. For the sake of comparison, chloroplatinic acid is used as an example below, but it does not mean that only chloroplatinic acid can be used. This is hereby explained.

[0018] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the materials, reagents, etc. used in the following examples, unless otherwise specified, can be obtained from commercial channels.

[0019] Example 1 A method for preparing an acetylenic alcohol-modified fluorinated polysiloxane, the specific steps are as follows: 1) Preparation of fluorinated polysiloxane: A 500 mL four-necked flask was thoroughly dried and nitrogen was passed through for 10 min. 49.3 g of octamethylcyclotetrasiloxane, 97.5 g of trifluoropropylmethylcyclotrisiloxane, 101.25 g of hexamethyldisiloxane and 46.25 g of hydrogenated tetramethylcyclotetrasiloxane (D4 H ) was placed in a four-necked flask with a thermometer and a 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~-0.099 MPa), 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, and the structural formula is as follows: .

[0020] 2) Preparation of acetylenic alcohol modified fluorinated silicone: The structural formula of the acetylene alcohol polyoxyethylene ether (C1) used is as follows: ; Add 75 g of fluorinated polysiloxane (A1) and 69.54 g of acetylene alcohol polyoxyethylene ether (C1) to a reaction flask equipped with a N2 tube, a thermometer and a distillation device, and slowly heat it with N2. When the temperature rises to 50 °C, add 13.17 mg of chloroplatinic acid as a catalyst and continue stirring and heating. After adding the catalyst, when the temperature stabilizes at 80-90 °C, add 75 g of fluorinated polysiloxane (A1) dropwise, maintain the temperature at 80-90 °C, and perform addition polymerization for 2 h to obtain the target product, acetylene alcohol-modified fluorinated polysiloxane B1, with the structural formula as follows: .

[0021] Example 2 A method for preparing an acetylenic alcohol-modified fluorinated polysiloxane, the specific steps are as follows: 1) Preparation of fluorinated polysiloxane: A 500 mL four-necked flask was thoroughly dried and nitrogen was passed through for 10 min. 74 g of octamethylcyclotetrasiloxane, 156 g of trifluoropropylmethylcyclotrisiloxane, 81 g of hexamethyldisiloxane and 30 g of hydrogenated tetramethylcyclotetrasiloxane (D4 H) was placed in a four-necked flask with a thermometer and a 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~-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, and the structural formula is as follows: .

[0022] 2) Preparation of acetylenic alcohol modified fluorinated silicone: The structural formula of the acetylene alcohol polyoxyethylene ether (C2) used is as follows: ; Add 75 g of fluorinated polysiloxane (A2) and 84.56 g of acetylene alcohol polyoxyethylene ether (C2) to a reaction flask equipped with a N2 tube, a thermometer and a distillation device, and slowly heat it with N2. When the temperature rises to 50 °C, add 14.08 mg of chloroplatinic acid as a catalyst and continue stirring and heating. After adding the catalyst, when the temperature stabilizes to 80-90 °C, add 75 g of fluorinated polysiloxane (A2) dropwise, maintain the temperature at 80-90 °C, and perform addition polymerization for 2 h. The target product, acetylene alcohol modified fluorinated polysiloxane B2, can be obtained, and the structural formula is as follows: .

[0023] Example 3 A method for preparing acetylenic alcohol-modified fluorinated polysiloxane, the specific steps are as follows: 1) Preparation of fluorinated polysiloxane: A 500 mL four-necked flask was thoroughly dried and nitrogen was passed through for 10 min. 37 g of octamethylcyclotetrasiloxane, 78 g of trifluoropropylmethylcyclotrisiloxane, 81 g of hexamethyldisiloxane and 90 g of hydrogenated tetramethylcyclotetrasiloxane (D4 H ) was placed in a four-necked flask with a thermometer and a 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 hours to obtain a transparent product. Then, under negative pressure conditions (vacuum gauge pressure of -0.094~-0.099 MPa), low boiling substances were removed at 80°C for 60 minutes to obtain an intermediate product fluorinated polysiloxane A3 with a molecular weight of 572, and the structural formula is as follows: .

[0024] 2) Preparation of acetylenic alcohol modified fluorinated silicone: The structural formula of the acetylene alcohol polyoxyethylene ether (C3) used is as follows: ; Add 75 g of fluorinated polysiloxane (A3) and 74.66 g of acetylene alcohol polyoxyethylene ether (C3) to a reaction flask equipped with a N2 tube, a thermometer and a distillation device, and slowly heat it with N2. When the temperature rises to 50 °C, add 13.48 mg of chloroplatinic acid as a catalyst and continue stirring and heating. After adding the catalyst, when the temperature stabilizes at 80-90 °C, add 75 g of fluorinated polysiloxane (A3) dropwise, maintain the temperature at 80-90 °C, and perform addition polymerization for 2 h to obtain the target product, acetylene alcohol modified fluorinated polysiloxane B3, with the following structural formula: .

[0025] The preparation method of the comparative example allyl polyether modified silicone is as follows: 1) Preparation of hydrogen-containing polysiloxane: A 500 mL four-necked flask was thoroughly dried and nitrogen was passed through for 10 min. 231 g of octamethylcyclotetrasiloxane and 38 g of hydrogen-containing tetramethylcyclotetrasiloxane (D4 H ) was placed in a four-necked flask with a thermometer and a 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~-0.099 MPa), low boiling substances were removed at 80 °C for 60 min to obtain the intermediate product hydrogen-containing polysiloxane A4.

[0026] 2) Preparation of allyl polyether modified silicone: The structural formula of the allyl polyether used is as follows: ; Add 35 g of hydrogen-containing polysiloxane (A4) and 114.35 g of allyl polyether to a reaction flask equipped with a N2 tube, a thermometer and a distillation apparatus, and slowly heat with N2. When the temperature reaches 50°C, add 16.59 mg of chloroplatinic acid as a catalyst. Continue stirring and heating. When the temperature stabilizes at 80-90°C, add 35 g of hydrogen-containing polysiloxane (A4) dropwise, maintain the temperature at 80-90°C, and perform addition polymerization for 2 h to obtain allyl polyether-modified silicone B4.

[0027] Performance testing Test Example 1 Surface tension test The surface tension of the samples obtained in all the above embodiments and comparative examples was tested, and the specific steps were as follows: First, use a volumetric flask to prepare the sample to be tested into a 0.1 wt% aqueous solution, using pure water for preparation; stabilize the aqueous solution at 25±0.2 ℃; start the static surface tension instrument; use the platinum ring method; measure the corresponding value; repeat the test three times and take the average value. The test results are shown in Table 1; Table 1 Surface tension test results 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 .

[0028] Test Example 2 Water Dispersibility Test The water dispersibility of the samples obtained in all the above embodiments and comparative examples was tested, and the specific steps were as follows: Add the sample to a measuring cylinder filled with water, shake and observe the dispersion effect in water. If it is difficult to disperse in water and white flocs appear, the water dispersibility is poor; if the diffusion speed in water is slow and only a small amount of white flocs appear, the water dispersibility is good; if it disperses quickly and evenly in water, the water dispersibility is excellent. The test results are shown in Table 2; Table 2 Water dispersibility test results sample Water dispersibility B1 (Example 1) excellent B2 (Example 2) excellent B3 (Example 3) excellent B4 (Comparative Example) good .

[0029] Test Example 3 Wetting Performance Test The wetting properties of the samples obtained in all the above embodiments and comparative examples were tested, and the specific steps were as follows: First, use a volumetric flask to prepare a 0.1wt% aqueous solution of the sample to be tested, use a pipette to draw 10 μL and drop it on the PVC board, and observe its spreading speed and spreading area on the board. The test results are shown in Table 3; Table 3 Spreading performance test results sample Spreading performance B1 (Example 1) The droplets spread and expand at a faster speed B2 (Example 2) The droplets spread and expand at a faster speed B3 (Example 3) The droplets spread and expand at a faster speed B4 (Comparative Example) The droplets spread and expand at a slower speed .

[0030] Test Example 4 Antifoaming Performance Test The antifoaming properties of the samples obtained in all the above embodiments and comparative examples were tested, and the specific steps were as follows: Add 100 mL of foaming liquid (sodium dodecylbenzene sulfonate with a mass fraction of 1%) and 0.01 g of sample into a 500 mL measuring cylinder, insert a glass tube connected to a nitrogen bottle, control the nitrogen flow rate to 500 mL / min, and start the stopwatch at the same time. When the foam rises to the 500 mL mark, stop the timing. The obtained time is the foam suppression time. The test results are shown in Table 4. Table 4 Antifoaming performance test results sample Anti-foaming time (s) B1 (Example 1) 22.3 B2 (Example 2) 20.5 B3 (Example 3) 21.6 B4 (Comparative Example) 23.2 .

[0031] Test Example 5 Defoaming Performance Test The defoaming performance of the samples obtained in all the above embodiments and comparative examples was tested, and the specific steps were as follows: Add 100 mL of foaming liquid (sodium dodecylbenzene sulfonate with a mass fraction of 1%) and 0.01 g of sample to a 500 mL measuring cylinder, insert a glass tube connected to a nitrogen bottle, control the nitrogen flow rate to 500 mL / min, stop nitrogen flow when the foam is higher than the 500 mL mark, and pull out the glass tube. Start the stopwatch when the foam drops to the 500 mL mark, and stop the stopwatch when the foam is completely eliminated. The obtained time is the defoaming time. The test results are shown in Table 5; Table 5 Defoaming performance test results sample Defoaming time (s) B1 (Example 1) 23.8 B2 (Example 2) 25.2 B3 (Example 3) 25.4 B4 (Comparative Example) 25.9 .

[0032] Test Example 6 Centrifugal Stability Test The centrifugal stability of the samples obtained in all the above embodiments and comparative examples was tested, and the specific steps were as follows: Referring to GB / T 26527-2024 "Organic Silicone Defoamer", the defoamer stratification time at a speed of 3000 r / min is used to indicate its stability. The longer the defoamer stratification time, the better the stability of the sample. If there is no stratification within 15 minutes, the standard is met. The test results are shown in Table 6. Table 6 Centrifugal stability test results sample Centrifugal stability B1 (Example 1) No stratification B2 (Example 2) No stratification B3 (Example 3) No stratification B4 (Comparative Example) No stratification .

[0033] Test Example 7 Thermal Stability Test The thermal stability of the samples obtained in all the above embodiments and comparative examples was tested, and the specific steps were as follows: Take 5 g of sample, put it into a test tube, seal it, and then place it in an oven set at 60 °C for 48 h. After taking it out, cool it to room temperature and observe whether the defoamer is separated and floated. The test results are shown in Table 7; Table 7 Thermal stability test results sample Thermal stability B1 (Example 1) No stratification and no floating oil B2 (Example 2) No stratification and no floating oil B3 (Example 3) No stratification and no floating oil B4 (Comparative Example) No stratification, a little floating oil .

[0034] Test Example 8 Ultra-low foam wetting agent application performance test The application performance of the samples obtained in all the above embodiments and comparative examples was tested, and the specific steps were as follows: Prepare water-based acrylic paint according to conventional processes, and then add the samples obtained in the examples and comparative examples of the present application to the water-based acrylic paint at a ratio of 0.25wt%. Take an appropriate amount and drop it on the tinplate sheet, and immediately scrape it flat with a wire rod coater at a uniform speed to observe the shrinkage of the paint film on the tinplate sheet. 2The number of shrinkage holes with a diameter greater than 1 mm on the area coating film is used to measure the compatibility of the defoamer and the coating. The fewer the shrinkage holes, the better the compatibility of the ultra-low foam wetting agent with the coating. The test results are shown in Table 8. Table 8 Application test results sample Applicability B1 (Example 1) No orange peel, no shrinkage, no shrinkage B2 (Example 2) No orange peel, no shrinkage, no shrinkage B3 (Example 3) No orange peel, no shrinkage, no shrinkage B4 (Comparative Example) No orange peel, a little shrinkage, a little shrinkage .

[0035] In summary, the acetylene alcohol modified fluorinated polysiloxane prepared by the present invention has good defoaming and antifoaming properties as an ultra-low foaming wetting agent. The introduction of fluorine atoms and the presence of acetylene alcohol in the acetylene alcohol modified hydrogenated polysiloxane broaden the usable temperature range and reduce its surface tension in the action system, thereby improving the wetting properties of the ultra-low foaming wetting agent. The performance test results show that the ultra-low foaming wetting agent has excellent thermal stability, centrifugal stability and water dispersibility, and the application test shows that it also has good application prospects in practical applications.

[0036] The above embodiments are preferred implementations of the present invention, which mainly demonstrate and describe the main features and basic principles of the present invention. However, the implementation of the present invention is not limited to the above embodiments, and any modification, alteration, substitution, combination, simplification made by any person familiar with the relevant fields and technologies without departing from the spirit and scope of the present invention shall be deemed to be within the scope of the present invention.

Claims

1. An acetylenic alcohol-modified fluorinated polysiloxane, characterized in that: Its chemical structure is: ； Wherein, the values ​​of x and z are integers of 0-5, the value of y is integer of 1-5, the values ​​of m and n are integers of 0-10, and R is -OH, -OCH3 or .

2. The acetylenic alcohol-modified fluorinated polysiloxane according to claim 1, characterized in that: 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.

3. The method for preparing the acetylenic 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, a catalyst is added, and a ring-opening polymerization reaction occurs to obtain an intermediate, i.e., a side-chain fluorinated polysiloxane, and the reaction equation is as follows: ； The molar ratio of hexamethyldisiloxane, trifluoropropylmethylcyclotrisiloxane, hydrogen-containing tetramethylcyclotetrasiloxane and octamethylcyclotetrasiloxane is 1:x / 3:y / 4:z / 4; wherein the values ​​of x and z are both integers of 0-5, and the value of y is an integer of 1-5; Step 2), reacting the intermediate generated by the reaction in step 1) with acetylene alcohol polyoxyethylene ether in the presence of a second catalyst to obtain acetylene alcohol-modified fluorinated polysiloxane, the reaction equation of which is as follows: 。 4. The method for preparing the acetylenic 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 the acetylenic alcohol-modified fluorinated polysiloxane according to claim 3 or 4, characterized in that: The catalyst described 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 of step 1) is 40-100°C, and the reaction time is 2-5 h.

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

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

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

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

10. Use of the acetylenic alcohol modified fluorinated polysiloxane according to claim 1 as an ultra-low foaming wetting agent.

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