Superhydrophobic polyether polyols, methods of making, and uses thereof

Abstract

The application discloses a preparation method of super-hydrophobic polyether polyol, comprising the following steps: a) polymerization reaction: using a polyhydroxy compound as a starter, performing ring-opening polymerization reaction with an epoxide under the action of a catalyst, aging after the reaction, degassing, and obtaining polyether polyol A; b) esterification modification: performing esterification reaction of the polyether polyol A with a hydrophobic long-chain fatty acid under the action of a catalyst, and obtaining super-hydrophobic polyether polyol. The super-hydrophobic polyether polyol prepared by the method has a functionality of greater than or equal to 2.3 and a number average molecular weight of 3000-16000 g / mol. The polyurethane material prepared based on the high-functionality high-molecular-weight super-hydrophobic polyether polyol has excellent mechanical properties and extremely strong hydrophobic waterproof performance, and is good in application in the high-end building waterproof field and high-grade clothing and accessories.

Description

Technical Field

[0001] This invention belongs to the field of polyether polyol synthesis, specifically relating to a superhydrophobic polyether polyol, its preparation method, and its application. Background Technology

[0002] Polyether polyols prepared by ring-opening polymerization of epoxide alkane with active hydrogen compounds as initiators have limited applications in fields requiring superhydrophobicity, such as building waterproofing, oilfield demulsification, and high-end hydrophobic materials.

[0003] Patent CN112011046A discloses a method for preparing low-unsaturation random copolymer hydrophobic polyether polyols. It uses DMC as a catalyst and acid as a co-catalyst to prepare low-unsaturation random copolymer hydrophobic polyether polyols by ring-opening reaction of an initiator with propylene oxide or butane oxide. However, this method relies solely on the epoxides in the polyether polyol segments to achieve hydrophobicity, resulting in poor hydrophobic effects. Patent CN113105616A discloses a method for preparing hydrophobic polyether polyols. It uses a hydrophobic diol as an initiator and DMC or an alkali metal as a catalyst to react the initiator with propylene oxide, butane oxide, or 1,2-epoxypentane in a ring-opening reaction to prepare the hydrophobic polyether polyol. Compared to patent CN112011046A, this method adds a hydrophobic diol as an initiator, which improves the hydrophobicity of the polyether polyol to some extent. However, relying solely on a hydrophobic diol as an initiator still cannot achieve excellent hydrophobic effects, and it reduces the mechanical properties of polyurethane materials during application.

[0004] High-functionality, high-molecular-weight superhydrophobic polyether polyols can endow polyurethane materials with excellent hydrophobic properties, good tear and tensile properties, and excellent resilience. They are also beneficial for the synthesis of high-end polyurethane hydrophobic materials for application in the field of building spraying. However, how to prepare high-functionality, high-molecular-weight superhydrophobic polyether polyols is still an urgent problem to be solved. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention aims to provide a method for preparing superhydrophobic polyether polyols. This method involves polymerizing polyhydroxy compounds with epoxides and then modifying the polyether polyols with hydrophobic long-chain fatty acids. This results in polyether polyols with high functionality, long molecular chain segments, and good hydrophobicity, which greatly improves the hydrophobic properties of polyurethane materials while maintaining their excellent mechanical properties.

[0006] Another object of the present invention is to provide such a superhydrophobic polyether polyol.

[0007] Another object of the present invention is to provide applications of such superhydrophobic polyether polyols.

[0008] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0009] A method for preparing a superhydrophobic polyether polyol, characterized by comprising the following steps:

[0010] a) Polymerization reaction: Using a polyhydroxy compound as an initiator, a ring-opening polymerization reaction is carried out with an epoxide under the action of a catalyst. After the reaction is completed, the mixture is cured and degassed to obtain polyether polyol A.

[0011] b) Esterification modification: The polyether polyol A obtained in step a) is subjected to esterification reaction with hydrophobic long-chain fatty acids under the action of a catalyst to obtain the superhydrophobic polyether polyol.

[0012] In one specific implementation, the polyhydroxy compound mentioned in step a) is a polyhydroxy compound with a functionality ≥ 2.3;

[0013] Preferably, the polyhydroxy compound is selected from at least one of glycerol, sorbitol, sucrose, and oil polyols, and the oil polyols are preferably selected from one or more of castor oil, soybean oil polyol, palm oil polyol, cashew nut shell oil polyol, jatropha oil polyol, rapeseed oil polyol, sunflower seed oil polyol, microalgae oil polyol, and peanut oil polyol.

[0014] More preferably, the polyhydroxy compound is an oily polyol with a functionality ≥ 2.3, and its general structural formula is as follows:

[0015]

[0016] Among them, R1, R2, and R3 are all alkane chains with ≥10 carbon atoms, preferably 10≤25 carbon atoms, for example, carbon atoms of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, etc.

[0017] In one specific implementation, the epoxide mentioned in step a) is selected from any one or more of ethylene oxide, propylene oxide, butane oxide, cyclopentane oxide, cyclohexane oxide, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, and allyl glycidyl ether.

[0018] Preferably, the mass ratio of the polyhydroxy compound to the epoxide is 1:1-20, for example 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, etc., and more preferably 1:2-10.

[0019] In one specific implementation, the catalyst described in step a) is selected from DMC catalysts, alkali metal catalysts, or alkaline earth metal catalysts;

[0020] Preferably, the alkali metal catalyst is selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, sodium methoxide, potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, etc., and the alkaline earth metal catalyst is selected from at least one of calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, etc.

[0021] More preferably, the mass ratio of the catalyst to polyether polyol A (theoretical yield) is (1-1000):20000.

[0022] In one specific implementation, the reaction temperature of the ring-opening polymerization reaction in step a) is 80-180℃, preferably 100-150℃; the reaction time is 1-10h, preferably 2-6h.

[0023] In one specific implementation, the hydrophobic long-chain fatty acid mentioned in step b) is selected from one or more of ricinoleic acid, linolenic acid, linoleic acid, arachidic acid, tung oil acid, 12,13-epoxyoleic acid, oleic acid, etc.

[0024] Preferably, the general structural formula of the hydrophobic long-chain fatty acid is as follows:

[0025] Wherein R1 is an alkane chain or an alkane chain containing unsaturated double bonds, R2 is a hydroxyl or methyl group, and the total number of carbon atoms of the hydrophobic long-chain fatty acid is ≥10, preferably 10≤carbon atoms≤20, for example, the number of carbon atoms is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc.

[0026] More preferably, the molar ratio of the hydrophobic long-chain fatty acid to the polyether polyol A is 1-10:2, such as 1:2, 1:1, 3:2, 2:1, 5:2, 3:1, 7:2, 4:1, 9:2, 5:1, etc., preferably 1-4:1.

[0027] In one specific implementation, the catalyst described in step b) is a titanate catalyst, preferably selected from any one of isobutyl titanate, isopropyl titanate, isooctyl titanate, ethyl titanate, methyl titanate, n-butyl titanate, n-propyl titanate, etc.

[0028] Preferably, the mass ratio of the catalyst to the polyether polyol A (theoretical yield) is (1-1000):10000.

[0029] In one specific implementation, the esterification reaction in step b) is carried out at a temperature of 150-220°C, preferably 180-200°C, and for a reaction time of 2-8 hours, preferably 4-6 hours.

[0030] On the other hand, the superhydrophobic polyether polyol prepared by the aforementioned method preferably has a functionality ≥2.3 and a number-average molecular weight of 3000-16000 g / mol.

[0031] On the other hand, the superhydrophobic polyether polyols prepared by the aforementioned methods or the aforementioned superhydrophobic polyether polyols are used in the field of polyurethane materials.

[0032] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0033] This invention utilizes polyhydroxy compounds (preferably hydrophobic vegetable oil polyols) as initiators to achieve high functionality in polyether polyols while increasing their hydrophobicity. It employs epoxides as polymerization monomers to extend the polyether molecular chain, achieving high molecular weight in polyether polyols while further increasing their hydrophobicity. Furthermore, it uses superhydrophobic long-chain fatty acids to esterify the polyether polyols, further enhancing their hydrophobicity.

[0034] The superhydrophobic polyether polyol prepared by this invention has the characteristics of high functionality, high molecular weight, and superhydrophobicity, with a functionality ≥2.3 and a number-average molecular weight of 3000-16000 g / mol.

[0035] The polyurethane material prepared based on the high-functionality, high-molecular-weight superhydrophobic polyether polyol of the present invention maintains excellent mechanical properties and has extremely strong hydrophobic and waterproof properties, making it well-suited for use in high-end building waterproofing and high-end clothing. Detailed Implementation

[0036] To better understand the technical solution of the present invention, the following embodiments will further illustrate the method provided by the present invention. However, the present invention is not limited to the listed embodiments, but should also include any other known modifications within the scope of the claims of the present invention.

[0037] A method for preparing a high-functionality, high-molecular-weight superhydrophobic polyether polyol includes the following steps:

[0038] a) Polymerization reaction: Using a polyhydroxy compound (functionality ≥ 2.3, e.g. 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.2, 3.4, 3.5, 3.6, 3.8, 4.0, etc.) as the initiator, and DMC or alkali metal or alkaline earth metal as the catalyst, a ring-opening polymerization reaction is carried out with an epoxide at 80-180℃ (e.g. 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, etc., preferably 100-150℃) for a reaction time of 1-10h (e.g. 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, etc., preferably 2-6h), followed by aging and degassing to obtain polyether polyol A;

[0039] b) Esterification modification: The polyether polyol A obtained in step a) is subjected to esterification reaction with hydrophobic long-chain fatty acids at 150-220℃ (e.g., 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, etc., preferably 180-200℃) under the catalysis of titanate esters, for a reaction time of 2-8h (e.g., 2h, 3h, 4h, 5h, 6h, 7h, 8h, etc., preferably 4-6h) to obtain a high-functionality, high-molecular-weight superhydrophobic polyether polyol.

[0040] In step a), the polyhydroxy compound (functionality ≥ 2.3) includes, but is not limited to, glycerol, sorbitol, sucrose, and oily polyols such as castor oil, soybean oil polyol, palm oil polyol, cashew nut shell oil polyol, jatropha oil polyol, rapeseed oil polyol, sunflower seed oil polyol, microalgae oil polyol, peanut oil polyol, etc., any one or a combination thereof; preferably, the initiator of the polyhydroxy compound (functionality ≥ 2.3) in step a) is preferably an oily polyol, the general structural formula of which is as follows:

[0041]

[0042] Wherein, R1, R2, and R3 are all alkane chains, which can be straight-chain or multi-branched alkane chains, such as n-decane, isodecane, n-undecane, isoundecane, n-dodecane, isododecane, n-tridecane, isotridecane, n-tetradecane, isotetradecane, n-pentadecanane, isopentadecanane, n-hexadecane, isohexadecane, n-heptadecane, isoheptadecane, n-octadecane, isooctadecane, n-nonadecanane, isononadecanane, n-eicosane, isoeicosane, etc. R1, R2, and R3 can be the same or different, and the number of carbon atoms is ≥10, preferably ≥10 and ≤25, such as 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc.

[0043] In step a), the epoxide is any one or a combination of ethylene oxide, propylene oxide, butane oxide, cyclopentane oxide, cyclohexane oxide, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, and allyl glycidyl ether. The mass ratio of the polyhydroxy compound to the epoxide is 1:1-20, preferably 1:2-10.

[0044] In step a), the catalyst is a bimetallic cyanide catalyst (DMC), an alkali metal catalyst, or an alkaline earth metal catalyst. The DMC catalyst is a common catalyst in polyether preparation, and this invention does not have any particular limitations. Alkali metal catalysts include, but are not limited to, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, sodium methoxide, potassium methoxide, sodium tert-butoxide, and potassium tert-butoxide. Alkaline earth metal catalysts include, but are not limited to, calcium hydroxide, barium hydroxide, magnesium hydroxide, and strontium hydroxide. The mass ratio of the agent to polyether polyol A (theoretical yield) is 1-1000:20000, for example, 1:20000, 10:20000, 50:20000, 100:20000, 200:20000, 300:20000, 400:20000, 500:20000, 600:20000, 700:20000, 800:20000, 900:20000, 1000:20000, etc.

[0045] Unless otherwise specified in step a), the process can refer to existing technologies for polyether preparation, such as curing and degassing processes. There are no particular restrictions, and conventional technical means in this field can be used.

[0046] The hydrophobic long-chain fatty acids in step b) include, but are not limited to, one or more of the following fatty acids: ricinoleic acid, linolenic acid, linoleic acid, arachidic acid, tung oil acid, 12,13-epoxyoleic acid, and oleic acid. Preferably, the hydrophobic long-chain fatty acids in step b) have the following general structural formula: Wherein R1 is an alkane chain or an alkane chain containing unsaturated double bonds, such as n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecanane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecanane, 8-heptadecane, 8,11,14-heptadecanetriene, 8-heptadecane, 8,11-heptadecanediene, etc., and R2 is a hydroxyl or methyl group. The total number of carbon atoms in the hydrophobic long-chain fatty acid is ≥10, preferably ≥10 and ≤20, such as 10, 11, 12, 13, 14, 15, 16, 17, 18, 10, 19, 20, etc.

[0047] The titanate catalyst in step b) includes, but is not limited to, isobutyl titanate, isopropyl titanate, isooctyl titanate, ethyl titanate, methyl titanate, n-butyl titanate, n-propyl titanate, etc.; the mass ratio of the catalyst to polyether polyol A is 1-1000:10000, for example, 1:10000, 5:10000, 10:10000, 50:10000, 100:10000, 200:10000, 300:10000, 400:10000, 500:10000, 600:10000, 700:10000, 800:10000, 900:10000, 1000:10000, etc.

[0048] The high-functionality, high-molecular-weight superhydrophobic polyether polyol B prepared by the above method has the following characteristics: functionality ≥ 2.3, and number-average molecular weight of 3000-16000 g / mol.

[0049] The present invention will be further explained and illustrated below through more specific embodiments, but these do not constitute any limitation.

[0050] The main sources of the raw materials used in the following examples are as follows:

[0051] Castor oil is sourced from Jinhu Oil Factory in Yuci (castor oil specifications are as follows: hydroxyl value: 158-175 mgKOH / g, acid value: ≤2 mgKOH / g, moisture: ≤0.05%, iodine value: 82-88 gI / 100g);

[0052] The epoxidized soybean oil is sourced from Haierma Vegetable Oil Co., Ltd. (The indicators of epoxidized soybean oil are as follows: epoxidation value: ≥6%, acid value: ≤0.5mgKOH / g, moisture: ≤0.1%, iodine value: ≤5gI / 100g).

[0053] The remaining standard raw materials are all from Inokai or Aladdin reagents.

[0054] The test methods involved in the following embodiments are as follows:

[0055] GPC test conditions: Gel permeation chromatograph, EC2000; Column: Shodex GPC KF 802 (size limit 5000, inner diameter 8 mm, length 300 mm); Mobile phase: Tetrahydrofuran; Detector: RT1230 differential refractive index detector.

[0056] Example 1:

[0057] a) Add 1000g castor oil (functionality approximately 2.7) and 0.16g DMC catalyst to a high-pressure reactor, purge with nitrogen 10 times, and continuously introduce a mixture of ethylene oxide, propylene oxide, and butane oxide (215g ethylene oxide, 1500g propylene oxide, and 500g butane oxide) at 150℃ with stirring over 2 hours; mature for 1 hour, then increase N2 stripping and remove volatile small molecules under a vacuum of -0.095MPa for 30 minutes;

[0058] b) Add 3.2g of isobutyl titanate and 800g of ricinoleic acid to the above reaction product, purge with nitrogen three times, and react at 200℃ with stirring for 6h to carry out esterification modification. During the reaction, maintain a vacuum environment of -0.095MPa to remove moisture. After the reaction is complete, cool to 50℃ to obtain a high-functionality, high-molecular-weight superhydrophobic polyether polyol with a molecular weight of approximately 3730g / mol as determined by GPC.

[0059] Example 2:

[0060] Preparation method of epoxidized soybean oil polyol: 1000g epoxidized soybean oil, 256g methanol, 1.7g phosphoric acid, and 0.5g sulfuric acid were added to a high-pressure reactor and fully purged with nitrogen 10 times. The reaction was maintained at 100℃ with stirring for 3 hours. After the reaction was completed, unreacted methanol was removed under a vacuum of -0.090MPa for 1 hour. The mixture was then cooled and discharged to obtain soybean oil polyol (functionality of approximately 4).

[0061] Preparation method of high-functionality, high-molecular-weight superhydrophobic polyether polyols:

[0062] a) Add 500g of soybean oil polyol (functionality approximately 4) and 2.4g of DMC catalyst to a high-pressure reactor. Purge the reactor with nitrogen 10 times. At 135°C, under stirring, continuously introduce a mixture of ethylene oxide, propylene oxide, and butane oxide (215g ethylene oxide, 3800g propylene oxide, and 250g butane oxide). Mature for 1 hour, then increase N2 stripping and remove volatile small molecules under a vacuum of -0.095MPa for 30 minutes.

[0063] b) Add 0.47 g of isopropyl titanate and 140 g of linoleic acid to the above reaction product, purge with nitrogen three times, and react at 180 °C with stirring for 4 h to carry out esterification modification. During the reaction, maintain a vacuum environment of -0.095 MPa to remove moisture. After the reaction is complete, cool to 50 °C to obtain a high-functionality, high-molecular-weight superhydrophobic polyether polyol with a molecular weight of approximately 10200 g / mol as determined by GPC.

[0064] Example 3:

[0065] a) Add 1000g castor oil (functionality approximately 2.7) and 160g cesium hydroxide to a high-pressure reactor. Purge with nitrogen 10 times. Degas at 130°C for 3 hours. Then, maintain the temperature at 100°C and continuously introduce a mixture of propylene oxide, butane oxide, and allyl glycidyl ether (1000g propylene oxide, 670g butane oxide, and 45g allyl glycidyl ether) for 5 hours with stirring. Mature for 1 hour, then increase N2 stripping and remove volatile small molecules under a vacuum of -0.095MPa for 30 minutes.

[0066] b) Add 32g of tetrapropyl titanate, 1000g of ricinoleic acid, and 150g of linolenic acid to the above reaction product. Replace with nitrogen three times and react at 190℃ with stirring for 5h to carry out esterification modification. During the reaction, maintain a vacuum environment of -0.095MPa to remove moisture. After the reaction is completed, cool down to 50℃ to obtain a high-functionality, high-molecular-weight superhydrophobic polyether polyol with a molecular weight of approximately 3430g / mol as determined by GPC.

[0067] Example 4:

[0068] a) Add 1000g castor oil (functionality approximately 2.7) and 16g DMC catalyst to a high-pressure reactor, purge with nitrogen 10 times, and continuously introduce a mixture of propylene oxide, butane oxide, and methyl glycidyl ether (2022g propylene oxide, 3300g butane oxide, and 109g methyl glycidyl ether) into the reactor at 145℃ with stirring for 3 hours; allow to mature for 1 hour, then increase N2 stripping and remove volatile small molecules under a vacuum of -0.095MPa for 30 minutes;

[0069] b) Add 13g of tetrabutyl titanate, 1000g of castor oil acid, and 230g of oleic acid to the above reaction product. Replace with nitrogen three times and react at 200℃ with stirring for 5h to carry out esterification modification. During the reaction, maintain a vacuum environment of -0.095MPa to remove moisture. After the reaction is completed, cool down to 50℃ to obtain a high-functionality, high-molecular-weight superhydrophobic polyether polyol with a molecular weight of 6350g / mol as determined by GPC.

[0070] Example 5:

[0071] a) Add 350g of sucrose and 167g of calcium hydroxide to a high-pressure reactor, purge with nitrogen 10 times, degas at 145℃ for 3 hours, then maintain at 180℃ and continuously introduce a mixture of propylene oxide, butane oxide, and cyclopentane oxide (2022g of ethylene oxide, 4200g of butane oxide, and 109g of cyclopentane oxide) for 5 hours with stirring; mature for 1 hour, then increase N2 stripping and remove volatile small molecules under a vacuum of -0.095MPa for 30 minutes;

[0072] b) Add 325g of methyl titanate, 1000g of arachidic acid, and 500g of 12,13-epoxyoleic acid to the above reaction product. Purge with nitrogen three times and react at 220℃ with stirring for 8h to carry out esterification modification. During the reaction, maintain a vacuum environment of -0.095MPa to remove moisture. After the reaction is complete, cool to 50℃ to obtain a high-functionality, high-molecular-weight superhydrophobic polyether polyol with a molecular weight of 8056g / mol as determined by GPC.

[0073] Example 6:

[0074] a) Add 190g of sorbitol and 15g of potassium methoxide to a high-pressure reactor, purge with nitrogen 10 times, degas at 125℃ for 3 hours, then maintain at 150℃ and continuously introduce a mixture of propylene oxide, butane oxide, and cyclohexane oxide (2100g of propylene oxide, 300g of butane oxide, and 500g of cyclohexane oxide) for 10 hours with stirring; mature for 1 hour, then increase N2 stripping and remove volatile small molecules under a vacuum of -0.095MPa for 30 minutes;

[0075] b) Add 32g of tetrapropyl titanate, 150g of ricinoleic acid, and 100g of arachidic acid to the above reaction product. Replace with nitrogen three times and react at 160℃ with stirring for 2h to carry out esterification modification. During the reaction, maintain a vacuum environment of -0.095MPa to remove moisture. After the reaction is complete, cool to 50℃ to obtain a high-functionality, high-molecular-weight superhydrophobic polyether polyol with a molecular weight of approximately 3290g / mol as determined by GPC.

[0076] Comparative Example 1:

[0077] Synthesis method of ester-free modified polyether polyol: 1000g castor oil (functionality about 2.7) and 0.16g catalyst DMC were added to a high-pressure reactor. The reactor was fully purged with nitrogen 10 times. Under stirring at 150℃, a mixture of ethylene oxide, propylene oxide and butane oxide (215g ethylene oxide, 1500g propylene oxide and 500g butane oxide) was continuously introduced over 2 hours. After aging for 1 hour, N2 stripping was added, and volatile small molecules were removed under a vacuum of -0.095MPa for 30 minutes. The temperature was then lowered to 50℃ to obtain polyether polyol. The molecular weight was 3011g / mol according to GPC analysis.

[0078] Comparative Example 2:

[0079] Synthesis method of hydrophobic polyether polyol with functionality less than 2.3: Replace 1000g castor oil in Example 1 with 895g castor oil and 105g C12-14 fatty alcohol (CAS: 80206-82-2), the average functionality is converted to 2.1, and the other conditions remain unchanged to synthesize the polyether of Comparative Example 2.

[0080] Application performance testing:

[0081] Polyurethane coating materials were prepared using the following components:

[0082] MDI (diphenylmethane diisocyanate, produced by Wanhua Chemical Group Co., Ltd.);

[0083] IPDA (isophorone diamine, produced by Wanhua Chemical Group Co., Ltd.);

[0084] DBTDL (Dibutyltin dilaurate);

[0085] Silicone oil BYK-038;

[0086] Catalyst T9 (stannous octoate).

[0087] The formulation and properties of the polyurethane hydrophobic coating are as follows:

[0088]

[0089]

[0090] The mechanical properties of the polyurethane coating were tested using a material testing machine. Dumbbell-shaped tensile specimens of 20mm*4mm*2mm were prepared according to GB / 19250-2013, and tensile strength, elongation, and tear strength were tested using a SUN500 universal material testing machine.

[0091] The hydrophobic properties of the polyurethane coating were characterized by static water contact angle using the Theta Lite optical contact angle meter, Biolin GmbH, Sweden.

[0092] As can be seen from the table above, the polyurethane coating material prepared using the embodiments of the present invention has a static water contact angle of over 140°, which is significantly better than that of the comparative example, indicating that it has excellent hydrophobic properties. From the tensile and tear data, it can be seen that the polyurethane material prepared by the polyether polyol of the present invention has also been further improved in mechanical properties, indicating that the present invention has good practical value.

[0093] Although the present invention has been described in detail through the preferred embodiments described above, it should be understood that the above description should not be considered as a limitation of the present invention. Those skilled in the art will understand that modifications or adjustments can be made to the present invention based on the teachings of this specification. These modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims

1. A method for preparing a superhydrophobic polyether polyol, characterized in that, Includes the following steps: a) Polymerization reaction: Using a polyhydroxy compound with a functionality of ≥2.3 as an initiator, a ring-opening polymerization reaction is carried out with an epoxide under the action of a catalyst. After the reaction is completed, the mixture is cured and degassed to obtain polyether polyol A. b) Esterification modification: The polyether polyol A obtained in step a) is subjected to esterification reaction with hydrophobic long-chain fatty acids under the action of a catalyst to obtain the superhydrophobic polyether polyol. The general structural formula of the hydrophobic long-chain fatty acid is as follows: , Wherein R1 is an alkane chain or an alkane chain containing unsaturated double bonds, R2 is a hydroxyl or methyl group, and the hydrophobic long-chain fatty acid has 10 ≤ carbon atoms ≤ 25. The molar ratio of the hydrophobic long-chain fatty acid to the polyether polyol A is 1-10:2; The polyhydroxy compound mentioned in step a) is selected from at least one of glycerol, sorbitol, sucrose, and lipid polyols.

2. The preparation method according to claim 1, characterized in that, The oil-based polyols are selected from one or more of the following: castor oil, soybean oil, palm oil, cashew nut shell oil, jatropha oil, rapeseed oil, sunflower seed oil, microalgae oil, and peanut oil.

3. The preparation method according to claim 2, characterized in that, The polyhydroxy compound is an oily polyol with a functionality ≥ 2.3, and its general structural formula is as follows: Among them, R1, R2, and R3 are all alkane chains with ≥10 carbon atoms.

4. The preparation method according to claim 3, characterized in that, 10 ≤ number of carbon atoms ≤ 25.

5. The preparation method according to any one of claims 1-4, characterized in that, The epoxide mentioned in step a) is selected from one or more of ethylene oxide, propylene oxide, butane oxide, cyclopentane oxide, cyclohexane oxide, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, and allyl glycidyl ether.

6. The preparation method according to claim 5, characterized in that, The mass ratio of the polyhydroxy compound to the epoxide is 1:1-20.

7. The preparation method according to claim 6, characterized in that, The mass ratio of the polyhydroxy compound to the epoxide is 1:2-10.

8. The preparation method according to any one of claims 1 to 4, characterized in that, The catalyst mentioned in step a) is selected from DMC catalysts, alkali metal catalysts or alkaline earth metal catalysts.

9. The preparation method according to claim 8, characterized in that, The alkali metal catalyst is selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, sodium methoxide, potassium methoxide, sodium tert-butoxide, and potassium tert-butoxide, and the alkaline earth metal catalyst is selected from at least one of calcium hydroxide, barium hydroxide, magnesium hydroxide, and strontium hydroxide.

10. The preparation method according to claim 9, characterized in that, The mass ratio of the catalyst to polyether polyol A is (1-1000):20000.

11. The preparation method according to any one of claims 1 to 4, characterized in that, The reaction temperature for the ring-opening polymerization reaction in step a) is 80-180℃; the reaction time is 1-10h.

12. The preparation method according to claim 11, characterized in that, The reaction temperature for the ring-opening polymerization reaction in step a) is 100-150℃; the reaction time is 2-6h.

13. The preparation method according to claim 1, characterized in that, The hydrophobic long-chain fatty acid mentioned in step b) is selected from one or more of ricinoleic acid, linolenic acid, linoleic acid, arachidic acid, tung oil acid, 12,13-epoxyoleic acid, and oleic acid.

14. The preparation method according to any one of claims 1 to 4, characterized in that, The catalyst described in step b) is a titanate catalyst.

15. The preparation method according to claim 14, characterized in that, The catalyst is selected from any one of isobutyl titanate, isopropyl titanate, isooctyl titanate, ethyl titanate, methyl titanate, n-butyl titanate, and n-propyl titanate.

16. The preparation method according to claim 15, characterized in that, The mass ratio of the catalyst to the polyether polyol A is (1-1000):10000.

17. The preparation method according to any one of claims 1 to 4, characterized in that, The esterification reaction in step b) is carried out at a temperature of 150-220℃ and for a time of 2-8 hours.

18. The preparation method according to claim 17, characterized in that, The esterification reaction in step b) is carried out at a temperature of 180-200℃ and for a time of 4-6 hours.

19. The superhydrophobic polyether polyol prepared by the preparation method according to any one of claims 1 to 18.

20. The superhydrophobic polyether polyol according to claim 19, characterized in that, The superhydrophobic polyether polyol has a functionality ≥2.3 and a number-average molecular weight of 3000-16000 g / mol.

21. The application of the superhydrophobic polyether polyol prepared by the preparation method according to any one of claims 1 to 18, or the superhydrophobic polyether polyol according to claim 19 or 20, in the field of polyurethane materials.

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