CN117050294A - Super-hydrophobic polyether polyol, preparation method and application thereof - Google Patents

Super-hydrophobic polyether polyol, preparation method and application thereof Download PDF

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CN117050294A
CN117050294A CN202311091150.3A CN202311091150A CN117050294A CN 117050294 A CN117050294 A CN 117050294A CN 202311091150 A CN202311091150 A CN 202311091150A CN 117050294 A CN117050294 A CN 117050294A
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polyether polyol
polyol
hydrophobic
catalyst
reaction
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周昕志
韩志鹏
范军
石正阳
秦承群
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyethers (AREA)

Abstract

The invention discloses a preparation method of super-hydrophobic polyether polyol, which comprises the following steps: a) Polymerization reaction: taking polyhydroxy compound as an initiator, carrying out ring-opening polymerization reaction with epoxide under the action of a catalyst, curing and degassing after the reaction is finished to obtain polyether polyol A; b) Esterification modification: under the action of a catalyst, the polyether polyol A and hydrophobic long-chain fatty acid are subjected to esterification reaction to obtain the super-hydrophobic polyether polyol. The functionality of the super-hydrophobic polyether polyol prepared by the invention is more than or equal to 2.3, the number average molecular weight is 3000-16000g/mol, and the polyurethane material prepared by the high-functionality high-molecular-weight super-hydrophobic polyether polyol based on the invention not only maintains excellent mechanical properties, but also has extremely strong hydrophobic waterproof performance, and is well applied to the waterproof field of high-end buildings and high-grade clothing and apparel.

Description

Super-hydrophobic polyether polyol, preparation method and application thereof
Technical Field
The invention belongs to the field of polyether polyol synthesis, and particularly relates to super-hydrophobic polyether polyol, a preparation method and application thereof.
Background
Polyether polyol prepared by ring-opening polymerization of an active hydrogen-containing compound serving as an initiator and alkylene oxide is limited in application in fields requiring superhydrophobicity, such as building waterproofing, oilfield demulsification, high-end hydrophobic materials and the like.
Patent CN112011046a discloses a preparation method of low-unsaturation degree random copolymerization hydrophobic polyether polyol, DMC is used as a catalyst, acid is used as a cocatalyst, and the initiator and propylene oxide or butylene oxide are subjected to ring-opening reaction to prepare the low-unsaturation degree random copolymerization hydrophobic polyether polyol, and the method only depends on alkylene oxide in a polyether polyol chain segment to realize hydrophobicity, so that the hydrophobic effect is poor. Patent CN113105616a discloses a preparation method of hydrophobic polyether polyol, hydrophobic diol is adopted as a starter, DMC or alkali metal is adopted as a catalyst, and the starter is subjected to ring-opening reaction with propylene oxide, butylene oxide or 1, 2-pentane oxide to prepare the hydrophobic polyether polyol.
The high-functionality high-molecular-weight super-hydrophobic polyether polyol can endow the polyurethane material with excellent hydrophobic performance, good tearing tensile property and excellent rebound resilience, and is also beneficial to the application of the synthesized high-end polyurethane hydrophobic material in the field of building spraying, but how to prepare the high-functionality high-molecular-weight super-hydrophobic polyether polyol is still a problem to be solved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a preparation method of super-hydrophobic polyether polyol, which adopts polyhydroxy compounds and epoxide to polymerize and then utilizes hydrophobic long-chain fatty acid to modify, so as to realize the preparation of polyether polyol with high functionality, long molecular chain segment and good hydrophobicity, greatly improve the hydrophobic property of polyurethane materials and simultaneously maintain the excellent mechanical property of the polyurethane materials.
It is another object of the present invention to provide such superhydrophobic polyether polyols.
It is a further object of the present invention to provide the use of such superhydrophobic polyether polyols.
In order to achieve the above object, the present invention adopts the following technical scheme:
the preparation method of the super-hydrophobic polyether polyol is characterized by comprising the following steps of:
a) Polymerization reaction: taking polyhydroxy compound as an initiator, carrying out ring-opening polymerization reaction with epoxide under the action of a catalyst, curing and degassing after the reaction is finished to obtain polyether polyol A;
b) Esterification modification: and c), carrying out esterification reaction on the polyether polyol A obtained in the step a) and hydrophobic long-chain fatty acid under the action of a catalyst to obtain the super-hydrophobic polyether polyol.
In a specific embodiment, the polyol in step a) is a polyol having a functionality of not less than 2.3;
preferably, the polyhydroxy compound is at least any one of glycerol, sorbitol, sucrose and grease polyol, and the grease polyol is preferably any one or more of castor oil, soybean oil polyol, palm oil polyol, cashew nut shell oil polyol, jatropha curcas oil polyol, rapeseed oil polyol, sunflower seed oil polyol, microalgae oil polyol, peanut oil polyol and the like;
more preferably, the polyhydroxy compound is grease polyol with the functionality of more than or equal to 2.3, and the structural general formula is as follows:
wherein R is 1 、R 2 、R 3 Are all alkane chains having a carbon number of 10 or more, preferably 10 or less and 25 or less, for example, 10, 11, 12,13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 or the like.
In a specific embodiment, the epoxide in step a) is selected from any one or more of ethylene oxide, propylene oxide, butylene oxide, cyclopentane oxide, cyclohexane oxide, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, and the like;
preferably, the mass ratio of the polyol to epoxide is from 1:1 to 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., preferably 1:2-10.
In a specific embodiment, the catalyst described in step a) is selected from DMC catalysts, alkali metal catalysts or alkaline earth metal catalysts;
preferably, the alkali metal catalyst is selected from at least any one of sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, sodium methoxide, potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, and the like, and the alkaline earth metal catalyst is selected from at least any one of calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, and the like;
more preferably, the mass ratio of the catalyst to polyether polyol A (theoretical yield) is (1-1000): 20000.
In a specific embodiment, the reaction temperature of the ring-opening polymerization reaction of step a) is 80-180 ℃, preferably 100-150 ℃; the reaction time is 1 to 10 hours, preferably 2 to 6 hours.
In a specific embodiment, the hydrophobic long chain fatty acid in step b) is selected from one or more of ricinoleic acid, linolenic acid, linoleic acid, arachic acid, eleostearic acid, 12, 13-epoxyoleic acid, oleic acid, and the like;
preferably, the hydrophobic long chain fatty acid has the structural formula of
Wherein R is 1 Is an alkane chain or an alkane chain containing unsaturated double bonds, R 2 Is a hydroxyl group or a methyl group, and the total carbon number of the hydrophobic long-chain fatty acid is not less than 10, preferably not less than 10 and not more than 20, for example, the carbon numbers are 10, 11, 12,13, 14, 15, 16, 17, 18, 19, 20, etc.;
more preferably, the molar ratio of the hydrophobic long-chain fatty acid to the polyether polyol a is from 1 to 10:2, for example 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.
In a specific embodiment, the catalyst in step b) is a titanate catalyst, preferably any one selected from isobutyl titanate, isopropyl titanate, isooctyl titanate, ethyl titanate, methyl titanate, n-butyl titanate, n-propyl titanate, and the like;
preferably, the mass ratio of the catalyst to the polyether polyol A (theoretical yield) is (1-1000): 10000.
In a specific embodiment, the reaction temperature of the esterification reaction of step b) is 150 to 220 ℃, preferably 180 to 200 ℃; the reaction time is 2 to 8 hours, preferably 4 to 6 hours.
On the other hand, the super-hydrophobic polyether polyol prepared by the preparation method preferably has the functionality of more than or equal to 2.3 and the number average molecular weight of 3000-16000g/mol.
In yet another aspect, the superhydrophobic polyether polyol prepared by the foregoing preparation method or the use of the foregoing superhydrophobic polyether polyol in the field of polyurethane materials.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses polyhydroxy compound (preferably hydrophobic vegetable oil polyol) as initiator, realizes the characteristic of high functionality of polyether polyol, and increases the hydrophobicity of polyether polyol; epoxide is adopted as a polymerization monomer, so that a polyether molecular chain segment is prolonged, the characteristic of high molecular weight of polyether polyol is realized, and meanwhile, the hydrophobicity of the polyether polyol is increased; and then the super-hydrophobic long-chain fatty acid is used for carrying out esterification modification on the polyether polyol, so that the hydrophobicity of the polyether polyol is further enhanced.
The super-hydrophobic polyether polyol prepared by the invention has the characteristics of high functionality, high molecular weight and super-hydrophobicity, the functionality is more than or equal to 2.3, and the number average molecular weight is 3000-16000g/mol.
The polyurethane material prepared from the high-functionality high-molecular weight super-hydrophobic polyether polyol maintains excellent mechanical properties, has extremely strong hydrophobic waterproof performance, and is well applied to the waterproof field of high-end buildings and high-grade clothing.
Detailed Description
The following examples will further illustrate the method provided by the present invention for a better understanding of the technical solution of the present invention, but the present invention is not limited to the examples listed but should also include any other known modifications within the scope of the claims of the present invention.
A method for preparing a high functionality high molecular weight superhydrophobic polyether polyol, comprising the steps of:
a) Polymerization reaction: using polyhydroxy compound (functionality not less than 2.3, such as 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 starter, DMC or alkali metal or alkaline earth metal as catalyst, ring-opening polymerizing with epoxide at 80-180deg.C (such as 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, etc., preferably 100-150 deg.C) for 1-10h (such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, etc.), curing, degassing to obtain polyether polyol A;
b) Esterification modification: the polyether polyol A obtained in the step a) is subjected to esterification reaction with hydrophobic long-chain fatty acid under the catalysis of titanate at 150-220 ℃ (such as 150 ℃,160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃ and the like, preferably 180-200 ℃) for 2-8 hours (such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours and the like, preferably 4-6 hours) to obtain the high-functionality high-molecular-weight super-hydrophobic polyether polyol.
Wherein, the polyhydroxy compound (functionality is more than or equal to 2.3) in the step a) comprises any one or a combination of a plurality of glycerol, sorbitol, sucrose, lipid polyols such as castor oil, soybean oil polyol, palm oil polyol, cashew nut shell oil polyol, jatropha curcas oil polyol, rapeseed oil polyol, sunflower seed oil polyol, microalgae oil polyol, peanut oil polyol and the like; preferably, the polyhydroxy compound (functionality > 2.3) initiator in step a) is preferably a lipid polyol having the following structural formula:
wherein R is 1 、R 2 、R 3 Are all alkane chains and 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-pentadecane, isopentadecane, n-hexadecane, isohexadecane, n-heptadecane, isoheptadecane, n-octadecane, isooctadecane, n-nonadecane, isononadecane, n-eicosane, isoeicosane and the like, R 1 、R 2 、R 3 The carbon atoms may be the same or different and are preferably 10 or more and 25 or less, for example 10, 11, 12,13, 14, 15, 16, 17, 18, 19, 20, etc.
The epoxide in the step a) is any one or a combination of a plurality of ethylene oxide, propylene oxide, butylene oxide, cyclopentane oxide, cyclohexane oxide, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether and the like. Wherein the mass ratio of the polyhydroxy compound to the epoxide is 1:1-20, preferably 1:2-10..
The catalyst in step a) is a double metal cyanide catalyst (DMC), an alkali metal or alkaline earth metal catalyst, and the DMC catalyst is a common catalyst for polyether preparation, and the invention is not particularly limited; 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, potassium tert-butoxide, and the like; the alkaline earth metal catalysts include, but are not limited to, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, and the like; wherein the mass ratio of catalyst 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.
The processes not specifically described in step a) are all applicable to the prior art for polyether preparation, such as curing and degassing, and may be carried out by conventional techniques in the art.
The hydrophobic long chain fatty acid in step b) includes, but is not limited to, one or more of ricinoleic acid, linolenic acid, linoleic acid, arachic acid, eleostearic acid, 12, 13-epoxyoleic acid, oleic acid, and the like. Preferably, the hydrophobic long chain fatty acid in step b) has the general structural formulaWherein R is 1 Is an alkane chain or an unsaturated double bond-containing alkane chain, for example, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, 8-heptadecane, 8,11, 14-heptadecane triene, 8-heptadecane, 8, 11-heptadecanediene and the like, R 2 Is a hydroxyl group or methyl group, and the total carbon number of the hydrophobic long-chain fatty acid is not less than 10, preferably not less than 10 and not more than 20, for example, 10, 11, 12,13, 14, 15, 16, 17, 18, 10, 19, 20, etc.
Titanate catalysts in step b) include, but are not limited to, isobutyl titanate, isopropyl titanate, isooctyl titanate, ethyl titanate, methyl titanate, n-butyl titanate, n-propyl titanate, and the like; the mass ratio of 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.
The high-functionality high-molecular-weight super-hydrophobic polyether polyol B prepared by the method has the following characteristics: the functionality is more than or equal to 2.3, and the number average molecular weight is 3000-16000g/mol.
The invention is further illustrated, but not limited, by the following more specific examples.
The main raw material sources used in the following examples are as follows:
the castor oil is derived from Ulmus pumila golden lake oil factory (castor oil index is as follows: hydroxyl value: 158-175mgKOH/g, acid value: 2mgKOH/g, moisture: 0.05% or less, iodine value: 82-88gI/100 g);
the epoxidized soybean oil is derived from sea-lug-ma vegetable oil limited company (the index of the epoxidized soybean oil is as follows: epoxy value is more than or equal to 6%, acid value is less than or equal to 0.5mgKOH/g, moisture is less than or equal to 0.1%, iodine value is less than or equal to 5gI/100 g);
the remaining conventional raw materials are from enoKai or ala Ding Shiji.
The test methods involved in the following examples are as follows:
GPC test conditions: gel permeation chromatography, EC2000; chromatographic column: shodex GPC KF 802 (exclusion limit 5000, inner diameter 8mm, length 300 mm); mobile phase: tetrahydrofuran; a detector: RT1230 shows a differential refractive detector.
Example 1:
a) 1000g of castor oil (functionality about 2.7), 0.16g of catalyst DMC, and fully nitrogen gas are added into a high-pressure reaction kettle to replace for 10 times, and under the condition of stirring at 150 ℃, ethylene oxide, propylene oxide and butylene oxide mixture (215 g of ethylene oxide, 1500g of propylene oxide and 500g of butylene oxide) is continuously introduced into the high-pressure reaction kettle within 2 hours; curing for 1h, adding N 2 Stripping, removing volatile micromolecules under the vacuum condition of-0.095 MPa, and maintaining for 30min;
b) 3.2g of isobutyl titanate, 800g of ricinoleic acid and nitrogen are added into the reaction product to replace 3 times, esterification modification is carried out for 6 hours under stirring at 200 ℃, moisture is removed in a vacuum environment of-0.095 MPa in the reaction process, the reaction is completed, the temperature is reduced to 50 ℃, and the high-functionality high-molecular-weight super-hydrophobic polyether polyol with the GPC test molecular weight of about 3730g/mol is obtained.
Example 2:
the preparation method of the epoxidized soybean oil polyol comprises the following steps: 1000g of epoxidized soybean oil, 256g of methanol, 1.7g of phosphoric acid and 0.5g of sulfuric acid are added into a high-pressure reaction kettle, fully replaced by nitrogen for 10 times, and kept for reaction for 3 hours under stirring at 100 ℃; after the reaction, unreacted methanol is removed under the vacuum condition of-0.090 MPa, the reaction is maintained for 1h, and the temperature is reduced and the material is discharged, so as to prepare the soybean oil polyol (the functionality is about 4).
The preparation method of the high-functionality high-molecular weight super-hydrophobic polyether polyol comprises the following steps:
a) 500g of soybean oil polyol (with the functionality of about 4), 2.4g of catalyst DMC (DMC) and fully nitrogen gas is replaced for 10 times, and under the condition of 135 ℃, ethylene oxide, propylene oxide and butylene oxide mixture (215 g of ethylene oxide, 3800g of propylene oxide and 250g of butylene oxide) are continuously introduced in 6h under stirring; curing for 1h, adding N 2 Stripping, removing volatile micromolecules under the vacuum condition of-0.095 MPa, and maintaining for 30min;
b) Adding 0.47g isopropyl titanate and 140g linoleic acid into the reaction product, replacing with nitrogen for 3 times, carrying out esterification modification under stirring at 180 ℃ for 4 hours, maintaining a vacuum environment of-0.095 MPa in the reaction process to remove water, cooling to 50 ℃ after the reaction is completed, and obtaining the high-functionality high-molecular-weight super-hydrophobic polyether polyol with the GPC test molecular weight of about 10200g/mol.
Example 3:
a) 1000g of castor oil (functionality about 2.7), 160g of cesium hydroxide are added into a high-pressure reaction kettle, the mixture is fully replaced by nitrogen for 10 times, after degassing for 3 hours at 130 ℃,100 ℃ is maintained, and under stirring, the mixture of propylene oxide, butylene oxide and allyl glycidyl ether (1000 g of propylene oxide, 670g of butylene oxide and 45g of allyl glycidyl ether) is continuously introduced into the kettle within 5 hours; curing for 1h, adding N 2 Stripping, removing volatile micromolecules under the vacuum condition of-0.095 MPa, and maintaining for 30min;
b) 32g of n-propyl titanate, 1000g of ricinoleic acid, 150g of linolenic acid and nitrogen are added into the reaction product to replace 3 times, esterification modification is carried out for 5 hours under stirring at 190 ℃, moisture is removed in a vacuum environment of-0.095 MPa in the reaction process, the reaction is completed, the temperature is reduced to 50 ℃, the high-functionality high-molecular-weight super-hydrophobic polyether polyol is obtained, and the GPC test molecular weight is about 3430g/mol.
Example 4:
a) 1000g of castor oil (functionality about 2.7), 16g of catalyst DMC, are added into a high-pressure reaction kettle, are fully replaced by nitrogen for 10 times, and are continuously introduced with propylene oxide and butylene oxide in 3 hours under stirring at 145 DEG CAnd methyl glycidyl ether mixtures (2022 g of propylene oxide, 3300g of butylene oxide, 109g of methyl glycidyl ether); curing for 1h, adding N 2 Stripping, removing volatile micromolecules under the vacuum condition of-0.095 MPa, and maintaining for 30min;
b) 13g of n-butyl titanate, 1000g of ricinoleic acid, 230g of oleic acid and nitrogen are added into the reaction product to replace 3 times, esterification modification is carried out for 5 hours under stirring at 200 ℃, the vacuum environment of-0.095 MPa is kept in the reaction process to remove water, the reaction is completed, the temperature is reduced to 50 ℃, and the high-functionality high-molecular-weight super-hydrophobic polyether polyol with the GPC test molecular weight of 6350g/mol is obtained.
Example 5:
a) Adding 350g of sucrose and 167g of calcium hydroxide into a high-pressure reaction kettle, fully replacing nitrogen for 10 times, maintaining 180 ℃ after degassing for 3 hours, and continuously introducing a mixture of propylene oxide, butylene oxide and cyclopentane oxide (2022 g of ethylene oxide, 4200g of butylene oxide and 109g of cyclopentane oxide) in 5 hours under stirring; curing for 1h, adding N 2 Stripping, removing volatile micromolecules under the vacuum condition of-0.095 MPa, and maintaining for 30min;
b) 325g of methyl titanate, 1000g of peanut oleic acid, 500g of 12, 13-epoxy oleic acid and nitrogen are added into the reaction product to replace 3 times, esterification modification is carried out for 8 hours under stirring at 220 ℃, moisture is removed in a vacuum environment of-0.095 MPa in the reaction process, the reaction is completed, the temperature is reduced to 50 ℃ to obtain the high-functionality high-molecular-weight super-hydrophobic polyether polyol, and the GPC test molecular weight is 8056g/mol.
Example 6:
a) 190g of sorbitol, 15g of potassium methoxide are added into a high-pressure reaction kettle, nitrogen is fully replaced for 10 times, after the mixture is degassed for 3 hours at 125 ℃, the temperature is maintained at 150 ℃, and a mixture of propylene oxide, butylene oxide and cyclohexane oxide (2100 g of propylene oxide, 300g of butylene oxide and 500g of cyclohexane oxide) is continuously introduced in 10 hours under stirring; curing for 1h, adding N 2 Stripping, removing volatile micromolecules under the vacuum condition of-0.095 MPa, and maintaining for 30min;
b) 32g of n-propyl titanate, 150g of ricinoleic acid, 100g of arachic acid and nitrogen are added into the reaction product to replace 3 times, esterification modification is carried out for 2 hours under stirring at 160 ℃, moisture is removed in a vacuum environment of-0.095 MPa in the reaction process, the reaction is completed, the temperature is reduced to 50 ℃, the high-functionality high-molecular-weight super-hydrophobic polyether polyol is obtained, and the GPC test molecular weight is about 3290g/mol.
Comparative example 1:
the synthesis method of the esterification-free modified polyether polyol comprises the following steps: 1000g of castor oil (functionality about 2.7), 0.16g of catalyst DMC, and fully nitrogen gas are added into a high-pressure reaction kettle to replace for 10 times, and under the condition of stirring at 150 ℃, ethylene oxide, propylene oxide and butylene oxide mixture (215 g of ethylene oxide, 1500g of propylene oxide and 500g of butylene oxide) is continuously introduced into the high-pressure reaction kettle within 2 hours; curing for 1h, adding N 2 Stripping, removing volatile micromolecules under the vacuum condition of minus 0.095MPa, maintaining for 30min, cooling to 50 ℃ to obtain polyether polyol, and analyzing and detecting that the GPC test molecular weight is 3011g/mol.
Comparative example 2:
a method for synthesizing hydrophobic polyether polyol with functionality less than 2.3: the polyether of comparative example 2 was synthesized by changing 1000g of castor oil in example 1 to 895g of castor oil and 105g of C12-14 fatty alcohol (CAS: 80206-82-2), with an average functionality of 2.1 in terms of conversion, and the remaining conditions unchanged.
Application performance test:
the polyurethane coating material was prepared using the following components:
MDI (diphenylmethane diisocyanate, manufactured by vancomic chemical group inc.);
IPDA (isophorone diamine, manufactured by Wanhua chemical group Co., ltd.);
DBTDL (dibutyltin dilaurate);
silicone oil BYK-038;
catalyst T9 (stannous octoate).
The polyurethane hydrophobic coating has the following formula and performance:
the mechanical property test of the polyurethane coating is carried out by the following instruments: the material testing machine, referring to GB/19250-2013, is used for manufacturing 20mm 4mm 2mm dumbbell-shaped tensile bars, and SUN500 universal material testing machine is used for testing tensile strength, tensile rate and tearing strength.
The hydrophobic properties of polyurethane coatings are characterized by static water contact angles, the instrument is: theta Lite optical contact angle tester, biolin sweden.
From the table above, the polyurethane coating material prepared by the embodiment of the invention has a static water contact angle exceeding 140 degrees, which is obviously better than that of the comparative example, and shows that the polyurethane coating material has excellent hydrophobic property; from the tensile and tearing data, the polyurethane material prepared from the polyether polyol has further improved mechanical properties, which indicates that the polyurethane material has good practical value.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.

Claims (10)

1. The preparation method of the super-hydrophobic polyether polyol is characterized by comprising the following steps of:
a) Polymerization reaction: taking polyhydroxy compound as an initiator, carrying out ring-opening polymerization reaction with epoxide under the action of a catalyst, curing and degassing after the reaction is finished to obtain polyether polyol A;
b) Esterification modification: and c), carrying out esterification reaction on the polyether polyol A obtained in the step a) and hydrophobic long-chain fatty acid under the action of a catalyst to obtain the super-hydrophobic polyether polyol.
2. The process according to claim 1, wherein the polyol in step a) is a polyol having a functionality of 2.3 or more;
preferably, the polyhydroxy compound is at least any one of glycerol, sorbitol, sucrose and grease polyol, and the grease polyol is preferably one or more of castor oil, soybean oil polyol, palm oil polyol, cashew nut shell oil polyol, jatropha curcas oil polyol, rapeseed oil polyol, sunflower seed oil polyol, microalgae oil polyol and peanut oil polyol;
more preferably, the polyhydroxy compound is grease polyol with the functionality of more than or equal to 2.3, and the structural general formula is as follows:
wherein R is 1 、R 2 、R 3 Are all alkane chains, and the carbon atom number is more than or equal to 10, preferably more than or equal to 10 and less than or equal to 25.
3. The process according to claim 1 or 2, wherein the epoxide in step a) is selected from one or more of ethylene oxide, propylene oxide, butylene oxide, cyclopentane oxide, cyclohexane oxide, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether;
preferably, the mass ratio of the polyhydroxy compound to the epoxide is 1:1-20, preferably 1:2-10.
4. A process according to any one of claims 1 to 3, wherein the catalyst in step a) is selected from DMC catalysts, alkali metal catalysts or alkaline earth metal catalysts;
preferably, the alkali metal catalyst is selected from at least any 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 any one of calcium hydroxide, barium hydroxide, magnesium hydroxide and strontium hydroxide;
more preferably, the mass ratio of the catalyst to polyether polyol A is (1-1000): 20000.
5. The process according to any one of claims 1 to 4, wherein the reaction temperature of the ring-opening polymerization reaction of step a) is 80-180 ℃, preferably 100-150 ℃; the reaction time is 1 to 10 hours, preferably 2 to 6 hours.
6. The method according to any one of claims 1 to 5, wherein the hydrophobic long-chain fatty acid in step b) is one or more selected from ricinoleic acid, linolenic acid, linoleic acid, arachic acid, eleostearic acid, 12, 13-epoxyoleic acid, oleic acid and the like;
preferably, the hydrophobic long chain fatty acid has the structural formula of
Wherein R is 1 Is an alkane chain or an alkane chain containing unsaturated double bonds, R 2 Is hydroxyl or methyl, the total carbon number of the hydrophobic long-chain fatty acid is more than or equal to 10, preferably more than or equal to 10 and less than or equal to 20;
more preferably, the molar ratio of the hydrophobic long-chain fatty acid to the polyether polyol a is from 1 to 10:2, preferably 1-4:1.
7. The process according to any one of claims 1 to 6, wherein the catalyst in step b) is a titanate catalyst, preferably any one selected from the group consisting of isobutyl titanate, isopropyl titanate, isooctyl titanate, ethyl titanate, methyl titanate, n-butyl titanate, n-propyl titanate;
preferably, the mass ratio of the catalyst to the polyether polyol A is (1-1000): 10000.
8. The preparation process according to any one of claims 1 to 7, characterized in that the reaction temperature of the esterification reaction of step b) is 150-220 ℃, preferably 180-200 ℃; the reaction time is 2 to 8 hours, preferably 4 to 6 hours.
9. The superhydrophobic polyether polyol produced by the production method of any one of claims 1-8, preferably, the superhydrophobic polyether polyol has a functionality of not less than 2.3 and a number average molecular weight of 3000-16000g/mol.
10. Use of the superhydrophobic polyether polyol produced by the production method of any one of claims 1-8 or the superhydrophobic polyether polyol of claim 9 in the field of polyurethane materials.
CN202311091150.3A 2023-08-29 2023-08-29 Super-hydrophobic polyether polyol, preparation method and application thereof Pending CN117050294A (en)

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