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CN114369236B - High-performance polyester ether polyol, and preparation method and application thereof - Google Patents

High-performance polyester ether polyol, and preparation method and application thereof Download PDF

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CN114369236B
CN114369236B CN202111441635.1A CN202111441635A CN114369236B CN 114369236 B CN114369236 B CN 114369236B CN 202111441635 A CN202111441635 A CN 202111441635A CN 114369236 B CN114369236 B CN 114369236B
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anhydride
reaction
polyol
polyester ether
propylene oxide
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CN114369236A (en
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公维英
孙兆任
于腾飞
张德江
王腾
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Shandong Inov New Material Co Ltd
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Shandong Inov New Material 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/6795—Unsaturated polyethers
    • 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
    • C08G65/2642—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 characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C08G2150/00—Compositions for coatings

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyethers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a high-performance polyester ether polyol, a preparation method and application thereof. The high-performance polyester ether polyol is prepared by polymerizing dihydric alcohol with side groups with alkylene oxide to obtain intermediate refined polyether polyol, mixing the intermediate refined polyether polyol with anhydride, and polymerizing with alkylene oxide; the dihydric alcohol with side group is one or more of 2, 4-trimethyl-1, 3-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol and 3-methyl-1, 5-pentanediol. The invention adopts a unique initiator to design different molecular structures, and the prepared single-component polyurethane waterproof coating has the excellent performances of polyether and polyester, and has good flexibility, hydrolysis resistance and higher mechanical strength.

Description

High-performance polyester ether polyol, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polyether polyol, and particularly relates to high-performance polyester ether polyol, and a preparation method and application thereof.
Background
The polyurethane waterproof coating is a high-grade durable synthetic resin coating, has the advantages of excellent overall waterproof effect, light waterproof layer, high strength, good elasticity, strong binding power, high and low temperature resistance, corrosion resistance, easy repair and the like, and can be used for waterproof of projects such as building roofs, outer walls, basements, kitchens and bathrooms, water reservoirs, swimming pools, roof gardens, subways, expansion joints of concrete members, roads, bridges and the like. The polyurethane waterproof paint comprises two main types of double-component polyurethane waterproof paint and single-component polyurethane waterproof paint. Compared with the double-component polyurethane waterproof coating, the single-component polyurethane waterproof coating does not need to be prepared on site when in use, is simpler and more convenient to construct, has excellent coating performance, and has good waterproof and mechanical properties due to the moderate viscosity of the prepolymer, no dilution by solvent and the urea bond structure generated after the prepolymer is solidified. However, because the single-component polyurethane waterproof coating adopts moisture curing in the film-forming curing process, the formed polyurethane material has less component content for forming a hard segment, and the mechanical property of the material is generally poorer than that of the double-component coating. In order to achieve better mechanical property indexes, various properties of the polyurethane waterproof coating can be improved by using high-quality main polyol.
The polyol used in the polyurethane waterproof paint mainly comprises polyether type and polyester type. The polyester polyol has high tensile strength and low elongation due to the ester group, and the synthesized polyurethane material has good weather resistance, excellent physical properties and thermal stability, but has insufficient hydrolysis resistance and high price. The polyurethane material synthesized by polyether polyol has lower cohesive energy of ether bond, and the product is generally softer and has higher elongation; meanwhile, the hydrolysis resistance of the ether bond is better than that of the ester group, but the mechanical property of the polyether polyurethane material is not as good as that of the polyester.
The patent CN201811467843.7 discloses a waterproof coating for building waterproofing and a preparation method thereof, wherein polyether polyol and polyester polyol are mixed in the preparation process, so that the waterproof coating for building waterproofing has better flexibility, low temperature resistance and higher bonding strength, but the formula system is a double-component polyurethane waterproof coating, wherein the component A is polyether polyol, polyester polyol and isocyanate, and the component B is defoaming agent, curing agent, modified nano calcium carbonate filler, silane coupling agent modified nano silicon dioxide, thickener, dispersing agent and water.
Patent CN201410350004.2 discloses a hydrophilic single-component water-cured polyurethane and a preparation method thereof, which adopts an anionic ring-opening polymerization means, uses polyethylene glycol as an initial dihydric alcohol, carries out ring-opening polymerization with propylene oxide in the presence of KOH, and synthesizes polyalcohols with different molecular weights and hydrophilic and hydrophobic chain segment lengths by adjusting the molecular weight of the polyethylene glycol, the addition amount of the polyethylene glycol and the addition amount of the propylene oxide; under the action of a catalyst, polyol reacts with isocyanate, and a proper amount of plasticizer, antioxidant and ultraviolet absorber are added to prepare polyurethane prepolymer with-NCO group as a terminal group; the prepolymer is mixed with water in a certain proportion to obtain the single-component water-cured polyurethane. The product obtained by the invention has high solid content, high curing speed, high water retention, good storage stability, good flexibility, weather resistance, acid and alkali resistance, and wide application prospect in the aspects of water and soil loss control, waterproof material preparation and the like. There is no case of using polyester ether polyol in the aspect of polyurethane waterproof coating.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects of the prior art, provides a high-performance polyester ether polyol which has excellent performance by adopting a special initiator and a molecular structure design; the invention also provides a preparation method thereof, which is suitable for industrial mass production; and the polyurethane waterproof coating is applied to preparing single-component polyurethane waterproof coating, has excellent hydrolysis resistance and mechanical strength, and simultaneously has better flexibility, low temperature resistance and higher bonding strength.
One of the technical schemes of the invention is as follows:
the preparation process of high performance polyester ether polyol includes polymerizing dihydric alcohol with side group and alkylene oxide to obtain intermediate refined polyether polyol, mixing the intermediate refined polyether polyol with anhydride and polymerizing with alkylene oxide to obtain the polyester ether polyol.
As a preferred scheme, the preparation method of the high-performance polyester ether polyol comprises the following steps of:
(1) Adding dihydric alcohol with side groups and a catalyst A into a pressure-resistant reaction kettle, mixing, replacing nitrogen, dehydrating in vacuum, adding propylene oxide for polymerization, continuing internal pressure reaction for 1-1.5 h after the reaction is finished, vacuumizing to remove unreacted propylene oxide monomer and micromolecular byproducts, and neutralizing, adsorbing, drying and filtering in sequence to obtain an intermediate refined polyether polyol;
(2) Adding the intermediate refined polyether polyol prepared in the step (1), anhydride and a catalyst B into a pressure-resistant reaction kettle, mixing, replacing nitrogen, vacuumizing, heating, adding a first part of propylene oxide for initiating reaction, adding a second part of propylene oxide for polymerization reaction after the reaction activity is opened, continuing the internal pressure reaction for 1-1.5 h after the reaction is finished, and vacuumizing to remove unreacted propylene oxide monomers and micromolecular byproducts, thus obtaining the polyester ether polyol.
In step (1):
the dihydric alcohol with side group is one or more of 2, 4-trimethyl-1, 3-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol and 3-methyl-1, 5-pentanediol. The use of a diol with pendant groups increases the flexibility and hydrolysis resistance of the target polyol.
The mass ratio of the dihydric alcohol with the side group to the epoxypropane is 1:1-1:4.
The catalyst A is an alkali metal catalyst, preferably one of KOH, naOH, potassium alkoxide and sodium alkoxide, and the dosage of the catalyst A is 0.2-0.3% of the molecular weight of the intermediate polyether polyol.
The molecular weight of the prepared intermediate polyether polyol is 400-500, and the hydroxyl value is 220-290 mgKOH/g.
In the synthesis process, nitrogen is replaced until the oxygen content in the kettle is less than 50ppm, the water content in the reaction system is less than 0.03% by vacuum dehydration, the vacuum dehydration temperature is 100-115 ℃, the vacuum degree is minus 0.09-minus 0.093MPa, and the dehydration time is 1-2 h.
The polymerization reaction temperature of the dihydric alcohol with the side group and the alkylene oxide is 100-115 ℃, and the polymerization reaction time is 2-8 h.
In the step (2):
the anhydride is one or more of maleic anhydride, phthalic anhydride, glutaric anhydride, succinic anhydride, citraconic anhydride, itaconic anhydride, 1, 2-cyclopentanedioic anhydride and cyclopropane-1, 2-dicarboxylic anhydride.
The mass ratio of the intermediate polyether polyol to the anhydride is (2-7) 1.
The catalyst B is a double metal cyanide complex catalyst, and the dosage of the catalyst B is 0.02-0.06% of the molecular weight of the polyester ether polyol product.
The first part of propylene oxide accounts for 8-20% of the mass of the intermediate polyether polyol.
The dosage of the second part of propylene oxide is 2-6% of the mass of the intermediate polyether polyol.
In the synthesis process, nitrogen is replaced until the oxygen content in the kettle is less than 50ppm, the kettle is vacuumized until the vacuum degree is-0.09 to-0.093 MPa, and the temperature is raised to 120-160 ℃.
The polymerization reaction temperature of the intermediate refined polyether polyol, the anhydride and the propylene oxide is 120-160 ℃, preferably 135-145 ℃ and the polymerization reaction time is 3-8 h. The reaction temperature is more favorable for ring-opening polymerization of polyether polyol, anhydride and propylene oxide.
The second technical scheme of the invention is as follows:
the polyether ester polyol prepared by the preparation method has the molecular weight of 1800-2200, the hydroxyl value of 45-70 mgKOH/g and the viscosity of 700-1100 mPas at 25 ℃.
The third technical scheme of the invention is as follows:
the application of the high-performance polyester ether polyol is mainly applied to waterproof coatings.
When the polyester-ether polyol is used for waterproof paint, the polyester-ether polyol and polyether triol are matched according to the weight ratio of (2-4): 1.
As a preferable scheme, the polyester ether polyol is mixed according to normal distribution, wherein the molecular weight of the polyester ether polyol is 2-5 of 1800, 1900, 2000, 2100 and 2200 respectively, the relaxation time of a molecular chain can be increased by adopting the method, the mechanical strength of the polyurethane waterproof coating can be regulated and controlled according to actual needs, and the polyurethane waterproof coating with high elongation at break can be obtained.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts a unique initiator to design different molecular structures, and the polyester ether molecular structure prepared by adopting a bimetallic catalytic system contains both ether bonds and ester bonds, so that the prepared single-component polyurethane waterproof coating has the excellent performances of polyether and polyester, and has good flexibility, hydrolysis resistance and higher mechanical strength;
(2) The elongation at break and the tensile strength of the single-component polyurethane waterproof coating prepared by the invention can be improved by 20-40% compared with the traditional single-component polyurethane waterproof coating;
(3) The preparation method provided by the invention is scientific, reasonable, simple and feasible, and can realize industrial production by adopting the existing process equipment.
Detailed Description
The invention is further described below with reference to examples, which are not intended to limit the scope of the invention. The materials used in the examples, except for the specific descriptions, were all commercially available.
Example 1
The preparation method of the polyester ether polyol for the high-performance hydrolysis-resistant waterproof paint comprises the following specific steps:
adding 284 g of 2, 4-trimethyl-1, 3-pentanediol and 4.15g of KOH into a pressure-resistant reaction kettle, replacing with nitrogen, heating to 100 ℃ after the oxygen content in the kettle is measured to be less than 50ppm, maintaining the vacuum degree to 0.093MPa, vacuumizing and dehydrating for 1h, continuously adding 1076g of propylene oxide to carry out polymerization reaction after the water content in the kettle is measured to be less than 0.03%, maintaining the pressure in the kettle to be less than or equal to 0.25MPa in the dripping process, continuing the internal pressure reaction for 1h after the feeding is finished, vacuumizing and dehydrating for 0.5h, cooling to 80 ℃, adding 10.2g of phosphoric acid, 58g of water and 1.66g of magnesium silicate to carry out aftertreatment, and carrying out suction filtration to obtain the intermediate polyether polyol A (hydroxyl value 275.9 mgKOH/g).
382.3g of intermediate polyether polyol A, 144.3g of maleic anhydride and 0.9g of DMC are added into a pressure-resistant reaction kettle, nitrogen is substituted, after the oxygen content in the kettle is measured to be less than 50ppm, vacuumizing is carried out until the oxygen content is between minus 0.09 and minus 0.093MPa, heating to 135 ℃, 50g of propylene oxide is added for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is rapidly increased, the catalyst is successfully induced and activated, the temperature in the kettle is controlled to be 140+/-2 ℃, 1227g of propylene oxide is continuously added for carrying out polymerization reaction, the internal pressure reaction is continued for 1h after the feeding is finished, vacuumizing is carried out for removing monomers for 0.5h, and the target polyester ether polyol 1 (hydroxyl value of 58.6mgKOH/g and viscosity of 798 mPa.s) is obtained.
Example 2
The preparation method of the polyester ether polyol for the high-performance hydrolysis-resistant waterproof paint comprises the following specific steps:
adding 472g of 3-methyl-1, 5-pentanediol, 4.1g of KOH and nitrogen replacement into a pressure-resistant reaction kettle, heating to 100 ℃ after the oxygen content in the kettle is measured to be less than 50ppm, maintaining the vacuum degree to 0.093MPa, vacuumizing and dehydrating for 1h, continuously adding 1168g of propylene oxide to carry out polymerization reaction after the water content in the kettle is measured to be less than 0.03%, maintaining the pressure in the kettle to be less than or equal to 0.25MPa in the dripping process, continuing the internal pressure reaction for 1h after the feeding is finished, vacuumizing and dehydrating for 0.5h, cooling to 80 ℃, adding 10.0g of phosphoric acid, 57g of water and 1.64g of magnesium silicate for post-treatment, and carrying out suction filtration to obtain the intermediate polyether polyol B (hydroxyl value 279.3 mgKOH/g).
361.6g of intermediate polyether polyol B, 90.9g of maleic anhydride and 0.73g of DMC are added into a pressure-resistant reaction kettle, nitrogen is substituted, after the oxygen content in the kettle is measured to be less than 50ppm, vacuumizing is carried out until the oxygen content is between-0.09 and-0.093 MPa, heating to 135 ℃, adding 40g of propylene oxide for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is rapidly increased, indicating that the catalyst is successfully activated, controlling the temperature in the kettle to be 140+/-2 ℃, continuously adding 1326g of propylene oxide for polymerization, continuing the internal pressure reaction for 1h after the addition, vacuumizing and removing monomers for 0.5h, and obtaining the target polyester ether polyol 2 (hydroxyl value of 55.7mgKOH/g and viscosity of 910 mPa.s).
Example 3
The preparation method of the polyester ether polyol for the high-performance hydrolysis-resistant waterproof paint comprises the following specific steps:
adding 640g of 2-butyl-2-ethyl-1, 3-propanediol and 4.4g of KOH into a pressure-resistant reaction kettle, replacing with nitrogen, heating to 100 ℃ after the oxygen content in the kettle is measured to be less than 50ppm, maintaining the vacuum degree to 0.093MPa, vacuumizing and dehydrating for 1h, continuously adding 1120g of propylene oxide to carry out polymerization reaction after the water content in the kettle is measured to be less than 0.03%, maintaining the pressure in the kettle to be less than or equal to 0.25MPa in the dripping process, continuing the internal pressure reaction for 1h after the feeding is finished, vacuumizing and dehydrating for 0.5h, cooling to 80 ℃, adding 10.8g of phosphoric acid, 62g of water and 1.76g of magnesium silicate for aftertreatment, and carrying out suction filtration to obtain the intermediate polyether polyol C (hydroxyl value of 260.2 mgKOH/g).
366.5g of intermediate polyether polyol C, 144.2g of citraconic anhydride and 0.73g of DMC are added into a pressure-resistant reaction kettle, nitrogen is substituted, after the oxygen content in the kettle is measured to be less than 50ppm, vacuumizing is carried out to minus 0.09 to minus 0.093MPa, the temperature is raised to 135 ℃, 51g of propylene oxide is added for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is rapidly raised, the catalyst is successfully induced and activated, the temperature in the kettle is controlled to 140+/-2 ℃, 1241g of propylene oxide is continuously added for carrying out polymerization reaction, the internal pressure reaction is continued for 1h after the feeding is finished, vacuumizing is carried out for removing monomers for 0.5h, and the target polyester ether polyol 3 (hydroxyl value of 53.0mgKOH/g and viscosity of 1022 mPa.s) is obtained.
Comparative example 1
Adding 304g of propylene glycol, 4.15g of KOH and nitrogen into a pressure-resistant reaction kettle for replacement, heating to 100 ℃ after measuring that the oxygen content in the kettle is less than 50ppm, keeping the vacuum degree to 0.093MPa, vacuumizing and dehydrating for 1h, continuously adding 1356g of propylene oxide for polymerization reaction after measuring that the water content in the kettle is less than 0.03%, keeping the pressure in the kettle to be less than or equal to 0.25MPa in the dripping process, continuing the internal pressure reaction for 1h after the feeding is finished, vacuumizing and removing monomers for 0.5h, cooling to 80 ℃, adding 10.2g of phosphoric acid, 58g of water and 1.66g of magnesium silicate for post-treatment, and performing suction filtration to obtain the intermediate polyether polyol D (hydroxyl value 277.1 mgKOH/g).
382.3g of intermediate polyether polyol D, 144.3g of maleic anhydride and 0.9g of DMC are added into a pressure-resistant reaction kettle, nitrogen is substituted, after the oxygen content in the kettle is measured to be less than 50ppm, vacuumizing is carried out until the oxygen content is between-0.09 and-0.093 MPa, heating to 135 ℃, adding 50g of propylene oxide for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is rapidly increased, indicating that the catalyst is successfully activated, controlling the temperature in the kettle to be 140+/-2 ℃, continuously adding 1227g of propylene oxide for polymerization reaction, continuing the internal pressure reaction for 1h after the addition, vacuumizing and removing monomers for 0.5h, and obtaining the target polyester ether polyol A (hydroxyl value of 58.8mgKOH/g and viscosity of 805 mPa.s).
Comparative example 2
Adding 304g of propylene glycol, 4.1g of KOH and nitrogen into a pressure-resistant reaction kettle for replacement, heating to 100 ℃ after measuring that the oxygen content in the kettle is less than 50ppm, keeping the vacuum degree to 0.093MPa, vacuumizing and dehydrating for 1h, continuously adding 1336g of propylene oxide for polymerization reaction after measuring that the water content in the kettle is less than 0.03%, keeping the pressure in the kettle to be less than or equal to 0.25MPa in the dripping process, continuing the internal pressure reaction for 1h after the feeding, vacuumizing and removing monomers for 0.5h, cooling to 80 ℃, adding 10.0g of phosphoric acid, 57g of water and 1.64g of magnesium silicate for post-treatment, and performing suction filtration to obtain the intermediate polyether polyol E (hydroxyl value 278.0 mgKOH/g).
361.6g of intermediate polyether polyol E, 90.9g of maleic anhydride and 0.73g of DMC are added into a pressure-resistant reaction kettle, nitrogen is substituted, after the oxygen content in the kettle is measured to be less than 50ppm, vacuumizing is carried out until the oxygen content is between-0.09 and-0.093 MPa, heating to 135 ℃, adding 40g of propylene oxide for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is rapidly increased, indicating that the catalyst is successfully activated, controlling the temperature in the kettle to be 140+/-2 ℃, continuously adding 1326g of propylene oxide for polymerization, continuing the internal pressure reaction for 1h after the addition, vacuumizing and removing monomers for 0.5h, and obtaining the target polyester ether polyol B (hydroxyl value of 55.4mgKOH/g and viscosity 924 mPa.s).
Comparative example 3
Adding 424g of diethylene glycol, 4.4g of KOH and nitrogen into a pressure-resistant reaction kettle for replacement, heating to 100 ℃ after measuring that the oxygen content in the kettle is less than 50ppm, maintaining the vacuum degree to 0.093MPa, vacuumizing and dehydrating for 1h, continuously adding 1336g of propylene oxide for polymerization reaction after measuring that the water content in the kettle is less than 0.03%, maintaining the pressure in the kettle to be less than or equal to 0.25MPa in the dripping process, continuing the internal pressure reaction for 1h after the feeding, vacuumizing and removing monomers for 0.5h, cooling to 80 ℃, adding 10.8g of phosphoric acid, 62g of water and 1.76g of magnesium silicate for post-treatment, and performing suction filtration to obtain the intermediate polyether polyol F (hydroxyl value 261.4 mgKOH/g).
366.5g of intermediate polyether polyol F, 144.2g of citraconic anhydride and 0.73g of DMC are added into a pressure-resistant reaction kettle, nitrogen is substituted, after the oxygen content in the kettle is measured to be less than 50ppm, vacuumizing is carried out to minus 0.09 to minus 0.093MPa, the temperature is raised to 135 ℃, 51g of propylene oxide is added for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is rapidly raised, the catalyst is successfully induced and activated, the temperature in the kettle is controlled to 140+/-2 ℃, 1241g of propylene oxide is continuously added for carrying out polymerization reaction, the internal pressure reaction is continued for 1h after the feeding is finished, vacuumizing is carried out for removing monomers for 0.5h, and the target polyester ether polyol C (hydroxyl value of 52.5mgKOH/g and viscosity of 1039 mPa.s) is obtained.
Examples 4 to 6 and comparative examples 4 to 8
The polyester ether polyols prepared in examples 1 to 3 and comparative examples 1 to 3 were used in waterproof coating materials, and the raw material compositions thereof are shown in Table 1 in parts by weight. Wherein the waterproof coating formulations of examples 4-6 correspond to the polyester ether polyols prepared in examples 1-3, respectively, the waterproof coating formulations of comparative examples 4-6 correspond to the polyester ether polyols prepared in comparative examples 1-3, respectively, and the formulations of comparative examples 7-8 do not contain polyester ether polyol.
The polyether triol is commercially available from INOVOL F330N, new material, mono, shandong.
The polyether glycol is INOVOL C220, a product sold by New material Co., ltd.
The polyester diol adopts POL-156, which is commercially available from Qingdao Xinyutian chemical industry Co.
TDI was toluene diisocyanate (TDI-80), a commercially available product from Shandong Jimmy macroisocyanate Co., ltd.
The chain extender adopts an amine aliphatic chain extender and is a product sold in the air chemical industry in the United states.
The silane coupling agent adopts KH550 and is commercially available from Shandong Zibo Kabushiki Kaisha.
The filler is kaolin, heavy calcium carbonate powder or a mixture of light calcium carbonate powder, and is commercially available from Tianjin chemical reagent Co., ltd.
The plasticizer is cyclohexane 1, 2-diisononyl phthalate, which is commercially available from Basff, germany.
The latent curing agent is WHA-208, which is a commercial product of Yao Yuwei company, inc. of Taiyuan, shanxi.
The catalyst adopts dibutyl tin dilaurate (DBTDL), which is a commercial product of national medicine group chemical reagent Co.
The preparation method of the waterproof coating comprises the following steps:
polyether triol, polyester diol/polyester ether polyol, plasticizer and filler are put into a reaction kettle, dispersed uniformly at high speed, vacuumized to-0.093 MPa and heated to 110 ℃ to start dehydration for 3 hours. Sampling and detecting moisture, cooling to 60 ℃ after the moisture is qualified, adding metered TDI, slowly heating to 80 ℃ for reaction for 2 hours, sampling and testing NCO content, adding 150# solvent oil when the NCO content reaches or approaches a theoretical value, continuing to react for 1 hour, cooling to 70 ℃, adding a latent curing agent and a catalyst, stirring and reacting for 0.5 hour, cooling to below 60 ℃, discharging, and sealing with nitrogen gas to obtain the single-component polyurethane waterproof coating.
The single-component polyurethane waterproof coatings prepared in examples 4-6 and comparative examples 1-2 were uniformly mixed, uniformly coated on a mold coated with a release agent by a doctor blade, and the coating was completed in 2-3 times to give a final coating film thickness of 1.5mm, and the final coating film was left to stand under standard test conditions of (23.+ -. 2) DEG C and relative humidity (50.+ -. 5)% for 7d, and the performance test of the coating film was carried out in accordance with the method of the standard GB/T19250-2013 polyurethane waterproof coating. The results of the performance test are shown in Table 1.
Table 1 the waterproof coating formulations and performance test results of examples 4-6 and comparative examples 4-8
From the results of the performance test in Table 1, it is understood that the one-component polyurethane waterproof paint obtained in each example has better tensile strength, elongation at break and hydrolysis resistance than the product obtained in the comparative example under the same conditions.

Claims (3)

1. A preparation method of high-performance polyester ether polyol is characterized in that: the method comprises the following steps:
(1) Adding dihydric alcohol with side group and catalyst A into pressure-resistant reaction kettle, mixing, nitrogen displacing, vacuum dewatering,
adding propylene oxide for polymerization reaction, continuing internal pressure reaction for 1-1.5 h after the reaction is finished, vacuumizing to remove unreacted propylene oxide monomer and micromolecular byproducts, and sequentially neutralizing, adsorbing, drying and filtering to obtain an intermediate refined polyether polyol;
(2) Adding the intermediate refined polyether polyol prepared in the step (1), anhydride and a catalyst B into a pressure-resistant reaction kettle, mixing, replacing nitrogen, vacuumizing, heating, adding a first part of propylene oxide for initiating reaction, adding a second part of propylene oxide for polymerization reaction after the reaction activity is opened, continuing the internal pressure reaction for 1-1.5 h after the reaction is finished, vacuumizing to remove unreacted propylene oxide monomers and micromolecular byproducts, and obtaining polyester ether polyol;
in the step (1), the dihydric alcohol with side groups is one or more of 2, 4-trimethyl-1, 3-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol and 3-methyl-1, 5-pentanediol; the mass ratio of the dihydric alcohol with the side group to the epoxypropane is 1:1-1:4; the molecular weight of the prepared intermediate refined polyether polyol is 400-500, and the hydroxyl value is 220-290 mgKOH/g;
in the step (2), the anhydride is one or more of maleic anhydride, phthalic anhydride, glutaric anhydride, succinic anhydride, citraconic anhydride, itaconic anhydride, 1, 2-cyclopentanedioic anhydride and cyclopropane-1, 2-dicarboxylic anhydride; the mass ratio of the intermediate refined polyether polyol to the anhydride is (2-7) 1; the molecular weight of the prepared polyester ether polyol is 1800-2200, the hydroxyl value is 45-70 mgKOH/g, and the viscosity at 25 ℃ is 700-1100 mPa.s.
2. A high performance polyester ether polyol prepared by the preparation process of claim 1, characterized in that: the molecular weight is 1800-2200, the hydroxyl value is 45-70 mgKOH/g, and the viscosity at 25 ℃ is 700-1100 mPa.s.
3. Use of the high performance polyester ether polyol of claim 2, wherein: the high-performance polyester ether polyol and polyether triol are matched according to the weight ratio of (2-4): 1, and are applied to waterproof paint.
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