CN113512189A - Citric acid triester modified polyether polyol and application thereof in polyurethane waterproof coating - Google Patents

Citric acid triester modified polyether polyol and application thereof in polyurethane waterproof coating Download PDF

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CN113512189A
CN113512189A CN202110336730.9A CN202110336730A CN113512189A CN 113512189 A CN113512189 A CN 113512189A CN 202110336730 A CN202110336730 A CN 202110336730A CN 113512189 A CN113512189 A CN 113512189A
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citric acid
polyether polyol
acid triester
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    • 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
    • C08G65/2615—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 the other compounds containing carboxylic acid, ester or anhydride 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
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    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • 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
    • C09D175/08—Polyurethanes from polyethers

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Abstract

The invention relates to citric acid triester modified polyether polyol and application thereof in polyurethane waterproof paint, belonging to the technical field of high polymer materials. The citrate modified polyether polyol is prepared by introducing citric acid triester into a polyether polyol molecular side chain through a chemical bond, wherein the preparation method comprises the steps of firstly preparing citric acid triester through reaction of citric acid and alcohol, then preparing anhydride acylated citric acid triester through diacid anhydride acylation, and then respectively reacting with triglycidyl ether and propylene oxide. The citric acid triester is positioned on the side chain of the polyether polyol molecule, so that the reactivity of the polyether polyol is not influenced, the polyurethane material is endowed with excellent strength and elasticity, and the branched citric acid triester enables the polyether polyol to have lower viscosity and has good wrapping effect on the filler. The citric acid triester modified polyether polyol prepared by the method has potential wide application value in the field of polyurethane materials.

Description

Citric acid triester modified polyether polyol and application thereof in polyurethane waterproof coating
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to citric acid triester modified polyether polyol and application thereof in polyurethane waterproof coating.
Background
Polyether polyols are important raw materials for polyurethane products, and the raw materials for synthesizing polyether polyols are basically petroleum downstream products. With the gradual depletion of petroleum resources and the increasing increase of environmental protection requirements, petroleum substitutes are sought in the polyurethane industry, and it is very important to reduce the dependence on non-renewable resources from the source. In recent years, the development trend of domestic and foreign polyurethanes is mainly towards the aspect of environment-friendly renewable resources, and the polyurethane substitutes for the increasingly-reduced non-renewable mineral resources such as coal, petroleum and the like. The citric acid is an organic triprotic acid, is natural and non-toxic, and has the chemical reaction activity of common organic acids. The carboxyl and hydroxyl in the citric acid structure are reacted with other compounds to prepare various biodegradable materials with excellent performance, such as tributyl citrate, acetylated tributyl citrate and other nontoxic environment-friendly plasticizers with excellent plasticizing effect, good light resistance and water resistance. In the preparation of polyurethane materials, in order to improve the strength of the materials, trifunctional or higher polyether polyols are usually required to be added, and plasticizers for improving toughness and elasticity, such as citrate, are inevitably added at the same time, however, the physical addition mode causes the citrate to easily exude, so that the performance stability of the polyurethane materials is reduced.
Disclosure of Invention
Aiming at the defects of citrate in the application of polyurethane materials in the prior art, the invention aims to provide a citrate triester modified polyether polyol.
The invention also aims to provide a method for preparing the citric acid triester modified polyether polyol, which has the advantages of wide raw material source, simple operation and mild reaction conditions.
It is another object of the present invention to provide a polyurethane waterproofing coating prepared by using citric acid triester modified polyether polyol.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a citrate triester-modified polyether polyol, wherein the citrate triester-modified polyether polyol has the following structure:
Figure BDA0002997976340000021
wherein R has a structure represented by formula (I):
Figure BDA0002997976340000022
in the formula (I), R1、R2、R3Each independently selected from one of C4-C12 straight chain or branched chain alkyl; r4Is a C2-C10 hydrocarbyl group.
Preferably, R in the citric acid triester modified polyether polyol1、R2、R3Are the same group.
The technical scheme of the preparation method of the citric acid triester modified polyether polyol comprises the following steps:
a method for preparing a citrate triester-modified polyether polyol, comprising the steps of:
step (1): preparation of citric acid triester
Adding citric acid, alcohol, a proper amount of catalyst and a water-carrying agent into a reaction kettle, and reacting under a certain condition to obtain citric acid triester;
step (2): preparation of diacid anhydride acylated citric acid triester
Adding the citric acid triester and dianhydride into a reaction kettle, and reacting to obtain dianhydride acylated citric acid triester;
and (3): preparation of citric acid triester modified triol
Adding the diacid anhydride acylated citric acid triester prepared in the step (2) and triglycidyl ether into a reaction kettle, adding a proper amount of catalyst, and reacting to obtain citric acid triester modified trihydric alcohol;
and (4): preparation of citric acid triester-modified polyether polyol
And (3) reacting the citric acid triester modified trihydric alcohol prepared in the step (3), propylene oxide and a proper amount of catalyst under a certain condition to obtain the citric acid triester modified polyether polyol.
The preparation method of the citric acid triester modified polyether polyol comprises the following preferred schemes:
preferably, the alcohol in the step (1) is a mixed alcohol of C4-C12 or a single alcohol of C4-C12.
Preferably, the water-carrying agent in step (1) is toluene or cyclohexane.
Preferably, the catalyst in the step (1) is p-toluenesulfonic acid, and the mass fraction of the p-toluenesulfonic acid is 1-5% of the total mass of the citric acid and the alcohol.
Preferably, the reaction conditions in the step (1) are that the reaction kettle is heated to 120-150 ℃, the reaction kettle is stirred and reacts for 4-8 hours, after the reaction is finished, excess alcohol is removed through reduced pressure distillation, the product is washed by 1-3% sodium bicarbonate solution, and the citric acid triester is obtained after drying.
Preferably, the dibasic acid anhydride in the step (2) is succinic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, octanic anhydride, maleic anhydride, hexahydrophthalic anhydride, phthalic anhydride or tetrahydrophthalic anhydride.
Preferably, the reaction conditions in step (2) are reaction at a temperature of 50-80 ℃ for 5-8 h.
Preferably, the triglycidyl ether in step (3) is selected from glycerol triglycidyl ether and trimethylolpropane triglycidyl ether.
Preferably, the dianhydride acylated citric acid triester and triglycidyl ether are reacted in step (3) in a molar ratio of 3: 1.
Preferably, the reaction condition in the step (3) is that diacid anhydride acidylates the citric acid triester, and the triglycidyl ether is stirred and reacts for 4-6h under the condition that the temperature is 80-110 ℃.
Preferably, the molar ratio of the citric acid triester-modified triol to propylene oxide in step (4) is 1:5 to 80.
Preferably, the catalyst in step (4) is one of potassium hydroxide, sodium hydroxide, ethylenediamine, toluenediamine, diethylenetriamine, dimethylamine or trimethylamine.
Preferably, the catalyst in the step (4) is 0.3 to 3% of the total mass of the citric acid triester-modified trihydric alcohol and the propylene oxide.
Preferably, the reaction conditions in the step (4) are that the citric acid triester modified trihydric alcohol and a proper amount of catalyst are stirred and heated to 90-120 ℃ under the protection of nitrogen, the vacuum pumping is carried out until the pressure is less than or equal to 0.1MPa, the propylene oxide is added after the reaction is kept for 1-3h, the reaction is carried out under the conditions that the temperature is 100-120 ℃ and the pressure is 0.05-0.3MPa until the hydroxyl value is stable, then the reaction is carried out under the conditions that the temperature is 110-120 ℃, and the vacuum pumping is carried out to remove the unreacted micromolecule monomer, so as to obtain the citric acid triester modified polyether polyol.
The technical scheme of the polyurethane waterproof coating is as follows:
the polyurethane waterproof coating comprises polyether polyol, wherein the polyether polyol is the citric acid triester modified polyether polyol.
The invention has the following beneficial effects:
1. the citric acid triester modified polyether polyol prepared by the method has the characteristics of easy biodegradation, no harm to human bodies and no skin irritation.
2. According to the invention, the citric acid triester is introduced into the polyether polyol molecular side chain through a chemical bond, and due to the branched structure of the side chain, the polyether polyol has lower viscosity, has good wrapping effect on the filler, and can ensure that the prepared coating has lower viscosity and good leveling property without adding an organic solvent.
3. According to the invention, the citric acid triester is introduced into the polyether polyol molecular side chain through a chemical bond, so that the reaction activity of the polyether polyol is not influenced, and meanwhile, the prepared polyurethane material has excellent strength and elasticity, so that the citric acid ester is prevented from being separated from the polyurethane material, the stability of the polyurethane material is improved, and the service life of the polyurethane material is prolonged.
4. The preparation method of the invention has simple process and is easy for industrialization.
Drawings
FIG. 1 is a schematic representation of a tripentyl citrate modified polyether polyol prepared in example 21H-NMR spectrum.
Detailed Description
The following examples are intended to further illustrate the content of the invention, but not to limit the scope of the invention.
The test method in the embodiment is as follows:
the hydroxyl value of the polyether polyol prepared was measured according to GBT 12008.3-1989 "method for measuring hydroxyl value in polyether polyol".
The polyether polyol prepared was subjected to viscosity measurement according to GBT 12008.8 "viscosity measurement of polyether polyol".
The number average molecular weight of the polyether polyol was measured by room temperature Gel Permeation Chromatography (GPC).
The structure of the polyether polyol is characterized by adopting a nuclear magnetic resonance hydrogen spectrum.
Example 1
(1) Preparation of tributyl citrate: adding 30mol of citric acid, 115mol of butanol, 110mol of cyclohexane with water and p-toluenesulfonic acid with the mass being 2.5 percent of the total mass of the citric acid and the alcohol into a reaction kettle equipped with a temperature-controlled oil bath, a stirrer, a water separator and a reflux condenser, stirring and heating to 150 ℃, carrying out reflux reaction for 4 hours, cooling to room temperature, carrying out reduced pressure distillation on a product to remove excessive alcohol and cyclohexane with water, washing by a sodium bicarbonate solution with the mass fraction being 3 percent to remove the catalyst, and finally drying to obtain tributyl citrate.
(2) Preparation of succinic anhydride acylated tributyl citrate: adding 80mol of carbon tetrachloride, 50mol of tributyl citrate and 50mol of succinic anhydride into a reaction kettle provided with a temperature-controlled oil bath, a condenser tube and a stirrer, stirring and heating to 80 ℃, reacting for 5 hours, cooling to room temperature, and distilling the product to remove the solvent to obtain succinic anhydride acylated tributyl citrate.
(3) Preparing tributyl citrate modified trihydric alcohol: adding 90mol of succinic anhydride acylated tributyl citrate, 30mol of glycerol triglycidyl ether, 50mol of butanone and N, N-dimethylformamide with the mass being 1.5% of that of the glycerol triglycidyl ether into a reaction kettle provided with a temperature-controlled oil bath, a condenser tube and a stirrer, introducing nitrogen, heating to 110 ℃ under stirring, reacting for 4 hours, then carrying out reduced pressure distillation to remove a solvent and a catalyst, and cooling to room temperature to obtain the tributyl citrate modified trihydric alcohol.
(4) Preparing tributyl citrate modified polyether polyol: adding 2mol of tributyl citrate modified triol and a catalyst trimethylamine with the mass being 0.9% of the total mass of the tributyl citrate modified triol and the propylene oxide into a reaction kettle provided with a temperature-controlled oil bath and a stirrer, introducing nitrogen, heating to 90 ℃ under stirring, vacuumizing to the pressure of 0.1MPa, keeping for 3 hours, stopping vacuumizing, adjusting the temperature of the reaction kettle to 100 ℃, slowly adding 160mol of propylene oxide, adjusting the pressure to 0.1MPa, continuing to react until the hydroxyl value of the product is stable after adding the propylene oxide, then heating to 110 ℃, and vacuumizing to remove unreacted small molecular monomers to obtain the tributyl citrate modified polyether polyol N1.
The physical and chemical parameters of the tributyl citrate modified polyether polyol N1 are as follows: the hydroxyl value was 26.5mgKOH/g, the viscosity at 25 ℃ was 725 mPas, and the number average relative molecular mass was 5968 g/mol.
Example 2
(1) Preparation of tripentyl citrate: adding 30mol of citric acid, 120mol of amyl alcohol, 115mol of cyclohexane with water and p-toluenesulfonic acid with the mass being 1.0% of the total mass of the citric acid and the alcohol into a reaction kettle equipped with a temperature-controlled oil bath, a stirrer, a water separator and a reflux condenser, stirring and heating to 120 ℃, carrying out reflux reaction for 8 hours, cooling to room temperature, carrying out reduced pressure distillation on a product to remove excessive alcohol and cyclohexane with water, washing by a sodium bicarbonate solution with the mass fraction being 1% to remove the catalyst, and finally drying to obtain the tripentyl citrate.
(2) Preparation of glutaric anhydride acylated citric acid tripentyl ester: adding 80mol of carbon tetrachloride, 50mol of citric acid tripentyl ester and 50mol of glutaric anhydride into a reaction kettle provided with a temperature-controlled oil bath, a condenser tube and a stirrer, stirring and heating to 50 ℃, reacting for 8 hours, cooling to room temperature, and distilling the product to remove the solvent to obtain glutaric anhydride acylated citric acid tripentyl ester.
(3) Preparation of tripentyl citrate modified triol: adding 90mol of glutaric anhydride acylated citric acid tripentyl ester, 30mol of glycerol triglycidyl ether, 50mol of butanone and N, N-dimethylformamide with the mass being 1.8 percent of that of the glycerol triglycidyl ether into a reaction kettle provided with a temperature-controlled oil bath, a condenser tube and a stirrer, introducing nitrogen, heating to 80 ℃ under stirring, reacting for 6h, then carrying out reduced pressure distillation to remove a solvent and a catalyst, and cooling to room temperature to obtain the citric acid tripentyl ester modified trihydric alcohol.
(4) Preparation of citric acid tripentyl ester modified polyether polyol: adding 2mol of tributyl citrate modified triol and a catalyst trimethylamine with the mass being 0.5% of the total mass of the tributyl citrate modified triol and the propylene oxide into a reaction kettle provided with a temperature-controlled oil bath and a stirrer, introducing nitrogen, heating to 120 ℃ under stirring, vacuumizing to the pressure of 0.08MPa, keeping for 1h, stopping vacuumizing, adjusting the temperature of the reaction kettle to 120 ℃, slowly adding 120mol of propylene oxide, adjusting the pressure to 0.3MPa, continuing to react until the hydroxyl value of the product is stable after adding the propylene oxide, then heating to 120 ℃, and vacuumizing to remove unreacted small molecular monomers to obtain the tributyl citrate modified polyether polyol N2.
The physical and chemical parameters of the citric acid tripentyl ester modified polyether polyol N2 are as follows: the hydroxyl value was 32.1mgKOH/g, the viscosity at 25 ℃ was 680 mPas, and the number-average relative molecular mass was 5193 g/mol.
Example 3
(1) Preparation of trioctyl citrate: adding 30mol of citric acid, 110mol of octanol, 115mol of cyclohexane with a water-carrying agent and p-toluenesulfonic acid with the mass being 4.0% of the total mass of the citric acid and the alcohol into a reaction kettle equipped with a temperature-controlled oil bath, a stirrer, a water separator and a reflux condenser, stirring and heating to 130 ℃, carrying out reflux reaction for 5 hours, cooling to room temperature, carrying out reduced pressure distillation on a product to remove excessive alcohol and cyclohexane with the water-carrying agent, washing by a sodium bicarbonate solution with the mass fraction being 2% to remove the catalyst, and finally drying to obtain trioctyl citrate.
(2) Preparation of caprylic anhydride acylated trioctyl citrate: adding 100mol of carbon tetrachloride, 60mol of trioctyl citrate and 60mol of octanedioic anhydride into a reaction kettle provided with a temperature-controlled oil bath, a condensing tube and a stirrer, stirring and heating to 75 ℃, reacting for 6 hours, and distilling the product to remove the solvent to obtain the octanedioic anhydride acylated trioctyl citrate.
(3) Preparing trioctyl citrate modified trihydric alcohol: adding 90mol of caprylic anhydride acylated trioctyl citrate, 30mol of trimethylolpropane triglycidyl ether, 60mol of butanone and N, N-dimethylformamide with the mass being 2% of that of the trimethylolpropane triglycidyl ether into a reaction kettle provided with a temperature-controlled oil bath, a condensing tube and a stirrer, introducing nitrogen, heating to 100 ℃ while stirring, reacting for 5 hours, then carrying out reduced pressure distillation to remove a solvent and a catalyst, and cooling to room temperature to obtain trioctyl citrate modified trihydric alcohol.
(4) Preparing trioctyl citrate modified polyether polyol: adding 2mol of trioctyl citrate modified triol and a catalyst trimethylamine with the mass of 0.7 percent of the total mass of the trioctyl citrate modified triol and the propylene oxide into a reaction kettle provided with a temperature-controlled oil bath and a stirrer, introducing nitrogen, heating to 100 ℃ under stirring, vacuumizing to the pressure of 0.09MPa, keeping for 2 hours, stopping vacuumizing, adjusting the temperature of the reaction kettle to 110 ℃, slowly adding 100mol of propylene oxide, adjusting the pressure to 0.1MPa, continuing to react until the hydroxyl value of the product is stable, heating to 115 ℃, and vacuumizing to remove unreacted small molecular monomers to obtain the trioctyl citrate modified polyether polyol N3.
The physical and chemical parameters of the trioctyl citrate modified polyether polyol N3 are as follows: the hydroxyl value was 31.8mgKOH/g, the viscosity at 25 ℃ was 665 mPas, and the number-average relative molecular mass was 5180 g/mol.
Example 4
(1) Preparation of trilauryl citrate: adding 30mol of citric acid, 120mol of lauryl alcohol, 125mol of cyclohexane with water and p-toluenesulfonic acid with the mass being 5% of the total mass of the citric acid and the alcohol into a reaction kettle equipped with a temperature-controlled oil bath, a stirrer, a water separator and a reflux condenser, stirring and heating to 140 ℃, carrying out reflux reaction for 4.5h, cooling to room temperature, carrying out reduced pressure distillation on a product to remove excessive alcohol and cyclohexane with water, washing by using a sodium bicarbonate solution with the mass fraction being 2% to remove a catalyst, and finally drying to obtain the trilauryl citrate.
(2) Preparation of succinic anhydride acylated trilauryl citrate: adding 70mol of carbon tetrachloride, 50mol of trilauryl citrate and 50mol of succinic anhydride into a reaction kettle provided with a temperature-controlled oil bath, a condenser tube and a stirrer, stirring and heating to 70 ℃, reacting for 7 hours, and distilling the product to remove the solvent to obtain the succinic anhydride acylated trilauryl citrate.
(3) Preparing the trilaurin citrate modified trihydric alcohol: adding 90mol of succinic anhydride acylated trilauryl citrate, 30mol of trimethylolpropane triglycidyl ether, 65mol of butanone and N, N-dimethylformamide with the mass being 1.5% of that of the trimethylolpropane triglycidyl ether into a reaction kettle provided with a temperature-controlled oil bath, a condenser tube and a stirrer, introducing nitrogen, heating to 95 ℃ under stirring, reacting for 5 hours, then carrying out reduced pressure distillation to remove a solvent and a catalyst, and cooling to room temperature to obtain the trilauryl citrate modified trihydric alcohol.
(4) Preparation of trilauryl citrate modified polyether polyol: adding 2mol of trilauryl citrate modified triol and a catalyst trimethylamine with the mass of 0.4% of the total mass of trilauryl citrate modified triol and propylene oxide into a reaction kettle provided with a temperature-controlled oil bath and a stirrer, introducing nitrogen, heating to 120 ℃ under stirring, vacuumizing to the pressure of 0.1MPa, keeping for 2 hours, stopping vacuumizing, adjusting the temperature of the reaction kettle to 110 ℃, slowly adding 70mol of propylene oxide, adjusting the pressure to 0.25MPa, continuing to react until the hydroxyl value of the product is stable after adding the propylene oxide, heating to 120 ℃, and vacuumizing to remove unreacted small molecular monomers to obtain trilauryl citrate modified polyether polyol N4.
The physical and chemical parameters of the trilauryl citrate modified polyether polyol N4 are as follows: the hydroxyl value was 34.4mgKOH/g, the viscosity at 25 ℃ was 550 mPas, and the number-average relative molecular mass was 4716 g/mol.
Example 5
(1) Preparation of trinonyl citrate: adding 30mol of citric acid, 125mol of nonanol, 120mol of cyclohexane with a water-carrying agent and p-toluenesulfonic acid with the mass being 2.0 percent of the total mass of the citric acid and the alcohol into a reaction kettle equipped with a temperature-controlled oil bath, a stirrer, a water separator and a reflux condenser, stirring and heating to 125 ℃, carrying out reflux reaction for 6 hours, cooling to room temperature, carrying out reduced pressure distillation on a product to remove excessive alcohol and cyclohexane with the water-carrying agent, washing by a sodium bicarbonate solution with the mass fraction being 3 percent to remove the catalyst, and finally drying to obtain trinonyl citrate.
(2) Preparation of pimelic anhydride acylated citric acid trinonyl ester: adding 80mol of carbon tetrachloride, 60mol of trinonyl citrate and 60mol of pimelic anhydride into a reaction kettle provided with a temperature-controlled oil bath, a condensing tube and a stirrer, stirring and heating to 60 ℃, reacting for 7 hours, and distilling the product to remove the solvent to obtain the pimelic anhydride acylated trinonyl citrate.
(3) Preparation of trinary alcohol modified by trinonyl citrate: adding 90mol of isononyl citrate acylated with pimelic anhydride, 30mol of glycerol triglycidyl ether, 50mol of butanone and N, N-dimethylformamide with the mass being 1.5% of that of the glycerol triglycidyl ether into a reaction kettle provided with a temperature-controlled oil bath, a condensing tube and a stirrer, introducing nitrogen, heating to 100 ℃ under stirring, reacting for 4 hours, then carrying out reduced pressure distillation to remove a solvent and a catalyst, and cooling to room temperature to obtain the isononyl citrate modified trihydric alcohol.
(4) Preparation of trinonyl citrate modified polyether polyol: adding 2mol of trinonyl citrate modified triol and a catalyst trimethylamine with the mass of 0.3 percent of the total mass of the trinonyl citrate modified triol and the propylene oxide into a reaction kettle provided with a temperature-controlled oil bath and a stirrer, introducing nitrogen, heating to 110 ℃ under stirring, vacuumizing to the pressure of 0.07MPa, keeping for 1h, stopping vacuumizing, adjusting the temperature of the reaction kettle to 120 ℃, slowly adding 40mol of propylene oxide, adjusting the pressure to 0.2MPa, continuing to react until the hydroxyl value of the product is stable after adding the propylene oxide, then heating to 110 ℃, and vacuumizing to remove unreacted small molecular monomers to obtain the trinonyl citrate modified polyether polyol N5.
The physical and chemical parameters of the trinonyl citrate modified polyether polyol N5 are as follows: a hydroxyl value of 48.1mgKOH/g, a viscosity at 25 ℃ of 472 mPas, and a number-average relative molecular mass of 3418 g/mol.
Comparative example 1
Adding 2mol of glycerol and a catalyst trimethylamine with the mass being 1% of the total mass of the glycerol and the propylene oxide into a reaction kettle provided with a temperature-controlled oil bath and a stirrer, introducing nitrogen, heating to 105 ℃ under stirring, vacuumizing to the pressure of 0.09MPa, stopping vacuumizing after keeping for 1h, adjusting the temperature of the reaction kettle to 120 ℃, slowly adding 140mol of propylene oxide, adjusting the pressure to 0.2MPa, adding the propylene oxide, continuing to react until the hydroxyl value of the product is stable, heating to 110 ℃, and vacuumizing to remove unreacted micromolecule monomers to obtain the polyether polyol C1.
The physical and chemical parameters of the polyether polyol C1 are as follows: a hydroxyl value of 40.3mgKOH/g, a viscosity at 25 ℃ of 690 mPas, and a number-average relative molecular mass of 4013 g/mol.
Comparative example 2
Adding 2mol of glycerol and a catalyst trimethylamine with the mass being 1.2 percent of the total mass of the glycerol and the propylene oxide into a reaction kettle provided with a temperature-controlled oil bath and a stirrer, introducing nitrogen, heating to 100 ℃ under stirring, vacuumizing to the pressure of 0.08MPa, keeping for 1.5h, stopping vacuumizing, adjusting the temperature of the reaction kettle to 110 ℃, slowly adding 170mol of propylene oxide, adjusting the pressure to 0.25MPa, adding the propylene oxide, continuing to react until the hydroxyl value of the product is stable, heating to 120 ℃, vacuumizing to remove unreacted micromolecule monomers, and obtaining the polyether polyol C2.
The physical and chemical parameters of the polyether polyol C2 are as follows: the hydroxyl value was 33.4mgKOH/g, the viscosity at 25 ℃ was 850 mPas, and the number-average relative molecular mass was 4985 g/mol.
Comparative example 3
Adding 2mol of trimethylolpropane and catalyst trimethylamine with the mass being 1.5 percent of the total mass of the trimethylolpropane and the propylene oxide into a reaction kettle provided with a temperature-controlled oil bath and a stirrer, introducing nitrogen, heating to 100 ℃ under stirring, vacuumizing to the pressure of 0.08MPa, keeping for 1.5h, stopping vacuumizing, adjusting the temperature of the reaction kettle to 110 ℃, slowly adding 150mol of propylene oxide, adjusting the pressure to 0.3MPa, adding the propylene oxide, continuing to react until the hydroxyl value of the product is stable, heating to 110 ℃, and vacuumizing to remove unreacted micromolecule monomers to obtain polyether polyol C3.
The physical and chemical parameters of the polyether polyol C3 are as follows: the hydroxyl value was 37.4mgKOH/g, the viscosity at 25 ℃ was 720 mPas, and the number-average relative molecular mass was 4352 g/mol.
Preparation and testing of polyurethane waterproof coating
The polyurethane waterproof coating is obtained by curing a polyurethane waterproof coating, and the polyurethane waterproof coating comprises a component A and a component B.
Preparation of the component A: adding polyether polyol, butanediol, a plasticizer ATOC, talcum powder and heavy calcium powder into a reaction kettle according to the proportion in the table 1, stirring and heating to 120 ℃, dehydrating for 5h under the condition of the pressure of 0.1MPa, then cooling to 45-70 ℃, adding stannous octoate, stirring for 2h, and cooling to room temperature to obtain a component A, wherein the viscosity of the component A at 25 ℃ is shown in the table 2;
preparation of the component B: adding 45 parts by mass of polyether diol (N210) and 40 parts by mass of polyether triol (330N) into a reaction kettle, uniformly stirring, heating to 110-120 ℃, and dehydrating for 8 hours under the condition that the pressure is 0.08-0.1 MPa; after dehydration, reducing the temperature to 60-75 ℃, adding 72 parts by mass of diphenylmethane diisocyanate (fumitory Wanhua MDI-50), reacting for 3-5h at 75-90 ℃, and reducing the temperature to room temperature after the reaction is finished to obtain a component B, wherein the viscosity of the component B at 25 ℃ is 3100mPa · s.
The prepared two-component polyurethane waterproof coating is subjected to performance measurement according to the specification of GB/T19250-2013, and the test results are shown in Table 3.
TABLE 1 composition and parts by mass of component A of polyurethane waterproofing paint
Figure BDA0002997976340000091
Figure BDA0002997976340000101
Note: n330 is polyether polyol N330, ATOC is acetyl trioctyl citrate, the particle size of talcum powder is 1000 meshes, and the particle size of heavy calcium powder is 800 meshes.
TABLE 2 viscosity of polyurethane waterproofing paint A component
Figure BDA0002997976340000102
TABLE 3 Performance test results of polyurethane waterproofing coatings
Figure BDA0002997976340000103
Figure BDA0002997976340000111
Note: the heat treatment condition is 80 ℃ and 168 hours; acid treatment conditions were 2% H2SO4168 h; the alkali treatment conditions were 0.1% NaOH + saturated Ca (OH)2Solution, 168 h; the aging treatment condition is artificial weathering aging for 1000 h.
As can be seen from tables 2 and 3, the synthesized citric acid triester modified polyether polyol can well wrap the solid filler to uniformly disperse the solid filler, the viscosity of the formed mixture is low, no toxic and odorous solvent can be added, and the good leveling property of the coating can be ensured. The citric acid triester is positioned on the side chain of the polyether polyol, so that the reaction activity of the polyether polyol is not influenced, the prepared polyurethane material has excellent strength and elasticity, the citric acid ester is prevented from being separated from the polyurethane material, and the stability and the service life of the polyurethane material are improved. In addition, the citric acid triester modified polyether polyol prepared by the method has the characteristics of easy biodegradation, no harm to human bodies and no skin irritation, and the preparation method is simple in process and easy to industrialize.

Claims (8)

1. A citrate triester-modified polyether polyol, wherein the citrate triester-modified polyether polyol has the following structure:
Figure FDA0002997976330000011
wherein R has a structure represented by formula (I):
Figure FDA0002997976330000012
in the formula (I), R1、R2、R3Each independently selected from one of C4-C12 straight chain or branched chain alkyl; r4Is a C2-C10 hydrocarbyl group.
2. The citrate triester-modified polyether of claim 1A polyol, characterized in that R is1、R2、R3Are the same group.
3. A preparation method of citric acid triester modified polyether polyol is characterized by comprising the following steps:
step (1): preparation of citric acid triester
Adding citric acid, alcohol, a proper amount of catalyst and a water-carrying agent into a reaction kettle, and reacting under a certain condition to obtain citric acid triester;
step (2): preparation of diacid anhydride acylated citric acid triester
Adding the citric acid triester and dianhydride into a reaction kettle, and reacting to obtain dianhydride acylated citric acid triester;
and (3): preparation of citric acid triester modified triol
Adding the diacid anhydride acylated citric acid triester prepared in the step (2) and triglycidyl ether into a reaction kettle, adding a proper amount of catalyst, and reacting to obtain citric acid triester modified trihydric alcohol;
and (4): preparation of citric acid triester-modified polyether polyol
And (3) reacting the citric acid triester modified trihydric alcohol prepared in the step (3), propylene oxide and a proper amount of catalyst under a certain condition to obtain the citric acid triester modified polyether polyol.
4. The preparation method according to claim 3, wherein the water-carrying agent in step (1) is toluene or cyclohexane; in the step (1), the catalyst is p-toluenesulfonic acid, and the mass fraction of the p-toluenesulfonic acid is 1-5% of the total mass of the citric acid and the alcohol.
5. The method according to claim 3, wherein the dibasic acid anhydride in the step (2) is succinic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, suberic anhydride, maleic anhydride, hexahydrophthalic anhydride, phthalic anhydride, tetrahydrophthalic anhydride.
6. The method according to claim 3, wherein the triglycidyl ether in the step (3) is selected from glycerol triglycidyl ether and trimethylolpropane triglycidyl ether.
7. The method according to claim 3, wherein the molar ratio of the citric acid triester-modified triol to the propylene oxide in the step (4) is 1:5 to 80.
8. A polyurethane waterproofing coating comprising a polyether polyol, characterized in that the polyether polyol is the citric acid triester-modified polyether polyol of claim 1.
CN202110336730.9A 2021-03-29 2021-03-29 Citric acid triester modified polyether polyol and application thereof in polyurethane waterproof coating Withdrawn CN113512189A (en)

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