CN117143328B - Preparation method of high-carbon alcohol polyether ester for defoamer - Google Patents

Preparation method of high-carbon alcohol polyether ester for defoamer Download PDF

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CN117143328B
CN117143328B CN202311046111.1A CN202311046111A CN117143328B CN 117143328 B CN117143328 B CN 117143328B CN 202311046111 A CN202311046111 A CN 202311046111A CN 117143328 B CN117143328 B CN 117143328B
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alcohol
acid
carbon
polyether ester
initiator
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CN117143328A (en
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李顺民
吕兴连
王超
崔继东
宗光喜
张凡举
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Shandong Binhua Juhe New Material Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • 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
    • 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
    • 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

Abstract

The invention belongs to the technical field of defoamers, and particularly relates to a preparation method of high-carbon alcohol polyether ester for a defoamer. The method comprises the following steps: (1) Adopting fatty alcohol with carbon chain length of more than 12 as an initiator, adding small molecular alcohol dissolved with a bimetallic catalyst and sulfuric acid, heating while stirring to completely melt the initiator, uniformly mixing the initiator with the added bimetallic catalyst, sulfuric acid and small molecular alcohol, removing water and small molecular alcohol in the initiator by reduced pressure distillation, adding an epoxy compound, and carrying out polymerization reaction to obtain the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether; (2) And (3) carrying out esterification reaction on the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether and fatty acid under the action of a catalyst to obtain the high-carbon alcohol polyether ester for the defoamer. The preparation method of the high-carbon alcohol polyether ester provided by the invention has the characteristics of simple production process, low cost, excellent defoaming performance and foam inhibition performance of the product, good storage stability and the like when being used for preparing the defoamer.

Description

Preparation method of high-carbon alcohol polyether ester for defoamer
Technical Field
The invention belongs to the technical field of defoamers, and particularly relates to a preparation method of high-carbon alcohol polyether ester for a defoamer.
Background
In recent years, high-carbon alcohol polyether intermediates prepared by a bimetallic catalysis process are widely used for preparing high-carbon fatty alcohol polyether ester defoamers. The defoaming agent product has the advantages of simple preparation process, low production cost and the like by virtue of excellent defoaming and foam inhibition performances, and is widely used in the field of industrial wastewater, particularly in the field of wastewater treatment in the paper industry.
In the industrial production process, when a bimetallic catalyst process is adopted to prepare polyether polyol, usually, a bimetallic catalyst is dissolved in a liquid initiator and stirred uniformly, and then the bimetallic catalyst is poured into a metal charging tank and then added into a reaction kettle. However, in the process of preparing polyether polyol by using high-carbon fatty alcohol, the high-carbon fatty alcohol is generally in solid particles at normal temperature, and the mutual solubility with the bimetallic catalyst cannot be realized. If the method of heating and melting high-carbon fatty alcohol, mixing the high-carbon fatty alcohol with a bimetallic catalyst and adding the bimetallic catalyst into a metal charging tank is adopted, the high-carbon fatty alcohol is influenced by the environmental temperature, particularly in winter, the high-carbon fatty alcohol can lose fluidity quickly due to the influence of low-temperature environment, and part of materials are solidified in the metal charging tank, so that the bimetallic catalyst cannot be added normally and sufficiently, the initiation process is influenced, and the quality of the product is unstable; if the powder bimetallic catalyst is directly put into a reaction kettle, the bimetallic catalyst tends to scatter on the wall of the reaction kettle or a stirrer, so that the feeding amount error is caused, the initiation in the preparation process of the polyether polyol is difficult, the polymerization system cannot be normally initiated when the preparation process is serious, and the problems of abnormal product index and performance, waste and the like are caused.
Patent CN106975247A discloses a novel polyether ester defoamer and a preparation method thereof, and the novel polyether ester defoamer is prepared by taking higher fatty alcohol with a carbon chain length of more than 18 as an initiator. The preparation method of the novel polyether ester defoamer comprises the following steps: (1) Taking higher fatty alcohol as an initiator, and carrying out polyether reaction with ethylene oxide and propylene oxide under the action of a first catalyst to prepare fatty alcohol polyoxyethylene polyoxypropylene ether; (2) And (3) carrying out esterification reaction on the fatty alcohol polyoxyethylene polyoxypropylene ether prepared in the step (1) and fatty acid under the action of a second catalyst to prepare polyether ester. However, the method does not solve the problem that the addition amount of the bimetallic catalyst is inaccurate in the process of preparing polyether polyol by adopting high-carbon fatty alcohol, and the abnormal condition is easily caused in the process of preparing polyether polyol. In the preparation process of polyether polyol, if the addition amount of the catalyst is inaccurate, the abnormality is easy to cause, so that the viscosity of the material is higher, and the subsequent use performance of the product is further affected.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of high-carbon alcohol polyether ester for defoamer, and the high-carbon alcohol polyether intermediate for defoamer prepared by the method has the advantages of simple operation process, good production stability, stable product performance and the like.
The technical scheme adopted by the invention is as follows:
The preparation method of the high-carbon alcohol polyether ester for the defoamer comprises the following steps:
(1) Adopting fatty alcohol with carbon chain length of more than 12 as an initiator, adding small molecular alcohol dissolved with a bimetallic catalyst and sulfuric acid, heating while stirring to completely melt the initiator, uniformly mixing the initiator with the added bimetallic catalyst, sulfuric acid and small molecular alcohol, removing water and small molecular alcohol in the initiator by reduced pressure distillation, adding an epoxy compound, and carrying out polymerization reaction to obtain the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether;
(2) The high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether prepared in the step (1) is subjected to esterification reaction with fatty acid under the action of a catalyst to prepare high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether fatty acid ester, namely high-carbon alcohol polyether ester for a defoaming agent; the catalyst is a mixture of p-toluenesulfonic acid and hypophosphorous acid.
The adding amount of the bimetallic catalyst in the step (1) is 20-60 ppm of the total mass of fatty alcohol and epoxy compound; the mass fraction of the sulfuric acid is 10%, and the addition amount of the 10% sulfuric acid is 100-400 ppm of the mass of the initiator.
In the step (1), the fatty alcohol is one or more of dodecanol (C12), tetradecanol (C14), hexadecanol (C16), octadecanol (C18), icosanol (C20), icosanol (C22), tetracosanol (C24), C12-14 mixed alcohol, C16-18 mixed alcohol or C20-22 mixed alcohol.
The small molecular alcohol in the step (1) is more than one of methanol, ethanol, n-butanol, isobutanol, propanol, n-nonanol and isooctanol, and the addition amount is 2-5 per mill of the mass of the initiator.
The epoxy compound in the step (1) is a mixture of propylene oxide and ethylene oxide, and the mass ratio of the propylene oxide to the ethylene oxide is (60-90) (40-10).
The pressure of the polymerization reaction in the step (1) is-0.09-0.1 MPa, and the temperature is 130-160 ℃; the pressure of reduced pressure distillation is-0.09 to-0.06 MPa, the temperature is 100-130 ℃ and the time is 60-180 min; in the step (2), the esterification reaction pressure is minus 0.1 to minus 0.06MPa, and the temperature is 140 to 170 ℃.
The number average molecular weight of the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether in the step (1) is 1000-4000.
In the step (2), the fatty acid is more than one of stearic acid, oleic acid, lauric acid, ricinoleic acid, linoleic acid, palmitic acid, palmitoleic acid, linolenic acid, myristic acid or abietic acid.
The molar ratio of the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether to the fatty acid in the step (2) is (0.96-1) to (1-1.2).
The adding amount of the p-toluenesulfonic acid in the step (2) is 1-5 per mill of the total mass of the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether and the fatty acid, and the adding amount of the hypophosphorous acid is 0.1-0.5 per mill of the total mass of the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether and the fatty acid.
Compared with the prior art, the invention has the following beneficial effects:
(1) When the preparation method provided by the invention is used for preparing the defoamer, the defoamer has the advantages of simple production process, low cost, excellent defoaming performance and foam inhibition performance of the product, good storage stability and the like.
(2) The preparation process of the bimetal catalysis high-carbon polyether polyol can effectively solve the problem of stable feeding of the bimetal catalyst in the process of preparing the polyether polyol by adopting the high-carbon fatty alcohol, further realize the industrialized stable production of the product and ensure the stability of the service performance of the product.
(3) The preparation method provided by the invention is scientific, reasonable, simple and feasible.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, but the invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The starting materials are commercially available from the public unless otherwise specified.
Example 1
(1) 1191Kg of eicosol was first added to a 5m 3 stainless steel reaction vessel, then 0.08kg of a bimetallic catalyst and 0.1191kg of 10% sulfuric acid were added to 2.382kg of n-nonanol and stirred well, and then poured into the reaction vessel. And heating and stirring the reaction kettle, fully and uniformly mixing materials in the reaction kettle, controlling the pressure of the reaction kettle to be-0.09 MPa, controlling the temperature to be 100 ℃, and starting a vacuum pump to decompress and remove water and n-nonanol for 60 minutes. The pressure of the reaction kettle is controlled to be-0.09-0.1 MPa, a mixture of 1684.2kg of propylene oxide and 1122.8kg of ethylene oxide is continuously introduced at the temperature of 130 ℃, and then the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether is prepared through curing reaction.
The analytical index was as follows, hydroxyl number: 56mgKOH/g, number average molecular weight: 1000, moisture: 0.01wt.%, acid number: 0.02mgKOH/g.
(2) 2983Kg of the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether, 1017kg of stearic acid, 20kg of p-toluenesulfonic acid and 2kg of hypophosphorous acid are respectively added into a stainless steel reaction kettle of 5m 3. Esterification is carried out for 8 hours under the pressure of minus 0.06 to minus 0.1MPa and the temperature of 140 ℃ to obtain the high-carbon alcohol polyether ester for the defoamer.
Example 2
(1) First 259kg of cetostearyl alcohol (mass ratio of cetostearyl alcohol to stearyl alcohol is 3:7) was added to a stainless steel reaction vessel of 5m 3, then 0.2398kg of bimetallic catalyst and 0.1036kg of 10% sulfuric acid were added to 1.295kg of n-butanol and stirred well, and then poured into the reaction vessel. And heating and stirring the reaction kettle, fully and uniformly mixing materials in the reaction kettle, controlling the pressure of the reaction kettle to be-0.08 MPa, controlling the temperature to be 110 ℃, and starting a vacuum pump to decompress and remove water and n-butanol for 180 minutes. The pressure of the reaction kettle is controlled to be-0.09-0.1 MPa, a mixture of 3363.3kg of propylene oxide and 373.3kg of ethylene oxide is continuously introduced at 160 ℃, and then the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether is prepared through curing reaction.
The analytical index was as follows, hydroxyl number: 14mgKOH/g, number average molecular weight: 4000, moisture: 0.02wt.%, acid number: 0.03mgKOH/g.
(2) 3726Kg of the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether, 274kg of oleic acid, 20kg of p-toluenesulfonic acid and 2kg of hypophosphorous acid are respectively added into a stainless steel reaction kettle with a diameter of 5m 3. Esterification is carried out for 5 hours under the pressure of minus 0.06 to minus 0.1MPa and the temperature of 170 ℃ to obtain the high-carbon alcohol polyether ester for the defoamer.
Example 3
(1) 348Kg of stearyl alcohol was first added to a stainless steel reaction vessel of 5m 3, then 0.12kg of a bimetallic catalyst and 0.1044kg of 10% sulfuric acid were added to a mixture of 1.0kg of ethanol and 0.392kg of n-butanol and stirred well, and then poured into the reaction vessel. And heating and stirring the reaction kettle, fully and uniformly mixing materials in the reaction kettle, controlling the pressure of the reaction kettle to be-0.07 MPa, controlling the temperature to be 120 ℃, and starting a vacuum pump to decompress and remove the mixture of water, ethanol and n-butanol for 120 minutes. The pressure of the reaction kettle is controlled to be-0.09-0.1 MPa, a mixture of 2923.2kg of propylene oxide and 730.8kg of ethylene oxide is continuously introduced at the temperature of 140 ℃, and then the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether is prepared through curing reaction.
The analytical index was as follows, hydroxyl number: 18mgKOH/g, number average molecular weight: 3000, moisture: 0.01wt.%, acid number: 0.02mgKOH/g.
(2) 3727Kg of the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether, 273kg of lauric acid, 12kg of p-toluenesulfonic acid and 1.2kg of hypophosphorous acid are respectively added into a stainless steel reaction kettle with a diameter of 5m 3. Esterification is carried out for 6 hours under the pressure of minus 0.06 to minus 0.1MPa and the temperature of 150 ℃ to obtain the high-carbon alcohol polyether ester for the defoamer.
Example 4
(1) 485Kg of hexadecanol was first added to a 5m 3 stainless steel reaction vessel, then 0.16kg of bimetallic catalyst and 0.097kg of 10% sulfuric acid were added to 1.455kg of methanol and stirred well, and then poured into the reaction vessel. The reaction kettle is started to stir while heating, so that materials in the reaction kettle are fully and uniformly mixed, the pressure of the reaction kettle is controlled to be minus 0.06MPa, the temperature is 130 ℃, a vacuum pump is started to decompress and remove water and methanol, and the removal time is 90 minutes. The pressure of the reaction kettle is controlled to be-0.09-0.1 MPa, a mixture of 2461.2kg of propylene oxide and 1054.8kg of ethylene oxide is continuously introduced at the temperature of 130 ℃, and then the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether is prepared through curing reaction.
The analytical index was as follows, hydroxyl number: 28mgKOH/g, number average molecular weight: 2000, moisture: 0.01wt.%, acid number: 0.015mgKOH/g.
(2) 3490Kg of the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether, 510kg of linolenic acid, 16kg of p-toluenesulfonic acid and 1.6kg of hypophosphorous acid are respectively added into a stainless steel reaction kettle with the length of 5m 3. Esterification is carried out for 6 hours under the pressure of minus 0.06 to minus 0.1MPa and the temperature of 160 ℃, thus obtaining the high-carbon alcohol polyether ester for the defoamer.
Comparative example 1
(1) 348Kg of stearyl alcohol were initially introduced into a stainless steel reaction vessel of 5m 3, and then 0.12kg of bimetallic catalyst and 0.1044kg of 10% sulfuric acid were poured into the reaction vessel. And heating and stirring the reaction kettle, fully and uniformly mixing materials in the reaction kettle, controlling the pressure of the reaction kettle to be-0.07 MPa, controlling the temperature to be 120 ℃, and starting a vacuum pump to decompress and remove water for 120 minutes. The pressure of the reaction kettle is controlled to be-0.09-0.1 MPa, a mixture of 2923.2kg of propylene oxide and 730.8kg of ethylene oxide is continuously introduced at the temperature of 140 ℃, and then the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether is prepared through curing reaction.
The analytical index was as follows, hydroxyl number: 19.7mgKOH/g, number average molecular weight: 2847, moisture: 0.01wt.%, acid number: 0.02mgKOH/g.
(2) 3727Kg of the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether, 273kg of lauric acid and 12kg of p-toluenesulfonic acid are respectively added into a stainless steel reaction kettle with a diameter of 5m 3. Esterification is carried out for 6 hours under the pressure of minus 0.06 to minus 0.1MPa and the temperature of 150 ℃ to obtain the high-carbon alcohol polyether ester for the comparative defoamer.
Comparative example 2
(1) 485Kg of hexadecanol was first added to a 5m 3 stainless steel reaction vessel, and then 0.16kg of bimetallic catalyst and 0.097kg of 10% sulfuric acid were poured into the reaction vessel. The reaction kettle is started to stir while heating, so that materials in the reaction kettle are fully and uniformly mixed, the pressure of the reaction kettle is controlled to be minus 0.06MPa, the temperature is 130 ℃, a vacuum pump is started to decompress and remove water, and the removal time is 90 minutes. The pressure of the reaction kettle is controlled to be-0.09-0.1 MPa, a mixture of 2461.2kg of propylene oxide and 1054.8kg of ethylene oxide is continuously introduced at the temperature of 130 ℃, and then the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether is prepared through curing reaction.
The analytical index was as follows, hydroxyl number: 29.8mgKOH/g, number average molecular weight: 1882, moisture: 0.01wt.%, acid number: 0.02mgKOH/g.
(2) 3490Kg of the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether, 510kg of linolenic acid and 16kg of p-toluenesulfonic acid are respectively added into a stainless steel reaction kettle with a length of 5m 3. Esterification is carried out for 6 hours under the pressure of minus 0.06 to minus 0.1MPa and the temperature of 160 ℃, thus obtaining the high-carbon alcohol polyether ester for the defoamer of the comparative example.
Performance test:
the defoaming effect of the high-carbon alcohol polyether ester for the defoamer prepared by the invention is evaluated by adopting a circulation bubbling method, and the specific evaluation method is as follows:
400mL of industrial wastewater from a paper mill is taken, heated to 40 ℃, placed in a measuring cylinder, a circulating pump is started, the foam height is raised to 400mL, then 100ppm of defoamer is added, and the change rule of the foam height along with time is recorded. The smaller the foam height within the first 30 seconds, the better the defoaming effect is shown; the smaller the foam height at 300 seconds, the better the foam suppressing effect. The experimental results are shown in table 1.
TABLE 1 foam height over time test results, mL
As can be seen from Table 1, the higher alcohol polyether ester for defoamer prepared in examples 1-4 had a lower foam height than comparative examples 1-2 at 30 seconds of experimental timing, indicating that the higher alcohol polyether ester for defoamer prepared in examples 1-4 had more excellent defoaming performance; the higher polyether ester for defoamer prepared in examples 1-4 had a lower foam height than comparative examples 1-2 at 300 seconds of experimental timing, indicating that the higher polyether ester for defoamer prepared in examples 1-4 had more excellent foam inhibition properties.
In addition, as can be seen from table 1, in the same formulation system, examples 1 to 4 adopted the method of preparing polyether polyol by dissolving DMC catalyst in small molecular alcohol and then adding the small molecular alcohol into the reaction system, the prepared polyether polyol has higher monomer conversion rate, lower product hydroxyl value and higher molecular weight, and the prepared high-carbon polyether ester has more excellent defoaming and foam inhibiting effects.
The storage stability test results are shown in Table 2, and the test temperature was room temperature (25 ℃ C.).
TABLE 2 high carbon alcohol polyether ester storage stability test results
As can be seen from Table 2, the higher alcohol polyether ester prepared in comparative example 2 changed from a pale yellow transparent liquid to a pale yellow turbid liquid in appearance after 3 months of storage. After the high-carbon alcohol polyether ester prepared in comparative example 1 is stored for 6 months, the appearance of the high-carbon alcohol polyether ester is changed from light yellow transparent liquid to light yellow turbid liquid, and after the high-carbon alcohol polyether ester for defoamer prepared in examples 1-4 is stored for 12 months, the appearance of the high-carbon alcohol polyether ester for defoamer is still light yellow transparent liquid, which shows that the high-carbon alcohol polyether ester for defoamer prepared in the invention has better storage stability.

Claims (5)

1. A preparation method of high-carbon alcohol polyether ester for defoamer is characterized by comprising the following steps: the method comprises the following steps:
(1) Adopting fatty alcohol with carbon chain length of more than 12 as an initiator, adding small molecular alcohol dissolved with a bimetallic catalyst and sulfuric acid, heating while stirring to completely melt the initiator, uniformly mixing the initiator with the added bimetallic catalyst, sulfuric acid and small molecular alcohol, removing water and small molecular alcohol in the initiator by reduced pressure distillation, adding an epoxy compound, and carrying out polymerization reaction to obtain the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether;
(2) The high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether prepared in the step (1) is subjected to esterification reaction with fatty acid under the action of a catalyst to prepare high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether fatty acid ester, namely high-carbon alcohol polyether ester for a defoaming agent; the catalyst is a mixture of p-toluenesulfonic acid and hypophosphorous acid;
The fatty alcohol in the step (1) is more than one of dodecanol, tetradecanol, hexadecanol, octadecanol, icosanol, docosyl alcohol, tetracosanol, C12-14 mixed alcohol, C16-18 mixed alcohol or C20-22 mixed alcohol;
the small molecular alcohol in the step (1) is more than one of methanol, ethanol, n-butanol, isobutanol, propanol, n-nonanol and isooctanol, and the addition amount is 2-5 per mill of the mass of the initiator;
the epoxy compound in the step (1) is a mixture of propylene oxide and ethylene oxide, and the mass ratio of the propylene oxide to the ethylene oxide is (60-90) (40-10);
the number average molecular weight of the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether in the step (1) is 1000-4000;
in the step (2), the fatty acid is more than one of stearic acid, oleic acid, lauric acid, ricinoleic acid, linoleic acid, palmitic acid, palmitoleic acid, linolenic acid, myristic acid or abietic acid.
2. The process for producing a high-carbon alcohol polyether ester for defoaming agent according to claim 1, wherein: the adding amount of the bimetallic catalyst in the step (1) is 20-60 ppm of the total mass of fatty alcohol and epoxy compound; the mass fraction of the sulfuric acid is 10%, and the addition amount of the 10% sulfuric acid is 100-400 ppm of the mass of the initiator.
3. The process for producing a high-carbon alcohol polyether ester for defoaming agent according to claim 1, wherein: the pressure of the polymerization reaction in the step (1) is-0.09-0.1 MPa, and the temperature is 130-160 ℃; the pressure of reduced pressure distillation is-0.09 to-0.06 MPa, the temperature is 100-130 ℃ and the time is 60-180 min; in the step (2), the esterification reaction pressure is minus 0.1 to minus 0.06MPa, and the temperature is 140 to 170 ℃.
4. The process for producing a high-carbon alcohol polyether ester for defoaming agent according to claim 1, wherein: the molar ratio of the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether to the fatty acid in the step (2) is (0.96-1) to (1-1.2).
5. The process for producing a high-carbon alcohol polyether ester for defoaming agent according to claim 1, wherein: the adding amount of the p-toluenesulfonic acid in the step (2) is 1-5 per mill of the total mass of the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether and the fatty acid, and the adding amount of the hypophosphorous acid is 0.1-0.5 per mill of the total mass of the high-carbon fatty alcohol polyoxypropylene polyoxyethylene ether and the fatty acid.
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