CN108744612B - Mineral oil defoaming agent and preparation method thereof - Google Patents
Mineral oil defoaming agent and preparation method thereof Download PDFInfo
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- CN108744612B CN108744612B CN201810513725.9A CN201810513725A CN108744612B CN 108744612 B CN108744612 B CN 108744612B CN 201810513725 A CN201810513725 A CN 201810513725A CN 108744612 B CN108744612 B CN 108744612B
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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
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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
- B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
Abstract
The invention discloses a mineral oil defoaming agent and a preparation method thereof, belonging to the technical field of fine chemical additives. The invention discloses a mineral oil defoaming agent which comprises the following components in parts by weight, 3-10 parts of hydroxyl-terminated polydimethylsiloxane; 5-20 parts of hydrophobic silicon dioxide; 40-80 parts of hydrocarbon oil; 10-35 parts of a defoaming active assistant; 5-15 parts of a surface active emulsifier; 1-6 parts of hydroxyl acrylic resin. The mineral oil defoamer prepared by the invention can effectively inhibit harmful foams in polymerization, steam stripping and filling in the production process of the styrene-butadiene latex; but also realizes the effective control of oil shrinkage, pinholes, fish eyes and bubble suppression of subsequent coatings; meanwhile, the method has the advantages of good stability, small addition amount and the like.
Description
Technical Field
The invention belongs to the technical field of fine chemical additives, and particularly relates to a mineral oil defoaming agent and a preparation method thereof.
Background
The synthesis of the styrene-butadiene latex adopts butadiene and styrene as main monomers and unsaturated carboxylic acid, nitrile, amide and other functional monomers as auxiliary materials, and adopts an anionic and nonionic compound emulsification system and a thermal initiation system to carry out free radical emulsion polymerization. Because of the existence of the anion and nonionic compound emulsification system, the latex can generate harmful foam in the polymerization reaction process, the steam stripping process, the filling process and the subsequent application process, which brings great harm to industrial production, and the harmful foam is generally eliminated by adding the defoaming agent in the production.
It is known that a good defoamer must have the following conditions: chemical inertness, which should not react chemically with the defoamed media (at various pH values, temperatures); secondly, the foaming agent has a positive spreading coefficient, and can be quickly spread on a gas-liquid interface of a foaming system; thirdly, a compound containing surface tension makes the foam form a local weak point; (iv) it should not be readily soluble by the surfactant in the foaming system. The defoaming agent can be classified into alcohols, fatty acids (esters), metal soaps, polyethers and polysiloxanes (also known as silicones) according to chemical compositions, the silicone defoaming agent has good inhibition effect, but has poor compatibility with a system, floating oil appears on the liquid surface along with the lengthening of storage time, and harmful effects such as coating film depression, fish eye defect and the like are easily generated on the subsequent working procedure of latex. Therefore, the mineral oil antifoaming agent is selected at home and abroad to be applied to the styrene-butadiene latex industry mostly.
For the mineral oil defoaming agent, the harmful foam of a system is eliminated, the defoaming agent has good foam inhibition performance, the defoaming agent has good compatibility with the system, and the defects of coating film depression, fish eyes, pin holes and the like cannot be generated in the subsequent process.
The prior art of Chinese patent application No. CN200510088437.6 discloses a defoaming agent which takes three hydrocarbons with different structures as carriers, and takes aluminum fatty acid and silicon dioxide as main defoaming substances, wherein alkyl modified silicone oil with substituents of 2-6 carbon atoms is introduced, and coating defects are easily caused.
The prior art of Chinese patent No. CN104479439B discloses that vegetable oil and derivatives thereof are introduced into a system of alkyl silicone oil and silicon dioxide, the alkyl silicone oil and mineral oil are well dissolved mutually by controlling the average carbon number of the alkyl silicone oil, and the ratio of the mineral oil to the vegetable oil and the derivatives thereof is controlled to be 1: 6-4: 7, so that the problems of shrinkage cavity, shrinkage edge and depression of a coating are effectively solved, the defoaming property and stability of a defoaming agent are improved, the defoaming agent is suitable for defoaming of water-based building coatings, but the problems of pin holes, fish eyes and depression of the styrene-butadiene latex in the subsequent process can not be well solved.
The prior art of Chinese patent No. CN102649021B discloses a non-silicon composite emulsion type defoaming agent, which comprises the following components in percentage by mass: 30-70% of hydrocarbonated oil, 3-15% of defoaming active component, 5-15% of lipophilic emulsifier and hydrophilic emulsifier, 1-5% of thickening agent and 15-50% of defoaming auxiliary agent, wherein the defoaming auxiliary agent is glycerol polyether fatty acid triglyceride; the stable non-silicon composite emulsion defoamer is prepared by adding a mixture of an emulsifier and a thickener aqueous solution into a stock solution of the non-silicon defoamer and emulsifying under certain process conditions, so that the stability and defoaming and foam inhibiting performance of the mineral oil defoamer are effectively solved, but the problems of shrinkage cavity, pin hole, fish eye and later-stage foam inhibiting performance of a coating film in a later process of styrene butadiene latex cannot be well solved.
The prior art of Chinese patent No. CN105169756B discloses a high-efficiency environment-friendly defoaming agent and a preparation method thereof, which comprises the following components: 20 to 30 percent of dimethyl siloxane, 5 to 20 percent of hydroxyl-terminated dimethyl polysiloxane, 5 to 8 percent of polyether modified dimethyl polysiloxane, 3 to 8 percent of silicon dioxide, 10 to 20 percent of isomeric tridecanol emulsifier, 0.5 to 1 percent of sodium carboxymethyl cellulose, 0.5 to 1 percent of sodium benzoate and 30 to 45 percent of deionized water, wherein the percentages are mass percentages. The prior art discloses the use of hydroxyl-terminated polydimethylsiloxane, polyether-modified polydimethylsiloxane, silicon dioxide and other components in a defoaming agent, and although a good defoaming function is realized, the problems of shrinkage cavity, pinholes, fish eyes and late-stage foam inhibition of a coating film in a later process of styrene-butadiene latex are not improved.
Therefore, the technical problem to be solved is to provide a method which has a good defoaming function, can effectively inhibit harmful foams generated in polymerization, stripping and filling processes of the styrene-butadiene latex production process, and simultaneously solves the problems of oil shrinkage, pinholes and fish eyes of subsequent coatings.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems of shrinkage cavity, pinhole, fish eye and late-stage foam inhibition of a coating film in the subsequent procedure of the styrene-butadiene latex caused by the use of the existing mineral oil defoamer, the invention provides the mineral oil defoamer which can effectively inhibit harmful foams generated in polymerization, stripping and filling in the production process of the styrene-butadiene latex and effectively control oil shrinkage, pinhole and fish eye of a subsequent coating, and a preparation method thereof.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A mineral oil defoaming agent comprises the following components in parts by weight,
preferably, the hydroxyl-containing acrylic resin has a structural formula:
m, n and z are integers of 10-100, R1、R2The carbon-containing group is an integer of 2-4 carbon atoms, and the dissolution initiator is azobisisobutyronitrile or dibenzoyl peroxide.
Preferably, m, n and z are integers of 20-25.
Preferably, the ratio z: (m + n) is 1: (2-5).
Preferably, the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the hydroxyl acrylic resin is 1: (1-2).
Preferably, the mass ratio of the hydrocarbon oil to the hydroxyl acrylic resin is (10-20): 1.
Preferably, a hydroxyl-containing monomer is introduced into the main chain of the acrylate polymer, so that the side chain of the polymer has polar hydroxyl, and the monomer is prepared by solution polymerization in the presence of an initiator, wherein the hydroxyl-containing acrylic resin is prepared by the following reaction formula:
preferably, the hydroxyl-terminated polydisiloxanes have a viscosity of ≤ 40mm at 25 deg.C2(s), the hydroxyl content is more than 9.0 percent.
Preferably, the hydroxyl-terminated polydiorganosiloxane is used in an amount of 3 to 6 parts.
Preferably, the hydrocarbon oil is one or a mixture of mineral white oil, spindle oil, machine oil and refrigerator oil.
Preferably, the dynamic viscosity of the hydrocarbon oil at 25 ℃ is 5-40 mm2Mineral white oil/s.
Preferably, the hydrophobic silica is a hydrophobic fumed silica.
Preferably, the hydrophobic fumed silica is dispersed in a methanol/water solution with the volume content M of 30-80%. The M value is a value indicating hydrophobicity, and a higher M value indicates lower hydrophilicity, and when hydrophobic fumed silica is used and uniformly dispersed in a water/methanol mixed solution, the M value is expressed by using a volume ratio of a minimum required amount of methanol, and can be obtained by the following equation: 0.2g of the hydrophobic silica sample was added to 50mL of water in a 250mL beaker, followed by dropwise addition of methanol from a burette until the entire sample was suspended. At this time, the solution in the beaker was stirred constantly by a magnetic stirrer, and the volume percentage of methanol in the liquid mixture in the beaker at the end point was set to the value of M when all the samples were uniformly suspended in the solution.
Preferably, the M value is 35-75.
Preferably, the M value is 40-70.
Preferably, the mass ratio of the hydrophobic fumed silica to the hydroxyl acrylic resin is (2-6): 1.
Preferably, the defoaming active assistant is one or more of ethylene bis-fatty acid amide, metal soap, modified polyether ester, fatty alcohol, fatty acid and fatty wax.
Preferably, the defoaming active assistant is 25-30 parts.
Preferably, the ethylene bis-fatty acid amide is one or more of ethylene bis-oleic acid amide, ethylene bis-stearic acid amide and ethylene bis-palmitic acid amide.
Preferably, the fatty acid is a fatty acid with 2-30 carbon atoms.
Preferably, the fatty acid is a fatty acid with 12-22 carbon atoms.
Preferably, the fatty alcohol is a fatty alcohol with 2-30 carbon atoms, and comprises monohydric alcohol or polyhydric alcohol.
Preferably, the fatty wax is animal wax, beeswax, microcrystalline wax, polypropylene wax, polyethylene wax, paraffin wax,
preferably, the fatty wax is a polypropylene wax.
Preferably, the metal soap is magnesium stearate, calcium stearate, zinc stearate, aluminum stearate.
Preferably, the metal soap is aluminum stearate.
Preferably, the modified polyether ester is fatty acid modified polyether ester, and is synthesized by esterification reaction of polyoxyalkylether and fatty acid under the action of catalyst, wherein the catalyst is sulfuric acid or solid super acid (SO)4 2-/ZrO2) Strongly acidic ion exchange resins or molecular sieves.
Preferably, the structural formula of the polyoxyalkylene ether is RO (EO)X(PO)YH, wherein R is CbH2b+1N is an integer of 4 to 24, b is the number of carbon atoms, subscripts X and Y represent the polymerization degrees of EO and PO, EO is ethylene oxide after ring opening, PO is propylene oxide after ring opening, X is an integer of 1 to 50, and Y is an integer of 1 to 50.
Preferably, b is an integer of 4 to 18, X is an integer of 3 to 24, and Y is an integer of 4 to 24.
Preferably, the fatty acid used for modification is a saturated or unsaturated fatty acid with 6-20 carbon atoms, and the fatty acid is preferably lauric acid, palmitic acid, myristic acid, oleic acid, palmitic acid or stearic acid.
Preferably, the fatty acid used for modification is lauric acid.
Preferably, the surface active emulsifier is 10-15 parts.
Preferably, the surface active emulsifier is a lipophilic emulsifier and a hydrophilic emulsifier, and the hydrophilic-lipophilic balance (HLB) between the lipophilic emulsifier and the hydrophilic emulsifier is 8-12.
Preferably, the hydrophilic-lipophilic balance (HLB) between the lipophilic emulsifier and the hydrophilic emulsifier is 8-9.
Preferably, the lipophilic emulsifier is sorbitan monostearate, sorbitan monooleate, sorbitan tristearate or sorbitan trioleate; the hydrophilic emulsifier is polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate or polyoxyethylene sorbitan trioleate.
Preferably, the lipophilic emulsifier is sorbitan trioleate, and the hydrophilic emulsifier is polyoxyethylene sorbitan trioleate.
A method of preparing a mineral oil defoamer as hereinbefore described comprising the steps of:
(1) adding 1/2 mass hydroxyl-terminated polydimethylsiloxane and hydrophobic silicon dioxide in raw materials into a clean reaction kettle, stirring, heating to 130-150 ℃ at the speed of 5 ℃/min, preserving heat for 2-4 hours, vacuumizing for 0.5-1 hour (the vacuum degree is-0.05 Mpa) at the temperature, and dispersing at high speed for 0.5 hour after the heat preservation is finished to obtain an active silicon premix A liquid;
(2) adding hydrocarbon oil and a defoaming active assistant into a clean reaction kettle, stirring, heating to 120-150 ℃ at the speed of 5 ℃/min, preserving heat for 1.5-4 hours, and vacuumizing at the temperature for 0.5-1 hour, wherein the vacuum degree is-0.05 Mpa;
(3) adding a surface active emulsifier into the mixture obtained in the step (2) at the vacuumizing temperature, and preserving the heat for 0.5-1 hour to obtain a solution B;
(4) adding the active silicon premix A in the step (1) into the mixture in the step (3), and preserving the heat at 90-120 ℃ for 1-2 hours to obtain a solution C;
(5) mixing the residual 1/2 amount of hydroxyl-terminated polydimethylsiloxane and all hydroxyl acrylic resin, and heating to 90-120 ℃ to obtain solution D;
(6) dropwise adding the mixture D liquid obtained in the step (5) into the mixture C liquid obtained in the step (4), and keeping the temperature for 1.5-2.5 hours;
(7) and cooling to 40-70 ℃, preserving heat for 0.5-1 hour, and passing through a homogenizer to obtain the mineral oil defoaming agent.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the hydroxyl-terminated polydimethylsiloxane and the hydroxyl acrylic resin are added into the defoaming agent, the proportion of the two is controlled, and the proportion of the hydroxyl-containing monomer introduced into the main chain of the acrylate polymer is adjusted, so that oil shrinkage, pinholes and fish eyes of a subsequent coating of the styrene-butadiene latex are effectively controlled, and foam inhibition is achieved.
(2) The invention is obtained by repeated tests, and the triblock copolymer formed by two kinds of acrylic ester and acrylic ester with a small amount of hydroxyl is added into the defoaming agent, so that the compatibility and the fluidity of the defoaming agent are improved, and the phenomena of pinholes and fish eyes are less generated during coating; when the hydroxyl content in the hydroxyl acrylate is too high, the hydroxyl acrylate is dissolved in the coating film, a new interface is difficult to form on the surface of the coating film, and the coating film has no obvious effect on eliminating fish eyes and pinholes, and when the hydroxyl content in the hydroxyl acrylate is too low, the hydroxyl acrylate has poor compatibility, is difficult to uniformly distribute on the surface of the coating film, and is easy to generate shrinkage cavities due to aggregation, so that the number ratio of the monomer containing the hydroxyl group to the monomer without the hydroxyl group in the block polymer adopted by the invention is z: (m + n) is 1: and (2) in the case of (5), the defoaming agent is stable in performance and does not layer, and the number of fish eyes and pinholes on the coating is minimum.
(3) The mass ratio of the hydroxyl-terminated polydimethylsiloxane to the hydroxyl acrylic resin is 1: (1-6), the compatibility is better, no layering occurs, and fish eyes and pinholes are fewer than those of the non-added technical scheme during coating.
(4) The mass ratio of the added hydrophobic fumed silica to the hydroxyl acrylic resin is (2-6): 1, wherein the hydrophobic fumed silica is dispersed in a methanol water solution with the volume percentage of 35-75%, and is emulsified by combining a surface active emulsifier and a defoaming active assistant, so that the obtained defoaming agent is stable in property, and the defoaming time is greatly shortened compared with that of a commercially available defoaming agent.
(5) According to the invention, firstly, 1/2 hydroxyl-terminated polydimethylsiloxane and hydrophobic silicon dioxide are subjected to mixing and dissolving treatment, then the mixture is added into a mixture treated by hydrocarbon oil, a defoaming agent active assistant and a surface active emulsifier for treatment, 1/2 hydroxyl-terminated polydimethylsiloxane and hydroxyl acrylic resin are mixed and heated, then the mixture is added into the mixed solution for mixing, and the mineral oil defoaming agent is obtained through heat preservation treatment at 90-120 ℃, 1/2 hydroxyl-terminated polydimethylsiloxane (the hydroxyl content is more than 9%) and hydroxyl acrylic resin are mixed and heated to form a stable mixture, so that the obtained defoaming agent has the advantages of low surface tension, small viscosity-temperature coefficient, high compressibility and high gas permeability coefficient, can effectively inhibit harmful foams of polymerization, stripping and filling in the production process of styrene-butadiene latex, and can also effectively inhibit oil shrinkage, oil shrinkage and filling of subsequent coatings, The bubble inhibition is effectively controlled by the pinholes and the fish eyes; meanwhile, the method has the advantages of good stability, small addition amount and the like.
Detailed Description
The invention is further described with reference to specific examples.
The hydroxy acrylic resin producer is the Tech company of Tech Limited responsibility of new materials of Zhuhai Xiandade; the hydroxyl-terminated polydimethylsiloxane is sold by Kafen Biotech, Guangzhou; the hydrophobic fumed silica is sold by Shandong Youso chemical technology, Inc.
Example 1
A mineral oil antifoaming agent of example 1, comprising the following components in parts by weight,
a method of preparing a mineral oil defoamer as hereinbefore described comprising the steps of:
adding 3 parts of hydroxyl-terminated polydimethylsiloxane into a cleaned reactor, slowly stirring in batches (the stirring speed is 40rpm), adding hydrophobic fumed silica, uniformly stirring, accelerating the stirring speed to 80rpm, heating to 130 +/-2 ℃ at the speed of 5 ℃/min, preserving heat for 2 hours, vacuumizing (the vacuum degree is-0.05 mpa) while maintaining the temperature for 0.5 hour, and dispersing at a high speed for 0.5 hour after the heat preservation is finished, wherein the dispersing speed is 2000r/min to obtain the active silicon premix A liquid.
Adding mineral white oil, ethylene bis stearamide and modified polyether ester into another cleaned reactor, stirring, heating to 120 +/-2 ℃ at the speed of 5 ℃/min, preserving heat for 2 hours, maintaining the temperature, vacuumizing for 0.5 hour (the vacuum degree is-0.05 mpa), adding a surface active emulsifier (sorbitan trioleate or polyoxyethylene sorbitan trioleate), maintaining the temperature for 0.5 hour to obtain a solution B, adding the active silicon premix A solution, maintaining the temperature at 90 +/-2 ℃ for 1 hour, dropwise adding 3 parts of a mixture D solution of hydroxyl-terminated polydimethylsiloxane and hydroxyl acrylic resin which is heated to 90 ℃, cooling to 40 ℃ after maintaining the temperature for 1.5 hours, preserving heat for 0.5 hour, and passing through a homogenizer to obtain the defoaming agent 1.
Example 2
A mineral oil antifoaming agent of example 2, comprising the following components in parts by weight,
a method of preparing a mineral oil defoamer as hereinbefore described comprising the steps of:
adding 1.5 parts of hydroxyl-terminated polydimethylsiloxane into a cleaned reactor, slowly stirring in batches (the stirring speed is 50rpm), adding hydrophobic fumed silica, uniformly stirring, accelerating the stirring speed to 100rpm, heating to 140 +/-2 ℃ at the speed of 5 ℃/min, preserving heat for 3 hours, vacuumizing (the vacuum degree is-0.05 mpa) while maintaining the temperature for 0.6 hour, and dispersing at a high speed for 0.5 hour after the heat preservation is finished, wherein the dispersing speed is 2000r/min to obtain the active silicon premix A solution.
Adding mineral white oil, fatty acid with eighteen carbon atoms, ethylene bis stearamide and modified polyether ester into another cleaned reactor, stirring, heating to 130 +/-2 ℃ at the speed of 5 ℃/min, preserving heat for 3 hours, maintaining the temperature, vacuumizing for 0.6 hour (the vacuum degree is-0.05 mpa), adding a surface active emulsifier (sorbitan trioleate and polyoxyethylene sorbitan trioleate), maintaining the temperature for 0.6 hour to obtain a solution B, adding the active silicon premix A, maintaining the temperature at 100 +/-2 ℃ for 1 hour, dropwise adding 1.5 parts of a mixture D of hydroxyl-terminated polydimethylsiloxane and hydroxyl acrylic resin which is heated to 100 ℃, cooling to 50 ℃ after maintaining the temperature for 2 hours, preserving heat for 0.6 hour, and passing through a homogenizer to obtain the defoaming agent 2.
Example 3
A mineral oil antifoaming agent of example 2, comprising the following components in parts by weight,
a method of preparing a mineral oil defoamer as hereinbefore described comprising the steps of:
adding 5 parts of hydroxyl-terminated polydimethylsiloxane into a cleaned reactor, slowly stirring in batches (the stirring speed is 70rpm), adding hydrophobic fumed silica, uniformly stirring, accelerating the stirring speed to 120rpm, heating to 150 +/-2 ℃ at the speed of 5 ℃/min, preserving heat for 4 hours, vacuumizing (the vacuum degree is-0.05 mpa) while maintaining the temperature for 1 hour, and dispersing at a high speed for 0.5 hour after the heat preservation is finished, wherein the dispersing speed is 2000r/min, thus obtaining the active silicon premix A liquid.
Adding mineral white oil, aluminum bisstearate and modified polyether ester into another cleaned reactor, stirring, heating to 150 +/-2 ℃ at the speed of 5 ℃/min, preserving heat for 4 hours, maintaining the temperature, vacuumizing for 1 hour (the vacuum degree is-0.05 mpa), adding a surface active emulsifier (sorbitan monooleate and polyoxyethylene sorbitan monooleate), maintaining the temperature for 1 hour to obtain a solution B, adding the active silicon premix A, maintaining the temperature at 120 +/-2 ℃ for 1 hour, dropwise adding 5 parts of a mixture D of hydroxyl-terminated polydimethylsiloxane and hydroxyacrylic acid resin which is heated to 120 ℃, cooling to 70 ℃ after maintaining the temperature for 2 hours, preserving heat for 1 hour, and passing through a homogenizer to obtain the defoaming agent 3.
Comparative example 1
Comparative example 1 is different from example 1 only in that the hydroxyacrylic resin is not added, and other components and preparation methods are the same, namely, the defoaming agent comparative example 1.
Comparative example 2
Comparative example 1 differs from example 1 only in that the hydroxyl group content of the hydroxyl terminated polydimethylsiloxane was 6.3%, which is comparative example 3 of the defoaming agent.
Comparative example 3
Comparative example 1 differs from example 1 only in that hydrophobic fumed silica is dispersed in 100% methanol (M ═ 100), which is the antifoaming agent comparative example 3.
Performance test method of defoaming agent
1. Stability of
Test method
Thermal stability: standing for 48 hours at the temperature of 45-60 ℃, and observing whether the materials are layered or not.
TABLE 1
And (3) effect analysis: as shown by the experimental results in Table 1, comparative example 1 is different from example 1 in that no hydroxyacrylic resin is added in the comparative example, and under the same conditions, the sample to which the hydroxyacrylic resin is added does not delaminate, while the sample to which no hydroxyacrylic resin is added delaminates, indicating that the obtained defoaming agent sample is unstable; in comparative example 2, compared with example 1, the hydroxyl content of the hydroxyl-terminated polydimethylsiloxane is 6.3 percent and less than 9.0 percent, and a small amount of delamination occurs in the sample, which indicates that the obtained defoaming agent sample is unstable; comparative example 3 compared to example 1, the hydrophobic fumed silica was dispersed in 100% methanol (M ═ 100) and the sample delaminated, demonstrating that the resulting defoamer sample was unstable.
2. Defoaming and foam suppressing performance test
Foaming liquid: 20 g of styrene-butadiene latex and 80 g of deionized water
And (3) testing defoaming and foam inhibiting performance: add 100mL of foaming solution to a 500mL graduated cylinder and mix with N2Inserting the glass tube connected with the bottle into the foaming liquid to swell the bubbles, and controlling N2The flow is 4L/min, when the foam reaches 500mL, the defoaming agent with the amount of 0.5% of the foaming liquid is added, the time for eliminating the foam is recorded, the shorter the time is, the better the defoaming performance is, the time for the foam volume to reach 500mL is recorded, and the longer the required time is, the better the foam inhibition performance of the defoaming agent is.
TABLE 2
And (3) effect analysis:
as can be seen from the data in Table 2, the defoaming agents used in examples 1 to 3 had defoaming times of 6s, 10s and 15s under the same experimental conditions, while the commercially available defoaming agent had defoaming times of 25s under the same conditions; the defoaming agent prepared in the embodiment 1 has the best effect, only needs 6s, and the defoaming time of the corresponding comparative examples 1-3 is 8s,13s and 16s respectively.
3. Brushing Performance test
The test method comprises the following steps: after 0.002 g of an antifoaming agent was added to 20 g of styrene-butadiene latex and stirred uniformly, it was poured onto 2g of a cleaned glass plate, the styrene-butadiene latex to which the antifoaming agent was added was scraped off with a 75 μm wet film maker, and the state of a coating film was observed and expressed by grades:
and 5, stage: the number of coating film depressions or pit marks is 2 or less
4, level: 2-5 coating film pits or pit marks
And 3, level: 5-10 coating film pits or pit marks
And 2, stage: 10-20 coating film pits or pit marks
Level 1: 20 coating film depressions or pit marks
TABLE 3 comparison of coating effectiveness of defoamers
And (3) effect analysis:
the above experiments have been carried out to show that: the viscosity of the hydroxyl-terminated polydimethylsiloxane is more than 40, the hydroxyl content is less than 9.0, the M value of the hydrophobic silicon dioxide is more than 80, or no hydroxyl acrylic resin is added, and the brushing depressions or pit marks of the prepared defoaming agent are all more than those of the defoaming agent.
Claims (8)
1. The mineral oil defoaming agent is characterized by comprising the following components in parts by weight:
3-10 parts of hydroxyl-terminated polydimethylsiloxane
5-20 parts of hydrophobic silicon dioxide
40-80 parts of hydrocarbon oil
10-35 parts of defoaming active assistant
5-15 parts of surface active emulsifier
1-6 parts of hydroxyl acrylic resin;
the preparation method of the mineral oil defoaming agent comprises the following steps:
(1) adding 1/2 mass hydroxyl-terminated polydimethylsiloxane and hydrophobic silicon dioxide in raw materials into a clean reaction kettle, stirring, heating to 130-150 ℃ at the speed of 5 ℃/min, preserving heat for 2-4 hours, vacuumizing for 0.5-1 hour at the temperature, wherein the vacuum degree is-0.05 Mpa, and dispersing at high speed for 0.5 hour after the heat preservation is finished to obtain an active silicon premix A liquid;
(2) adding hydrocarbon oil and a defoaming active assistant into a clean reaction kettle, stirring, heating to 120-150 ℃ at the speed of 5 ℃/min, preserving heat for 1.5-4 hours, and vacuumizing at the temperature for 0.5-1 hour, wherein the vacuum degree is-0.05 Mpa;
(3) adding a surface active emulsifier into the mixture obtained in the step (2) at a vacuumizing temperature, and preserving the heat for 0.5-1 hour to obtain a mixture B liquid;
(4) adding the active silicon premix A in the step (1) into the mixture B in the step (3), and preserving the heat at 90-120 ℃ for 1-2 hours to obtain a solution C;
(5) mixing the residual 1/2 amount of hydroxyl-terminated polydimethylsiloxane and all hydroxyl acrylic resin, and heating to 90-120 ℃ to obtain solution D;
(6) dropwise adding the mixture D liquid obtained in the step (5) into the mixture C liquid obtained in the step (4), and keeping the temperature for 1.5-2.5 hours;
(7) and cooling to 40-70 ℃, preserving heat for 0.5-1 hour, and passing through a homogenizer to obtain the mineral oil defoaming agent.
2. The mineral oil defoamer as set forth in claim 1, wherein the hydroxyacrylic resin has the structural formula:
the hydroxyl acrylic resin is prepared by the following reaction formula:
3. the mineral oil defoamer as set forth in claim 2, wherein the ratio of z: (m + n) is 1: (2-5).
4. The mineral oil defoamer as set forth in claim 1, wherein the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the hydroxyl acrylic resin is 1: (1-2).
5. The mineral oil defoamer as claimed in claim 1, wherein the mass ratio of the hydrocarbon oil to the hydroxy acrylic resin is (10-20): 1.
6. The mineral oil defoamer of claim 2, wherein said hydroxyl terminated polydiorganosiloxane has a viscosity of 40mm or less at 25 ℃2(s), the hydroxyl content is more than 9.0 percent.
7. The mineral oil defoamer as set forth in claim 1, wherein the hydrophobic silica is hydrophobic fumed silica dispersed in a methanol/water solution having a volume content of 30-80%.
8. The mineral oil defoamer as set forth in claim 7, wherein the mass ratio of the hydrophobic fumed silica to the hydroxyl acrylic resin is (2-6): 1.
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| CN110327665B (en) * | 2019-08-05 | 2022-12-02 | 安徽广成新材料科技有限公司 | Water-based environment-friendly nano copolymer multifunctional defoaming agent and preparation method thereof |
| CN110465119A (en) * | 2019-08-28 | 2019-11-19 | 启东曦瑞新材料科技有限公司 | A kind of preparation method of mineral oil antifoam agent |
| CN111888803B (en) * | 2020-06-30 | 2021-10-29 | 浙江传化华洋化工有限公司 | Oleate modified organic silicon defoaming agent for coating and preparation method thereof |
| CN112023452B (en) * | 2020-08-19 | 2022-02-11 | 肇庆领誉环保实业有限公司 | Defoaming agent for domestic sewage treatment and preparation method thereof |
| CN114316298A (en) * | 2020-12-03 | 2022-04-12 | 南京瑞思化学技术有限公司 | Preparation method of polysiloxane emulsion |
| CN113174778A (en) * | 2021-04-29 | 2021-07-27 | 玖龙纸业（东莞）有限公司 | Coating for papermaking and preparation method thereof |
| CN113713440B (en) * | 2021-07-16 | 2023-03-17 | 中铁第五勘察设计院集团有限公司 | Defoaming agent for shield and preparation and application thereof |
| CN113368544A (en) * | 2021-07-21 | 2021-09-10 | 安徽博纳新材料科技有限公司 | Safe and efficient defoaming agent and preparation method thereof |
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