CN108744612A - A kind of mineral oil antifoam agent and preparation method thereof - Google Patents
A kind of mineral oil antifoam agent and preparation method thereof Download PDFInfo
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- CN108744612A CN108744612A CN201810513725.9A CN201810513725A CN108744612A CN 108744612 A CN108744612 A CN 108744612A CN 201810513725 A CN201810513725 A CN 201810513725A CN 108744612 A CN108744612 A CN 108744612A
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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 kind of mineral oil antifoam agents and preparation method thereof, belong to fine chemistry industry auxiliary agent technical field.The invention discloses a kind of mineral oil antifoam agents, including following components by weight, 3~10 parts of hydroxyl endblocked polydimethylsiloxane；5~20 parts of hydrophobic silica；40~80 parts of hydrocarbon ils；10~35 parts of defoaming activity auxiliary agent；5~15 parts of surface-active emulsifiers；1~6 part of Hydroxylated acrylic resin.Mineral oil antifoam agent prepared by the present invention is not only able to effectively inhibit the polymerization of styrene-butadiene latex production process, stripping, filling unwanted bubbles；And it realizes to the oily contracting of postorder coating, pin hole, flake, effective control of suds；It is provided simultaneously with the advantages that stability is good, additive amount is few.
Description
Technical field
The invention belongs to fine chemistry industry auxiliary agent technical fields, more specifically to a kind of mineral oil antifoam agent and its system
Preparation Method.
Background technology
The synthesis of styrene-butadiene latex is used using butadiene and styrene as principal monomer, is aided with unsaturated carboxylic acid class, nitrile, acyl
It is poly- to carry out free radical emulsion using the emulsification system and hot initiator system of anion and nonionic compounding for the function monomers such as amine
It closes.Due to the presence of anion and nonionic compound emulsion system so that latex is in polymerization process, stripping process, filling
Process and subsequent applications process will produce unwanted bubbles, and prodigious harm is brought to industrial production, and in production, general use adds
Add antifoaming agent to eliminate unwanted bubbles.
It is well known that a kind of good antifoaming agent must have following condition：1. chemical inertness, should not be with the medium that is defoamed
(in various pH value, at a temperature of) chemically react；2. there is positive spreading coefficient, you can with fast on the liquid-vapor interface of foamed system
Speed is sprawled；3. the compound containing surface tension makes formation of foam local weak point；4. it should be not easy by the surface in foamed system
Activating agent institute is molten.Antifoaming agent can be divided into alcohols, aliphatic acid (ester) class, metal soap, polyethers and polysiloxanes by chemical composition
(custom be also known as organic silicon) etc., the organic silicon antifoaming agent suppression effect that disappears is good, but it is poor with Miscibility, with the resting period
Lengthening liquid level have oil slick appearance, and the adverse effects such as film recess, flake defect are easy tod produce to latex later process.Cause
And it is in the majority to select mineral oil antifoam agent to be applied to styrene-butadiene latex industry both at home and abroad.
For mineral oil antifoam agent, not only to eliminate the unwanted bubbles of system, there are good suds suppressing properties, and
There is good compatibility with system, the defects of film recess, flake, pin hole cannot be generated to later process.
Chinese Patent Application No. CN200510088437.6 prior art discloses a kind of hydrocarbon with three kinds of different structures
It is main defoaming material matter for carrier, fatty acid aluminium and silica, wherein it is 2~6 carbon atom numbers to introduce some substituent groups
Alkyl modified silicon oil easily causes holiday.
Chinese patent Authorization Notice No. CN104479439B prior art discloses the bodies in alkyl-silicone oil, silica
In system introduced plant oil and its derivative, by control alkyl-silicone oil average carbon atom number to make its with mineral oil well
It dissolves each other, and the control of the ratio of mineral oil and vegetable oil and its derivative is 1:6~4:Between 7, film is finally efficiently solved
The problem of shrinkage cavity, cissing, recess, while the antifoaming performance and stability of antifoaming agent are also improved, it is suitble to disappearing for aqueous architectural painting
Bubble, but the component cannot be well solved to the postorder pin hole, flake, depression problem of styrene-butadiene latex.
Chinese patent Authorization Notice No. CN102649021B prior art discloses a kind of defoamings of non-silicon composite emulsion type
Agent, based on mass percentage, including following components：Alkymer 30%~70%, defoaming activity component 3%~15%, oleophylic
Property emulsifier and hydrophilic emulsifier 5%~15%, thickener 1%~5% and antifoam additives 15%~50%, the defoaming
Auxiliary agent is glycerin polyether tri-fatty acid ester；By the way that emulsifier, aqueous thickener solution mixture is added to non-silicon class antifoaming agent stoste
It is emulsified under certain process conditions, is prepared into stable non-silicon complex emulsions antifoaming agent, efficiently solves mineral oil and disappear
The stability and antifoaming performance of infusion, but due to its fail to solve very well the shrinkage cavity of styrene-butadiene latex later process film, pin hole,
Flake, later stage suds.
Chinese patent Authorization Notice No. CN105169756B prior art discloses a kind of defoamings of efficient context friendly
Agent and preparation method thereof, including following components：20%~30% dimethyl siloxane, 5%~20% hydroxy-end capped poly dimethyl
Siloxanes, 5%~8% polyether-modified dimethyl silicone polymer, 3%~8% silica, 10%~20% isomerous tridecanol breast
Agent, 0.5%~1% sodium carboxymethylcellulose, 0.5%~1% sodium benzoate, 30%~45% deionized water, the above percentage
Than being mass percent.The prior art discloses hydroxyl endblocked polydimethylsiloxane, polyether-modified polydimethylsiloxanes
Alkane, use of the components such as silica in antifoaming agent are not directed to styrene-butadiene latex although realizing preferable defoaming function
The problem of shrinkage cavity of later process film, pin hole, flake, later stage suds, is improved.
Therefore it provides one kind having both good defoaming function, while it can effectively inhibit the poly- of styrene-butadiene latex production process again
It closes, stripping, filling unwanted bubbles simultaneously ask the oily contracting of postorder coating, pin hole, flake problem as technology urgently to be resolved hurrily
Topic.
Invention content
1, it to solve the problems, such as
For existing mineral oil antifoam agent use cause the shrinkage cavity of styrene-butadiene latex later process film, pin hole, flake, after
The problem of phase suds, the present invention provide a kind of polymerization that can effectively inhibit styrene-butadiene latex production process, stripping, filling
The mineral oil antifoam agent and preparation method thereof that unwanted bubbles simultaneously effectively control the oily contracting of postorder coating, pin hole, flake.
2, technical solution
To solve the above problems, the present invention adopts the following technical scheme that.
A kind of mineral oil antifoam agent, including following components by weight,
Preferably, the hydroxy acryl acid resin, structural formula are：
M, the integer that n, z are 10~100, R1、R2For 2~4 integer, dissolving initiator is azodiisobutyronitrile or peroxide
Change dibenzoyl.
Preferably, the integer that described m, n, z are 20~25.
Preferably, the z：(m+n) it is 1：(2~5).
Preferably, the mass ratio of the hydroxyl endblocked polydimethylsiloxane and Hydroxylated acrylic resin is 1：(1~6).
Preferably, the mass ratio of the hydrocarbon ils and Hydroxylated acrylic resin is (10~20):1.
Preferably, using introducing hydroxyl monomer in the main chain of acrylate polymer so that carried in polymer lateral chain
Polar hydroxyl groups, monomer are prepared in the presence of initiator by polymerisation in solution, prepare the hydroxy acryl acid resin reaction such as
Shown in following formula：
Preferably, viscosity (25 DEG C of mm of hydroxy-end capped poly- two radical siloxane2/ s)≤40, hydroxy radical content > 9.0%.
Preferably, the hydroxy-end capped poly- two radical siloxanes dosage is 3~6 parts.
Preferably, the hydrocarbon ils is the mixing of one or more of mineral white oil, bobbin oil, machine oil and refrigerator oil
Object.
Preferably, the dynamic viscosity when hydrocarbon ils is 25 DEG C is 5~40mm2/ s mineral white oils.
Preferably, hydrophobic silica is hydrophobic fumed silica.
Preferably, hydrophobic fumed silica is dispersed in the methanol/water solution that volume content M values are 30~80%.Institute
The M values stated are to indicate hydrophobic degree, and M values are higher, and expressions hydrophily is lower, use hydrophobicity aerosil water/
When evenly dispersed in methanol mixed solution, indicated using the volume ratio of the methanol of minimum demand, it can be by following
Side is found out：By sample hydrophobic silica 0.2g be added to volume be 250mL beakers in 50mL water in, then from buret
Methanol is added dropwise until whole specimen suspensions.The solution in beaker is constantly stirred with magnetic stirring apparatus at this time, whole samples are equal
It is even at the time of be suspended in solution as accounting for eventually, the percentage by volume of the methanol of liquid mixture when terminal in beaker becomes M
Value.
Preferably, the M values are 35~75.
Preferably, the M values are 40~70.
Preferably, the mass ratio of the hydrophobic fumed silica and Hydroxylated acrylic resin is (2~6):1.
Preferably, the defoaming activity auxiliary agent is ethylene bis-fatty acid amides, metallic soap, modified polyether ester, fatty alcohol, fat
One or more of fat acid, fatty wax.
Preferably, the defoaming activity auxiliary agent is 25~30 parts.
Preferably, the ethylene bis-fatty acid amides are the double oleamides of ethylene, ethylene bis stearic acid amide, the double palm fibres of ethylene
One or more of palmitic acid acid amide.
Preferably, the aliphatic acid is the aliphatic acid that carbon atom is 2~30.
Preferably, the aliphatic acid is the aliphatic acid that carbon atom is 12~22.
Preferably, the fatty alcohol is the fatty alcohol that carbon atom number is 2~30, including unitary or polyalcohol.
Preferably, the fatty wax is animal wax, beeswax, microwax, polypropylene wax, polyethylene wax, paraffin,
Preferably, the fatty wax is polypropylene wax.
Preferably, the metallic soap is magnesium stearate, calcium stearate, zinc stearate, aluminum stearate.
Preferably, the metallic soap is aluminum stearate.
Preferably, the modified polyether ester is fatty acid modified polyether ester, is being catalyzed by polyoxy alkane alkene ether and aliphatic acid
Be esterified under the action of agent it is counter synthesize, the catalyst is sulfuric acid, solid super-strong acid (SO4 2-/ZrO2) highly acid from
Sub-exchange resin or molecular sieve.
Preferably, the general structure of the polyoxy alkane alkene ether is RO (EO)X(PO)YH, wherein R are CbH2b+1, n is 4~24
Integer, b indicates that carbon atom number, subscript X and Y indicate that the degree of polymerization of EO and PO, EO are the ethylene oxide after open loop, and PO is open loop
Propylene oxide afterwards, the integer that X is 1~50, the integer that Y is 1~50.
Preferably, the integer that the b is 4~18, the integer that X is 3~24, the integer that Y is 4~24.
Preferably, the aliphatic acid for modification is the saturation or unsaturated fatty acid that carbon atom number is 6~20, institute
The aliphatic acid stated is preferably lauric acid, palmitic acid, myristic acid, oleic acid, palmitic acid or stearic acid.
Preferably, described is lauric acid for modified aliphatic acid.
Preferably, the surface-active emulsifiers are 10~15 parts.
Preferably, the surface-active emulsifiers be lipophilic emulsifier and hydrophilic emulsifier, lipophilic emulsifier and
Hydrophilic lipophilic balance (HLB) between hydrophilic emulsifier is 8~12.
Preferably, the hydrophilic lipophilic balance between the lipophilic emulsifier and hydrophilic emulsifier (HLB) is 8~9.
Preferably, the lipophilic emulsifier is sorbitan monostearate, sorbitan monooleate, mistake
Water sorbierite tristearate or sorbitan trioleate；The hydrophilic emulsifier is polyoxyethylene sorbitan
Monostearate, polyoxyethylene 20 sorbitan monooleate, polyoxyethylene 20 sorbitan tristearate or polyoxyethylene
Sorbitan trioleate.
Preferably, the lipophilic emulsifier is sorbitan trioleate, and the hydrophilic emulsifier is poly-
Ethylene oxide sorbitan trioleate.
A kind of preparation method of foregoing mineral oil antifoam agent, includes the following steps：
(1) hydroxyl endblocked polydimethylsiloxane, hydrophobic silica of 1/2 amount in raw material are added to clean reaction
In kettle, stirs and be warming up to 130~150 DEG C with the speed of 5 DEG C/min, after keeping the temperature 2~4 hours, then vacuumize 0.5 at a temperature of this
~1 hour (vacuum degree is -0.05Mpa), high speed dispersion 0.5 hour after heat preservation obtains activated silica pre-composition A liquid；
(2) hydrocarbon ils, defoaming activity auxiliary agent are added in clean reaction kettle, stir and is warming up to the speed of 5 DEG C/min
It 120~150 DEG C, after keeping the temperature 1.5~4 hours, then vacuumizes at this temperature 0.5~1 hour, vacuum degree is -0.05Mpa；
(3) surface-active emulsifiers are added into the mixture of step (2) under vaporization temperature and keep the temperature 0.5~1 hour
Obtain B liquid；
(4) activated silica pre-composition A liquid in step (1) is added into step (3) described mixture, 1 is kept the temperature in 90~120 DEG C
Obtain C liquid within~2 hours；
(5) hydroxyl endblocked polydimethylsiloxane of remaining 1/2 amount and whole Hydroxylated acrylic resins are mixed and heated
To 90~120 DEG C, D liquid is obtained；
(6) the mixture D drop that step (5) obtains is added in the C liquid that step (4) obtains, keeps the temperature 1.5~2.5 hours；
(7) 40~70 DEG C are cooled to, keeps the temperature 0.5~1 hour, homogenizer is crossed, obtains the mineral oil antifoam agent.
3, advantageous effect
Compared with the prior art, beneficial effects of the present invention are：
(1) present invention is added to hydroxyl endblocked polydimethylsiloxane, Hydroxylated acrylic resin, control two in antifoaming agent
Person's ratio adjusts the ratio of the hydroxyl monomer introduced in the main chain of acrylate polymer, makes styrene-butadiene latex postorder coating
Oily contracting, pin hole, flake, suds have obtained effective control.
(2) present invention is obtained by repetition test, using two kinds of acrylate and with the acrylate shape of a small amount of hydroxyl
At triblock copolymer, be added in antifoaming agent so that the compatibility and mobility of antifoaming agent are improved, when coating compared with
Occur pin hole, flake phenomenon less；And when the hydroxy radical content in hydroxy acrylate is excessively high, hydroxy acrylate is dissolved in film
In, it is difficult to new interface is formed in film coated surface, does not have positive effect to the elimination of flake, pin hole, and works as hydroxy acrylic acid
When hydroxy radical content in ester is too low, compatibility is poor, it is difficult to is uniformly distributed in film coated surface, contracting is also easy to produce due to aggregation
Hole, therefore, the monomer number ratio of the monomer containing hydroxyl group and not hydroxyl group in the block polymer that the present invention uses
For z：(m+n) it is 1：When (2~5), antifoaming agent performance stablizes not stratified, coating flake, pin hole minimum number.
(3) mass ratio of hydroxyl endblocked polydimethylsiloxane and Hydroxylated acrylic resin is 1 in the present invention：(1~6)
When, compatibility is more preferably, not stratified, and flake, the pin hole when coating are few compared with un-added technical solution.
(4) hydrophobic fumed silica and the Hydroxylated acrylic resin mass ratio of technical solution of the present invention addition be (2~
6):1, wherein hydrophobic fumed silica is dispersed in the methanol aqueous solution that percentage by volume is 35~75%, and mating surface is lived
Property emulsifier and defoaming activity auxiliary agent emulsified, obtained antifoaming agent property is stablized, and foam time is big compared to Commercial antifoam agent
It is big to shorten.
(5) present invention carries out miscible processing by 1/2 hydroxyl endblocked polydimethylsiloxane, hydrophobic silica first
Afterwards, be then added to hydrocarbon ils, active defoaming agent auxiliary agent, surface-active emulsifiers processing mixing in handled, then by 1/2 hydroxyl
It is then added in above-mentioned mixed liquor and mixes and through 90 after base sealing end dimethyl silicone polymer and Hydroxylated acrylic resin Hybrid Heating
The mineral oil antifoam agent that~120 DEG C of isothermal holdings obtain passes through 1/2 hydroxyl endblocked polydimethylsiloxane (hydroxy radical content >
9%) and Hydroxylated acrylic resin Hybrid Heating be initially formed relatively stable mixture, so as to get antifoaming agent surface tension it is low,
Viscosity-temperature coefficient is small, and compressibility is high, gas transmission coefficient is high, be not only able to effectively to inhibit the polymerization of styrene-butadiene latex production process,
Stripping, filling unwanted bubbles, and to the oily contracting of postorder coating, pin hole, flake, suds have obtained effective control；Have simultaneously
The advantages that good, additive amount is few for stability.
Specific implementation mode
The present invention is further described below with reference to specific embodiment.
Hydroxylated acrylic resin manufacturer is Zhuhai elder generation moral new material science and technology limited Company；Hydroxy-end capped poly dimethyl
Siloxanes retailer is the Guangzhou bio tech ltd Ka Fen；Hydrophobic fumed silica retailer is the excellent rope industry science in Shandong
Skill Co., Ltd.
Embodiment 1
A kind of mineral oil antifoam agent of embodiment 1, including following components by weight,
A kind of preparation method of foregoing mineral oil antifoam agent, includes the following steps：
3 parts of hydroxyl endblocked polydimethylsiloxanes are taken, is added in clean reactor, is slowly stirred (mixing speed in batches
For 40rpm) hydrophobic fumed silica is added, after stirring evenly, quickening mixing speed is 80rpm, and with the speed of 5 DEG C/min
130 ± 2 DEG C are warming up to, after keeping the temperature 2 hours, while vacuumizing (vacuum degree is -0.05mpa), while maintaining this temperature 0.5 hour, is protected
High speed dispersion 0.5 hour after temperature, rate of dispersion are 2000r/min to get activated silica pre-composition A liquid.
In another clean reactor, mineral white oil, ethylene bis stearamide, modified polyether fat is added and stirs and with 5
DEG C/speed of min is warming up to 120 ± 2 DEG C, keep the temperature 2 hours, then maintain this temperature vacuumize 0.5 hour (vacuum degree is-
0.05mpa), surface-active emulsifiers (sorbitan trioleate, polyoxyethylene 20 sorbitan trioleate), dimension is added
It holds this temperature and obtains B liquid after 0.5 hour, above-mentioned activated silica pre-composition A liquid is added, maintained 1 hour in 90 ± 2 DEG C, then add dropwise
Enter to be heated to 90 DEG C of 3 parts of hydroxyl endblocked polydimethylsiloxanes and the mixture D liquid of Hydroxylated acrylic resin, maintains this temperature
After 1.5 hours, 40 DEG C are cooled to, keeps the temperature 0.5 hour, crosses homogenizer, as antifoaming agent 1.
Embodiment 2
A kind of mineral oil antifoam agent of embodiment 2, including following components by weight,
A kind of preparation method of foregoing mineral oil antifoam agent, includes the following steps：
1.5 parts of hydroxyl endblocked polydimethylsiloxanes are taken, are added in clean reactor, are slowly stirred (stirring speed in batches
Degree is 50rpm) hydrophobic fumed silica is added, after stirring evenly, quickening mixing speed is 100rpm, and with 5 DEG C/min's
Speed is warming up to 140 ± 2 DEG C, after keeping the temperature 3 hours, while (vacuum degree is -0.05mpa) is vacuumized, while maintaining this temperature 0.6 small
When, high speed dispersion 0.5 hour after heat preservation, rate of dispersion is 2000r/min to get activated silica pre-composition A liquid.
In another clean reactor, mineral white oil is added, the aliphatic acid that carbon atom is 18, ethylene stearic bicine diester
Amine, the stirring of modified polyether fat are simultaneously warming up to 130 ± 2 DEG C with the speed of 5 DEG C/min, keep the temperature 3 hours, then this temperature is maintained to vacuumize
(vacuum degree is -0.05mpa, and surface-active emulsifiers (sorbitan trioleate, polyoxyethylene sorbitan mountain is added within 0.6 hour
Pears alcohol trioleate), it maintains this temperature to obtain B liquid after 0.6 hour, above-mentioned activated silica pre-composition A liquid is added, in 100 ± 2 DEG C of dimensions
It holds 1 hour, then is added dropwise and is heated to 100 DEG C of 1.5 parts of hydroxyl endblocked polydimethylsiloxanes and Hydroxylated acrylic resin
Mixture D liquid maintains this temperature after 2 hours, is cooled to 50 DEG C, keeps the temperature 0.6 hour, crosses homogenizer, as antifoaming agent 2.
Embodiment 3
A kind of mineral oil antifoam agent of embodiment 2, including following components by weight,
A kind of preparation method of foregoing mineral oil antifoam agent, includes the following steps：
5 parts of hydroxyl endblocked polydimethylsiloxanes are taken, is added in clean reactor, is slowly stirred (mixing speed in batches
For 70rpm) hydrophobic fumed silica is added, after stirring evenly, quickening mixing speed is 120rpm, and with the speed of 5 DEG C/min
Degree is warming up to 150 ± 2 DEG C, after keeping the temperature 4 hours, while vacuumizing (vacuum degree is -0.05mpa), while maintaining this temperature 1 hour, protects
High speed dispersion 0.5 hour after temperature, rate of dispersion are 2000r/min to get activated silica pre-composition A liquid.
In another clean reactor, be added the double aluminium of mineral white oil, stearic acid, the stirring of modified polyether fat and with 5 DEG C/
The speed of min is warming up to 150 ± 2 DEG C, keeps the temperature 4 hours, then this temperature is maintained to vacuumize 1 hour (vacuum degree is -0.05mpa),
Surface-active emulsifiers (sorbitan monooleate, polyoxyethylene 20 sorbitan monooleate) are added, maintain this temperature 1
B liquid is obtained after hour, above-mentioned activated silica pre-composition A liquid is added, is maintained 1 hour in 120 ± 2 DEG C, then be added dropwise and be heated to 120
DEG C 5 parts of hydroxyl endblocked polydimethylsiloxanes and Hydroxylated acrylic resin mixture D liquid, maintain this temperature to terminate for 2 hours
Afterwards, 70 DEG C are cooled to, keeps the temperature 1 hour, crosses homogenizer, as antifoaming agent 3.
Comparative example 1
Comparative example 1 is differed only in embodiment 1, and Hydroxylated acrylic resin, other components and preparation method are not added
All same, as antifoaming agent comparative example 1.
Comparative example 2
Comparative example 1 is differed only in embodiment 1, and the hydroxy radical content of hydroxyl endblocked polydimethylsiloxane is 6.3%,
As antifoaming agent comparative example 3.
Comparative example 3
Comparative example 1 is differed only in embodiment 1, and hydrophobic fumed silica is scattered in 100% methanol (M=100)
In, as antifoaming agent comparative example 3.
The performance test methods of antifoaming agent
1, stability
Test method
Thermal stability：48h is put under conditions of 45~60 DEG C, sees whether to be layered.
Table 1
Effect analysis：Shown in experimental result in table 1, comparative example 1 compared with Example 1, difference lies in comparative example not
Hydroxylated acrylic resin is added, under similarity condition, lamination does not occur for the sample for adding Hydroxylated acrylic resin, and does not add
The sample added is layered, and illustrates that obtained antifoaming agent sample is unstable；Comparative example 2 compared with Example 1, hydroxy-end capped poly- diformazan
The hydroxy radical content of radical siloxane is 6.3%, is less than 9.0%, and a small amount of layering occurs for sample, illustrates that obtained antifoaming agent sample is unstable
It is fixed；Compared with Example 1, hydrophobic fumed silica is scattered in 100% methanol (M=100) comparative example 3, and sample occurs to divide
Layer, illustrates that obtained antifoaming agent sample is unstable.
2, antifoaming performance is tested
Foam liquid：+ 80 grams of deionized waters of 20 grams of styrene-butadiene latexes
Antifoaming performance is tested：100mL foam liquids are added in 500mL graduated cylinders, it will be with N2The connected glass tube of bottle is inserted into
Air-blowing is steeped in foam liquid, controls N2Flow is 4L/min, and the antifoaming agent of blistering liquid measure 0.5%, note are added when foam is to 500mL
The time of the removal of foam is recorded, the time is shorter to illustrate that antifoam performance is better, re-records the time that foam volume reaches 500mL, required
Time is longer, illustrates that the suds suppressing properties of antifoaming agent are better.
Table 2
Effect analysis：
By data in table 2 it is found that foam time is distinguished under same experiment condition using antifoaming agent in Examples 1 to 3
For 6s, 10s, 15s, and foam time of the Commercial antifoam agent under similarity condition is 25s；Wherein again to prepare in embodiment 1
Antifoaming agent effect is optimal, it is only necessary to which the 6s times, corresponding 1~3 foam time of comparative example is respectively 8s, 13s, 16s.
3. brushing performance test
Test method：After 0.002 gram of antifoaming agent stirring will be added in 20 grams of styrene-butadiene latexes, 2 grams are poured into clean glass
In glass plate, the styrene-butadiene latex that antifoaming agent is added is struck off with 75 μm of wet film makers, the state of film is observed, table of grading is used in combination
Show：
5 grades：Film is recessed or pit trace has 2 or less
4 grades：Film is recessed or pit trace has 2~5
3 grades：Film is recessed or pit trace has 5~10
2 grades：Film is recessed or pit trace has 10~20
1 grade：Film is recessed or pit trace has 20
The coating result of 3 antifoaming agent of table compares
Effect analysis：
General excessively above-mentioned experiment can be seen that：Hydroxyl endblocked polydimethylsiloxane viscosity>40, hydroxy radical content<9.0, it dredges
Water silica M values>80, or it is not added with Hydroxylated acrylic resin, the brushing recess or pit trace of the antifoaming agent of preparation are more than this
Invention antifoaming agent.
Claims (10)
1. a kind of mineral oil antifoam agent, which is characterized in that including following components by weight：
2. a kind of mineral oil antifoam agent according to claim 1, which is characterized in that the hydroxy acryl acid resin structure
Formula is：
M, the integer that n, z are 10~100, R1、R2For 2~4 integer, dissolving initiator is azodiisobutyronitrile or peroxidating two
Benzoyl.
3. a kind of mineral oil antifoam agent according to claim 2, which is characterized in that the z：(m+n) it is 1：(2~5).
4. a kind of mineral oil antifoam agent according to claim 1, which is characterized in that the hydroxy-end capped polydimethylsiloxanes
The mass ratio of alkane and Hydroxylated acrylic resin is 1：(1~6).
5. a kind of mineral oil antifoam agent according to claim 1, which is characterized in that the hydrocarbon ils and Hydroxylated acrylic resin
Mass ratio be (10~20):1.
6. a kind of mineral oil antifoam agent according to claim 5, which is characterized in that prepare the hydroxy acryl acid resin
Reaction is shown below：
7. a kind of mineral oil antifoam agent according to claim 6, which is characterized in that hydroxy-end capped poly- two radical siloxane
Viscosity (25 DEG C of mm2/ s)≤40, hydroxy radical content > 9.0.
8. a kind of mineral oil antifoam agent according to claim 1, which is characterized in that the hydrophobic silica is hydrophobic gas
Aerosil is dispersed in the methanol/water solution that volume content is 30~80%.
9. a kind of mineral oil antifoam agent according to claim 8, which is characterized in that the hydrophobic fumed silica and hydroxyl
The mass ratio of base acrylic resin is (2~6):1.
10. the preparation method of the mineral oil antifoam agent described in a kind of any one of claim 1~9, which is characterized in that including
Following steps：
(1) hydroxyl endblocked polydimethylsiloxane, hydrophobic silica of 1/2 amount in raw material are added to clean reaction kettle
In, it stirs and is simultaneously warming up to 130~150 DEG C with the speed of 5 DEG C/min, vacuumize 0.5 after heat preservation 2~4 hours, then at a temperature of this~
1 hour, vacuum degree was -0.05Mpa, and high speed dispersion 0.5 hour after heat preservation obtains activated silica pre-composition A liquid；
(2) hydrocarbon ils, defoaming activity auxiliary agent are added in clean reaction kettle, stir and 120 are warming up to the speed of 5 DEG C/min~
It 150 DEG C, after keeping the temperature 1.5~4 hours, then vacuumizes at this temperature 0.5~1 hour, vacuum degree is -0.05Mpa；
(3) surface-active emulsifiers heat preservation is added into the mixture of step (2) under vaporization temperature and obtains B in 0.5~1 hour
Liquid；
(4) activated silica pre-composition A liquid in step (1) is added into step (3) described mixture, 1~2 is kept the temperature in 90~120 DEG C
Hour obtains C liquid；
(5) hydroxyl endblocked polydimethylsiloxane of remaining 1/2 amount and whole Hydroxylated acrylic resins are mixed and heated to 90
~120 DEG C, obtain D liquid；
(6) the mixture D drop that step (5) obtains is added in the C liquid that step (4) obtains, keeps the temperature 1.5~2.5 hours；
(7) 40~70 DEG C are cooled to, keeps the temperature 0.5~1 hour, homogenizer is crossed, obtains the mineral oil antifoam agent.
Priority Applications (1)
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327665A (en) * | 2019-08-05 | 2019-10-15 | 江苏广成化工有限公司 | Multi-functional defoaming agent of aqueous, environmental protective nanometer copolymer 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 |
| CN111888803A (en) * | 2020-06-30 | 2020-11-06 | 浙江传化华洋化工有限公司 | Oleate modified organic silicon defoaming agent for coating and preparation method thereof |
| CN112023452A (en) * | 2020-08-19 | 2020-12-04 | 肇庆领誉环保实业有限公司 | Defoaming agent for domestic sewage treatment and preparation method thereof |
| 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 |
| 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 |
| CN113713440A (en) * | 2021-07-16 | 2021-11-30 | 中铁第五勘察设计院集团有限公司 | Defoaming agent for shield and preparation and application 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489049A (en) * | 2011-12-26 | 2012-06-13 | 南京四新科技应用研究所有限公司 | Mineral oil type antifoaming agent and preparation method thereof |
| CN106621478A (en) * | 2016-11-23 | 2017-05-10 | 北京麦尔化工科技有限公司 | Light-colored mineral oil de-foaming agent and preparation method thereof |
| CN106700079A (en) * | 2016-11-22 | 2017-05-24 | 青岛科技大学 | Preparation method of polyorganosiloxane de-foaming agent |
-
2018
- 2018-05-25 CN CN201810513725.9A patent/CN108744612B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489049A (en) * | 2011-12-26 | 2012-06-13 | 南京四新科技应用研究所有限公司 | Mineral oil type antifoaming agent and preparation method thereof |
| CN106700079A (en) * | 2016-11-22 | 2017-05-24 | 青岛科技大学 | Preparation method of polyorganosiloxane de-foaming agent |
| CN106621478A (en) * | 2016-11-23 | 2017-05-10 | 北京麦尔化工科技有限公司 | Light-colored mineral oil de-foaming agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 常彩彩等: "高固体分羟基丙烯酸树脂的制备", 《电镀与涂饰》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327665A (en) * | 2019-08-05 | 2019-10-15 | 江苏广成化工有限公司 | Multi-functional defoaming agent of aqueous, environmental protective nanometer copolymer 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 |
| CN111888803A (en) * | 2020-06-30 | 2020-11-06 | 浙江传化华洋化工有限公司 | Oleate modified organic silicon defoaming agent for coating and preparation method thereof |
| CN112023452A (en) * | 2020-08-19 | 2020-12-04 | 肇庆领誉环保实业有限公司 | Defoaming agent for domestic sewage treatment 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 |
| CN113713440A (en) * | 2021-07-16 | 2021-11-30 | 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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