CN107115695A - Defoamer of fluorine richness silicone oil and preparation method thereof - Google Patents
Defoamer of fluorine richness silicone oil and preparation method thereof Download PDFInfo
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- CN107115695A CN107115695A CN201710265261.XA CN201710265261A CN107115695A CN 107115695 A CN107115695 A CN 107115695A CN 201710265261 A CN201710265261 A CN 201710265261A CN 107115695 A CN107115695 A CN 107115695A
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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
- B01D19/0427—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing halogen-atoms
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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
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—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
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
- C08G65/3312—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
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Abstract
The invention discloses a kind of defoamer of fluorine richness silicone oil, comprising linear fluorine richness organic siloxane polymer, the linear fluorine richness organosiloxane polymerization has following structural formula：, wherein, X is, E is-C2H4- and/or-C3H6-, m, n, a are positive integer.The defoamer of fluorine richness silicone oil of the present invention, comprising linear fluorine richness organic siloxane polymer, low-surface-energy can drop in contained fluorine pendant groups in the linear fluorine richness organic siloxane polymer, which thereby enhance the defoaming effect of defoamer.
Description
Technical field
The technical field of defoamer of the present invention, more particularly to fluorine richness silicone oil defoamer and preparation method thereof.
Background technology
Need to utilize foam during flotation, fire extinguishing, dedusting, washing, manufacture foamed ceramics and foamed plastics etc.；And
Fermentation, coating, papermaking, printing and dyeing, the manufacturing process for excluding intracorporeal organ flatulence, boiler feed water, wastewater treatment and prism or glass
In need eliminate foam, it is seen that bubble and foam along with people production and life.So-called " bubble " or " bubble " are by insoluble
Property gas be present in liquid or solid or formed by being surrounded with their film, it be it is a kind of have gas/liquid, it is gas/solid,
The dispersion at gas liquid solid interface, the common scattered bubble to gas liquid solid interface in ore dressing and oil field system.Many gas
Bubble is gathered in the accumulation state referred to as foam that one is separated with film each other.The generation of foam mainly has Physical, chemical method
With surfactant method etc..Physical include again inhalation conduction method (bubbling), solubility reduction method, ebuillition of heated method and it is industrial often
Such as vibrate, stir foaming processes.Wherein inhalation conduction method is the most commonly used, and technical key is by adjusting aspirated pressure i.e.
The formation speed of adjustable bubble.Typically supplying gas, speed is faster, and surface pressing reduces more, then the easier generation of bubble.Shortcoming
It is that aspirated pressure size is contradicted with evaporation rate, aspirated pressure is lower, evaporate faster.Chemical method refers to that all thermal decompositions are anti-
The reaction that should can produce gas may serve to foaming.Heat resolve and biofermentation such as sodium bicarbonate sodium acid carbonate
During the gas that produces can make bubble.Either Physical or chemical method, steep the difficulty or ease and degree of stability size of generation all
Low surface free energy must be kept.It is exactly to add surfactant to reduce surface free energy most efficient method.According to surface
The effect of activating agent is different, and foaming agent, foam stabilizer and defoamer etc. are divided into again.
In the prior art, the defoaming effect of defoamer is poor.
The content of the invention
In view of this, one aspect of the present invention provides a kind of defoamer of fluorine richness silicone oil, and the defoamer has higher disappear
Steep effect.
A kind of defoamer of fluorine richness silicone oil, includes linear fluorine richness organic siloxane polymer, the linear fluorine richness
Organosiloxane polymerization has following structural formula：
Wherein, X is, E is-C2H4- and/or-C3H6-, m, n, a are just whole
Number.
Above-mentioned, m, n, a are positive integer, it is to be understood that can be 1,2,5,8 etc..
In structure above as the present invention, preferably m is that 10~30, n is that 20~50, a is 2~6.
Linear fluorine richness organic siloxane polymer has froth breaking effect, its be in molecular structure containing-SiO structures, this
Effect with regard to two aspects can be produced.On the one hand it is tension force with very low table, has on bubble film and sprawl well
Performance, can spread expansion in foam table rapidly, the table that bubble film table is had to stabilization during expansion is spread
And active agent molecule arranges and reduces the local table of foam wall and tension force, foam is destroyed " self recovery from illness " effect, make foam
Rupture.Another aspect effect is exactly that it may be inserted into foam liquid wall when organic silicon defoamer is dispersed in frothed liquid,
But very limited degree is only spread to, mixed monolayer liquid film is formed together with foaming agent, but the cohesion of this mixing liquid film is not good,
Local viscosity declines, and equally causes lather collapse.In addition, low-surface-energy can drop in the C-F structures carried in its molecular structure, with
Improve its defoaming capacity.
As the present invention defoamer, linear fluorine richness organic siloxane polymer can as defoamer main component.
Certainly, other components can also be added.Preferably, according to mass parts its can comprising 5~9 parts of white carbons, 20~40 parts it is linear
Fluorine richness organic siloxane polymer, 2~5 parts of surfactants, 1~3 part of coupling agent.Specifically, the mass parts of white carbon can
Think 5 parts, 5.5 parts, 6 parts, 7 parts, 8 parts, 8.5 parts or 9 parts etc.；The mass parts of linear fluorine richness organic siloxane polymer can be with
For 20 parts, 22 parts, 25 parts, 30 parts, 35 parts, 38 parts or 40 parts etc.；The mass parts of surfactant can for 2 parts, 2.5 parts, 3
Part, 3.5 parts, 4 parts, 4.5 parts or 5 parts etc.；The mass parts of coupling agent can be 1 part, 1.2 parts, 1.5 parts, 2 parts, 2.5 parts, 2.8 parts
Or 3 parts etc..
Above-mentioned white carbon is i.e. Nano-meter SiO_22Popular name.As the present invention white carbon granularity preferably for 30~
50nm, such as can be 30nm, 32nm, 35nm, 40nm, 45nm or 50nm.
Surfactant functions as emulsifying agent.It can for cationic surfactant, anion surfactant,
Nonionic surfactant or high molecular surfactant.
Cationic surfactant can be quaternary surfactant, such as DTAB, hexadecane
Base trimethylammonium bromide etc..
Anion surfactant, refers to the surfactant with hydrophilic radical and lipophilic group in anion.It is cloudy from
Sub- surfactant can think soap, such as odium stearate, calcium stearate, magnesium stearate；Or can be sulfate, such as
Lauryl sodium sulfate, hexadecanol sodium sulphate etc.；Or can be sulfonate, such as neopelex, dihexyl butanedioic acid
Sodium sulfonate, sodium dioctyl sulfosuccinate etc.；Or can be cholate, such as sodium glycocholate, ox courage sodium sulfonate.The present invention it is cloudy from
Sub- surfactant is preferably lauryl sodium sulfate.
High molecular type surfactant, refers to those molecular weight thousands of（5000）More than, and with surface active function
High-molecular compound.High molecular type surfactant of the present invention can be anionic, such as with carboxymethyl cellulose, carboxylic
Sodium methacrylate, carboxyl modified polypropylene acid amides, Sodium Polyacrylate are the carboxylic acid type of representative, to be condensed naphthalene sulfonic acids, polyphenyl
Vinyl sulfonate, lignosulfonates are the Sulfonates of representative, to be condensed sulfuric acid ester of the alkylbenzene ether sulfuric ester as representative,
Sulfuric acid ester etc.；Or can be cationic, such as using amino alkyl acrylates copolymer, modified poly ethylene as representative amine
Class, with poly- 1- dodecyls -4-vinylpyridine bromide [polysoap（Polysoap）], poly- 4- ethene dodecyl bromide pyridine,
Polystyrene methyl trimethoxy ammonium salt is the quaternary ammonium salt of representative；Or can be amphion, such as polymer-amino-acid；Or
Can be to be non-ionic, such as betaines, using hydroxyethyl cellulose, polyvinyl alcohol as representative polyalcohol, it is polyacrylamide, poly-
Vinylpyrrolidone, polyoxyethylene polyoxypropylene glycol ethers, polyoxyethylene condensation alkyl phenylate etc. are other.Preferably polyacrylic acid
Sodium.
Certainly coupling agent can be also added, to improve the stability of white carbon, in order to prevent the reunion of its particle.Coupling agent can
Think silicone coupling agents, titanate coupling agent, aluminate coupling agent, titanium aluminate coupling agent, boric acid ester coupler etc..
Silicone coupling agents refer to structureMaterial, here R be hydrolyzable groups, be specially
Halogen, alkoxy or acetamido, R' are the alkyl containing double bond, specially vinyl, methacryloxy or methyl-prop
Alkene acryloxypropylethoxysilane.γ-glycidyl ether oxygen propyl trimethoxy silicane can be included（KH560）, γ-methacryloxy
Propyl trimethoxy silicane（KH570）, γ-aminopropyl triethoxysilane（KH550）Deng.
Aluminate coupling agent refers to the structured (C of tool3H7O)x·Al(OCOR)m·(OCOR1) n (OAB) y, R, R1Can
For alkyl etc..Aluminate coupling agent can include SG-Al821 (distearyl acyl-oxygen isopropyl Aluminate), DL-411, DL-
411AF, DL-411D, DL-411DF, Aluminate ASA instantiation.
Titanate coupling agent refers to ROO (4-n) Ti (OX-R ＇ Y) n (here, n=2,3) expression；Wherein RO- is hydrolyzable
Lower alkyloxy, can react with mineral surfaces hydroxyl, so as to reach the purpose of chemical coupling；OX- can be carboxyl, alcoxyl
Base, sulfonic group, phosphorus base etc..Titanate coupling agent can be KR-TTS, its chemical entitled isopropyl three (different tallow phthalidyl) titanium
Vinegar；Or titanate coupling agent TMC-10, its chemical entitled isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters；Or be
Titanate coupling agent TMC-101, its chemical entitled oleic acid acyloxy of isopropyl two（Dioctyl phosphoric acid acyloxy）Titanate esters etc..
The preparation method of the above-mentioned defoamer of the present invention, comprises the following steps：
A linear fluorine richness organic siloxane polymer is provided, it is by octamethylcy-clotetrasiloxane, trifluoro propyl methyl ring four
Siloxanes and hydrogeneous double seal head ring-opening reaction obtain holding hydrogen polysiloxanes, and allyl polyether to carry out addition reaction and obtain；
Raw material comprising the linear fluorine richness organic siloxane polymer is mixed.
The molecular structure of above-mentioned end hydrogen polysiloxanes is。
In above-mentioned ring-opening reaction, temperature can be 40~60 DEG C, such as 40 DEG C, 42 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 58 DEG C or 60
℃.At a temperature of this, the time of open loop condensation reaction is 2~6h, such as 2h, 2.25h, 2.5h, 3h, 4h, 5h, 5.5h or 6h.
As in ring-opening reaction, the mol ratio of octamethylcy-clotetrasiloxane and trifluoro propyl methyl cyclotetrasiloxane does not make spy
Do not limit, such as elected the need for end hydrogen polysiloxanes that can be as needed.Octamethylcy-clotetrasiloxane is also known as D4, and it is tied
Structure formula is.Entitled (the 3,3,3- of 2,4,6,8- tetramethyls -2,4,6,8- four of trifluoro propyl methyl cyclotetrasiloxane
Trifluoro propyl) cyclotetrasiloxane, its structural formula is,, its No. CAS is 429-67-4.
Ring-opening reaction is carried out under the catalysts conditions of strong acid, is preferably trifluoroacetic acid and the mixture of the concentrated sulfuric acid, example
As catalyst can be made up of 90~95wt% trifluoroacetic acids and 5~10wt% concentrated sulfuric acids.
It is 90~95 DEG C as the temperature of the addition reaction of the present invention, at a temperature of this addition, the time of addition reaction
For 2~4h.
As the present invention addition reaction catalyst, there is no particular limitation, for example can for Speier catalyst,
Karstedt catalyst, platinum complex catalyst, preferably platinum complex catalyst.Platinum complex catalyst, such as include platinum-
A kind of and its any combination in alcohol complex, platinum-vinyl siloxane complex, platinum-olefin complex.Here, chloroplatinic acid
Alcoholic solution can be dissolved in ethanol, methanol, isopropanol, octanol etc. for chloroplatinic acid.The collocation method of chloroplatinic acid isopropanol
Can be specially：By 3g H2PtCl·6H2O is dissolved in 100ml anhydrous isopropyl alcohols, is sufficiently stirred at a certain temperature（Such as room
Temperature）, make its complete molten rear standing a period of time, both obtain product, be finally that orange colour is molten, its chemical equation is H2PtCl·6H2O+
（CH3）2CHOH→H2PtCl4(CH3)2CO+2HCl+6H2O.The collocation method of chloroplatinic acid octanol is specially：H2PtCl·6H2O and
2-ethylhexanol（Specific one kind of octanol）For 1：The reactant mixture of 7 generations, 4h is reacted under 250mm Hg pressure at 70 DEG C
Lower water is removed, and being then depressurized to 2mmHg removes unreacted alcohol, is cooled to room temperature, filtering, and filtrate is sticky light brown liquid
Body, as platinum containing amount are 21%（Weight）, chloride 8.3 % platinum catalyst.Here, platinum-vinyl siloxane complex refers to chlorine
Platinic acid is obtained with vinyl silicone compounds complex reaction, and vinyl silicone compounds can be tetramethyl divinyl two
Siloxanes（Vinyl double seal head）, dimethoxy-methyl vinylsiloxane, t etram-ethyltetravinylcyclotetrasiloxane etc..With second
Alkenyl siloxane is exemplified by tetramethyl divinyl disiloxane, the preparation method of platinum-vinyl siloxane complex can be：It is attached
Have in reflux condenser, the reaction bulb of thermometer, 32g chloroplatinic acids and 210g tetramethyl divinyl disiloxanes are added, normal
Pressure and 120 DEG C of backflow 1h, black precipitate is filtered off after cooling（Platinum black）And during the anti-handy distillation of light grey acid solution is washed to
Property（Remove chloride acidic by-products）Then add anhydrous CaCl2Dry, filter out CaCl2Afterwards, platiniferous 2.2% is obtained（Quality point
Number）And chloride 0.43%（Mass fraction）Platinum-vinyl siloxane complex.Or using vinylsiloxane as tetramethyl four
Exemplified by vinyl cyclotetrasiloxane, the preparation method of platinum-vinyl siloxane complex can be 6g chloroplatinic acids, the anhydrous second of 180ml
Alcohol and 6g NaCO3, 300g t etram-ethyltetravinylcyclotetrasiloxanes flowed back at 80 DEG C 2h, washing（It can not wash）Dry filter
Product.Here, platinum-carboxylate complex refers to that chloroplatinic acid carries out the product obtained by complex reaction with carboxylate.Carboxylate can be
The aliphatic carboxylic acid esterss such as ethyl acetate, Ethyl formate, or with the aromatic carboxylic acid esters of diethyl phthalate etc..With carboxylic acid
Exemplified by ester, the preparation method of platinum-carboxylate complex is：In the 500ml there-necked flasks with reflux condenser thermometer, add
1g chloroplatinic acids and 200ml absolute ethyl alcohols, lead to N2（Dry）Under, 80 DEG C of backflow 2h are warming up to, 40 DEG C are then cooled to, decompression is steamed
Go out ethanol, obtain clear yellow viscous thing, after chloroform and removing solvent, just obtain solid product（Extracting 10 times or so）, add 50g
Diethyl phthalate dissolved solid thing, filters off the co-ordination complex catalyst that solid slag makes to obtain diethyl phthalate.
Except this, platinum-non-metal complexes can also be platinum-tetrahydrofuran complex.The preparation method of platinum-tetrahydrofuran complex can be：
In the reaction bulb with reflux condenser and thermometer, 1g chloroplatinic acids and 200ml tetrahydrofurans are added, in logical N2Situation
Lower backflow 1h, Na is added after cooling2SO4Dry, filter off solid scoriform thing, both obtain tetrahydrofuran co-ordination complex solution.This platinum is matched somebody with somebody
It is the referring to property of content of platinum 3000~10000ppm in mixture catalyst.
It is above-mentioned not address part, it is adaptable to prior art.
Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of art of the present invention
The identical implication that art personnel are generally understood that.When there is contradiction, the definition in this specification is defined.
Term as used herein：
" by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing " or its
Any other deformation, it is intended that cover including for non-exclusionism.For example, composition, step, method, product comprising listed elements
Or device is not necessarily limited to those key elements, but not expressly listed other key elements or such a composition, step, side can be included
Method, product or the intrinsic key element of device.
Conjunction " by ... constitute " exclude any key element do not pointed out, step or component.If be used in claim,
This phrase will make claim be closed, it is not included the material in addition to materials of those descriptions, but relative
Except customary impurities.When phrase " by ... constitute " be rather than immediately following theme in the clause that appears in claim main body after
When, it is only limited to the key element described in the clause;Other key elements are not excluded outside as the overall claim.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
Scope " when 1~5 ", described scope should be interpreted as including scope " 1~4 ", " 1~3 ", " 1~2 ", " 1~2 and 4~
5 ", " 1~3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
" mass parts " refer to the basic measurement unit for the mass ratio relation for representing multiple components, and 1 part can represent arbitrary list
Position quality, can such as be expressed as 1g, may also indicate that 2.689g etc..If we say that the mass parts of component A are a parts, the matter of B component
It is b parts to measure part, then it represents that the quality of component A and the mass ratio a of B component：b.Or, the quality for representing component A is aK, B groups
The quality divided is bK（K is Arbitrary Digit, represents multiplying factor）.It can not misread, and unlike mass fraction, all components
Mass parts sum be not limited to 100 parts of limitation.
"and/or" is used to represent that one of illustrated situation or both may to occur, for example, A and/or B includes (A
And B) and (A or B)；
In addition, the indefinite article " one kind " and " one " before key element of the present invention or component are to key element or the quantitative requirement of component（I.e.
Occurrence number）Unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and singulative
Key element or component also include plural form, unless the obvious purport of the quantity refers to singulative.
The defoamer of fluorine richness silicone oil of the present invention, includes linear fluorine richness organic siloxane polymer, the linear fluorine richness
Low-surface-energy can drop in contained fluorine pendant groups in organic siloxane polymer, which thereby enhance the defoaming effect of defoamer.
Embodiment
Technical scheme is further illustrated with reference to embodiment.
Embodiment 1
Step 1: preparing linear fluorine richness organic siloxane polymer.In the there-necked flask of thermometer and agitating device is equipped with
Appropriate D4 min of decompression dehydration 30 at 30 DEG C are taken, appropriate hydrogeneous double seal head H-MM and catalyst is added（By 90wt% and
10wt% trifluoroacetic acids, the concentrated sulfuric acid are constituted）, inflated with nitrogen is warming up to 40 DEG C, appropriate trifluoro propyl first is added dropwise after 30 min of reaction
(mol ratio is maintained at as 2 basic ring tetrasiloxane：1：4, completion of dropping is reacted certain time again, and total reaction time is controlled in 6h.
It is end hydrogen polysiloxanes to obtain transparent and blueing light liquid.There is minimal amount of immiscible faint yellow drop to use below
NaHCO3Filtering is neutralized, with standby.
F-6 ethers are taken to make it with holding the mol ratio of hydrogen polysiloxanes to be 1.2：1 is added to 250 equipped with agitator and thermometer
Stirred in mL three-necked flask, and it is 0.02 to add the catalyst amount of platinum ethanol, is warming up to 90 DEG C of reaction 4h.Question response
After end, then the small molecule that generation is sloughed in 125 DEG C of vacuum distillations is warming up to, obtains slightly yellow homogeneous grease, as linear fluorine
Azo polyether polyeste polymer
Step 2: proportioning raw material.5 parts of white carbons, 20 parts of linear fluorine richness organic siloxane polymers, 2 parts of surfactants, 1
Part coupling agent.
Step 3: adding water into above-mentioned all raw materials, stir, obtain defoamer.
Embodiment 2
Step 1: preparing linear fluorine richness organic siloxane polymer.In the there-necked flask of thermometer and agitating device is equipped with
Appropriate D4 min of decompression dehydration 30 at 30 DEG C are taken, appropriate hydrogeneous double seal head H-MM and catalyst is added（By 95wt% and
5wt% trifluoroacetic acids, the concentrated sulfuric acid are constituted）, inflated with nitrogen is warming up to 60 DEG C, appropriate trifluoro propyl first is added dropwise after 30 min of reaction
(mol ratio is maintained at as 3 basic ring tetrasiloxane：1：5, completion of dropping is reacted certain time again, total reaction time control 2~
6h.It is end hydrogen polysiloxanes to obtain transparent and blueing light liquid.There is minimal amount of immiscible faint yellow drop to use below
NaHCO3Filtering is neutralized, with standby.
F-6 ethers are taken to make the mol ratio of itself and hydrogeneous fluorosilicon oil be 1.4：1 is added to equipped with agitator and thermometer
250 mL three-necked flask in stir, and it is 0.02 to add the catalyst amount of platinum ethanol, be warming up to 95 DEG C it is anti-
Answer 2h.After question response terminates, then the small molecule that generation is sloughed in 125 DEG C of vacuum distillations is warming up to, obtains slightly yellow homogeneous grease,
As linear fluorine richness organic siloxane polymer
Step 2: proportioning raw material.9 parts of white carbons, 40 parts of linear fluorine richness organic siloxane polymers, 5 parts of surfactants, 3
Part coupling agent.
Step 3: adding water into above-mentioned all raw materials, stir, obtain defoamer.
Embodiment 3
Step 1: preparing linear fluorine richness organic siloxane polymer.In the there-necked flask of thermometer and agitating device is equipped with
Appropriate D4 min of decompression dehydration 30 at 30 DEG C are taken, appropriate hydrogeneous double seal head H-MM and catalyst is added（By 92.5wt%
Constituted with 7.5wt% trifluoroacetic acids, the concentrated sulfuric acid）, inflated with nitrogen is warming up to 50 DEG C, appropriate trifluoropropyl is added dropwise after 30 min of reaction
(mol ratio is maintained at as 4 ylmethyl cyclotetrasiloxane：1：20, completion of dropping is reacted certain time again, total reaction time control
In 2~6h.It is end hydrogen polysiloxanes to obtain transparent and blueing light liquid.There is minimal amount of immiscible light yellow liquid below
Drop uses NaHCO3Filtering is neutralized, with standby.
F-6 ethers are taken to make the mol ratio of itself and hydrogeneous fluorosilicon oil be 1.6：1 is added to equipped with agitator and thermometer
250 mL three-necked flask in stir, and add platinum ethanol catalyst amount be 0.02, be warming up to 92.5 DEG C
React 3h.After question response terminates, then the small molecule that generation is sloughed in 125 DEG C of vacuum distillations is warming up to, obtains slightly yellow homogeneous oily
Thing, as linear fluorine richness organic siloxane polymer
Step 2: proportioning raw material.7 parts of white carbons, 30 parts of linear fluorine richness organic siloxane polymers, 3.5 parts of surfactants,
2 parts of coupling agents.
Step 3: adding water into above-mentioned all raw materials, stir, obtain defoamer.
Embodiment 4
Step 1: preparing linear fluorine richness organic siloxane polymer.In the there-necked flask of thermometer and agitating device is equipped with
Appropriate D4 min of decompression dehydration 30 at 30 DEG C are taken, appropriate hydrogeneous double seal head H-MM and catalyst is added（By 92wt% and
8wt% trifluoroacetic acids, the concentrated sulfuric acid are constituted）, inflated with nitrogen is warming up to 50 DEG C, appropriate trifluoro propyl first is added dropwise after 30 min of reaction
(mol ratio is maintained at as 50 basic ring tetrasiloxane：1：10, completion of dropping is reacted certain time again, and total reaction time control exists
4h.It is end hydrogen polysiloxanes to obtain transparent and blueing light liquid.There is minimal amount of immiscible faint yellow drop to use below
NaHCO3Filtering is neutralized, with standby.
F-6 ethers are taken to make the mol ratio of itself and hydrogeneous fluorosilicon oil be 1.4：1 is added to equipped with agitator and thermometer
250 mL three-necked flask in stir, and it is 0.02 to add the catalyst amount of platinum ethanol, be warming up to 92 DEG C it is anti-
Answer 3h.After question response terminates, then the small molecule that generation is sloughed in 125 DEG C of vacuum distillations is warming up to, obtains slightly yellow homogeneous grease,
As linear fluorine richness organic siloxane polymer
Step 2: proportioning raw material.5 parts of white carbons, 30 parts of linear fluorine richness organic siloxane polymers, 2 parts of surfactants, 1
Part coupling agent.
Step 3: adding water into above-mentioned all raw materials, stir, obtain defoamer.
Embodiment 5
Step 1: preparing linear fluorine richness organic siloxane polymer.In the there-necked flask of thermometer and agitating device is equipped with
Appropriate D4 min of decompression dehydration 30 at 30 DEG C are taken, appropriate hydrogeneous double seal head H-MM and catalyst is added（By 92wt% and
8wt% trifluoroacetic acids, the concentrated sulfuric acid are constituted）, inflated with nitrogen is warming up to 50 DEG C, appropriate trifluoro propyl first is added dropwise after 30 min of reaction
(mol ratio is maintained at as 35 basic ring tetrasiloxane：1：20, completion of dropping is reacted certain time again, and total reaction time control exists
4h.It is end hydrogen polysiloxanes to obtain transparent and blueing light liquid.There is minimal amount of immiscible faint yellow drop to use below
NaHCO3Filtering is neutralized, with standby.
F-6 ethers are taken to make the mol ratio of itself and hydrogeneous fluorosilicon oil be 1.5:1 is added to equipped with agitator and thermometer
250 mL three-necked flask in stir, and it is 0.02 to add the catalyst amount of platinum ethanol, be warming up to 92 DEG C it is anti-
Answer 3h.After question response terminates, then the small molecule that generation is sloughed in 125 DEG C of vacuum distillations is warming up to, obtains slightly yellow homogeneous oily
Thing, as linear fluorine richness organic siloxane polymer
Step 2: proportioning raw material.7 parts of white carbons, 30 parts of linear fluorine richness organic siloxane polymers, 3 parts of surfactants, 2
Part coupling agent.
Step 3: adding water into above-mentioned all raw materials, stir, obtain defoamer.
The defoaming effect of embodiment 1 to embodiment 5 is tested in accordance with the following methods.
Antifoam performance is tested：White washing powder, neopelex and water will be found according to 0.5:0.5:99 ratio is mixed
Close uniform, obtain bubble liquid standby.200 mL foam liquids are added in 1000 mL graduated cylinder, lead to nitrogen bubble to 800 mL
Scale at, then add the defoamer that mass fraction is 0.2%, record foam from 800 mL scale are down to 300 mL quarter
The degree time used, it is repeated 3 times, takes its average value, is the foam time of the defoamer, the time, shorter defoaming effect was better.
Suds suppressing properties are tested：200 mL foam liquid is added into 1000 mL graduated cylinders, 0.2% defoamer is added, led to
Enter nitrogen continuous bubbling, keep nitrogen flow stable, continue ventilation record foam and rise to 800 mL's by 300 mL scale
Time used in scale, it is repeated 3 times, it is the suds time to take its average value.Time is longer, and suds effect is better.As a result it is as follows
Table：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Foam time（S） | 65 | 60 | 54 | 62 | 49 |
| Suppress the bubble time（S） | 209 | 220 | 236 | 215 | 248 |
Because the number range of each technological parameter involved in the present invention can not possibly all embody in the above-described embodiments, but this
As long as the technical staff in the field envisioned any numerical value fallen into the above-mentioned number range completely can implement the present invention,
Certainly any combination of occurrence in the range of some numerical value is also included.Herein, for the consideration of length, eliminate and provide a certain
The embodiment of occurrence in item or multinomial number range, this is not to be construed as the insufficient disclosure of technical scheme.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. a kind of defoamer of fluorine richness silicone oil, it is characterised in that include linear fluorine richness organic siloxane polymer, the line
Property the polymerization of fluorine richness organosiloxane there is following structural formula：
Wherein, X is, E is-C2H4- and/or-C3H6-, m, n, a are positive integer.
2. defoamer according to claim 1, it is characterised in that the m is that 10~30, n is that 20~50, a is 2~6.
3. defoamer according to claim 1, it is characterised in that according to mass parts its comprising 5~9 parts of white carbons, 20~
40 parts of linear fluorine richness organic siloxane polymers, 2~5 parts of surfactants, 1~3 part of coupling agent.
4. defoamer according to claim 1, it is characterised in that the granularity of the white carbon is 30~50nm.
5. defoamer according to claim 1, it is characterised in that the coupling agent is silicone coupling agents.
6. a kind of preparation method of defoamer as claimed in claim 1, it is characterised in that comprise the following steps：
A linear fluorine richness organic siloxane polymer is provided, it is by octamethylcy-clotetrasiloxane, trifluoro propyl methyl ring four
Siloxanes and hydrogeneous double seal head ring-opening reaction obtain holding hydrogen polysiloxanes, and allyl polyether to carry out addition reaction and obtain；
Raw material comprising the linear fluorine richness organic siloxane polymer is mixed.
7. preparation method according to claim 6, it is characterised in that the temperature of the ring-opening reaction is 40~60 DEG C, institute
The time for stating ring-opening reaction is 2~6h.
8. preparation method according to claim 6, it is characterised in that the catalyst of the ring-opening reaction be trifluoroacetic acid and
The mixture of the concentrated sulfuric acid.
9. preparation method according to claim 6, it is characterised in that the temperature of the addition reaction is 90~95 DEG C, institute
The time for stating addition reaction is 2~4h.
10. preparation method according to claim 6, it is characterised in that the catalyst of the addition reaction is platinum complex
Catalyst.
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| CN109867791A (en) * | 2018-12-24 | 2019-06-11 | 南京美思德新材料有限公司 | A kind of Organosiliconcopolymere and preparation method thereof with clear structure |
| CN111111266A (en) * | 2019-12-30 | 2020-05-08 | 枣阳市金鹏化工有限公司 | Modified organic silicon defoaming agent and preparation method thereof |
| CN115283143A (en) * | 2022-08-09 | 2022-11-04 | 东北大学 | Defoaming agent for amine flotation collector and preparation method and application method thereof |
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