CN102284198A - Water-soluble polyether modified organic silicon defoaming agent as well as preparation and compounding methods thereof - Google Patents
Water-soluble polyether modified organic silicon defoaming agent as well as preparation and compounding methods thereof Download PDFInfo
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Abstract
The invention relates to a water-soluble polyether modified organic silicon defoaming agent. The preparation method of the polyether modified organic silicon defoaming agent comprises the following steps: firstly adding end-allyl polyoxyalkylene aether into a vessel, stirring and dewatering; adding a solvent and low containing hydrogen silicone oil into the solution and stirring; adding a catalyst, and stirring and heating for reactions in the existence of N2 and under the condition of reflux condensation; and removing the solvent and a low-boiling-point substance to obtain water-soluble polyether modified silicon after the reactions are completed. The invention also provides a compounding method of the water-soluble polyether modified organic silicon defoaming agent which is prepared by the preparation method. By utilizing the defoaming agent, the problems that polysiloxane is hard to dissolve in water and has poor high temperature resistance and poor strong base resistance, and the defoaming speed and foam inhibiting time of polyether defoaming agents are not perfect can be solved. According to the compounding method of the water-soluble polyether modified organic silicon defoaming agent, the problem that a dimethicone defoaming agent is not completely emulsified, can be demulsified when in use, does not resist high temperature, and has poor foam inhibitation capability can be solved.
Description
Technical field
The present invention relates to a kind of water soluble polyether modified organic silicon defoamer and preparation and preparation method, be mainly used in water color ink, the coating industry.
Background technology
It is rapid that the polysiloxanes defoamer has a froth breaking, presses down characteristics such as long and safety non-toxic of bubble time.But it is insoluble in water, and is high temperature resistant, strong basicity resisting is poor.Polyethers defoamer good water solubility, high temperature resistant, strong basicity resisting is strong, but its antifoaming speed and to press down the bubble time all not satisfactory.
Dimethyl-silicon oil type defoamer generally has higher froth breaking usefulness, key when it uses is the emulsification of dimethicone, the dimethyl-silicon oil type is often because emulsification is incomplete, breakdown of emulsion, floating oil phenomenon take place when causing using, influence its result of use, tradition dimethicone emulsion defoamer heat-resisting quantity is poor, and breakdown of emulsion, floating oil phenomenon also can take place under the high temperature high shear, and it is relatively poor that while dimethyl-silicon oil type defoamer presses down the bubble ability.
Summary of the invention
Primary and foremost purpose of the present invention provides a kind of water soluble polyether modified organic silicon defoamer, this defoamer not only efficiently solves the polysiloxane-based water that is insoluble in, high temperature resistant, the problem of strong basicity resisting difference has also solved its antifoaming speed of polyethers defoamer and has pressed down all not satisfactory problem of bubble time.
In order to realize the foregoing invention purpose, the technical solution adopted in the present invention is:
A kind of water soluble polyether modified organic silicon defoamer, its chemical structural formula are any one or a few in following three kinds:
In the formula: m is 0～50 integer, and n is 1～50 integer.X is 0～20 integer, and y is the integer of 0-30, wherein x: y=1: 7～1: between 3; R is that ester group or H or carbon number are 1～4 alkyl; EO is CH
2-CH
2-CH
2O; R
2Be CH
2-CH
2-CH
2
A further object of the present invention provides the preparation method of water soluble polyether modified organic silicon defoamer.
In order to realize the foregoing invention purpose, the technical solution adopted in the present invention is:
A kind of preparation method of water soluble polyether modified organic silicon defoamer may further comprise the steps:
A, will hold pi-allyl polyoxy alkene ether to add in the container to stir, dewater;
B, adding solvent and silicon oil of low hydrogen content stirring in described step a system then;
C, then add catalyst at N
2Carry out the agitating heating reaction under atmosphere and the reflux condensation mode condition;
After d, reaction finish, slough solvent and low-boiling-point substance, get the water soluble polyether modified organic silicon.
A further object of the invention provides a kind of preparation method of water soluble polyether modified organic silicon defoamer, and it is incomplete that this method has solved the emulsification of dimethyl-silicon oil type defoamer, can breakdown of emulsion during use, non-refractory and it press down the relatively poor problem of bubble ability.
In order to realize the foregoing invention purpose, the technical solution adopted in the present invention is:
A kind of preparation method of water soluble polyether modified organic silicon defoamer, its step comprises:
A, get gas-phase silica or nano titanium oxide and add the hydrophobic treatment agent and react, centrifugation is then collected product and is carried out white carbon or nano titanium oxide after drying obtains hydrophobic treatment;
B, get white carbon or nano titanium oxide after methyl-silicone oil, polyether modified silicon oil and the hydrophobic treatment, stir also and heat up, make silicon cream and dry;
C, in silicon cream, add emulsifying agent, emulsion adjuvant, emulsifying agent, emulsion adjuvant are dissolved, after mixing, the powerful stirring, dropwise adding thickening solution;
D, drip off the back and continue to stir the composite emulsion of the organic silicon modified by polyether defoamer that last high-speed stirred must be stable.
Good effect of the present invention is, according to processing method of the present invention, silicon oil of low hydrogen content by end pi-allyl polyoxy alkene ether and specified molecular weight ad hoc structure prepares polyether-modified silicon, utilize the characteristics of polyether-modified silicon with the easily disperse of the low surface tension of polysiloxanes and polyethers, make polyether-modified silicon not only have self-emulsifying ability, the stability and compatible, dispersed in water thereof of emulsion have been increased, also guaranteed to disappear to press down and steeped effect, and high temperature resistant, acid and alkali-resistance and inorganic salts, can be used to the froth breaking under the harsh conditions.
Utilize organic silicon modified by polyether as the emulsifying agent of dimethicone and bring into play dispersion, emulsification in the composite emulsion of organic silicon modified by polyether, guarantee the stability (as high-temperature stability, low-temperature stability, centrifugal stability) of dimethicone defoamer, make its no breakdown of emulsion, floating oil phenomenon.The dispersiveness of the composite emulsion of organic silicon modified by polyether and froth breaking, to press down the bubble effect all fine.In addition, the composite emulsion of polyether-modified silicon defoaming agent is also with chemical inertness or the like.The organic silicon modified by polyether defoamer can use in all expanding foam solutions, and can improve the quality of products, operating efficiency, improve aspects such as environment and play a role.
The present invention is further illustrated below by specific embodiment.
The specific embodiment
A kind of water soluble polyether modified organic silicon defoamer, its chemical structural formula are any one or a few in following three kinds:
Wherein: subscript m is 0～50 integer, and n is 1～50 integer; X is 0～20 integer, and y is the integer of 0-30, wherein x: y=1: 7～1: between 3; R is that ester group or H or carbon number are 1～4 alkyl; EO is CH
2-CH
2-CH
2O; R
2Be CH
2-CH
2-CH
2
Organic silicon modified by polyether has very strong emulsifying capacity, and energy silicone emulsion and self-emulsifying make whole emulsification system highly stable; Because with the low surface tension of polysiloxanes and the easily disperse of polyethers, make defoamer be easy to disperse to sprawl, increased the stability of emulsion and compatible, dispersed in water thereof.
A kind of preparation method of water soluble polyether modified organic silicon defoamer may further comprise the steps:
A, will hold pi-allyl polyoxy alkene ether to add in the container to stir, vacuum distillation dewaters, and reaches 0.5～1 ‰ to water content.Adding its water removal effect of solvent when dewatering can be relatively good, but subsequent treatment can be cumbersome.End pi-allyl polyoxy alkene ether needs the strict reason that dewaters: Si-H group generation hydrolysis also further takes place to shrink crosslinked in the silicon oil of low hydrogen content even micro-moisture also can make, make that molecular weight of product greatly increases, structure is more complicated, thereby easier formation gel is not tolerant.
B, adding solvent and silicon oil of low hydrogen content stirring in described step a system then, the amount and the adding speed of control silicon oil of low hydrogen content, dropwise slowly add reaction system, at the uniform velocity stir, prevent side reaction silicon oil of low hydrogen content cross-linking reaction, avoid cross-linking products to generate, also can simplification principle, disposable adding, range of molecular weight distributions can broaden.The C=C group amount of substance of its middle-end pi-allyl polyoxy alkene ether and the Si-H group amount of substance ratio of silicon oil of low hydrogen content are between 1.1: 1～1.4: 1, solvent accounts for 20～35% of end pi-allyl polyoxy alkene ether and silicon oil of low hydrogen content gross mass, and solvent is one or more in toluene, dimethylbenzene, benzene, the 120# solvent naphtha.End pi-allyl polyoxy alkene ether obtains for buying in market, here silicon oil of low hydrogen content is that the high containing hydrogen silicone oil of employing is that full side chain containing hydrogen silicone oil prepares with telomerization method, under acid condition, by connecting octamethylcy-clotetrasiloxane, under the effect of two hydrogen closure agent tetramethyl dihydro disiloxane, synthetic promptly have the dimethyl silica segment, has the containing hydrogen silicone oil of silica segment again.
Silicon oil of low hydrogen content has three kinds, and first kind is that the main chain two ends contain si-h bond, and second kind is that side chain contains si-h bond, and the third is the mixed type silicon oil of low hydrogen content.
First kind of main chain two ends contain the preparation method of the silicon oil of low hydrogen content of si-h bond can be referring to following concrete experimental procedure: 1. four-hole boiling flask oven dry, 80 ℃ of baking ovens bakings of relevant connection device 24h; 2. take by weighing in the 500mL four-hole boiling flask of octamethylcy-clotetrasiloxane alkane 148.6g adding with electronic agitator, thermometer, 80 ℃ of thermal dehydration 1h reduce pressure; 3. add two hydrogen end-capping reagent tetramethyl dihydro disiloxane 2.5g, 4. add the concentrated sulfuric acid of gross mass 2%,, stir as catalyst; 5. 50～75 ℃ of stirring reaction 4h; 6. naturally cool to room temperature, slowly add the solid sodium bicarbonate neutralization, fully stir and be transferred to PH=6～7; 7. use the vavuum pump suction filtration, in the elimination and the sodium sulphate solid that generates; 8. the product that obtains is added and be furnished with in the 250ml four-hole boiling flask of thermometer, agitator, reflux condenser, decompression distillation is stirred, be heated to 110 ℃, steam low-boiling point material, the product that obtains transparent thickness is the silicon oil of low hydrogen content that the main chain two ends contain si-h bond, and its chemical equation is:
Second kind of side chain contains the preparation method of the silicon oil of low hydrogen content of si-h bond can be referring to following concrete experimental procedure: 1. four-hole boiling flask oven dry, 80 ℃ of baking ovens bakings of relevant connection device 24h; 2. take by weighing octamethylcy-clotetrasiloxane 146.6g, the vacuum evaporation pretreated high containing hydrogen silicone oil that dewaters adds in the 500mL four-hole boiling flask with electronic agitator, thermometer, and 80 ℃ of thermal dehydration 1h reduce pressure; 3. add closure agent HMDO 40g, the concentrated sulfuric acid of adding 2% stirs as catalyst; 4. 80～85 ℃ of stirring reaction 4h, the time is long, temperature is low, reaction temperature and, narrow molecular weight distribution designs the more realistic number-average molecular weight of molecular weight, the yield height is crosslinked few; 5. naturally cool to room temperature, slowly add solid sodium bicarbonate neutralization, fully stir and be transferred to PH=6～7, the time is about 30min, can not add too fastly, produces too many CO
2Gas; 6. use the vavuum pump suction filtration, in the elimination and the sodium sulphate solid that generates; 7. the product that obtains is added and be furnished with in the 250ml four-hole boiling flask of thermometer, agitator, reflux condenser, be heated to 110 ℃, stir, decompression distillation, steam low-boiling point material, the product that obtains transparent thickness is the silicon oil of low hydrogen content that side chain contains si-h bond, and its chemical equation is:
The preparation method of the third mixed type silicon oil of low hydrogen content can be referring to following concrete experimental procedure: 1. four-hole boiling flask oven dry, 80 ℃ of baking ovens bakings of relevant connection device 24h; 2. take by weighing in the 500mL four-hole boiling flask of octamethylcy-clotetrasiloxane 150g and 5g tetramethyl-ring tetrasiloxane adding with electronic agitator, thermometer, 80 ℃ of thermal dehydration 1h reduce pressure; 3. add two hydrogen end-capping reagent tetramethyl dihydro disiloxane 2.5g; 4. the concentrated sulfuric acid that adds gross mass 2% as catalyst, stirs; 5. 50～75 ℃ of stirring reaction 4h; 6. naturally cool to room temperature, slowly add the solid sodium bicarbonate neutralization, fully stir and be transferred to PH=6～7; 7. use the vavuum pump suction filtration, in the elimination and the sodium sulphate solid that generates; 8. the product that obtains is added and be furnished with in the 250ml four-hole boiling flask of thermometer, agitator, reflux condenser.Decompression distillation is stirred, and is heated to 110 ℃, steams low-boiling point material, and the product that obtains transparent thickness is the mixed type silicon oil of low hydrogen content, and its chemical equation is:
High containing hydrogen silicone oil is because its price height, and behind itself and the polyether reactant, low, the hydrophobic silicon-oxygen backbone content of surface tension is few, and content of polyether is many, the cloud point height, and hydrophily is strong, and froth breaking is not obvious.So generally directly do not use high containing hydrogen silicone oil to carry out polyether reactant.
C, then add catalyst, at N
2Carry out the agitating heating reaction under atmosphere and the reflux condensation mode condition.Promptly install reflux condensing tube additional, in N
2Being heated to reaction temperature under the atmosphere is 90～120 ℃, reacts 4～6 hours, and insulation reaction to terminal.The amount of catalyst is 25/1000000ths～45 of a reaction system gross mass, catalyst is the aqueous isopropanol of chloroplatinic acid, the many more reactions of catalyst are fast more, but surpassing the use amount reaction rate no longer changes, the range of molecular weight distributions of polymer accelerates, the low polymerization degree product increases, and influences the productive rate of target product.Reaction temperature is a very important reaction condition, and it is low to cross low catalyst efficient, and product yield is also low, reaction temperature is too high, reacts too violent, causes runaway reaction easily, cross-linking reaction between silicone oil and the silicone oil takes place easily, generates floccule or even the very big vitreum of viscosity do not allowed.
Wherein main chain two ends silicon oil of low hydrogen content that contains si-h bond and the reaction structure formula that end pi-allyl polyoxy alkene ether carries out chemical reaction is:
The silicon oil of low hydrogen content that side chain contains si-h bond with the reaction structure formula that end pi-allyl polyoxy alkene ether carries out chemical reaction is:
The mixed type silicon oil of low hydrogen content with the reaction structure formula that end pi-allyl polyoxy alkene ether carries out chemical reaction is:
Wherein: subscript a, b are 0～2 integer, a+b=2; M is 0～50 integer, and n is 1～50 integer; X is 0～20 integer, and y is 0～30 integer, wherein x: y=1: 7～1: be advisable between 3; R is ester group or H, also can be that carbon number is 1～4 alkyl; EO is CH
2-CH
2-CH
2O; R
2Be CH
2-CH
2-CH
2
After d, reaction finished, decompression distillation got the water soluble polyether modified organic silicon to slough solvent and low-boiling-point substance.Wherein vacuum distillation temperature is 90～120 ℃.Here low-boiling-point substance is the product of low-boiling low polymerization degree, also has low boiling impurity.
Before carrying out described steps d, generally also need in reaction system, add the hydrochloric acid stirring reaction again to remove the possible stink of industrial polyether product.Wherein the amount of hydrochloric acid is about 3% of c step reaction system gross mass, and concentration of hydrochloric acid is 0.001mol/L, and reaction temperature is 90 ± 2 ℃, and the reaction time is 1～2h.Here be to utilize aldolisation to remove the aldehyde material that contains in the industrial polyethers.
The preparation method of water soluble polyether modified organic silicon defoamer, its step comprises:
A, get gas-phase silica or nano titanium oxide and add water-repelling agent and put into autoclave and react, reaction temperature is 180～240 ℃, reaction time is 6h, reflection finishes the back centrifugation, and the collection product places white carbon or the nano titanium oxide after thermostatic drying chamber carries out obtaining hydrophobic treatment in dry 24 hours.Wherein the quality wall of gas-phase silica or nano titanium oxide and water-repelling agent is 2～5: 10, and water-repelling agent is an octamethylcy-clotetrasiloxane, also can be organo-silicon coupling agent, silicone oil with low viscosity, hydroxy silicon oil etc.The activity hydroxy that exists without the polysiloxane structure and the outer surface of the white carbon inside of hydrophobic treatment makes its surface can be bigger, and aggregation tends to cohesion, forms secondary structure, thereby white carbon shows hydrophily, is difficult to soak into and disperse in organic facies.Reduce on white carbon surface after hydrophobic treatment, hydroxy radical content, assembles tendency and weaken, and surface free energy reduces, by hydrophilic transfer to hydrophobic.
B, to get mass ratio be white carbon or nano titanium oxide after 8: 1～2: 1～2.5 methyl-silicone oils, polyether modified silicon oil and the hydrophobic treatment, stirring also is warming up to 110～200 ℃, make silicon cream and place the thermostatic drying chamber drying, baking temperature is 120 ℃, and be 3 hours drying time.
C, in silicon cream, add emulsifying agent, the emulsion adjuvant account for silicon cream quality 15～30%, emulsifying agent, emulsion adjuvant are dissolved at 50～90 ℃, after mixing, brute force stirs 1h, dropwise adds the sodium carboxy methyl cellulose thickening solution of mass concentration 0.8～1.8%.The effect of emulsifying agent mainly is the interfacial tension that reduces between silicone grease and the water, thereby realizes that silicone grease stably disperses in water.Emulsifying agent is general select as: Tween-20, Tween-60, Tween-65, Tween-80, Tween-85,, Span-20, Span-40, Span-60, Span-65, Span-85, it is composite to select for use several HLB to have the emulsifying agent of certain difference to carry out, and effect adopts single emulsifying agent good.
D, drip off the back and continue to stir, utilize the composite emulsion of the organic silicon modified by polyether defoamer that high speed homogenizer high-speed stirred 2h must be stable at last.High speed homogenizer or emulsifying agent emulsify at a high speed high speed shear form stable emulsion.
Embodiment 1, the preparation of organic silicon modified by polyether defoamer
A, the toluene that will hold pi-allyl polyoxy alkene ether and account for end pi-allyl polyoxy alkene ether and silicon oil of low hydrogen content gross mass 20% add in the container and stir, and vacuum distillation dewaters, and reach 0.5 ‰ to water content.
B, adding silicon oil of low hydrogen content stirring in described step a system then, the amount and the adding speed of control silicon oil of low hydrogen content dropwise slowly add reaction system, at the uniform velocity stir.The C=C group amount of substance of its middle-end pi-allyl polyoxy alkene ether and silicon oil of low hydrogen content Si-H group amount of substance ratio are 1.1: 1.
C, then add chloroplatinic acid aqueous isopropanol as catalyst, install reflux condensing tube additional, at N
2Be stirred and heated to 90 reactions 4 hours under the atmosphere, insulation reaction to terminal.The amount of catalyst is 25/1000000ths of a reaction system gross mass.
Adding accounts for reaction system gross mass 3% again in reaction system, and concentration is that the hydrochloric acid of 0.001mol/L stirs, and reacts 1h to remove the possible stink of industrial polyether product at 90 ℃.
After d, reaction finish, to slough solvent and low-boiling-point substance, get the water soluble polyether modified organic silicon 90 ℃ of decompression distillation.
Organic silicon modified by polyether defoamer composite:
A, get gas-phase silica and add octamethylcy-clotetrasiloxane and put into autoclave and react, wherein gas-phase silica and octamethylcy-clotetrasiloxane mass ratio are 2: 10, reaction temperature is 180～240 ℃, reaction time is 6h, reaction finishes the back centrifugation, and the collection product places the white carbon after thermostatic drying chamber carries out obtaining hydrophobic treatment in dry 24 hours.
B, to get mass ratio be white carbon after 8: 1: 1 methyl-silicone oil, polyether modified silicon oil and the hydrophobic treatment, stirs and be warming up to 110 ℃, makes silicon cream and placed thermostatic drying chamber dry 3 hours under 120 ℃.
C, add Span-60, the Tween-60 account for silicon cream quality 15% in silicon cream, Span-60, Tween-60 are dissolved at 50 ℃, after mixing, the powerful 1h that stirs dropwise adds the sodium carboxy methyl cellulose thickening solution of mass concentration 0.8%.
D, drip off the back and continue to stir, utilize the composite emulsion (sample 1) of the organic silicon modified by polyether defoamer that high speed homogenizer high-speed stirred 2h must be stable at last.
Embodiment 2, the preparation of organic silicon modified by polyether defoamer
A, the dimethylbenzene that will hold pi-allyl polyoxy alkene ether and account for end pi-allyl polyoxy alkene ether and silicon oil of low hydrogen content gross mass 35% add in the container and stir, and vacuum distillation dewaters, and reach 1 ‰ to water content.
B, adding silicon oil of low hydrogen content stirring in described step a system then, the amount and the adding speed of control silicon oil of low hydrogen content dropwise slowly add reaction system, at the uniform velocity stir.The C=C group amount of substance of its middle-end pi-allyl polyoxy alkene ether and silicon oil of low hydrogen content Si-H group amount of substance ratio are 1.4: 1.
C, then add chloroplatinic acid aqueous isopropanol as catalyst, install reflux condensing tube additional, at N
2Be stirred and heated to 120 ℃ of reactions 6 hours under the atmosphere, insulation reaction to terminal.The amount of catalyst is 45/1000000ths of a reaction system gross mass.
Adding accounts for 3% of reaction system gross mass again in reaction system, and concentration is that the hydrochloric acid of 0.001mol/L stirs, and reacts 2h to remove the possible stink of industrial polyether product at 92 ℃.
After d, reaction finish, to slough solvent and low-boiling-point substance, get the water soluble polyether modified organic silicon 120 ℃ of decompression distillation.
Organic silicon modified by polyether defoamer composite:
A, get nano titanium oxide and add octamethylcy-clotetrasiloxane and put into autoclave and react, wherein nano titanium oxide and octamethylcy-clotetrasiloxane mass ratio are 5: 10, reaction temperature is 240 ℃, reaction time is 6h, reaction finishes the back centrifugation, and the collection product places the nano titanium oxide after thermostatic drying chamber carries out obtaining hydrophobic treatment in dry 24 hours.
B, to get mass ratio be nano titanium oxide after 8: 2: 2.5 methyl-silicone oil, polyether modified silicon oil and the hydrophobic treatment, stirs and be warming up to 200 ℃, makes silicon cream and placed thermostatic drying chamber dry 3 hours under 120 ℃.
C, add Span-60, the Tween-60 account for silicon cream quality 30% in silicon cream, Span-60, Tween-60 are dissolved at 90 ℃, after mixing, the powerful 1h that stirs dropwise adds the sodium carboxy methyl cellulose thickening solution of mass concentration 1.8%.
D, drip off the back and continue to stir, utilize the composite emulsion (sample 2) of the organic silicon modified by polyether defoamer that high speed homogenizer high-speed stirred 2h must be stable at last.
Embodiment 3, the preparation of organic silicon modified by polyether defoamer
A, the benzene that will hold pi-allyl polyoxy alkene ether and account for end pi-allyl polyoxy alkene ether and silicon oil of low hydrogen content gross mass 30% add in the container and stir, and vacuum distillation dewaters, and reach 0.8 ‰ to water content.
B, adding silicon oil of low hydrogen content stirring in described step a system then, the amount and the adding speed of control silicon oil of low hydrogen content dropwise slowly add reaction system, at the uniform velocity stir.The C=C group amount of substance of its middle-end pi-allyl polyoxy alkene ether and silicon oil of low hydrogen content Si-H group amount of substance ratio are 1.2: 1.
C, then add chloroplatinic acid aqueous isopropanol as catalyst, install reflux condensing tube additional, at N
2Be stirred and heated to 100 ℃ of reactions 5 hours under the atmosphere, insulation reaction to terminal.The amount of catalyst is 35/1000000ths of a reaction system gross mass.
Adding accounts for 3% of reaction system gross mass again in reaction system, and concentration is that the hydrochloric acid of 0.001mol/L stirs, and reacts 1.5h to remove the possible stink of industrial polyether product at 91 ℃.
After d, reaction finish, to slough solvent and low-boiling-point substance, get the water soluble polyether modified organic silicon 100 ℃ of decompression distillation.
Organic silicon modified by polyether defoamer composite:
A, get gas-phase silica and add octamethylcy-clotetrasiloxane and put into autoclave and react, wherein gas-phase silica and octamethylcy-clotetrasiloxane mass ratio are 3.5: 10, reaction temperature is 200 ℃, reaction time is 6h, reaction finishes the back centrifugation, and the collection product places the white carbon after thermostatic drying chamber carries out obtaining hydrophobic treatment in dry 24 hours.
B, to get mass ratio be white carbon after 8: 1.5: 2 methyl-silicone oil, polyether modified silicon oil and the hydrophobic treatment, stirs and be warming up to 150 ℃, makes silicon cream and placed thermostatic drying chamber dry 3 hours under 120 ℃.
C, add Span-60, the Tween-60 account for silicon cream quality 20% in silicon cream, Span-60, Tween-60 are dissolved at 80 ℃, after mixing, the powerful 1h that stirs dropwise adds the sodium carboxy methyl cellulose thickening solution of mass concentration 1.2%.
D, drip off the back and continue to stir, utilize the composite emulsion (sample 3) of the organic silicon modified by polyether defoamer that high speed homogenizer high-speed stirred 2h must be stable at last.
Embodiment 4, the preparation of organic silicon modified by polyether defoamer
A, will hold pi-allyl polyoxy alkene ether to add in the container to stir, vacuum distillation dewaters, and reaches 0.6 ‰ to water content.
B, adding solvent and silicon oil of low hydrogen content stirring in described step a system then, the amount and the adding speed of control silicon oil of low hydrogen content dropwise slowly add reaction system, at the uniform velocity stir.The C=C group amount of substance of its middle-end pi-allyl polyoxy alkene ether and silicon oil of low hydrogen content Si-H group amount of substance ratio are 1.3: 1, and solvent accounts for 25% of end pi-allyl polyoxy alkene ether and silicon oil of low hydrogen content gross mass, and solvent is the 120# solvent naphtha.
C, then add chloroplatinic acid aqueous isopropanol as catalyst, install reflux condensing tube additional, at N
2Be stirred and heated to 105 ℃ of reactions 5 hours under the atmosphere, insulation reaction to terminal.The amount of catalyst is 40/1000000ths of a reaction system gross mass.
Adding accounts for 3% of reaction system gross mass again in reaction system, and concentration is that the hydrochloric acid of 0.001mol/L stirs, and reacts 2h to remove the possible stink of industrial polyether product at 90 ℃.
After d, reaction finish, to slough solvent and low-boiling-point substance, get the water soluble polyether modified organic silicon 110 ℃ of decompression distillation.
Embodiment 5, organic silicon modified by polyether defoamer composite
A, get gas-phase silica and add octamethylcy-clotetrasiloxane and put into autoclave and react, wherein gas-phase silica and octamethylcy-clotetrasiloxane mass ratio are 5: 10, reaction temperature is 220 ℃, reaction time is 6h, reaction finishes the back centrifugation, and the collection product places the white carbon after thermostatic drying chamber carries out obtaining hydrophobic treatment in dry 24 hours.
B, to get mass ratio be white carbon after 8: 1.5: 1.5 methyl-silicone oil, polyether modified silicon oil and the hydrophobic treatment, stirs and be warming up to 180 ℃, makes silicon cream and placed thermostatic drying chamber dry 3 hours under 120 ℃.
C, add Span-60, the Tween-60 account for silicon cream quality 20% in silicon cream, Span-60, Tween-60 are dissolved at 80 ℃, after mixing, the powerful 1h that stirs dropwise adds the sodium carboxy methyl cellulose thickening solution of mass concentration 1.0%.
D, drip off the back and continue to stir, utilize the composite emulsion (sample 4) of the organic silicon modified by polyether defoamer that high speed homogenizer high-speed stirred 2h must be stable at last.
The composite emulsion of organic silicon modified by polyether defoamer is as shown in the table with the product comparative result of domestic and international renowned company:
According to processing method of the present invention, silicon oil of low hydrogen content by end pi-allyl polyoxy alkene ether and specified molecular weight ad hoc structure prepares polyether-modified silicon, utilize the characteristics of polyether-modified silicon with the easily disperse of the low surface tension of polysiloxanes and polyethers, make polyether-modified silicon not only have self-emulsifying ability, the stability and compatible, dispersed in water thereof of emulsion have been increased, also guaranteed to disappear to press down and steeped effect, polyether-modified silicon is high temperature resistant, acid and alkali-resistance and inorganic salts, can be used to the froth breaking under the harsh conditions.
By above list data as can be known, sample 1, sample 2, sample 3, sample 4 are the composite emulsion of the resulting organic silicon modified by polyether of the present invention, and silicone defoaming agent KM73, silicone defoaming agent LD200, silicone defoaming agent ND130 are to be the commercially available defoamer of main component with the dimethicone.The present invention and commercially available defoamer compare, the result shows: utilize organic silicon modified by polyether as the emulsifying agent of dimethicone and bring into play dispersion, emulsification in the composite emulsion of organic silicon modified by polyether, guaranteed the stability (as high-temperature stability, low-temperature stability, centrifugal stability) of defoamer, make its no breakdown of emulsion, floating oil phenomenon, its dispersiveness and froth breaking, to press down the bubble effect also fine, presses down the bubble time and also improve to some extent.In addition, the composite emulsion of polyether-modified silicon defoaming agent is also with chemical inertness or the like.The organic silicon modified by polyether defoamer can use in all expanding foam solutions, and can improve the quality of products, operating efficiency, improve aspects such as environment and play a role.
Claims (14)
1. water soluble polyether modified organic silicon defoamer, its chemical structural formula is any one or a few in following three kinds:
Formula (1)
Formula (2)
Formula (3)
In the formula: subscript m is 0～50 integer, and n is 1～50 integer; X is 0～20 integer, and y is the integer of 0-30, wherein x: y=1: 7～1: between 3; R be ester group or or carbon number be 1～4 alkyl; EO is CH
2-CH
2-CH
2O; R
2Be CH
2-CH
2-CH
2
2. the preparation method of the described water soluble polyether modified organic silicon of claim 1 defoamer may further comprise the steps:
A, will hold pi-allyl polyoxy alkene ether to add in the container to stir, dewater;
B, adding solvent and silicon oil of low hydrogen content stirring in described step a system then;
C, then add catalyst at N
2Carry out the agitating heating reaction under atmosphere and the reflux condensation mode condition;
After d, reaction finish, slough solvent and low-boiling-point substance, get the water soluble polyether modified organic silicon.
3. the preparation method of water soluble polyether modified organic silicon defoamer according to claim 2 is characterized in that: it is to adopt the vacuum distillation mode that described step a dewaters, dewater to water content less than 0.5～1 ‰; When dewatering, described step a adds solvent.
4. the preparation method of water soluble polyether modified organic silicon defoamer according to claim 2 is characterized in that: the Si-H group amount of substance ratio of silicon oil of low hydrogen content is 1.1: 1～1.4: 1 among the C=C group of described step a middle-end pi-allyl polyoxy alkene ether and the step b.
5. according to the preparation method of claim 2 or 3 described water soluble polyether modified organic silicon defoamers, it is characterized in that: the solvent of described step b accounts for 20～35% of end pi-allyl polyoxy alkene ether and silicon oil of low hydrogen content gross mass, and described solvent is one or more in toluene, dimethylbenzene, benzene, the 120# solvent naphtha.
6. the preparation method of water soluble polyether modified organic silicon defoamer according to claim 2, it is characterized in that: the amount of catalyst is 25/1000000ths～45 of a reaction system gross mass among the described step c, catalyst is the aqueous isopropanol of chloroplatinic acid, described step c reaction temperature is 90～120 ℃, and the reaction time is 4～6 hours.
7. the preparation method of water soluble polyether modified organic silicon defoamer according to claim 2 is characterized in that: slough solvent and low-boiling-point substance in the described steps d and adopt the decompression distillation mode, vacuum distillation temperature is 90～120 ℃.
8. the preparation method of water soluble polyether modified organic silicon defoamer according to claim 2 is characterized in that: added hydrochloric acid again and carry out stirring reaction before carrying out described steps d in reaction system.
9. the preparation method of water soluble polyether modified organic silicon defoamer according to claim 8, it is characterized in that: the amount of described hydrochloric acid is 3% of a c step reaction system gross mass, concentration of hydrochloric acid is 0.001mol/L, and reaction temperature is 90 ± 2 ℃, and the reaction time is 1～2h.
10. the preparation method of the described organic silicon modified by polyether defoamer of claim 1, its step comprises:
A, get gas-phase silica or nano titanium oxide and add the hydrophobic treatment agent and react, centrifugation is then collected product and is carried out white carbon or nano titanium oxide after drying obtains hydrophobic treatment;
B, get white carbon or nano titanium oxide after methyl-silicone oil, polyether modified silicon oil and the hydrophobic treatment, stir also and heat up, make silicon cream and dry;
C, add emulsifying agent, emulsion adjuvant in silicon cream, emulsifying agent, emulsion adjuvant are dissolved, after mixing, the powerful stirring dropwise adds thickening solution;
D, drip off the back and continue to stir the composite emulsion of the organic silicon modified by polyether defoamer that last high-speed stirred must be stable.
11. the preparation method of water soluble polyether modified organic silicon defoamer according to claim 10, it is characterized in that: gas-phase silica or nano titanium oxide and hydrophobic treatment agent mass ratio are 2～5: 20 among the described step a, the hydrophobic treatment agent is an octamethylcy-clotetrasiloxane, reaction temperature is 180～240 ℃, reaction time is 6h, consersion unit is an autoclave, and drying equipment is a thermostatic drying chamber, and be 24 hours drying time.
12. the preparation method of water soluble polyether modified organic silicon defoamer according to claim 10, it is characterized in that: the mass ratio of the white carbon among the described step b after methyl-silicone oil, polyether modified silicon oil and the hydrophobic treatment is 8: 1～2: 1～2.5, the intensification temperature is 110～200 ℃, drying equipment is a thermostatic drying chamber, baking temperature is 120 ℃, and be 3 hours drying time.
13. the preparation method of water soluble polyether modified organic silicon defoamer according to claim 10, it is characterized in that: the mass ratio of emulsifying agent, emulsion adjuvant and polyether modified silicon oil is 1.5～3: 1～2 among the described step c, solution temperature is 50～90 ℃, mixing time 1h, thickening solution are the sodium carboxy methyl cellulose solution of mass concentration 0.8～1.8%.
14. the preparation method of water soluble polyether modified organic silicon defoamer according to claim 10 is characterized in that: mixing time is 2h in the described steps d, and high-speed mixing equipment is a high speed homogenizer.
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Application publication date: 20111221 |