CN102174778B - Self-emulsifiable defoaming composition and preparation method thereof - Google Patents
Self-emulsifiable defoaming composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a self-emulsifiable defoaming composition and a preparation method thereof. The defoaming composition comprises the following components by mass percent: 42-92.5% of modified polysiloxane, 3-27% of silica particles prepared by a polymer template method, 4-27% of dispersant and 0.5-4.0% of emulsifier. In the preparation process of the defoaming composition, rapid and even mixing of all the components can be achieved without high-temperature immersion, and the deforming composition has excellent foam inhibiting property even in a high-temperature alkali environment, and is applicable to the procedures of pulping, pigment dispersing and film coating in the papermaking industry process.
Description
Technical field
The present invention relates to defoaming composition and preparation method thereof, be specifically related to a kind of self-emulsifying type defoaming composition and preparation method thereof.
Background technology
In pulp production and paper forming process; The serious bubble that fibrous matter produces in whipping process can cause decreased performance such as paper performance such as porous, surface flatness, suppleness; And reduced the operating efficiency of pump, Mixing Machine, filter screen, must add antifoaming agent.Difference according to the froth breaking material; Can be divided into polyether-type, organosiloxane type, long carbochain alcohol type, mineral oil origin; Organosiloxane defoamer wherein; The organosiloxane of especially fluorine-containing organosiloxane and acrylic acid derivative modification is the focus of Recent study since its have that adding proportion is few, froth breaking and press down characteristics such as bubble speed is fast, chemical stability is good, received generally at paper industry and favored.
Usually add inorganic, metal oxide solid particle silica in the organosiloxane defoamer and serve as brokenly the main medium of bubble effect; The fluorine-containing organosiloxane of modification and the organosiloxane of acrylic acid derivative modification are because lower surface tension has spreading property preferably; The synergy on silicon grain and silicone oil surface makes and is constantly broken bubble between froth breaking medium and the inorganic, metal oxide particle and have lasting inhibitory action.
Contain a large amount of air and hydroxyl between silica particles and pore; Dimethyl silicone polymer had repulsive interaction; Need carry out hydrophobization with the method that catalyst add under the vacuum condition dipping and handle, make between dimethyl silicone polymer and the inorganic particle to reach even distribution and mix.Usually the method that adopts in the row is carried out vacuum simultaneously or is added a small amount of amines catalyst with the acceleration process in dimethyl silicone polymer, to heat dipping to silica dioxide granule, and process equipment is comparatively expensive, and destabilizing factor is arranged in process.
Summary of the invention
The objective of the invention is to: a kind of self-emulsifying type defoaming composition and preparation method thereof is provided; Said composition need not to experience the high temperature impregnation stage and can make and reach rapid and uniform between each composition and mix in its preparation process; The suds suppressing properties that under the high-temperature alkaline environment, still possesses the excellence of exchange is applicable to each process such as making beating, pigment dispersing and coating film forming in the paper industry process.
Technical solution of the present invention is: this defoaming composition is made up of following ingredients by percentage to the quality:
Modified polyorganosiloxane 42～92.5%
Polymer template method silica dioxide granule 3～27%
Organosilicon dispersant 4 ~ 27%
Emulsifying agent 0.5 ~ 4.0%.
Wherein, described modified polyorganosiloxane is fluorine-containing alkyl-modified dimethyl silicone polymer, and fluorine-containing alkyl-modified dimethyl silicone polymer is formed by fluorine-containing siloxanyl monomers and dimethyl silicone polymer condensation; Or described modified polyorganosiloxane is the ester modified dimethyl silicone polymer of acrylate long-chain fluorine alcohol, and the ester modified dimethyl silicone polymer of acrylate long-chain fluorine alcohol is formed by acrylic acid, long-chain fluorine-alcohol, the polycondensation of methyl hydrogen silicone oil; Or described modified polyorganosiloxane is propenyl polyethenoxy ether and the acrylic acid fluorine alcohol ester product of the modified dimethyl polysiloxane of 3:7 ~ 1:1 in molar ratio; Wherein preferred fluorine-containing alkyl-modified dimethyl silicone polymer.
Wherein, described silica dioxide granule is the hydrophilic particle with cellular structure, and through the preparation of polymer template method, the silica dioxide granule average diameter is 0.5 ~ 5 μ m, preferred 1 ~ 3 μ m, and specific area is 300 ~ 500m
2/ g, porosity is 50%～95%.
Wherein, Described organosilicon dispersant is a kind of block polymer microsphere suspension liquid that possesses the microcosmic nucleocapsid structure; The shell of polymer microballoon is that the acrylic monomer emulsions of hydroxyl is polymerized, and the nuclear of polymer microballoon is the organosilicon microballoon that emulsion polymerisation forms, and particle diameter is 250nm ~ 600nm; Mean molecule quantity is 100,000 ~ 500,000, directly uses with the mode of turbid liquid.
Wherein, Described emulsifying agent is ether type emulsifying agent or ionic emulsifying agent; Ether type emulsifying agent has polyoxyethylene alkane ether, polyoxyethylene polyols ether, polyoxyethylene polyoxypropylene block copolymer, and anionic emulsifier has alkyl sulfate, alkyl ether sulfate, alkylphosphonic, alkylamide sulfonate, octadecane hydrochlorate, dodecyl hydrochlorate.
Wherein, the mixing and emulsifying body of preferred ether type emulsifying agent and anionic emulsifier is the blend emulsified body of lauryl sodium sulfate and polyoxyethylene polyols ether mass ratio 1:1.
Defoaming composition of the present invention obtains through following steps:
(1) preparation of organosilicon seed emulsion: the catalyst DBSA of 0.5 ~ 1g, ionic emulsifying agent, 50 ~ 100g deionized water and the 20 ~ 30g cyclohexyl methyl siloxanes of 1 ~ 5g are added in the four-hole bottle high-speed stirred emulsification 0.5 ~ 1h; Be heated to 60 ~ 90 ℃, logical N
2, isothermal reaction 2 ~ 5h; Drip 1 ~ 5g silane coupler, drip off back isothermal reaction 1 ~ 3h, must be with the organosilicon seed emulsion of vinyl;
(2) preparation of organosilicon modified acrylic ester microemulsion: in above-mentioned 100g organosilicon seed emulsion, add 1 ~ 2g BPO, 1 ~ 5g ionic emulsifying agent and 5 ~ 15 acrylate monomers, stir and be warming up to 60 ~ 90 ℃; After the system of treating causes, begin to drip 30 ~ 50g acrylate monomer, drip off 60 ~ 90 ℃ of isothermal reaction 1 ~ 3h in back; Cooling adds ammoniacal liquor adjust pH to 7 ~ 7.5, gets organosilicon modified acrylic ester microemulsion;
(3) preparation of polymer template method silica dioxide granule: with mass ratio is that epoxy resin and the polyethylene glycol of 1:4～4:1 mixes and be heated to 40～90 ℃; Stirred 5～15 minutes; Adding is the diethylenetriamine liquid of 1:2～1:10 with the epoxy resin mass ratio again; Add again after stirring with the epoxy resin mass ratio be the positive tetraethyl orthosilicate of 1:1～2:1; Maintain the temperature at the solid shaped polymer blend that forms white in 40 ~ 90 ℃ after 1～10 hour, the heating rate with 5～10 ℃ in Muffle furnace rises to 600～900 ℃, gets polymer template method silica dioxide granule after grinding with ball mill;
(4) polymer template method silica dioxide granule was evenly mixed 3～5 hours in agitator with the organosilicon modified acrylic ester microemulsion that exists with the turbid liquid mode; Agitator is heated constant temperature to 80 ℃～100 ℃ in advance, make polymer beads in the dispersant fully combine with silica dioxide granule mixed system;
(5) in the mixed system of the 4th step preparation, add modified polyorganosiloxane, temperature keeps more than 100 ℃ stirring 2～4 hours, gets mixture;
(6) said mixture is cooled to normal temperature, and the interpolation emulsifier is even, gets defoaming composition.
The present invention has the following advantages: avoided routine need descend the process of dipping to the silica dioxide granule vacuum condition in 1, the preparation process, whole process of production can be carried out in a continuous preparation facilities, has increased production efficiency; 2, preparation process need not catalyst or high-temperature process, and production process and use equipment are simple, make things convenient for suitability for industrialized production, are applicable to fields such as papermaking, fine chemistry industry; 3, the nucleocapsid structure main body is an organosilicon, has increased the antifoam performance of composition, and modified polyorganosiloxane makes antifoam performance more excellent; 4, polymer template method silica dioxide granule has large aperture macroporosity, little apparent density, bigger serface, prepares characteristics simple, with low cost, can extensively promote.
The specific embodiment
Below in conjunction with embodiment technical solution of the present invention is done further explain, but technical scheme of the present invention is not limited thereto.
Embodiment 1: prepare defoaming composition according to following steps:
(1) preparation of organosilicon seed emulsion: the catalyst DBSA with 0.5,1 ionic emulsifying agent, 50 deionized waters and 20 cyclohexyl methyl siloxanes add in the four-hole bottle, high-speed stirred emulsification 0.5; Be heated to 60 ℃, logical N
2, isothermal reaction 2h; Drip the 1g silane coupler, drip off back isothermal reaction 1h, must be with the organosilicon seed emulsion of vinyl;
(2) preparation of organosilicon modified acrylic ester microemulsion: in above-mentioned 100g organosilicon seed emulsion, add 1g BPO, 1g ionic emulsifying agent and 5 acrylate monomers, stir and be warming up to 60 ℃; After the system of treating causes, begin to drip the 30g acrylate monomer, drip off back 600 ℃ of isothermal reaction 1h; Cooling adds ammoniacal liquor adjust pH to 7, gets organosilicon modified acrylic ester microemulsion;
(3) preparation of polymer template method silica dioxide granule: with mass ratio is that epoxy resin and the polyethylene glycol of 1:4 mixes and be heated to 40 ℃; Stirred 5 minutes; Adding is the diethylenetriamine liquid of 1:2 with the epoxy resin mass ratio again; Add again after stirring with the epoxy resin mass ratio be the positive tetraethyl orthosilicate of 1:1; Maintain the temperature at the solid shaped polymer blend that forms white in 40 ℃ after 1 hour, the heating rate with 5 ℃ in Muffle furnace rises to 600 ℃, gets polymer template method silica dioxide granule after grinding with ball mill;
(4) in mass fraction, 27 parts of average diameters are that 0.5 μ m, specific area are 300m
2/ g, porosity be in 50% the polymer template method silica dioxide granule polymer microballoon emulsion that to join 4 parts of shells be methacrylic acid nuclear forms for organosilicon 80 ℃ stir and mixed the formation mixed system 5 hours;
The dimethyl silicone polymer (Jiangsu Sterric Chemical Industry Co., Ltd.) of (5) 68.5 parts of trifluoromethyl modifications adds in the above-mentioned mixed system, 100
oC stirred 2 hours, was cooled to room temperature and got mixture;
(6) in said mixture, add 0.5 part of lauryl sodium sulfate (Shandong Wanda's chemical industry Co., Ltd) normal temperature and mixed 0.5 hour, pack through the outlet outflow.
Embodiment 2: prepare defoaming composition according to following steps:
(1) preparation of organosilicon seed emulsion: the catalyst DBSA of 1g, ionic emulsifying agent, 100g deionized water and the 30g cyclohexyl methyl siloxanes of 5g are added in the four-hole bottle high-speed stirred emulsification 1h; Be heated to 90 ℃, logical N
2, isothermal reaction 5h; Dropwise 5 g silane coupler drips off back isothermal reaction 3h, must be with the organosilicon seed emulsion of vinyl;
(2) preparation of organosilicon modified acrylic ester microemulsion: in above-mentioned 100g organosilicon seed emulsion, add 2g BPO, 5g ionic emulsifying agent and 15 acrylate monomers, stir and be warming up to 90 ℃; After the system of treating caused, beginning Dropwise 5 0g acrylate monomer dripped off back 90 ℃ of isothermal reaction 3h; Cooling adds ammoniacal liquor adjust pH to 7.5, gets organosilicon modified acrylic ester microemulsion;
(3) preparation of polymer template method silica dioxide granule: with mass ratio is that epoxy resin and the polyethylene glycol of 1:1 mixes and be heated to 65 ℃; Stirred 10 minutes; Adding is the diethylenetriamine liquid of 1:6 with the epoxy resin mass ratio again; Add again after stirring with the epoxy resin mass ratio be the positive tetraethyl orthosilicate of 1.5:1; Maintain the temperature at the solid shaped polymer blend that forms white in 65 ℃ after 5.5 hours, the heating rate with 7 ℃ in Muffle furnace rises to 750 ℃, gets polymer template method silica dioxide granule after grinding with ball mill;
(4)In mass fraction, 3 parts of average diameters are that 1 μ m, specific area are 400m
2/ g, porosity be in 70%% the polymer template method silica dioxide granule polymer microballoon emulsion that to join 27 parts of shells be methacrylic acid nuclear forms for organosilicon 90 ℃ stir and mixed the formation mixed system 4 hours;
(5) 67 parts of ester modified dimethyl silicone polymers (Jiangsu Sterric Chemical Industry Co., Ltd.) of acrylic acid perfluor octanol add in the above-mentioned mixed system, 100
oC stirred 3 hours down, was cooled to room temperature and got mixture;
(6) in said mixture, add 3 parts of octadecanoid acid sodium, normal temperature mixed 0.5 hour, flowed out through outlet to pack.
Embodiment 3: prepare defoaming composition according to following steps:
(1) preparation of organosilicon seed emulsion: the catalyst DBSA of 0.75g, ionic emulsifying agent, 75g deionized water and the 25g cyclohexyl methyl siloxanes of 3g are added in the four-hole bottle high-speed stirred emulsification 0.75h; Be heated to 75 ℃, logical N
2, isothermal reaction 3h; Drip the 3g silane coupler, drip off back isothermal reaction 2h, must be with the organosilicon seed emulsion of vinyl;
(2) preparation of organosilicon modified acrylic ester microemulsion: in above-mentioned 100g organosilicon seed emulsion, add 1.5g BPO, 3g ionic emulsifying agent and 10 acrylate monomers, stir and be warming up to 75 ℃; After the system of treating causes, begin to drip the 40g acrylate monomer, drip off back 75 ℃ of isothermal reaction 2h; Cooling adds ammoniacal liquor adjust pH to 7.25, gets organosilicon modified acrylic ester microemulsion;
(3) preparation of polymer template method silica dioxide granule: with mass ratio is that epoxy resin and the polyethylene glycol of 4:1 mixes and be heated to 90 ℃; Stirred 15 minutes; Adding is the diethylenetriamine liquid of 1:10 with the epoxy resin mass ratio again; Add again after stirring with the epoxy resin mass ratio be the positive tetraethyl orthosilicate of 2:1; Maintain the temperature at the solid shaped polymer blend that forms white in 90 ℃ after 10 hours, the heating rate with 10 ℃ in Muffle furnace rises to 900 ℃, gets polymer template method silica dioxide granule after grinding with ball mill;
(4)In mass fraction, 15 parts of average diameters are that 3 μ m, specific area are 500m
2/ g, porosity be in 95% the polymer template method silica dioxide granule polymer microballoon emulsion that to join 15 parts of shells be methacrylic acid nuclear forms for organosilicon 100 ℃ stir and mixed the formation mixed system 3 hours;
(5) 68 parts of propenyl polyethenoxy ethers and acrylic acid perfluor lauryl alcohol ester are the modified dimethyl polysiloxane (Jiangsu Sterric Chemical Industry Co., Ltd.) of 3:7 according to mol ratio, add in the above-mentioned mixed system, 100
oC stirred 4 hours down, was cooled to room temperature and got mixture;
(6) in said mixture, add 2 parts of polyoxyethylene lauryl alcohol ethers (the extremely prosperous chemical industry in Shanghai Co., Ltd), normal temperature mixed 0.2 hour, flowed out through outlet to pack.
Embodiment 4: prepare defoaming composition according to following steps:
(1) preparation of organosilicon seed emulsion: the catalyst DBSA of 0.75g, ionic emulsifying agent, 75g deionized water and the 25g cyclohexyl methyl siloxanes of 3g are added in the four-hole bottle high-speed stirred emulsification 0.75h; Be heated to 80 ℃, logical N
2, isothermal reaction 3h; Drip the 3g silane coupler, drip off back isothermal reaction 2h, must be with the organosilicon seed emulsion of vinyl;
(2) preparation of organosilicon modified acrylic ester microemulsion: in above-mentioned 100g organosilicon seed emulsion, add 1.5g BPO, 3g ionic emulsifying agent and 10 acrylate monomers, stir and be warming up to 80 ℃; After the system of treating causes, begin to drip the 40g acrylate monomer, drip off back 80 ℃ of isothermal reaction 2h; Cooling adds ammoniacal liquor adjust pH to 7.25, gets organosilicon modified acrylic ester microemulsion;
(3) preparation of polymer template method silica dioxide granule: with mass ratio is that epoxy resin and the polyethylene glycol of 2:3 mixes and be heated to 50 ℃; Stirred 8 minutes; Adding is the diethylenetriamine liquid of 1:4 with the epoxy resin mass ratio again; Add again after stirring with the epoxy resin mass ratio be the positive tetraethyl orthosilicate of 1:1; Maintain the temperature at the solid shaped polymer blend that forms white in 50 ℃ after 3 hours, the heating rate with 6 ℃ in Muffle furnace rises to 700 ℃, gets polymer template method silica dioxide granule after grinding with ball mill;
(4) in mass fraction, 3 parts of average diameters are that 2 μ m, specific area are 350m
2/ g, porosity be in 75% the polymer template method silica dioxide granule polymer microballoon emulsion that to join 4 parts of shells be methacrylic acid nuclear forms for organosilicon 90 ℃ stir and mixed the formation mixed system 4 hours;
(5) 92.5 parts of propenyl polyethenoxy ethers and acrylic acid perfluor lauryl alcohol ester are that the modified dimethyl polysiloxane (Jiangsu Sterric Chemical Industry Co., Ltd.) of 1:1 adds above-mentioned mixed system according to mol ratio, 100
oC stirred 2 hours, was cooled to room temperature and got mixture;
(6) the blend emulsified body of 0.5 part of lauryl sodium sulfate of adding and polyoxyethylene lauryl alcohol ether (the extremely prosperous chemical industry in Shanghai Co., Ltd) in said mixture, normal temperature mixed 0.3 hour, packed through the outlet outflow.
Embodiment 5: prepare defoaming composition according to following steps:
(1) preparation of organosilicon seed emulsion: the catalyst DBSA of 0.75g, ionic emulsifying agent, 75g deionized water and the 25g cyclohexyl methyl siloxanes of 3g are added in the four-hole bottle high-speed stirred emulsification 0.75h; Be heated to 70 ℃, logical N
2, isothermal reaction 3h; Drip the 3g silane coupler, drip off back isothermal reaction 2h, must be with the organosilicon seed emulsion of vinyl;
(2) preparation of organosilicon modified acrylic ester microemulsion: in above-mentioned 100g organosilicon seed emulsion, add 1.5g BPO, 3g ionic emulsifying agent and 10 acrylate monomers, stir and be warming up to 70 ℃; After the system of treating causes, begin to drip the 40g acrylate monomer, drip off back 70 ℃ of isothermal reaction 2h; Cooling adds ammoniacal liquor adjust pH to 7.25, gets organosilicon modified acrylic ester microemulsion;
(3) preparation of polymer template method silica dioxide granule: with mass ratio is that epoxy resin and the polyethylene glycol of 3:2 mixes and be heated to 80 ℃; Stirred 12 minutes; Adding is the diethylenetriamine liquid of 1:6 with the epoxy resin mass ratio again; Add again after stirring with the epoxy resin mass ratio be the positive tetraethyl orthosilicate of 2:1; Maintain the temperature at the solid shaped polymer blend that forms white in 80 ℃ after 8 hours, the heating rate with 9 ℃ in Muffle furnace rises to 800 ℃, gets polymer template method silica dioxide granule after grinding with ball mill;
(4)In mass fraction, 27 parts of average diameters are that 5 μ m, specific area are 450m
2/ g, porosity be in 85% the polymer template method silica dioxide granule polymer microballoon emulsion that to join 27 parts of shells be methacrylic acid nuclear forms for organosilicon 80 ℃ stir and mixed the formation mixed system 5 hours;
(5) 42 parts of propenyl polyethenoxy ethers and acrylic acid perfluor lauryl alcohol ester are that the modified dimethyl polysiloxane (Jiangsu Sterric Chemical Industry Co., Ltd.) of 5:8 adds above-mentioned mixed system according to mol ratio, 100
oC stirred 4 hours, was cooled to room temperature and got mixture;
(6) in said mixture, add 4.0 parts of alkylamide sodium sulfonates (the extremely prosperous chemical industry in Shanghai Co., Ltd), normal temperature mixed 0.3 hour, flowed out through outlet to pack.
Comparative example 1:
In mass fraction; The dimethyl silicone polymer of 100 parts of trimethylsiloxy groups (Japanese Toyo Ink Co., Ltd. buys); Join 15 parts of silica dioxide granule powder (the German Wacker H20 of company); Add 1.0 parts of lauryl sodium sulfate, 0.2 part diethylenetriamine base propyl trimethoxy silicane (Shandong Wanda's chemical industry Co., Ltd) normal temperature mixed 20 minutes, flowed out through outlet to pack.
Each item performance indications of defoaming composition are measured through following method: the graduated cylinder bottom of the defoaming composition in the embodiment that fills 1% neopelex solution and 0.1% weight feeds the nitrogen of constant flow; The height of foam behind the record ventilation 10min; Low highly more, explain that to press down the bubble ability strong more; Continue logical nitrogen then, after foam height reaches 40cm, close nitrogen, the height of foam is low highly more behind the record 5min, explains that the froth breaking ability is strong more.
The defoaming composition that the foregoing description and comparative example obtain is estimated through above-mentioned method of testing, and evaluation result is listed in the table below:
Can know that by table defoaming agent composition according to the present invention has tangible froth breaking and presses down the bubble effect, can be used as froth breaking use in the easy foaming process such as papermaking, fine chemistry industry.
Claims (4)
1. self-emulsifying type defoaming composition; This defoaming composition is made up of following ingredients by percentage to the quality: modified polyorganosiloxane 42～92.5%; Polymer template method silica dioxide granule 3～27%, organosilicon dispersant 4 ~ 27%, emulsifying agent 0.5 ~ 4.0%; Described modified polyorganosiloxane is fluorine-containing alkyl-modified dimethyl silicone polymer, and fluorine-containing alkyl-modified dimethyl silicone polymer is formed by fluorine-containing siloxanyl monomers and dimethyl silicone polymer condensation; Or described modified polyorganosiloxane is the ester modified dimethyl silicone polymer of acrylate long-chain fluorine alcohol, and the ester modified dimethyl silicone polymer of acrylate long-chain fluorine alcohol is formed by acrylic acid, long-chain fluorine-alcohol, the polycondensation of methyl hydrogen silicone oil; Or described modified polyorganosiloxane is propenyl polyethenoxy ether and the acrylic acid fluorine alcohol ester product of the modified dimethyl polysiloxane of 3:7 ~ 1:1 in molar ratio; Wherein, Described organosilicon dispersant is a kind of block polymer microsphere suspension liquid that possesses the microcosmic nucleocapsid structure; The shell of polymer microballoon is that the acrylic monomer emulsions of hydroxyl is polymerized, and the nuclear of polymer microballoon is the organosilicon microballoon that emulsion polymerisation forms, and particle diameter is 250nm ~ 600nm; Mean molecule quantity is 100,000 ~ 500,000, directly uses with the mode of turbid liquid; Wherein, Described emulsifying agent is ether type emulsifying agent or anionic emulsifier; Ether type emulsifying agent has polyoxyethylene alkane ether, polyoxyethylene polyols ether, polyoxyethylene polyoxypropylene block copolymer, and anionic emulsifier has alkyl sulfate, alkyl ether sulfate, alkylphosphonic, alkylamide sulfonate, octadecane hydrochlorate, dodecyl hydrochlorate; It is characterized in that: wherein, described silica dioxide granule is the hydrophilic particle with cellular structure, and through the preparation of polymer template method, the silica dioxide granule average diameter is 0.5 ~ 5 μ m, and specific area is 300 ~ 500m
2/ g, porosity is 50%～95%.
2. a kind of self-emulsifying type defoaming composition according to claim 1 is characterized in that: described silica dioxide granule is the hydrophilic particle with cellular structure, and through the preparation of polymer template method, the silica dioxide granule average diameter is 1 ~ 3 μ m.
3. a kind of self-emulsifying type defoaming composition according to claim 1; It is characterized in that: wherein; Described emulsifying agent is the mixing and emulsifying body of ether type emulsifying agent and anionic emulsifier, is the blend emulsified body of lauryl sodium sulfate and polyoxyethylene polyols ether.
4. the preparation method of self-emulsifying type defoaming composition is characterized in that this preparation method may further comprise the steps:
(1) preparation of organosilicon seed emulsion: the catalyst DBSA of 0.5 ~ 1g, ionic emulsifying agent, 50 ~ 100g deionized water and the 20 ~ 30g cyclohexyl methyl siloxanes of 1 ~ 5g are added in the four-hole bottle high-speed stirred emulsification 0.5 ~ 1h; Be heated to 60 ~ 90 ℃, logical N
2, isothermal reaction 2 ~ 5h; Drip 1 ~ 5g silane coupler, drip off back isothermal reaction 1 ~ 3h, must be with the organosilicon seed emulsion of vinyl;
(2) preparation of organosilicon modified acrylic ester microemulsion: in above-mentioned 100g organosilicon seed emulsion, add 1 ~ 2g BPO, 1 ~ 5g ionic emulsifying agent and 5 ~ 15 acrylate monomers, stir and be warming up to 60 ~ 90 ℃; After the system of treating causes, begin to drip 30 ~ 50g acrylate monomer, drip off 60 ~ 90 ℃ of isothermal reaction 1 ~ 3h in back; Cooling adds ammoniacal liquor adjust pH to 7 ~ 7.5, gets organosilicon modified acrylic ester microemulsion;
(3) preparation of polymer template method silica dioxide granule: with mass ratio is that epoxy resin and the polyethylene glycol of 1:4～4:1 mixes and be heated to 40～90 ℃; Stirred 5～15 minutes; Adding is the diethylenetriamine liquid of 1:2～1:10 with the epoxy resin mass ratio again; Add again after stirring with the epoxy resin mass ratio be the positive tetraethyl orthosilicate of 1:1～2:1; Maintain the temperature at the solid shaped polymer blend that forms white in 40 ~ 90 ℃ after 1～10 hour, the heating rate with 5～10 ℃ in Muffle furnace rises to 600～900 ℃, gets polymer template method silica dioxide granule after grinding with ball mill;
(4) polymer template method silica dioxide granule was evenly mixed 3～5 hours in agitator with the organosilicon modified acrylic ester microemulsion that exists with the turbid liquid mode; Agitator is heated constant temperature to 80 ℃～100 ℃ in advance, make polymer beads in the dispersant fully combine with silica dioxide granule mixed system;
(5) in the mixed system of the 4th step preparation, add modified polyorganosiloxane, temperature keeps more than 100 ℃ stirring 2～4 hours, gets mixture;
(6) said mixture is cooled to normal temperature, and the interpolation emulsifier is even, gets defoaming composition.
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| CN104353265B (en) * | 2014-11-12 | 2016-03-09 | 江苏赛欧信越消泡剂有限公司 | Low consumption environment-friendly type Seawater Desalination Project defoamer |
| CN106868935A (en) * | 2016-12-28 | 2017-06-20 | 广东中联邦精细化工有限公司 | A kind of paper grade (stock) defoamer and preparation method thereof |
| CN108070368B (en) * | 2018-01-18 | 2020-09-29 | 中国石油大学(华东) | Self-emulsifying emulsion and preparation method thereof |
| CN109020299B (en) * | 2018-09-20 | 2021-04-09 | 广东南辉新材料有限公司 | Defoaming agent suitable for polymer cement waterproof mortar and preparation method thereof |
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