CN103145887A - Method and device for preparing microballoons by bi-dispersible inverse suspension polymerization - Google Patents
Method and device for preparing microballoons by bi-dispersible inverse suspension polymerization Download PDFInfo
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- CN103145887A CN103145887A CN2013100732240A CN201310073224A CN103145887A CN 103145887 A CN103145887 A CN 103145887A CN 2013100732240 A CN2013100732240 A CN 2013100732240A CN 201310073224 A CN201310073224 A CN 201310073224A CN 103145887 A CN103145887 A CN 103145887A
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Abstract
The invention discloses a method and a device for preparing microballoons by bi-dispersible inverse suspension polymerization. The first dispersion is carried out in an agitating manner; the particle sizes of the microballoons are determined by the volume ratio of a water phase and an oil phase and the agitating speed; second dispersion is carried out by a gravity sedimentation method; adhesion generated by collision of the microballoons caused by agitation at middle and later periods of the reaction can be effectively avoided without adding a dispersing agent; and the instability of a reaction system is solved from the process and equipment.
Description
Technical field
The present invention relates to a kind of two method and device that disperses inverse suspension polymerization to prepare microballoon, belong to the Preparation of Functional Polymer Microspheres field.
Background technology
The research of polymeric microball material and application development in recent years are very fast, and due to its special size and pattern, polymer microsphere possesses the not available specific function of other materials.Be widely used in the fields such as pharmaceutical carrier, oil production, daily-use chemical industry, environment protection and food-processing.
Inverse suspension polymerization is the method for the comparative maturity of preparation suction microballoon.It is the method for carrying out polymerization water-soluble monomer (or its aqueous solution) is scattered in continuum-oil phase under tensio-active agent exists in.The advantages such as the method has the reaction conditions gentleness, and side reaction is few, and more have superiority than mass polymerization and aqueous solution polymerization on the problems such as heat transfer, stirring, therefore be widely used in polymerisation.Because the inverse suspension polymerization system is unstable, scholars (CN102408505) are by selecting suitable dispersion agent and thickening material to increase the stability of reaction system, and processing condition are strictly controlled, but caking and sticking still phenomenon easily occur, not getting on from technology and equipment really solves.
Summary of the invention
The object of the invention is to provide a kind of two inverse suspension polymerization that disperses to prepare micro-sphere method and preparation facilities, need not dispersion agent and thickening material and can solve microballoon adhesion and sticking still, and preparation facilities is simple in structure, and floor space is little, and production efficiency is high.
The present invention is achieved in that
A kind of two method of disperseing inverse suspension polymerization to prepare microballoon, in ice-water bath or 5-10 ° of C cooling bath, hydrophilic monomer, linking agent and initiator are dissolved in distilled water, are configured to the reaction system of water, described linking agent dosage is 0.025%～1% of hydrophilic monomer total mass; Described initiator dosage is 0.25%～4% of hydrophilic monomer total mass; Described distilled water quality is 3～10 times of monomer total mass; In in 5-10 ° of C cooling bath, the reaction system of water being added drop-wise to the oil phase dispersion medium, the reaction system volume of water accounts for 2%～30% of oil phase dispersion medium volume, stir while dripping, stir speed (S.S.) is 100～600r/min, after dripping end, continue to stir 5-10min, the reaction system of water is dispersed in forms dispersion system for the first time in the oil phase dispersion medium; Above-mentioned dispersion system is injected in the reaction kettle body that the dispersion medium that is heated in advance temperature of reaction is housed, described dispersion medium volume is 4～15 times of dispersion system volume, rely on gravity that the slow sedimentation of microballoon is disperseed for the second time, prevent that stirring violent in reaction process from making microballoon collision adhesion, 40 ℃～80 ℃ of temperature of reaction, reaction times 2～8h; Reaction is opened valve, and with screen cloth, microballoon is separated with dispersion medium after finishing, and then microballoon is cleaned, is dried.
Described method, described oil phase dispersion medium are Viscotrol C or rapeseed oil or soya-bean oil or Semen Maydis oil or peanut oil.
Described method, described reaction kettle body height 2～10m.
Described method, described reaction kettle body internal diameter 5～30cm.
Described method, described reaction kettle body material are polyethylene or polyvinyl chloride or polypropylene.
Be applied to the device in above-mentioned arbitrary described method, comprise cooling tube (11), heating tube (12), thermal insulation layer (13), reaction kettle body (17), cooling tube (11) and heating tube (12) be staggered is wrapped in reaction kettle body (17) outside, changes fast temperature of reaction by cooling and heating; Described reaction kettle body (17) material is polyethylene or polyvinyl chloride or polypropylene; Described reaction kettle body (17) height 2～10m; Described reaction kettle body (17) internal diameter 5～30cm.
Two inverse suspension polymerizations that disperse that the present invention proposes prepare micro-sphere method and preparation facilities, adopt the mode that stirs to disperse for the first time, utilize water and oil phase volume when stirring velocity determine microspherulite diameter, adopt the mode of gravity settling to disperse for the second time, do not need to add dispersion agent can effectively avoid reacting the middle and later periods and produce adhesion because stirring makes microballoon collision, solved the unstable of reaction system from technology and equipment.
Description of drawings
Fig. 1 is preparation facilities kettle structure schematic diagram (sectional side elevation);
Fig. 2 is the SEM figure of microballoon sample 1.
Fig. 3 is the SEM figure of microballoon sample 2
1 temperature controller, 2 temperature sensors, 3 cooling water outlet ends, 4 power end Ι, 5 power end II, 6 entrance of cooling water ends, 7 supports, 8 bases, 9 valves, 10 stationary shaft, 11 cooling tubes, 12 heating tubes, 13 thermal insulation layers, 14 kettle shells, 15 toggle joints, 16 kettle covers, 17 reaction kettle bodies;
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1:
With 20g acrylamide, 0.16g Potassium Persulphate and 0.04g sodium bisulfite (redox initiator), 0.04g N, N-methylene-bisacrylamide (linking agent) is made into reaction system (water) be dissolved in 120g distilled water in 10 ℃ of cooling baths in.Get 1 parts by volume reaction system, be added drop-wise in 10 parts by volume Semen Maydis oils (oil phase), stir 5min in 10 ℃ of cooling baths, stirring velocity is 200r/min, makes reaction system be dispersed into the drop of certain particle diameter in Semen Maydis oil, forms dispersion system.After stirring end, open kettle cover 16, dispersion system is injected the reaction kettle body 17 fill the 70 parts by volume Semen Maydis oils that are heated in advance 50 ℃ (be used for sedimentation disperse), reaction kettle body 17 internal diameter 5cm, height 2.5m can provide enough settling heights for microballoon, guarantees the reaction times, reaction kettle body 17 materials are polyethylene, and this non-polar material can prevent that hydrophilic microballoon from adhering to the still wall.Close kettle cover 16, connect good temperature sensor 2, open temperature controller 1, temperature setting is set to 50 ℃, by 17 heating of 12 pairs of reaction kettle bodies of heating tube, keeps temperature of reaction, the reaction of sedimentation limit, reaction system drop limit was reacted after 3 hours, opened entrance of cooling water end 6, water coolant enters and is wrapped in reaction kettle body 17 cold water pipe 11 on every side, after reaction kettle body 17 is cooled to room temperature, open kettle cover 16, open valve 9, leach microballoon with 400 purpose screen clothes, then reaction kettle body 17 half-twists are cleaned.Microballoon is cleaned, dried, and gained is designated as sample 1, and as shown in Figure 2, as can be seen from the figure, microballoon is without adhesion, and particle diameter is than homogeneous, and median size is 40 μ m.
Embodiment 2:
With 20g acrylamide, 0.16g Potassium Persulphate and 0.04g sodium bisulfite (redox initiator), 0.04g N, N-methylene-bisacrylamide (linking agent) is dissolved in cooling bath in 120g water and is made into reaction system, 1.5 parts of systems are answered in negate, add in 10 portions of Semen Maydis oils, stir 5min in cooling bath, stirring velocity is 250r/min.Stir and finish the rear reactor that fills 70 portions of Semen Maydis oils that injects, temperature setting is set to 50 ℃, reaction 3h, after reaction finishes, open valve, with 400 purpose screen cloth filtering microballoons, and clean, dry, thus obtained microsphere is designated as sample 2, as shown in Figure 3, as can be seen from the figure, microballoon is without adhesion, particle diameter is than homogeneous, and median size is 50 μ m.
Comparison diagram 2 and Fig. 3 as can be known, when water and oil phase volume when stir speed (S.S.) not simultaneously, the thus obtained microsphere particle diameter is also different.
Should be understood that, for those of ordinary skills, can be improved according to the above description or conversion, and all these improve and conversion all should belong to the protection domain of claims of the present invention.
Claims (6)
1. two method of disperseing inverse suspension polymerizations to prepare microballoon, it is characterized in that, in ice-water bath or 5-10 ° of C cooling bath, hydrophilic monomer, linking agent and initiator are dissolved in distilled water, be configured to the reaction system of water, described linking agent dosage is 0.025%～1% of hydrophilic monomer total mass; Described initiator dosage is 0.25%～4% of hydrophilic monomer total mass; Described distilled water quality is 3～10 times of monomer total mass; In in 5-10 ° of C cooling bath, the reaction system of water being added drop-wise to the oil phase dispersion medium, the reaction system volume of water accounts for 2%～30% of oil phase dispersion medium volume, stir while dripping, stir speed (S.S.) is 100～600r/min, after dripping end, continue to stir 5-10min, the reaction system of water is dispersed in forms dispersion system for the first time in the oil phase dispersion medium; Above-mentioned dispersion system is injected in the reaction kettle body that the dispersion medium that is heated in advance temperature of reaction is housed, described dispersion medium volume is 4～15 times of dispersion system volume, rely on gravity that the slow sedimentation of microballoon is disperseed for the second time, prevent that stirring violent in reaction process from making microballoon collision adhesion, 40 ℃～80 ℃ of temperature of reaction, reaction times 2～8h; Reaction is opened valve, and with screen cloth, microballoon is separated with dispersion medium after finishing, and then microballoon is cleaned, is dried.
2. method according to claim 1, is characterized in that, described oil phase dispersion medium is Viscotrol C or rapeseed oil or soya-bean oil or Semen Maydis oil or peanut oil.
3. method according to claim 1, is characterized in that, described reaction kettle body height 2～10m.
4. method according to claim 1, is characterized in that, described reaction kettle body internal diameter 5～30cm.
5. method according to claim 1, is characterized in that, described reaction kettle body material is polyethylene or polyvinyl chloride or polypropylene.
6. be applied to the device in the arbitrary described method of claim 1-5, it is characterized in that, comprise cooling tube (11), heating tube (12), thermal insulation layer (13), reaction kettle body (17), cooling tube (11) and heating tube (12) be staggered is wrapped in reaction kettle body (17) outside, changes fast temperature of reaction by cooling and heating; Described reaction kettle body (17) material is polyethylene or polyvinyl chloride or polypropylene; Described reaction kettle body (17) height 2～10m; Described reaction kettle body (17) internal diameter 5～30cm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360538A (en) * | 2013-07-26 | 2013-10-23 | 上海创始实业（集团）有限公司 | Polymerization device for preparing spherical water-absorbent resin and method of using same to prepare spherical water-absorbent resin |
| CN110862479A (en) * | 2019-12-06 | 2020-03-06 | 南京大学连云港高新技术研究院 | System and method for preparing spherical super absorbent resin by reverse phase suspension method |
| CN111807747A (en) * | 2020-07-27 | 2020-10-23 | 中国石油大学(华东) | Cement water replenishing shrinkage-proof agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829533A (en) * | 2010-04-30 | 2010-09-15 | 镇海石化建安工程有限公司 | Polymer reactor with novel structure |
| CN201669096U (en) * | 2010-04-30 | 2010-12-15 | 镇海石化建安工程有限公司 | Polymerization reactor with novel structure |
| CN102408505A (en) * | 2011-10-12 | 2012-04-11 | 浙江卫星石化股份有限公司 | Method for preparing super absorbent resin by inverse suspension polymerization |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829533A (en) * | 2010-04-30 | 2010-09-15 | 镇海石化建安工程有限公司 | Polymer reactor with novel structure |
| CN201669096U (en) * | 2010-04-30 | 2010-12-15 | 镇海石化建安工程有限公司 | Polymerization reactor with novel structure |
| CN102408505A (en) * | 2011-10-12 | 2012-04-11 | 浙江卫星石化股份有限公司 | Method for preparing super absorbent resin by inverse suspension polymerization |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360538A (en) * | 2013-07-26 | 2013-10-23 | 上海创始实业（集团）有限公司 | Polymerization device for preparing spherical water-absorbent resin and method of using same to prepare spherical water-absorbent resin |
| CN110862479A (en) * | 2019-12-06 | 2020-03-06 | 南京大学连云港高新技术研究院 | System and method for preparing spherical super absorbent resin by reverse phase suspension method |
| CN111807747A (en) * | 2020-07-27 | 2020-10-23 | 中国石油大学(华东) | Cement water replenishing shrinkage-proof agent and preparation method and application thereof |
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| CN103145887B (en) | 2015-02-25 |
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