CN105366980A - Method for preparing polymer coated rust inhibitor micro-capsule through spray drying - Google Patents
Method for preparing polymer coated rust inhibitor micro-capsule through spray drying Download PDFInfo
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- CN105366980A CN105366980A CN201510741140.9A CN201510741140A CN105366980A CN 105366980 A CN105366980 A CN 105366980A CN 201510741140 A CN201510741140 A CN 201510741140A CN 105366980 A CN105366980 A CN 105366980A
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- water
- microcapsule
- spray
- rust inhibitor
- resistance rust
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/61—Corrosion inhibitors
Abstract
The invention discloses a method for preparing a polymer coated rust inhibitor micro-capsule through spray drying. The method includes the following steps that film-forming polymers are dissolved in an organic solvent, surfactant is added, and the mixture is stirred to be uniform; water-soluble rust inhibitor is dissolved in water, and a rust inhibitor saturated water solution is formed; the solutions formed in the former two steps are mixed and placed in an ultrasonic disperser for ultrasonic dispersion; dispersed liquid is emulsified, and uniform oil coated water emulsion is formed; the prepared oil coated water emulsion is subjected to spray drying through a spray drier, and the polymer coated rust inhibitor micro-capsule is formed. Full dispersion and emulsification are conducted before spray, the stable oil coated water emulsion is formed and does not layer or settle in the spray process, and therefore micro-capsule particles formed through spray are uniform and high in encapsulation rate.
Description
[technical field]
The present invention relates to the preparation method of water-soluble resistance rust thing microcapsule, particularly relate to a kind of method that spraying dry prepares polymer wrapped resistance rust thing microcapsule.
[background technology]
The corrosion of reinforcing bar becomes the main factor of world today's impact building weather resistance, and the use of rust inhibitor is a kind of direct, effective, simple anti-corrosion measure.The U.S. will adopt reinforcing steel bar corrosion inhibitor as current techique measure, " be even unique safeguard procedures in some new construction." be loaded with provision about using reinforcing steel bar corrosion inhibitor in U.S.'s related design standard (NACERPO187-87) specially.The Soviet Union is mainly used in Industrial buildings (comprising nuclear power plant), has the engineering example of more than 30 year; Japan is mainly used in the situation and the marine building that use extra large sand.Reinforcing steel bar corrosion inhibitor is used in the construction of Okinawa power plant engineering for 1973 by Japan first, respond well so far.The research and apply of China's reinforcing steel bar corrosion inhibitor is started late, large-scale priority project (San-Shan-Dao Gold Mine) application in the whole nation first in 1985.In addition, rust inhibitor can also be used for the anticorrosion of metal in other place, as building roof, subsea equipment and mine etc.
In the use procedure of rust inhibitor now, because the inorganic rust inhibitor of major part and organic rust inhibitor are water-soluble, at concrete maintaining setting up period, these mix steel bar rust inhibitor and outflow with water seriously, waste larger.Build up several years ago at buildings; generally can not there is corrosion in the reinforcing bar in concrete, and start to occur corrosion at reinforcing bar, when needing reinforcing steel bar corrosion inhibitor to play a role in high alkali environment; water-soluble reinforcing steel bar corrosion inhibitor major part with water diffusion, does not have the provide protection to reinforcing bar.In addition, these water-soluble rust inhibitors are also inconvenient directly uses in coating.
The rust inhibitor water-soluble for some and toxicity is larger, as calcium nitrite, mainly adopt the construction technology of mixing concrete surface, this constructional method also exists the drawbacks such as service efficiency is lower, addition is larger, poisonous.And some rust inhibitors when using in concrete, mainly adopt the construction technology of concrete surface brushing solution, as environment-protecting asepsis rust inhibitor sodium monoflurophosphate, this constructional method also exists the drawbacks such as reverse osmosis effect, infiltration direction are single, easy loss.
For many defects that these water-soluble larger rust inhibitors exist in use, people propose to adopt microcapsule coated technology to improve the water tolerance of rust inhibitor, delay its release.When concrete construction does not need resistance rust in early days, due to the protection of capsule outer walls water-proof material, rust inhibitor is delayed release; Under high alkalinity concrete corrosion, capsule outer walls material decomposes gradually, and coated rust inhibitor is released slowly in concrete, continues to play the effect of resistance rust, improves resistance rust effect.
The discloseder microcapsule corrosion inhibitor of existing data, as the emulsion polymerisation process such as ChoiH prepare the protection of polystyrene/trolamine Nano capsule for metallic coating, urea-formaldehyde resin/CeO that the people such as SelvakumarN adopt situ aggregation method to prepare
2/ Cr
2o
3microcapsule, there is the effect delaying metallic corrosion and self-healing, the people such as Jia Fang describe the preparation method of the controlled release formulation of capsule for oil field system, cyst material and slowly-releasing performance evaluation, point out that usual microcapsule corrosion inhibitor cyst material used is only limitted to ethyl cellulose, gelatin, alginate calcium, polyvinyl alcohol etc.
The people such as Kuang Fei take alginate calcium as cyst material, and utilize oil-phase separating method and orifice-precipitation bath legal system for Sodium Nitrite microcapsule, applied environment is the NaCl solution of concentration 3.5%; In 60 hours, capsule-core just discharges completely, and the microcapsule resistance rust phase is too short, and alginate calcium is too low as wall material intensity, is not suitable for concrete system.The people such as Qi Xiuling prepare microcapsule with the coated inhibiter Sodium Nitrite of ethyl cellulose and thiocarbamide, and application system is 3.5%NaCl solution and 0.1mol/LH
2sO
4solution, microcapsule discharged completely in 24 hours, did not relate to the service condition of microcapsule under concrete strong alkali environment.The people such as MacA utilize multiphase emulsion legal system for the microcapsule of the coated sodium dichromate 99 of polystyrene, can be observed smooth, continuous print outer wall pattern by scanning electron microscope.The preparation method of above-mentioned microcapsule rust inhibitor all also exists complicated process of preparation, preparation efficiency is lower and cost is higher problem.
Korean Patent KR1317645 prepares a kind of etch-proof multilayer film, and wherein bottom on metal, applies benzene for pentadecanoic acid inhibiter, and then applies the coating that one deck comprises polyurethane microcapsule.A kind of method that US Patent No. 7790225 describes film carries out the anticorrosion of metal, comprises wherein homodisperse microcapsule corrosion inhibitor in film, but and the preparation method of not mentioned microcapsule corrosion inhibitor.In Chinese patent literature CN102517587A, CN102517590A, CN102953068A, adopt extrude-round as a ball and method that is dressing prepares the coated calcium nitrite microcapsule of ethyl cellulose respectively, the coated sodium monoflurophosphate microcapsule of polyacrylic, polystyrene type, by polymers soln by spray coating process will extrude-round as a ball core material particles is coated, its particle diameter is 400-800 μm, and the effect of microcapsule resistance rust is prepared from microcosmic and macroscopically analyzing, obtain certain effect, but the Microcapsules Size of preparation is comparatively large, the problems such as technique is comparatively complicated.
Spray-drying process is the coated hydrophilic and hydrophobic substance of the conventional one of medicine and food service industry, prepares microcapsule relative to multiphase emulsion method and extrusion-spheronization, has that production efficiency is high, throughput large, directly becomes powder and the easy advantage such as replacing wall material.The microcapsule that Chinese patent literature CN103833256A proposes to adopt poor solvent liberation method or spray-drying process to prepare a kind of chlorion to be triggered, this microcapsule wall material is the polymkeric substance of coated cuprous chloride solid particulate, and core is chlorion absorption agent or reinforcing steel bar corrosion inhibitor.But chlorion absorption agent described is in the method and is slightly soluble in water or water-fast, when water-in-oil solution spray is dry, because the situation of particle plugging shower nozzle often can occur comparatively greatly particle, do not reach the object of coated rust-preventive agent.
[summary of the invention]
It is comparatively even that the technical problem to be solved in the present invention is to provide a kind of particle, and the spraying dry that embedding rate is high prepares the method for polymer wrapped resistance rust thing microcapsule.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is, a kind of spraying dry prepares the method for polymer wrapped resistance rust thing microcapsule, comprises the following steps:
101, film-forming polymer is dissolved in organic solvent, adds tensio-active agent and stir;
102, by soluble in water for water-soluble resistance rust thing, the saturated aqueous solution of resistance rust thing is formed;
103, the solution that solution step 101 formed and step 102 are formed mixes, and puts into ultrasonic dispersers and carries out ultrasonic disperse;
104, emulsification is carried out to the liquid disperseed in step 103, form uniform water-in-oil emulsion;
105, with spray-drier, spraying dry is carried out to the water-in-oil emulsion that step 104 is formed, make polymer wrapped resistance rust thing microcapsule.
Above-described method, be 100 parts to hinder the quality of rust thing, film-forming polymer is 12-200 mass parts, and tensio-active agent is 0.3-2.5 mass parts, and organic solvent is 700-2000 mass parts.
Above-described method, described resistance rust thing is sodium monoflurophosphate, calcium nitrite or other water-soluble resistance rust things, described tensio-active agent is one or more in sorbester p17, sorbester p18, polysorbate60 or sodium lauryl sulphate, and described organic solution is at least one in methylene dichloride, trichloromethane, ethyl acetate, ethanol and acetone.
Above-described method, described film-forming polymer is the one in poly(lactic acid), ethyl cellulose, polymethylmethacrylate or polystyrene, and film-forming polymer consumption is 40-200 mass parts.
The present invention disperses fully and emulsification before spraying, forms stable water-in-oil emulsion, and emulsion can not layering and sedimentation in spray process, and the microcapsule granule that formed of therefore spraying is comparatively even, and embedding rate is high.
[embodiment]
Embodiment 1:
1. raw material:
Sodium monoflurophosphate (toothpaste level, Hubei Xing Fa Chemical Group company limited): 16.8g;
Sorbester p17 (chemical pure, Guangdong, Guangdong emigrant's reagent plastics company limited): 0.1g;
Poly(lactic acid) (injection grade, Shenzhen brilliance great achievement Industrial Co., Ltd.): 7.2g;
Methylene dichloride (chemical pure, Xilong Chemical Co., Ltd), 160mL (212g);
Distilled water: 40g.
2. equipment:
Magnetic stirring apparatus, homogeneous stirrer, spray-drier (airflow atomizing formula), air compressor
3. preparation technology:
I, poly(lactic acid) is added methylene dichloride stirring and dissolving in a reservoir, then add tensio-active agent sorbester p17; Sodium monoflurophosphate is added water and is made into saturated solution in a reservoir, abundant stirring and dissolving.
II, by PLA solution and the mixing of sodium monoflurophosphate saturated solution, ultrasonic dispersers dispersion 10 minutes is put into.
III, scattered mixed solution stirring and emulsifying 10 minutes (1 × 10 in homogeneous stirrer
4rpm), the stable water-in-oil emulsion that is uniformly dispersed is formed.
IV, spraying dry is carried out to water-in-oil emulsion spray-drier, emulsion enters from the sebific duct of peristaltic pump, from nozzle at high speeds ejection, wherein inlet temperature is inlet temperature 40 DEG C, atomizing pressure 0.5Mpa, flow velocity 30mL/ minute), obtain polymer wrapped resistance rust thing microcapsule.
V, the microcapsule of preparation are repeatedly washed, and dry in vacuum drying oven.
Embodiment 2:
1. raw material:
Sodium monoflurophosphate (toothpaste level, Hubei Xing Fa Chemical Group company limited): 8.4g;
Sorbester p18 (chemical pure, Guangdong, Guangdong emigrant's reagent plastics company limited): 0.2g;
Ethyl cellulose (Guangzhou Dao Jun Chemical Industry Science Co., Ltd, N-50): 14.6g;
Acetone (chemical pure, Xilong Chemical Co., Ltd), 180mL (141.84g);
Distilled water: 20g.
2. experimental installation:
Magnetic stirring apparatus, homogeneous stirrer, spray-drier, air compressor
3. preparation technology:
I, ethyl cellulose is dissolved in acetone, then add tensio-active agent sorbester p18; Sodium monoflurophosphate is dissolved in the water, is made into saturated solution, abundant stirring and dissolving.
II, by ethyl cellulose solution and the mixing of sodium monoflurophosphate saturated solution, ultrasonic disperse 10 minutes.
III, scattered mixed solution was homogeneous stirrer emulsification 10 minutes (1 × 10
4rpm), the stable water-in-oil emulsion that is uniformly dispersed is formed.
IV, spraying dry is carried out to water-in-oil emulsion, when spray drying parameters is inlet temperature 60 DEG C, atomizing pressure 0.3Mpa, flow velocity 20mL/ minute, carry out spraying dry, obtain polymer wrapped resistance rust thing microcapsule.
V, by the microcapsule of preparation, repeatedly wash and drying.
Embodiment 3:
1. raw material:
Sodium monoflurophosphate (toothpaste level, Hubei Xing Fa Chemical Group company limited): 16.8g;
Tween 80 (chemical pure, Guangdong, Guangdong emigrant's reagent plastics company limited): 0.1g;
Polymethylmethacrylate (Taiwan is very beautiful, CM203): 14.6g;
Ethyl acetate (chemical pure, Xilong Chemical Co., Ltd), 160mL (143.52g);
Distilled water: 40g.
2. experimental installation:
Magnetic stirring apparatus, homogeneous stirrer, spray-drier, air compressor
3. preparation technology:
I, polymethylmethacrylate is dissolved in ethyl acetate, then adds surface active agent tween 80; Sodium monoflurophosphate is dissolved in the water, is made into saturated solution, abundant stirring and dissolving.
II, by polymethylmethacrylate and the mixing of sodium monoflurophosphate saturated solution, ultrasonic disperse 10 minutes.
III, scattered mixed solution was homogeneous stirrer emulsification 10 minutes (1 × 10
4rpm), the stable water-in-oil emulsion that is uniformly dispersed is formed.
IV, spraying dry is carried out to water-in-oil emulsion, when spray drying parameters is inlet temperature 80 DEG C, atomizing pressure 0.3Mpa, flow velocity 20mL/ minute, carry out spraying dry, obtain polymer wrapped resistance rust thing microcapsule.
V, by the microcapsule of preparation, repeatedly wash and drying.
Embodiment 4:
1. raw material:
Calcium nitrite (chemical pure): 33.8g;
Sorbester p17 (chemical pure, Guangdong, Guangdong emigrant's reagent plastics company limited): 0.1g;
Polystyrene (Zhenjiang is very beautiful, GPPS-PG33): 4.8g;
Trichloromethane (chemical pure, Xilong Chemical Co., Ltd), 160mL (270 grams);
Distilled water: 40g.
2. experimental installation:
Magnetic stirring apparatus, homogeneous stirrer, spray-drier, air compressor
3. preparation technology:
I, polystyrene is dissolved in trichloromethane, then adds tensio-active agent sorbester p17; Calcium nitrite is dissolved in the water, is made into saturated solution, abundant stirring and dissolving.
II, by polystyrene solution and the mixing of calcium nitrite saturated solution, ultrasonic disperse 10 minutes.
III, scattered mixed solution was homogeneous stirrer emulsification 10 minutes (1 × 10
4rpm), the stable water-in-oil emulsion that is uniformly dispersed is formed.
IV, spraying dry is carried out to water-in-oil emulsion, when spray drying parameters is inlet temperature 60 DEG C, atomizing pressure 0.5Mpa, flow velocity 30mL/ minute, carry out spraying dry, obtain polymer wrapped resistance rust thing microcapsule.
V, by the microcapsule of preparation, repeatedly wash and drying.
Embodiment 5:
1. raw material:
Calcium nitrite (chemical pure): 16.9g;
Sodium lauryl sulphate (chemical pure, Guangdong, Guangdong emigrant's reagent plastics company limited): 0.05g;
Polystyrene (Zhenjiang is very beautiful, GPPS-PG33): 4.8g;
Methylene dichloride (chemical pure, Xilong Chemical Co., Ltd), 180mL (238.5g);
Distilled water: 20g.
2. experimental installation:
Magnetic stirring apparatus, homogeneous stirrer, spray-drier, air compressor
3. preparation technology:
I, polystyrene is dissolved in methylene dichloride, then adds Surfactant SDS; Calcium nitrite is dissolved in the water, is made into saturated solution, abundant stirring and dissolving.
II, by polystyrene solution and the mixing of calcium nitrite saturated solution, ultrasonic disperse 10 minutes.
III, scattered mixed solution was homogeneous stirrer emulsification 10 minutes (1 × 10
4rpm), the stable water-in-oil emulsion that is uniformly dispersed is formed.
IV, spraying dry is carried out to water-in-oil emulsion, when spray drying parameters is inlet temperature 50 DEG C, atomizing pressure 0.5Mpa, flow velocity 30mL/ minute, carry out spraying dry, obtain polymer wrapped resistance rust thing microcapsule.
V, by the microcapsule of preparation, repeatedly wash and drying.
Owing to disperseing fully and emulsification before spraying, form stable water-in-oil emulsion, emulsion can not layering and sedimentation in spray process, and the microcapsule granule that formed of therefore spraying is comparatively even, and embedding rate is high.
The component concentration table of table 1: embodiment 1-5
The embedding rate of the microcapsule that table 2 embodiment 1-5 obtains
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Embedding rate (%) | 50.1 | 27.4 | 38.8 | 32.6 | 21.1 |
The measuring method of embedding rate: get the powdery microcapsule rust inhibitor that 20 grams of spraying dry obtain, with acetic acid ethyl dissolution in a reservoir, then the distilled water of 50 milliliters is added, rust inhibitor coated in microcapsule is made to dissolve in distilled water, with the fluorinion concentration in ion chromatography distilled water, namely obtain the content of sodium monoflurophosphate in 20 grams of microcapsule.Embedding rate obtains according to following formulae discovery:
Actual embedding medicinal content is contained drug content in the 20 grams of microcapsule recorded, and theoretical embedding medicinal content is the ratio dropping into the quality of sodium monoflurophosphate and the total mass of polymkeric substance and sodium monoflurophosphate.
Microcapsule prepared by the table 3 embodiment 1-5 rate of release in simulation concrete solution
The definition of rate of release: microcapsule during use, the quality of the core-clad material discharged in the unit time.
The measuring method of rate of release: get the powdery microcapsule rust inhibitor that 50 grams of spraying dry obtain, be immersed in (saturated aqua calcis+3.5% sodium-chlor) in 200 milliliters of simulated seawater concrete solutions, get 5 milliliters of soak solutions in different soak times, supplement the saturated aqua calcis of equal volume simultaneously.The calcium ion be easy in saturated aqua calcis due to the fluorion discharged forms precipitation, therefore can not characterize the rate of release of resistance rust thing with the change of fluorion.Therefore use sodium ion (embodiment 1-3) concentration in ion chromatography simulated solution and nitrite ion concentration (embodiment 4-5), the difference of measured ionic concn and this ion original concentration is multiplied by liquor capacity and is the resistance discharged in microcapsule and becomes rusty the amount of thing.The per-cent that the quality of release resistance rust thing accounts for total mass is release percentage composition.
Claims (4)
1. spraying dry prepares a method for polymer wrapped resistance rust thing microcapsule, it is characterized in that, comprises the following steps:
101, film-forming polymer is dissolved in organic solvent, adds tensio-active agent and stir;
102, by soluble in water for water-soluble resistance rust thing, the saturated aqueous solution of resistance rust thing is formed;
103, the solution that solution step 101 formed and step 102 are formed mixes, and puts into ultrasonic dispersers and carries out ultrasonic disperse;
104, emulsification is carried out to the liquid disperseed in step 103, form uniform water-in-oil emulsion;
105, with spray-drier, spraying dry is carried out to the water-in-oil emulsion that step 104 is formed, make polymer wrapped resistance rust thing microcapsule.
2. method according to claim 1, is characterized in that, be 100 parts to hinder the quality of rust thing, film-forming polymer is 12-200 mass parts, and tensio-active agent is 0.3-2.5 mass parts, and organic solvent is 700-2000 mass parts.
3. method according to claim 1 and 2, it is characterized in that, described resistance rust thing is sodium monoflurophosphate, calcium nitrite or other water-soluble resistance rust things, described tensio-active agent is one or more in sorbester p17, sorbester p18, polysorbate60 or sodium lauryl sulphate, and described organic solution is at least one in methylene dichloride, trichloromethane, ethyl acetate, ethanol and acetone.
4. method according to claim 2, is characterized in that, described film-forming polymer is the one in poly(lactic acid), ethyl cellulose, polymethylmethacrylate or polystyrene, and film-forming polymer consumption is 40-200 mass parts.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862239A (en) * | 2019-12-23 | 2020-03-06 | 深圳大学 | Chloride ion triggered self-repairing aggregate and preparation method thereof |
| CN110975774A (en) * | 2019-12-25 | 2020-04-10 | 山东圣泉新材料股份有限公司 | Polymer microsphere and preparation method and application thereof |
| CN112471441A (en) * | 2020-11-19 | 2021-03-12 | 安徽靳氏食品有限公司 | Method for pickling salted duck eggs with high oil yield |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862239A (en) * | 2019-12-23 | 2020-03-06 | 深圳大学 | Chloride ion triggered self-repairing aggregate and preparation method thereof |
| CN110975774A (en) * | 2019-12-25 | 2020-04-10 | 山东圣泉新材料股份有限公司 | Polymer microsphere and preparation method and application thereof |
| CN110975774B (en) * | 2019-12-25 | 2021-12-17 | 山东圣泉新材料股份有限公司 | Polymer microsphere and preparation method and application thereof |
| CN112471441A (en) * | 2020-11-19 | 2021-03-12 | 安徽靳氏食品有限公司 | Method for pickling salted duck eggs with high oil yield |
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