CN102391710A - Self-repairing microcapsule used for metal anticorrosion coating and preparation method thereof - Google Patents
Self-repairing microcapsule used for metal anticorrosion coating and preparation method thereof Download PDFInfo
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- CN102391710A CN102391710A CN2011102617483A CN201110261748A CN102391710A CN 102391710 A CN102391710 A CN 102391710A CN 2011102617483 A CN2011102617483 A CN 2011102617483A CN 201110261748 A CN201110261748 A CN 201110261748A CN 102391710 A CN102391710 A CN 102391710A
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Abstract
The invention discloses a self-repairing microcapsule used for a metal anticorrosion coating and a preparation method thereof, which belong to the technical field of self-repairing materials. The wall material of the self-repairing microcapsule is urea resin, the core material of the self-repairing microcapsule is natural plant oil, and the self-repairing microcapsule is prepared with a one-step in-situ polymerization method. The natural plant oil has the advantages of wide source and low cost and is easy to obtain. The metal anticorrosion coating is coated on the surface of metal to form an anticorrosion coating. Microcracks appear in the long-term use process, the self-repairing microcapsule embedded in the coating is broken by external force, and released natural plant oil and oxygen in the air can directly generate crosslinking polymerization reaction without catalysts to repair the microcracks to prevent the surface of the metal from being further corroded. The self-repairing microcapsule synthetized by the core material substance has the advantages of good mechanical performance, simple preparation technology and low cost and can be widely applied to the self repairing of metal anticorrosion coatings, such as automobile industry, ship industry and the like.
Description
Technical field
The present invention relates to the self-repair material technical field, particularly a kind of self-repairing microcapsule that is used for metal anti-corrosive paint and preparation method thereof.
Background technology
One of major technique of control metallic corrosion is to form corrosion through cover one deck organic or inorganic metal anti-corrosive paint in the metallic surface to prevent extraneous corrosive medium contacting metal surface.Anti-corrosive metal coating in secular use owing to receive the influence of physical impact, temperature alternating, factor such as aging; Easily at the inner tiny crack that forms of coating; Crackle extends expansion gradually is exposed in atmospheric steam and the oxygen atmosphere metallic surface; Peeling off of aggravation coating reduced the use properties of coating.Except local corrosion, be coated with requirement again the surface is carried out Local treatment and reduced thickness, can increase cost and the work-ing life of reducing metal undoubtedly.
In recent years, the microencapsulation material with self-repair function obtains extensive concern, and it can need not to detect the inner crackle that produces of repair materials automatically under any extraneous artificial situation about getting involved.Microcapsulary is that a kind of polymeric membrane in solid or the stable performance of liquid particle surface coating one deck forms the composite technology with nucleocapsid structure.Self-repairing microcapsule is imbedded in the matrix; After matrix produces tiny crack; Cause being imbedded at inner self-repairing microcapsule and broken by external force, discharge core, under syphonic effect, repair crack surface with the catalyzer generation cross-linking polymerization of imbedding in advance in the matrix; Prevent that tiny crack from further expanding, realize selfreparing.Patent No. CN101659719A, US6518330, the disclosed self-repairing microcapsule of US7108914; The core that when breaking, discharges has randomness with contacting of catalyzer; Core is polymerization reaction take place all, reduces the selfreparing efficient of material, has increased the preparation difficulty of self-repair material; The high activated catalyst source is narrower simultaneously, costs an arm and a leg, and instability is prone to affected by environment and inactivation.In addition, the in-situ polymerization fado of preparation microcapsule is a two-step approach, and promptly addition reaction takes place under weak basic condition earlier wall material monomer, and the back under solutions of weak acidity polycondensation takes place, complex process, and time consumption and energy consumption is difficult to realize scale operation.
Summary of the invention
The objective of the invention is defective to prior art; A kind of self-repairing microcapsule that is used for metal anti-corrosive paint and preparation method thereof is provided; The self-repairing microcapsule of this method preparation has characteristics such as preparation technology is simple, cost is low, can be widely used in the selfreparing of metal anti-corrosive paints such as automotive industry and shipping industry.
The object of the invention is realized through following technical scheme:
A kind of self-repairing microcapsule that is used for metal anti-corrosive paint, said wall material is a urea-formaldehyde resin, said core is a crude vegetal.
At the above-mentioned self-repairing microcapsule that is used for metal anti-corrosive paint, described crude vegetal is more than one of tung oil, oleum lini, Chinese catalpa oil, perilla oil, cannabis oil, soya-bean oil, safflower oil, Trisun Oil R 80, oleum gossypii seminis, Oleum Cocois, Semen Maydis oil, Rice pollard oil.
Preparation process at the above-mentioned self-repairing microcapsule that is used for metal anti-corrosive paint comprises:
(1) emulsifying agent, urea are added in the deionized water;
(2) regulator solution pH is 2.00～3.50, and acidifying 30～180 min add skimmer;
(3) be under 1500～10000 r/min conditions at rotating speed, add crude vegetal emulsification 5 ~ 50min, form stable emulsion;
(4) under 40 ~ 80 ℃ of mechanical stirring, add formaldehyde, reaction 2～6h; Reaction product after washing, suction filtration, vacuum-drying, is obtained the self-repairing microcapsule product.
The preparation method who is used for the self-repairing microcapsule of metal anti-corrosive paint is characterized in that reaction process is a step in-situ polymerization.Said emulsifying agent consumption accounts for gross weight 0.01 ~ 3%; Said urea consumption accounts for gross weight 1 ~ 2%; Said skimmer consumption accounts for gross weight 0.01 ~ 1%; Said crude vegetal consumption accounts for gross weight 0.5% ~ 15%; Said formaldehyde consumption accounts for gross weight 1 ~ 2%; Surplus is a deionized water.
The self-repairing microcapsule that is used for metal anti-corrosive paint that makes, its core wall is than being 1:5 ~ 5:1, particle diameter is 1 ~ 1000 μ m.
Compared with prior art, the present invention has following beneficial effect:
(1) core of self-repairing microcapsule adopts crude vegetal, and wide material sources are cheap and easy to get, adopts the self-repairing microcapsule of this type core material preparation to have the favorable mechanical performance.
(2) crude vegetal that discharges behind the microcapsules rupture need not catalyzer can be directly and airborne oxygen polymerization reaction take place, repairs crack surface, prevents that tiny crack from further expanding, and realizes selfreparing, helps improving the selfreparing efficient of material.
(3) adopt the self-repairing microcapsule of step situ aggregation method preparation to improve two-step process defective in the past, have characteristics such as preparation technology is simple, cost is low, can be widely used in the selfreparing of metal anti-corrosive paints such as automotive industry and shipping industry.
Description of drawings
Fig. 1 is the optical microscope photograph of the self-repairing microcapsule for preparing of the present invention.
Fig. 2 is the size distribution figure of the self-repairing microcapsule for preparing of the present invention.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is done further to describe, but be not subject to these embodiment.
Embodiment 1
With 0.78g emulsifier op-10,5g urea, be dissolved in the 260 ml deionized waters; Regulator solution pH is 2.50, acidifying 90 min; Add 0.05g skimmer n-Octanol; At rotating speed is under the 3000 r/min conditions, adds 9.69g tung oil, and emulsification 15min forms stable emulsion; Under 70 ℃ of mechanical stirring, add 4.69g formaldehyde, reaction 4h; Through washing, suction filtration after the vacuum-drying, obtains the self-repairing microcapsule product with reaction product.Preparation gained microcapsule median size is 26.25 μ m, and core content is 62.3%.
With 0.97g emulsifying agent X 2073,5g urea, be dissolved in the 260 ml deionized waters; Regulator solution pH is 3.00, acidifying 120 min; Add 0.1g skimmer n-Octanol; At rotating speed is under the 5000 r/min conditions, adds the 19.38g oleum lini, and emulsification 30min forms stable emulsion; Under 70 ℃ of mechanical stirring, add 4.69g formaldehyde, reaction 4h; Through washing, suction filtration after the vacuum-drying, obtains the self-repairing microcapsule product with reaction product.Preparation gained microcapsule median size is 20.28 μ m, and core content is 78.9%.
With 1.16g emulsifier tween 80,5g urea, be dissolved in the 260 ml deionized waters; Regulator solution pH is 2.50, acidifying 120 min; Add 0.01g skimmer n-Octanol; At rotating speed is under the 7000 r/min conditions, and adding weight ratio is soya-bean oil and the composite 19.38g altogether of Trisun Oil R 80 of 1:1, and emulsification 40min forms stable emulsion; Under 70 ℃ of mechanical stirring, add 4.69g formaldehyde, reaction 4h; Through washing, suction filtration after the vacuum-drying, obtains the self-repairing microcapsule product with reaction product.Preparation gained microcapsule median size is 20.12 μ m, and core content is 75.2%.
Claims (5)
1. a self-repairing microcapsule that is used for metal anti-corrosive paint is characterized in that the wall material is a urea-formaldehyde resin, and core is a crude vegetal.
2. the self-repairing microcapsule that is used for metal anti-corrosive paint as claimed in claim 1; It is characterized in that said crude vegetal is more than one in tung oil, oleum lini, Chinese catalpa oil, perilla oil, cannabis oil, soya-bean oil, safflower oil, Trisun Oil R 80, oleum gossypii seminis, Oleum Cocois, Semen Maydis oil, the Rice pollard oil.
3. the method for preparing self-repairing microcapsule as claimed in claim 1 is characterized in that may further comprise the steps:
(1) emulsifying agent, urea are added in the deionized water;
(2) regulator solution pH is 2.00～3.50, and acidifying 30～180 min add skimmer;
(3) be under 1500～10000 r/min conditions at rotating speed, add crude vegetal emulsification 5 ~ 50min, form stable emulsion;
(4) under 40 ~ 80 ℃ of mechanical stirring, add formaldehyde, reaction 2～6h; Reaction product after washing, suction filtration, vacuum-drying, is obtained the self-repairing microcapsule product.
4. the preparation method who is used for the self-repairing microcapsule of metal anti-corrosive paint as claimed in claim 3 is characterized in that reaction process is a step in-situ polymerization.
5. the preparation method who is used for the self-repairing microcapsule of metal anti-corrosive paint as claimed in claim 4 is characterized in that said emulsifying agent consumption accounts for gross weight 0.01 ~ 3%; Said urea consumption accounts for gross weight 1 ~ 2%; Said skimmer consumption accounts for gross weight 0.01 ~ 1%; Said crude vegetal consumption accounts for gross weight 0.5% ~ 15%; Said formaldehyde consumption accounts for gross weight 1 ~ 2%; Surplus is a deionized water.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014032130A1 (en) * | 2012-08-29 | 2014-03-06 | Petróleo Brasileiro S.A. - Petrobras | Additives for self-regeneration of epoxy coatings |
| CN103897471A (en) * | 2014-02-24 | 2014-07-02 | 中南民族大学 | Linseed oil microcapsules capable of quickly forming films to timely repair scratches and preparation method thereof |
| CN104147987A (en) * | 2014-08-05 | 2014-11-19 | 叶氏化工研发（上海）有限公司 | Preparation method for microcapsules coating air-drying film forming material |
| CN107723609A (en) * | 2017-11-29 | 2018-02-23 | 宁波市鄞州龙腾工具厂 | A kind of ventilator cowling |
| WO2018040251A1 (en) * | 2016-08-29 | 2018-03-08 | 江苏金陵特种涂料有限公司 | Photoinitiated repairing microcapsule preparation method |
| CN108219610A (en) * | 2017-12-19 | 2018-06-29 | 常州市阿曼特化工有限公司 | A kind of impervious exterior wall latex paint of crack resistence |
| CN108395657A (en) * | 2018-01-16 | 2018-08-14 | 清华大学 | A kind of self-repair type self-lubricating material and preparation method thereof |
| CN108579627A (en) * | 2018-04-23 | 2018-09-28 | 吉林大学 | For naval vessel seawater pipe anticorrosion selfreparing micro-nano capsule and preparation method |
| CN108727908A (en) * | 2018-05-25 | 2018-11-02 | 万玉梅 | A kind of marble surface dedicated liquid protection membrane preparation method |
| CN109135403A (en) * | 2018-08-10 | 2019-01-04 | 西安交通大学 | A kind of selfreparing water paint and preparation method thereof based on PU/PUF microcapsules and PCL microcapsules |
| CN111808468A (en) * | 2020-06-05 | 2020-10-23 | 中国科学院金属研究所 | Small-size urea formaldehyde microcapsule, preparation and application in self-repairing coating |
| CN112547465A (en) * | 2020-10-27 | 2021-03-26 | 吉林大学 | Spraying method of anticorrosive paint for outer surface of marine pipeline of ship |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014032130A1 (en) * | 2012-08-29 | 2014-03-06 | Petróleo Brasileiro S.A. - Petrobras | Additives for self-regeneration of epoxy coatings |
| CN104640939A (en) * | 2012-08-29 | 2015-05-20 | 巴西石油公司 | Additives for self-regeneration of epoxy coatings |
| CN103897471A (en) * | 2014-02-24 | 2014-07-02 | 中南民族大学 | Linseed oil microcapsules capable of quickly forming films to timely repair scratches and preparation method thereof |
| CN103897471B (en) * | 2014-02-24 | 2015-08-12 | 中南民族大学 | Energy fast filming oleum lini minigel repairing cut in time and preparation method thereof |
| CN104147987A (en) * | 2014-08-05 | 2014-11-19 | 叶氏化工研发（上海）有限公司 | Preparation method for microcapsules coating air-drying film forming material |
| WO2018040251A1 (en) * | 2016-08-29 | 2018-03-08 | 江苏金陵特种涂料有限公司 | Photoinitiated repairing microcapsule preparation method |
| CN107723609A (en) * | 2017-11-29 | 2018-02-23 | 宁波市鄞州龙腾工具厂 | A kind of ventilator cowling |
| CN108219610B (en) * | 2017-12-19 | 2020-04-10 | 江门市肇和制漆化工有限公司 | Anti-cracking and anti-permeability exterior wall emulsion paint |
| CN108219610A (en) * | 2017-12-19 | 2018-06-29 | 常州市阿曼特化工有限公司 | A kind of impervious exterior wall latex paint of crack resistence |
| CN108395657A (en) * | 2018-01-16 | 2018-08-14 | 清华大学 | A kind of self-repair type self-lubricating material and preparation method thereof |
| CN108579627A (en) * | 2018-04-23 | 2018-09-28 | 吉林大学 | For naval vessel seawater pipe anticorrosion selfreparing micro-nano capsule and preparation method |
| CN108727908A (en) * | 2018-05-25 | 2018-11-02 | 万玉梅 | A kind of marble surface dedicated liquid protection membrane preparation method |
| CN109135403A (en) * | 2018-08-10 | 2019-01-04 | 西安交通大学 | A kind of selfreparing water paint and preparation method thereof based on PU/PUF microcapsules and PCL microcapsules |
| CN109135403B (en) * | 2018-08-10 | 2021-01-19 | 西安交通大学 | Self-repairing water-based paint based on PU/PUF (polyurethane/polyurethane elastomer) microcapsules and PCL (polycaprolactone) microcapsules and preparation method thereof |
| CN111808468A (en) * | 2020-06-05 | 2020-10-23 | 中国科学院金属研究所 | Small-size urea formaldehyde microcapsule, preparation and application in self-repairing coating |
| CN112547465A (en) * | 2020-10-27 | 2021-03-26 | 吉林大学 | Spraying method of anticorrosive paint for outer surface of marine pipeline of ship |
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Application publication date: 20120328 |