CN105536657A - Synthetic method for light-induced self-repair microcapsules - Google Patents
Synthetic method for light-induced self-repair microcapsules Download PDFInfo
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- CN105536657A CN105536657A CN201610002216.0A CN201610002216A CN105536657A CN 105536657 A CN105536657 A CN 105536657A CN 201610002216 A CN201610002216 A CN 201610002216A CN 105536657 A CN105536657 A CN 105536657A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention provides a synthetic method for light-induced self-repair microcapsules and relates to the technical field of metal corrosion resistance. The synthetic method comprises the steps that sodium dodecylbenzene sulfonate serves as a surfactant of a capsule core material, the capsule core material containing a cinnamic acid acyl functional group compound has the light-sensing property, and a cross-linking reaction can be generated to repair microcracks under the situation of light triggering induction. Copolycondensation resin of urea, melamine and methyl aldehyde serves as a capsule wall material, and thus environment friendliness is achieved.
Description
Technical field
The present invention relates to the technical field of anticorrosion of metal, particularly the technology of preparation method of environment amenable painting microcapsule.
Background technology
Corrosion of metal is that metal is subject to the chemistry of surrounding medium or electrochemical action and destroyed phenomenon.For a long time, protecting one of effective, the most most economical method of metal erosion is at metal surface coating corrosion-inhibiting coating.But using in coating process and can produce micro-crack because of the change of the factor such as environment or mechanical property, and owing to being exposed in air, micro-crack can spread gradually, expand, thus accelerate the stripping and layering that metal and coating interface coat, reduce service life and the antiseptic power of coating, also have impact on the use of metal simultaneously.Coating can regard the composite that the class that is made up of adhesive and pigment is special as, and therefore composite Crack Self technology can be applied to paint field equally, extends the durability of coating.
Material in use inevitably produces local damage and micro-crack, and causes macrocrack thus and rupture, and affects material and normally uses and reduction of service life.Self-repair material is an important branch of intellectual material, and without under external influence condition, material inherently can carry out self-recovery to internal flaw.
Microcapsules are by the solid of the coated dispersiveness of filmogen, liquid or gas and the small container with nucleocapsid structure formed, usually the coating film that filmogen is formed is called wall material or cyst wall (generally being formed by macromolecular material that is natural or synthesis), the inner material be wrapped by of filmogen is called core or capsule-core.Microcapsule size and shape, in very large range change along with the difference of preparation technology.Microcapsule size is usually within the scope of 2 ~ 1000 μm, and the capsule that diameter is less than 1 μm is called Nano capsule, and the capsule that diameter is greater than 1000 μm is called large capsule.At 0.2 ~ 10 μm not etc., the ratio shared in microcapsules gross mass of capsule-core also changes wall thickness in 20 ~ 95% scopes.Microcapsules are by being wrapped material and lapping forms.Be wrapped in inner material and be commonly referred to as active matter, activating agent, core material, interior phase, core, payload or filler.The so-called wall of coating material, carrier, shell, coating or film, it can be organic polymer, the hydrosol, sugar, wax, fat, metal or inorganic oxide etc.
Urea one melamine one formaldehyde condensation copolymerization resin has that Lauxite look shallow, quick solidifying, the advantage such as cheap, and its performance is better than Lauxite, close to urea melamine resin simultaneously.And the price of urea one melamine one formaldehyde condensation copolymerization resin is the half of urea melamine resin, close to Lauxite resin, synthesis technique is also similar with arteries and veins urea formaldehyde.Urea one melamine one formaldehyde condensation copolymerization resin can be widely used in damp-proof particieboard, glued board, medium density fibre board (MDF) and other large matter wood-based plate, and effect is more satisfactory
Cinnamic acid based compound is a kind of important organic synthesis intermediate.Cinnamic acid based compound is mainly used in the preparation etc. of the fine chemical products such as medicine, spices and photosensitive resin.
Summary of the invention
The present invention seeks to propose a kind ofly can to repair microcrack, the synthetic method of environmentally friendly, the photic self-repairing microcapsule that do not need catalyst.
The present invention includes following steps:
1) be scattered in neopelex after mixing with deionized water containing cinnamic acid acyl function based compound, form core materials;
2) urea, melamine are mixed with formalin, pH to 8 ~ 8.5 regulating mixture with NaOH, react, obtain cyst material under the temperature of mixture is 60 ~ 70 DEG C of conditions;
3) under stirring condition, cyst material is dissolved in core materials, then adds catalyst n H in batches
4cl, the pH of mixed system is reduced gradually, after starting to deposit to core materials surface by microscopic to cyst material, by the temperature to 60 of mixed system ~ 65 DEG C, add the hot water of 55 ~ 65 DEG C when the pH of mixed system is reduced to 2.5 ~ 3.0, insulation 1 ~ 2h, pH=7.0 ~ 7.5 are adjusted with NaOH, suction filtration after cooling, gets solid phase and washes rear drying with acetone, obtain microcapsules.
Core materials of the present invention is using neopelex as surfactant, and the core materials containing cinnamic acid acyl function based compound has photosensitive property, when light triggers induction, cross-linking reaction can occur, repair microcrack.And cyst material is the condensation copolymerization resin of urea/melamine/formaldehyde, environmentally friendly.
The hot water temperature that step 3) adds is close to reaction temperature, and main purpose is the dispersiveness in order to increase reactant, maintains the good heat insulation effect of reaction.
The coated process of the present invention is simple, and safety, does not need catalyst, and cost is lower, and the covering property of gained is white powder containing cinnamic acid acyl function based compound product, and containing the mass fraction of cinnamic acid acyl function based compound more than 80%, clad ratio is higher.The microcapsules of preparation are that a light triggers self-healing system, environmentally friendly, are applicable in reparation crack.
Further, the particle diameter containing cinnamic acid acyl function based compound of the present invention is 0.5 ~ 15 μm.The particle diameter of the microcapsules after the less synthesis of capsule-core is less, joins after in coating as filler, also can be little to the physics of coating itself and chemistry affect thereof.
In order to enable material fully disperse, the described mass ratio that feeds intake containing cinnamic acid acyl function based compound, deionized water and neopelex is 1: 4 ~ 6: 0.01 ~ 0.1.
The mass fraction of the described formalin mixed with urea, melamine is 37%.The mass fraction of this formaldehyde, for analyzing pure concentration, is the maximum concentration that formalin can reach, and the performed polymer adopting this concentration to obtain is best for the clad ratio of core materials.
The mass ratio that feeds intake of described urea, melamine and formalin is 1: 1 ~ 1.5: 2 ~ 3.Excellent results: the performance of performed polymer is best.
When cyst material is 1: 1 ~ 2 with the mixing quality ratio of core materials, capsule-core can be fully coated by cyst wall.
In described step 3), the total mass ratio of hot water and cyst material and core materials is 1: 1.5 ~ 2, and this amount ratio makes reactant have good dispersiveness, and it is high that core materials is wrapped by rate, and the capsule size distribution prepared is concentrated.
Accompanying drawing explanation
Fig. 1 is graphene oxide coated sulfur microcapsule surface topography stereoscan photograph.
Fig. 2 is for containing cinnamic acid acyl function based compound photo.
Fig. 3 is Fig. 1 is containing cinnamic acid acyl function based compound photo-crosslinking photo.
Detailed description of the invention
One, the synthetic method of photic self-repairing microcapsule:
Embodiment 1
1, prepare core materials: get 6.5g particle diameter be 0.5 ~ 15 μm containing cinnamic acid acyl function based compound, add 26g deionized water, with 0.07g neopelex as dispersion emulsifier, form 32.57g dispersion emulsifier after stirring, i.e. core materials.
2, prepare cyst material: get 6g urea, 6g melamine and 16.02g mass fraction be 37% formalin mix, regulate pH=8.5 with NaOH, at 70 DEG C, react 1h, obtain the sticky clear prepolymer of 29g, i.e. cyst material.
3, microcapsules are prepared: mix obtaining full dose core materials above with full dose cyst material (core materials is 1.123:1 with the mixing quality ratio of cyst material), fully stirring under 600r/min speed of agitator makes sticky clear prepolymer be dissolved in dispersion emulsifier, then adds catalyst n H in batches
4cl, the system pH of making reduces gradually, after starting to deposit to capsule-core surface by microscopic to polymer, system is heated to 65 DEG C, continues coated and solidify gradually, add the hot water of 80mL63 DEG C when pH is reduced to 2.5 ~ 3.0, pH=7.0 is adjusted with NaOH after insulation 2h, suction filtration after cooling, dry after getting the washing of solid phase acetone, obtain 27g microcapsules.
4, microcapsules this method prepared are known through SEM Electronic Speculum test analysis, and product cut size, at about 8 ~ 20 μm, has appearance of reuniting in a large number.
Embodiment 2
1, prepare core materials: get 6g particle diameter be 0.5 ~ 15 μm containing cinnamic acid acyl function based compound, add 30g deionized water, with 0.6g neopelex as dispersion emulsifier, form 36.6g dispersion emulsifier after stirring, i.e. core materials.
2, prepare cyst material: get 6g urea, 6g melamine and 12.02g mass fraction be 37% formalin mix, regulate pH=8 with NaOH, at 60 DEG C, react 0.5h, obtain the sticky clear prepolymer of 24.02g, i.e. cyst material.
3, microcapsules are prepared: mix obtaining full dose core materials above with full dose cyst material (core materials is 1.523:1 with the mixing quality ratio of cyst material), fully stirring under 600r/min speed of agitator makes prepolymer be dissolved in the decentralized medium water of emulsion, adds catalyst n H in batches
4cl, the system pH of making reduces gradually, after starting to deposit to capsule-core surface by microscopic to polymer, be heated to 60 DEG C, continue coated and solidify gradually, the hot water of 80mL60 DEG C is added when pH is reduced to 2.5 ~ 3.0, insulation 1h, adjusts pH=7.5 with NaOH, suction filtration after cooling, dry after getting the washing of solid phase acetone, obtain 25g microcapsules.
4, microcapsules this method prepared are known through SEM Electronic Speculum test analysis, and product cut size is at about 6 ~ 18 μm.
Embodiment 3
1, prepare core materials: get 6g particle diameter be 0.5 ~ 15 μm containing cinnamic acid acyl function based compound, add 36g deionized water, with 0.6g neopelex as dispersion emulsifier, form 42.6g dispersion emulsifier after stirring, i.e. core materials.
2, prepare cyst material: get 6g urea, 9g melamine and 18g mass fraction be 37% formalin mix, regulate pH=8 with NaOH, at 65 DEG C, react 0.5h, obtain the sticky clear prepolymer of 33g, i.e. cyst material.
3, microcapsules are prepared: mix obtaining full dose core materials above with full dose cyst material (core materials is 1.29:1 with the mixing quality ratio of cyst material), fully stirring under 600r/min speed of agitator makes prepolymer be dissolved in the decentralized medium water of emulsion, adds catalyst n H in batches
4cl, the system pH of making reduces gradually, after starting to deposit to capsule-core surface by microscopic to polymer, be heated to 65 DEG C, continue coated and solidify gradually, the hot water of 80mL65 DEG C is added when pH is reduced to 2.5 ~ 3.0, insulation 1h, adjusts pH=7.5 with NaOH, suction filtration after cooling, dry after getting the washing of solid phase acetone, obtain 32g microcapsules.
4, microcapsules this method prepared are known through SEM Electronic Speculum test analysis, and product cut size is at about 2 ~ 10 μm.
Two, verification experimental verification:
Fig. 1 is the SEM photo synthesizing microcapsules according to case study on implementation 1.
Be dissolved in coating by cinnamoyl compound, coating on the glass sheet, and portrays cut with sharp knife, as shown in Figure 2.
By the coating with cut of Fig. 1 gained, adopt ultraviolet light to irradiate, after cinnamoyl compound generation photo-crosslinking, cut is repaired, as shown in Figure 3.
Visible: the microcapsules with photo-crosslinking effect are applied to coating selfreparing, the incitant that selfreparing occurs is sunshine, has the feature of energy-saving, environment-friendly and high-efficiency.
Claims (7)
1. a synthetic method for photic self-repairing microcapsule, is characterized in that comprising the following steps:
1) be scattered in neopelex after mixing with deionized water containing cinnamic acid acyl function based compound, form core materials;
2) urea, melamine are mixed with formalin, pH to 8 ~ 8.5 regulating mixture with NaOH, react, obtain cyst material under the temperature of mixture is 60 ~ 70 DEG C of conditions;
3) under stirring condition, cyst material is dissolved in core materials, then adds catalyst n H in batches
4cl, the pH of mixed system is reduced gradually, after starting to deposit to core materials surface by microscopic to cyst material, by the temperature to 60 of mixed system ~ 65 DEG C, add the hot water of 55 ~ 65 DEG C when the pH of mixed system is reduced to 2.5 ~ 3.0, insulation 1 ~ 2h, pH=7.0 ~ 7.5 are adjusted with NaOH, suction filtration after cooling, gets solid phase and washes rear drying with acetone, obtain microcapsules.
2. preparation method according to claim 1, is characterized in that: the described particle diameter containing cinnamic acid acyl function based compound is 0.5 ~ 15 μm.
3. preparation method according to claim 1 and 2, is characterized in that: the described mass ratio that feeds intake containing cinnamic acid acyl function based compound, deionized water and neopelex is 1: 4 ~ 6: 0.01 ~ 0.1.
4. preparation method according to claim 1, is characterized in that: the mass fraction of the described formalin mixed with urea, melamine is 37%.
5. preparation method according to claim 4, is characterized in that: the mass ratio that feeds intake of described urea, melamine and formalin is 1: 1 ~ 1.5: 2 ~ 3.
6. preparation method according to claim 1, is characterized in that: cyst material is 1: 1 ~ 2 with the mixing quality ratio of core materials.
7. preparation method according to claim 1, is characterized in that: in described step 3), the total mass ratio of hot water and cyst material and core materials is 1: 1.5 ~ 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610002216.0A CN105536657A (en) | 2016-01-04 | 2016-01-04 | Synthetic method for light-induced self-repair microcapsules |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610002216.0A CN105536657A (en) | 2016-01-04 | 2016-01-04 | Synthetic method for light-induced self-repair microcapsules |
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| CN105536657A true CN105536657A (en) | 2016-05-04 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107617398A (en) * | 2017-09-01 | 2018-01-23 | 同济大学 | A kind of pitch micro-damage self-repairing microcapsule and preparation method thereof |
| CN107715811A (en) * | 2017-10-24 | 2018-02-23 | 南京林业大学 | A kind of wooden material surface water paint self-repairing microcapsule and preparation method thereof |
| 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 |
| CN115679708A (en) * | 2022-10-16 | 2023-02-03 | 武汉纺织大学 | Microcapsule coating fabric with photo-initiation self-warning or self-repairing function and preparation method thereof |
Citations (4)
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| GB2180358A (en) * | 1985-07-16 | 1987-03-25 | Mead Corp | Photosensitive microcapsules and their use on imaging sheets |
| WO2008080514A1 (en) * | 2007-01-04 | 2008-07-10 | Cognis Ip Management Gmbh | Use of aqueous emulsions in the form of foam for the reloading of textiles |
| CA2778251A1 (en) * | 2009-11-06 | 2011-05-12 | The Procter & Gamble Company | High efficiency capsules comprising benefit agent |
| CN105086396A (en) * | 2015-08-14 | 2015-11-25 | 陕西科技大学 | Preparation method of self-repair nanocapsule-thermosetting-resin-base composite material |
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2016
- 2016-01-04 CN CN201610002216.0A patent/CN105536657A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2180358A (en) * | 1985-07-16 | 1987-03-25 | Mead Corp | Photosensitive microcapsules and their use on imaging sheets |
| WO2008080514A1 (en) * | 2007-01-04 | 2008-07-10 | Cognis Ip Management Gmbh | Use of aqueous emulsions in the form of foam for the reloading of textiles |
| CA2778251A1 (en) * | 2009-11-06 | 2011-05-12 | The Procter & Gamble Company | High efficiency capsules comprising benefit agent |
| CN105086396A (en) * | 2015-08-14 | 2015-11-25 | 陕西科技大学 | Preparation method of self-repair nanocapsule-thermosetting-resin-base composite material |
Non-Patent Citations (1)
| Title |
|---|
| YOUNG-KYU SONG: "Sunlight-Induced Self-Healing of a Microcapsule-Type Protective Coating", 《ACS APPL. MATER. INTERFACES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107617398A (en) * | 2017-09-01 | 2018-01-23 | 同济大学 | A kind of pitch micro-damage self-repairing microcapsule and preparation method thereof |
| CN107715811A (en) * | 2017-10-24 | 2018-02-23 | 南京林业大学 | A kind of wooden material surface water paint self-repairing microcapsule and preparation method thereof |
| CN115679708A (en) * | 2022-10-16 | 2023-02-03 | 武汉纺织大学 | Microcapsule coating fabric with photo-initiation self-warning or self-repairing function and preparation method thereof |
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