CN108452750A - A kind of preparation method of self-healing electrophoretic coating microcapsules - Google Patents

A kind of preparation method of self-healing electrophoretic coating microcapsules Download PDF

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Publication number
CN108452750A
CN108452750A CN201810314621.5A CN201810314621A CN108452750A CN 108452750 A CN108452750 A CN 108452750A CN 201810314621 A CN201810314621 A CN 201810314621A CN 108452750 A CN108452750 A CN 108452750A
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preparation
healing
self
added
microcapsules
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CN201810314621.5A
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CN108452750B (en
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刘玉
胡强
陈小琴
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Tongling Lingyang Chemical Co Ltd
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Tongling Lingyang Chemical Co Ltd
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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
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C08G14/08—Ureas; Thioureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

The invention discloses a kind of preparation methods of self-healing electrophoretic coating microcapsules, gelatin modified Lauxite is added in the present invention as cyst wall, the flexibility for improving self-healing surface of microcapsule, obtained microencapsulated forms are good, surface is smooth, compact structure, have higher intensity；SiO is handled with silane coupling agent in the present invention2Lauxite cyst wall surface is grafted to behind surface, in the SiO that the surface of microcapsules is formed2Layer has good barrier property and intensity, and to reduce the generation of microcapsules adhesion phenomenon, the microcapsule stability of preparation is good, particle diameter distribution is uniform；The microcapsules being prepared using the method for the present invention, n-butyl glycidyl ether solvent is added in capsule-core, there is preferable diluting effect to modified epoxy capsule-core, utilize the principle of siphonic effect, epoxy resin solution can infiltrate into entire film damaged part completely along gap, curing reaction is crosslinked, to reach self-healing effect.

Description

A kind of preparation method of self-healing electrophoretic coating microcapsules
Technical field
The invention belongs to technical field of paint preparation, and in particular to a kind of preparation side of self-healing electrophoretic coating microcapsules Method.
Background technology
Cathode electrophoresis dope is a kind of erosion shield that the 1970s, mid-term grew up, and is applied compared to anodic electrophoresis Material has superior performance in terms of throwing power and anti-corrosive properties, and obtains industrial applications.In work piece production or use process In, the problems such as inevitably colliding with, scratch, the function of coating protection is thus greatly reduced, affects the whole of paint film Body anti-corrosive properties, so needing the self-healing capability of increase paint film.
In recent years, application of the microcapsules in self-repair material becomes research hotspot.The advantage of microcapsules technology is, can It is isolated from the outside with being wrapped up capsule-core by cyst wall, to protect capsule-core to be not affected, under suitable condition（As pressure, Heating, radiation）Make cyst wall rupture release capsule-core.The common preparation method of microcapsules has situ aggregation method, spray drying process, coagulates again Poly- method etc..The microcapsules chemical resistance synthesized using situ aggregation method is good and grain size is small, microcapsules pattern obtained well, intensity It is high.But it is excessive that there are emulsion viscosities in polymerization process in situ, makes the phenomenon that sticks together between microcapsules, the table of microcapsules There is disrepair phenomenon in face, causes the problems such as surface of microcapsule is coarse, stability is poor, particle diameter distribution is uneven；And capsule in microcapsules That there are viscositys in repair process is larger for core, is unfavorable for the problem of capillary siphoning effect occurs, to which self-healing effect be not achieved Fruit.
Invention content
To overcome deficiency in the prior art, the present invention provides a kind of preparation sides of self-healing electrophoretic coating microcapsules Method improves the form and stability of self-healing microcapsules.
In order to achieve the above objectives, the present invention uses following technical scheme：
A kind of preparation method of self-healing electrophoretic coating microcapsules, includes the following steps：
（1）SiO2The preparation of solution：
Claim a certain amount of silane coupling agent, SiO2, 95% ethyl alcohol and absolute ethyl alcohol after mixing, sonic oscillation 25-40min, it Mixed liquor is transferred in water-bath afterwards, 50-60 DEG C of constant temperature constant speed stirs 3-4h, after natural cooling, the mixed solution that will obtain It is centrifuged off supernatant liquor, obtained gluey SiO2It is for use after hydrolysis；
（2）The preparation of Lauxite prepolymer：
5.0-6.0g urea, the formalin that 10.0-12.5g mass fractions are 37% are added into three-necked flask at ambient temperature Middle mixing is added appropriate triethanolamine and pH value is transferred to 8.5-9.3 after urea dissolves, be placed in water-bath, protect Temperature is held at 65-80 DEG C, 60-90min is reacted, obtains transparent Lauxite pre-polymer solution；
（3）The preparation of microcapsules：
A, after above-mentioned Lauxite pre-polymer solution being cooled to 30-50 DEG C, the aqueous gelatin solution prepared is added, is dispersed with stirring After even, add the appropriate 3-5% emulsifier solutions of 10-20mL and 30-55mL water and be sufficiently stirred, be slowly added to 4-10mL solvents N-butyl glycidyl ether and the silane coupler modified epoxy resin of 18-23g, in 500-800 r/min stirring and emulsifyings 60- 80min；
B, it is 2.5- with 10% lemon acid for adjusting pH value later under 50-55 DEG C of water bath with thermostatic control and 400-500r/min speed conditions 3.5,0.2-0.4g ammonium chlorides and 0.4-0.6g resorcinols is added, above-mentioned steps are added after hybrid reaction 25-60min（1） SiO2Solution, the reaction was continued 2-3h, obtained suspension filters through decompression, washing, obtains filter cake, drying under room temperature is It can.
Wherein, the step（1）The dosage of middle silane coupling agent is 5-10%.
Wherein, the step（3）Mass fraction of the gelatin in entire reaction system is 0.25-0.6%.
Wherein, the step（3）Emulsifier includes that polyvinyl-maleic anhydride alternate copolymer, maleic anhydride of styrene are poly- Close object.
Wherein, the mass fraction of the surface of microcapsule Si is in 2.5-3.5%.
Compared with prior art, beneficial benefit of the invention is as follows：
Gelatin modified Lauxite is added in the present invention as cyst wall, solves the problems, such as that Lauxite brittleness is big, improves certainly Heal the flexibility of surface of microcapsule, and obtained surface of microcapsule is smooth, compact structure, has higher intensity, in addition gelatin Hydroxyl group be easy reacted with the amino of the amino of Lauxite, silane coupler modified epoxy resin, be conducive to ureaformaldehyde tree Fat is deposited in surface of microcapsule, keeps the form of microcapsules good, and clad ratio is high, cyst wall compact structure；With silane coupled in the present invention Agent handles SiO2Lauxite cyst wall surface, SiO are grafted to behind surface2It is tightly covered in the surface of microcapsules and forms SiO2Layer has good barrier property and intensity, and to reduce the generation of microcapsules adhesion phenomenon, the microcapsules of preparation are steady It is qualitative it is good, particle diameter distribution is uniform；The microcapsules being prepared using the method for the present invention, are added n-butyl glycidyl in capsule-core Ether solvents have preferable diluting effect to modified epoxy capsule-core, and using the principle of siphonic effect, epoxy resin solution can edge Gap infiltrates into entire film damaged part completely, crosslinks curing reaction, to reach self-healing effect.
Specific implementation mode
Embodiment 1
A kind of preparation method of self-healing electrophoretic coating microcapsules, includes the following steps：
（1）SiO2The preparation of solution：
Claim a certain amount of silane coupling agent, SiO2, 95% ethyl alcohol and absolute ethyl alcohol after mixing, sonic oscillation 30min, later Mixed liquor is transferred in water-bath, 55 DEG C of constant temperature constant speed stirring 4h, after natural cooling, obtained mixed solution is centrifuged off Supernatant liquor, obtained gluey SiO2It is for use after hydrolysis；
The dosage of the silane coupling agent is 8%；
（2）The preparation of Lauxite prepolymer：
5.5g urea, the formalin that 12g mass fractions are 37% are added in three-necked flask and are mixed at ambient temperature, After urea dissolves, appropriate triethanolamine is added, pH value is transferred to 9.0, be placed in water-bath, maintain the temperature at 70 DEG C, instead 60min is answered, transparent Lauxite pre-polymer solution is obtained；
（3）The preparation of microcapsules：
A, after above-mentioned Lauxite pre-polymer solution being cooled to 40 DEG C, the aqueous gelatin solution prepared is added, is dispersed with stirring uniformly Afterwards, the appropriate 3% polyvinyl-maleic anhydride alternate copolymer solution of 15mL and 45mL water are added and is sufficiently stirred, is slowly added to 8mL solvents n-butyl glycidyl ether and 20g silane-modified epoxy resins, in 600 r/min stirring and emulsifyings 60min；
Mass fraction of the gelatin in entire reaction system is 0.4%；
B, later under 50 DEG C of waters bath with thermostatic control and 400r/min speed conditions, it is 3.0 with 10% lemon acid for adjusting pH value, is added Above-mentioned steps are added after hybrid reaction 40min in 0.3g ammonium chlorides and 0.4g resorcinols（1）SiO2Solution, the reaction was continued 2h are obtained The suspension arrived is filtered through decompression, is washed, and obtains filter cake, is dried under room temperature.

Claims (5)

1. a kind of preparation method of self-healing electrophoretic coating microcapsules, which is characterized in that include the following steps：
（1）SiO2The preparation of solution：
Claim a certain amount of silane coupling agent, SiO2, 95% ethyl alcohol and absolute ethyl alcohol after mixing, sonic oscillation 25-40min, it Mixed liquor is transferred in water-bath afterwards, 50-60 DEG C of constant temperature constant speed stirs 3-4h, after natural cooling, the mixed solution that will obtain It is centrifuged off supernatant liquor, obtained gluey SiO2It is for use after hydrolysis；
（2）The preparation of Lauxite prepolymer：
5.0-6.0g urea, the formalin that 10.0-12.5g mass fractions are 37% are added into three-necked flask at ambient temperature Middle mixing is added appropriate triethanolamine and pH value is transferred to 8.5-9.3 after urea dissolves, be placed in water-bath, protect Temperature is held at 65-80 DEG C, 60-90min is reacted, obtains transparent Lauxite pre-polymer solution；
（3）The preparation of microcapsules：
A, after above-mentioned Lauxite pre-polymer solution being cooled to 30-50 DEG C, the aqueous gelatin solution prepared is added, is dispersed with stirring After even, add the appropriate 3-5% emulsifier solutions of 10-20mL and 30-55mL water and be sufficiently stirred, be slowly added to 4-10mL solvents N-butyl glycidyl ether and the silane coupler modified epoxy resin of 18-23g, in 500-800 r/min stirring and emulsifyings 60- 80min；
B, it is 2.5- with 10% lemon acid for adjusting pH value later under 50-55 DEG C of water bath with thermostatic control and 400-500r/min speed conditions 3.5,0.2-0.4g ammonium chlorides and 0.4-0.6g resorcinols is added, above-mentioned steps are added after hybrid reaction 25-60min（1） SiO2Solution, the reaction was continued 2-3h, obtained suspension filters through decompression, washing, obtains filter cake, drying under room temperature is It can.
2. a kind of preparation method of self-healing electrophoretic coating microcapsules according to claim 1, which is characterized in that described Step（1）The dosage of middle silane coupling agent is 5-10%.
3. a kind of preparation method of self-healing electrophoretic coating microcapsules according to claim 1, which is characterized in that described Step（3）Mass fraction of the gelatin in entire reaction system is 0.25-0.6%.
4. a kind of preparation method of self-healing electrophoretic coating microcapsules according to claim 1, which is characterized in that described Step（3）Emulsifier includes polyvinyl-maleic anhydride alternate copolymer, maleic anhydride of styrene polymer.
5. a kind of preparation method of self-healing electrophoretic coating microcapsules according to claim 1, which is characterized in that described The mass fraction of surface of microcapsule Si is in 2.5-3.5%.
CN201810314621.5A 2018-04-10 2018-04-10 Preparation method of microcapsule for self-healing electrophoretic coating Active CN108452750B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114957925A (en) * 2022-05-20 2022-08-30 重庆大学 Epoxy resin composite insulating medium of single-component ultraviolet photosensitive microcapsule, preparation method and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102604469A (en) * 2012-02-13 2012-07-25 中国船舶重工集团公司第七二五研究所 Latent self-repair microcapsule and preparation method thereof
CN102641703A (en) * 2011-05-27 2012-08-22 京东方科技集团股份有限公司 Electronic ink microcapsule and preparation method thereof
CN103788815A (en) * 2014-01-06 2014-05-14 沈阳化工大学 Preparation method of anticorrosive coating capable of self-repairing rapidly at room temperature
CN106398469A (en) * 2016-08-31 2017-02-15 浩力森涂料（上海）有限公司 Microcapsule, self-healing electrophoretic coating containing microcapsule and preparation method of microcapsule

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102641703A (en) * 2011-05-27 2012-08-22 京东方科技集团股份有限公司 Electronic ink microcapsule and preparation method thereof
CN102604469A (en) * 2012-02-13 2012-07-25 中国船舶重工集团公司第七二五研究所 Latent self-repair microcapsule and preparation method thereof
CN103788815A (en) * 2014-01-06 2014-05-14 沈阳化工大学 Preparation method of anticorrosive coating capable of self-repairing rapidly at room temperature
CN106398469A (en) * 2016-08-31 2017-02-15 浩力森涂料（上海）有限公司 Microcapsule, self-healing electrophoretic coating containing microcapsule and preparation method of microcapsule

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
杨婷婷等: ""明胶改性脲醛树脂黑白双粒子电泳微胶囊的制备及显示"", 《功能材料》 *
楼樱红: ""溶胶-凝胶法制备相变微胶囊及其在织物上的应用"", 《中国优秀硕士学位论文全文数据库》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114957925A (en) * 2022-05-20 2022-08-30 重庆大学 Epoxy resin composite insulating medium of single-component ultraviolet photosensitive microcapsule, preparation method and application

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