CN105505121B - It is a kind of that there is self-healing coating of collaboration antiseptic effect and preparation method thereof - Google Patents
It is a kind of that there is self-healing coating of collaboration antiseptic effect and preparation method thereof Download PDFInfo
- Publication number
- CN105505121B CN105505121B CN201610000354.5A CN201610000354A CN105505121B CN 105505121 B CN105505121 B CN 105505121B CN 201610000354 A CN201610000354 A CN 201610000354A CN 105505121 B CN105505121 B CN 105505121B
- Authority
- CN
- China
- Prior art keywords
- coating
- self
- collaboration
- epoxy resin
- antiseptic effect
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
-
- 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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The present invention devises a kind of self-healing coating for having and cooperateing with antiseptic effect and preparation method thereof, belongs to anti-corrosive metal coating field.Self-healing coating with collaboration antiseptic effect, it is characterised in that：The polymer microsphere for being packaged with corrosion inhibiter is distributed in epoxy resin, then a certain amount of spherical zinc powder and zinc flake are distributed in epoxy resin, it is ensured that corrosion inhibiter and metal generation diaphragm before, the cathodically protected effect of metal and from corrosion.The preparation method of self-healing coating with collaboration antiseptic effect, it is characterized in that, prepare the urea formaldehyde resin microsphere of encapsulating poly-aspartate corrosion inhibiter, the urea formaldehyde resin microsphere of encapsulating poly-aspartate corrosion inhibiter, spherical zinc powder, zinc flake are distributed in epoxy resin, epoxy resin and a certain amount of epoxy curing agent, dispersant, defoamer are mixed and made into coating, coating is coated in into metal surface forms the self-healing coating with collaboration antiseptic effect.
Description
Technical field
The present invention relates to a kind of self-healing coating for having and cooperateing with antiseptic effect and preparation method thereof, belong to anti-corrosion of metal painting
Layer field.
Background technology
Metal erosion can reduce the intensity of metal material, shorten the service life of hardware, and severe patient can cause disaster
Accident and personal injury.Anti-corrosive metal coating is a kind of most widely used process for corrosion control, there are about 90% anti-corrosion method and
Anti-corrosion expense is relevant with coating.Among a variety of coatings, organic coating is best to the protecting effect of metal and its alloy.But,
Aging can occur during long-term use for organic coating, coat inside formation micro-crack, further expand with micro-crack and
Extension, coating can occur bubbling and peeling, ultimately result in coating failure.Therefore, it is a kind of new, with " self-healing capability "
Organic coating arises at the historic moment, the study hotspot as anti-corrosive metal coating field.
At present, the self-healing coating of people's research and development can substantially be divided into two kinds：A kind of is by the work(of encapsulation consolidant
Energy property polymer microsphere is scattered in the coating, and when organic coating is destroyed, polymer microsphere is due to fragility and the rainbow of capillary
Suction is acted on, and can run into predetermined substance or condition to release consolidant at coating micro-crack, consolidant（Catalyst, water, oxygen, light）
Solidify, the micro-crack of coating can be crammed, play the effect of healing coating；Another is that the macromolecule that will be surrounded by corrosion inhibiter is micro-
Ball or nano container are distributed in coating, during coating breaks down, and corrosion inhibiter penetrates into metal base surface, generate layer protecting film,
So as to prevent metal erosion.
It is pointed out that the problem of current research for self-healing coating have ignored several important mostly：Metal
Corrosion is an electrochemical process, once coating damage, corrosive medium water, oxygen, chlorion are contacted with metal, in metal surface
Consolidant or corrosion inhibiter in corrosion product, self-healing coating, which can be quickly generated, to reach metal watch before metal erosion generation
FaceThe corrosion inhibiter diaphragm effect generated on corrosion product can or can not be affectedIt can be risen in consolidant or corrosion inhibiter
To before protecting effect, a kind of method for temporarily preventing metal erosion at coating breaks down is found.
The content of the invention
The purpose of the present invention proposes that a kind of self-healing with collaboration antiseptic effect is applied aiming at above-mentioned Railway Project
Layer, by adding a certain amount of zinc powder into self-healing coating, negative electrode guarantor is had concurrently before consolidant or corrosion inhibiter protection metal
Shield and physical shielding effect, another object of the present invention is to there is provided a kind of self-healing coating with collaboration antiseptic effect
Preparation method, this method preparation technology is simple, and cost is low, safety and environmental protection, and the functional high-polymer microballoon or nanometer reduced holds
The usage amount of device.
To achieve the above object, the technical solution adopted by the present invention is：A kind of self-healing with collaboration antiseptic effect is applied
Layer, the polymer microsphere for being packaged with corrosion inhibiter is distributed in epoxy resin, then by a certain amount of spherical zinc powder and zinc flake
Be distributed in epoxy resin, it is ensured that corrosion inhibiter and metal generation diaphragm before, the cathodically protected effect of metal and from
Corrosion；Spherical and zinc flake is used in combination, it is ensured that zinc powder provides cathodic protection and physical shielding effect simultaneously.
A kind of preparation method of the self-healing coating with collaboration antiseptic effect, comprises the following steps：
（1）Prepare the urea formaldehyde resin microsphere of encapsulating poly-aspartate corrosion inhibiter；
（2）The urea formaldehyde resin microsphere of encapsulating poly-aspartate corrosion inhibiter, spherical zinc powder, zinc flake are distributed to asphalt mixtures modified by epoxy resin
In fat；
（3）Above-mentioned epoxy resin and a certain amount of epoxy curing agent, dispersant, defoamer are mixed and made into coating；
（4）Above-mentioned coating is coated in metal surface and forms the self-healing coating with collaboration antiseptic effect.
Preferably, the step（1）The preparation process of urea formaldehyde resin microsphere for encapsulating poly-aspartate corrosion inhibiter is：
5-10g urea, 15-30mL water are added in the reactor, after adding 12-24mL formaldehyde after urea all dissolving, are used
Triethanolamine adjusts pH value to 8 or so, adjusts the temperature to 75 DEG C, reacts 1-1.5 hours, obtains thick Lauxite pre-polymerization
Thing；
Weigh between 0.05-0.1g neopelexes, 0.4-1mL Tween 80s, 0.1-0.3g ammonium chlorides, 0.1-0.3g
Benzenediol, 0.5-1g poly-aspartates, 30-60mL deionized waters, stable emulsion oil-in-water is formed in stirring 1h at 55 DEG C；
Urea resin prepolymer is mixed with emulsion, be added dropwise maleic acid to mixed liquor pH value be 4 or so, 60 DEG C at react 4-
5 hours.After reaction terminates, room temperature is cooled to, a certain amount of deionized water dilution is added, is filtered under diminished pressure, in 40 DEG C of forced air dryings
Placed two days in case.
Preferably, the step（2）In spherical zinc powder particle diameter be 2-5 μm, zinc flake granularity be 2-5 μm.
Preferably, the step（2）In spherical zinc powder and zinc flake and epoxy resin mass ratio be 30-45:
1。
Preferably, the step（2）The urea formaldehyde resin microsphere and epoxy resin of middle encapsulating poly-aspartate corrosion inhibiter
Mass ratio is 1:10.
Preferably, the step（3）The mass ratio of epoxy resin curing agent and epoxy resin is 2:1.
Beneficial effect of the present invention is：
There is the present invention corrosion inhibiter poly-aspartate in the self-healing coating of collaboration antiseptic effect, coating to be generated with metal
Before diaphragm, the zinc powder in coating plays cathodic protection effect to parent metal, and metal does not corrode, corrosion-free product,
The diaphragm that corrosion inhibiter is generated with metal is directly overlayed on metallic matrix, and more preferably, inhibition efficiency is higher for adhesion.
The corrosion inhibiter that the present invention is used is poly-aspartate, and synthesis technique is simple, with low cost, discharged without " three wastes "；It is poly-
Aspartic acid itself asepsis environment-protecting, with biological degradability and scale inhibition performance；
During the coating damage of the present invention, spherical zinc granule and sheet zinc granule play cathodic protection effect, with encapsulation corrosion inhibiter
Polymer microsphere formation collaboration antiseptic effect；After metal surface generates diaphragm, spherical and sheet zinc granule plays physical shielding
Effect.
Specific embodiment
With reference to specific embodiment, the invention will be further described：
Embodiment 1
5g urea, 15mL water are added in the reactor, after adding 12mL formaldehyde after urea all dissolving, are adjusted with triethanolamine
PH value is saved to 8 or so, 75 DEG C are adjusted the temperature to, reacts 1 hour, obtains thick Lauxite prepolymer；
0.05g neopelexes, 0.4mL Tween 80s, 0.1g ammonium chlorides, 0.1g resorcinols, 0.5g is weighed to gather
Aspartic acid, 30mL deionized waters, stable emulsion oil-in-water is formed in stirring 1h at 55 DEG C；
Urea resin prepolymer is mixed with emulsion, be added dropwise maleic acid to mixed liquor pH value be 4 or so, 60 DEG C at react 4
Hour.After reaction terminates, room temperature is cooled to, a certain amount of deionized water dilution is added, is filtered under diminished pressure, in 40 DEG C of air dry ovens
It is middle to place two days, obtain encapsulating the urea formaldehyde resin microsphere of poly-aspartate corrosion inhibiter；
Above-mentioned ureaformaldehyde microballoon 1g, epoxy resin 10g, spherical zinc powder 20g, zinc flake 20g are taken, epoxy resin is distributed to
In；Add 5g epoxy curing agents, 0.2g dispersants, 0.2g defoamers and be mixed and made into coating；
Above-mentioned coating is coated in Q235 carbon steels surface and forms the self-healing coating with collaboration antiseptic effect.
Embodiment 2
8g urea, 25mL water are added in the reactor, after adding 20mL formaldehyde after urea all dissolving, are adjusted with triethanolamine
PH value is saved to 8 or so, 75 DEG C are adjusted the temperature to, reacts 1 hour, obtains thick Lauxite prepolymer；
Weigh 0.08g neopelexes, 0.6mL Tween 80s, 0.2g ammonium chlorides, 0.2g resorcinols, the poly- days of 1g
Winter propylhomoserin, 50mL deionized waters, stable emulsion oil-in-water is formed in stirring 1h at 55 DEG C；
Urea resin prepolymer is mixed with emulsion, be added dropwise maleic acid to mixed liquor pH value be 4 or so, 60 DEG C at react 5
Hour.After reaction terminates, room temperature is cooled to, a certain amount of deionized water dilution is added, is filtered under diminished pressure, in 40 DEG C of air dry ovens
It is middle to place two days, obtain encapsulating the urea formaldehyde resin microsphere of poly-aspartate corrosion inhibiter；
Above-mentioned ureaformaldehyde microballoon 1g, epoxy resin 10g, spherical zinc powder 30g, zinc flake 10g are taken, epoxy resin is distributed to
In；Add 5g epoxy curing agents, 0.2g dispersants, 0.2g defoamers and be mixed and made into coating；
Above-mentioned coating is coated in Q235 carbon steels surface and forms the self-healing coating with collaboration antiseptic effect.
Above-mentioned specific embodiment is that, in order to illustrate the features of the present invention, case study on implementation describes inventive concept, experiment
The time of reaction and operating method, but the claim of the present invention can not be defined, it is other any without departing from this hair
Bright technical scheme is included within protection scope of the present invention.
Claims (2)
1. a kind of preparation method of the self-healing coating with collaboration antiseptic effect, it is characterised in that prepare the poly- asparagus fern ammonia of encapsulating
The urea formaldehyde resin microsphere of acid inhibitor, by the urea formaldehyde resin microsphere of encapsulating poly-aspartate corrosion inhibiter, spherical zinc powder, zinc flake
It is distributed in epoxy resin, epoxy resin and a certain amount of epoxy curing agent, dispersant, defoamer is mixed and made into painting
Layer, wherein, the urea formaldehyde resin microsphere is 1g, and epoxy resin is 10g, and spherical zinc powder is 20g, and zinc flake is 20g, asphalt mixtures modified by epoxy resin
Fat curing agent is 5g, and dispersant is 0.2g, and defoamer is 0.2g, and coating, which is coated in metal surface and formed, has collaboration anti-corrosion effect
The self-healing coating answered.
2. the preparation method of the self-healing coating according to claim 1 with collaboration antiseptic effect, described spherical zinc
A diameter of 2-5 μm of powder particles, zinc flake granularity is 2-5 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610000354.5A CN105505121B (en) | 2016-01-04 | 2016-01-04 | It is a kind of that there is self-healing coating of collaboration antiseptic effect and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610000354.5A CN105505121B (en) | 2016-01-04 | 2016-01-04 | It is a kind of that there is self-healing coating of collaboration antiseptic effect and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105505121A CN105505121A (en) | 2016-04-20 |
| CN105505121B true CN105505121B (en) | 2017-10-20 |
Family
ID=55713438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610000354.5A Expired - Fee Related CN105505121B (en) | 2016-01-04 | 2016-01-04 | It is a kind of that there is self-healing coating of collaboration antiseptic effect and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105505121B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674548B (en) * | 2017-11-01 | 2019-09-13 | 青岛农业大学 | A kind of preparation method based on magnetic gradient self-healing corrosion-inhibiting coating |
| CN107760163B (en) * | 2017-11-05 | 2020-02-21 | 青岛农业大学 | Self-repairing anticorrosive coating with antifouling function and preparation method thereof |
| CN108373536B (en) * | 2018-05-22 | 2020-04-14 | 河北工业大学 | Synthesis method and application of modified polyaspartic acid with Schiff base structure |
| CN111234566B (en) * | 2020-01-22 | 2021-04-20 | 湖南大学 | Acid-base double-response hollow mesoporous silica composite nano container, self-repairing anticorrosive coating and preparation method of self-repairing anticorrosive coating |
| CN112694824B (en) * | 2020-12-28 | 2021-10-01 | 青岛理工大学 | Deteriorated immune bionic protective coating for steel structure engineering and preparation method thereof |
| CN112852262A (en) * | 2021-01-15 | 2021-05-28 | 上海大学 | Lignocellulose-containing anti-corrosion self-repairing coating and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011087850A1 (en) * | 2011-12-06 | 2013-06-06 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Composite useful as e.g. components of primary structure and secondary structure of aircraft, and vehicles from a land- and sea transport e.g. roof components, bumpers and spoiler, comprises matrix material and several microcapsules |
| CN104177983A (en) * | 2014-08-28 | 2014-12-03 | 漳州鑫展旺化工有限公司 | Self-repairing anticorrosive coating and preparation method thereof |
| CN104178023A (en) * | 2014-08-27 | 2014-12-03 | 舟山市恒泰漆业有限责任公司 | Tough self-repair metal anti-corrosion paint and preparation method thereof |
| WO2015061522A1 (en) * | 2013-10-23 | 2015-04-30 | Autonomic Materials, Inc. | Self-healing agent formulations containing liquid corrosion inhibitors |
| CN105038502A (en) * | 2015-07-17 | 2015-11-11 | 南通南京大学材料工程技术研究院 | Self-healing epoxy powdery coating containing microcapsule and preparation method thereof |
-
2016
- 2016-01-04 CN CN201610000354.5A patent/CN105505121B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011087850A1 (en) * | 2011-12-06 | 2013-06-06 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Composite useful as e.g. components of primary structure and secondary structure of aircraft, and vehicles from a land- and sea transport e.g. roof components, bumpers and spoiler, comprises matrix material and several microcapsules |
| WO2015061522A1 (en) * | 2013-10-23 | 2015-04-30 | Autonomic Materials, Inc. | Self-healing agent formulations containing liquid corrosion inhibitors |
| CN104178023A (en) * | 2014-08-27 | 2014-12-03 | 舟山市恒泰漆业有限责任公司 | Tough self-repair metal anti-corrosion paint and preparation method thereof |
| CN104177983A (en) * | 2014-08-28 | 2014-12-03 | 漳州鑫展旺化工有限公司 | Self-repairing anticorrosive coating and preparation method thereof |
| CN105038502A (en) * | 2015-07-17 | 2015-11-11 | 南通南京大学材料工程技术研究院 | Self-healing epoxy powdery coating containing microcapsule and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105505121A (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105505121B (en) | It is a kind of that there is self-healing coating of collaboration antiseptic effect and preparation method thereof | |
| Umoren | Polymers as corrosion inhibitors for metals in different media-A review | |
| Zhong et al. | A novel approach to heal the sol–gel coating system on magnesium alloy for corrosion protection | |
| CN107674548B (en) | A kind of preparation method based on magnetic gradient self-healing corrosion-inhibiting coating | |
| RU2011135805A (en) | COMPOSITION OF ELECTRO-DEPOSITABLE COATING, INCLUDING SILANE AND YTTRIUM | |
| CN105585939B (en) | A kind of coatings with rust transformation and preparation method thereof | |
| Liu et al. | Simple spray method preparation of slow-release porous microcapsule for long-term active anti-corrosion and scale-inhibiting coatings | |
| CN105348870A (en) | Preparation method of chromium-free dacromet coating | |
| Zhao et al. | Microencapsulation of UV-curable self-healing agent for smart anticorrosive coating | |
| CN107760163A (en) | A kind of selfreparing corrosion-inhibiting coating with anti-pollution function and preparation method thereof | |
| CN104388944B (en) | A kind of microencapsulation vapor phase inhibitor and preparation method thereof | |
| CN103962072B (en) | A kind of chemistry triggers microcapsules and preparation method thereof | |
| CN108276811A (en) | Aqueous zinc-plated sealer of one kind and preparation method thereof | |
| CN104479549A (en) | Preparation method of heavy anti-corrosion coating containing nano titanium | |
| CN102993914A (en) | Anti-corrosion powder coating for automobile | |
| CN108425118B (en) | Quaternary compound vapor phase corrosion inhibitor for carbon steel and brass and preparation method thereof | |
| CN106928764B (en) | A kind of aqueous marine anticorrosion paint and preparation method thereof with self-healing properties | |
| CN109749499B (en) | Anticorrosion wear-resistant water-based functional filler and anticorrosion wear-resistant water-based paint applying same | |
| CN105949934A (en) | Microcapsule type self-repairing anticorrosive paint and preparation method thereof | |
| CN103992719B (en) | A kind of modified epoxy denitrification apparatus special-purpose coat and preparation method thereof | |
| CN109679446A (en) | Conductive anti-corrosion coating for grounded screen | |
| CN115820073A (en) | Ultralong salt-fog-resistant water-based graphene modified epoxy primer heavy-duty anticorrosive paint and preparation method thereof | |
| CN108070864B (en) | pH value response intelligent control release corrosion inhibitor and preparation method thereof | |
| CN101486880A (en) | Precoating anaerobic oxygen rubber and preparation thereof | |
| CN103897450A (en) | Acrylic resin anticorrosive paint |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171020 Termination date: 20190104 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |