CN106590321B - A kind of glass fibre corrosion inhibiter coatings and preparation method - Google Patents
A kind of glass fibre corrosion inhibiter coatings and preparation method Download PDFInfo
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Abstract
The present invention relates to anticorrosion field, specifically a kind of glass fibre corrosion inhibiter coatings and preparation method.Overcoating layer is made of glass fibre, corrosion inhibiter, organic resin and auxiliary agent, wherein in parts by weight, 90-95 parts of organic resin, 0.3-0.8 parts of glass fibre, 0.3-0.7 parts of thiocarbamide corrosion inhibiter and 1-4.5 parts of auxiliary agent.Corrosion inhibiter of the present invention evenly spreads to film-forming in organic resin using glass fibre as carrier, and making coating after disruption has good self-healing properties and corrosion resistance.Glass fibre in the present invention acts not only as the carrier of corrosion inhibiter, and cross-linked structure can also be formed in resin, improves coating toughness, reduces coating damage probability.The present invention has both good antistripping property and salt water penetration performance, simple process and low cost compared with other similar coating, after film-forming.
Description
Technical field
The present invention relates to anticorrosion field, specifically a kind of glass fibre corrosion inhibiter coatings and preparation method.
Background technique
Coatings are not necessarily to energy supply, real by means of the renovation agent system for encapsulating or embedding in advance in basis material
Existing self-repair function, makes material be able to carry out selfreparing to internal or outer damage, removes a hidden danger, and extends coating and uses the longevity
Life is realized and is protected to the long-effective corrosion of ground.Corresponding renovation agent is not contained in common coating, after coating is destroyed, corrosion
Property medium directly reaches substrate surface, keeps coating gradually peeling-off.In addition to this, renovation agent is directly appended in coating, is not had
There is corresponding carrier, can be quickly precipitated with coating self-defect, be difficult to play the role of long-term Conservative restoration.
Summary of the invention
For the deficiency of existing coating, it is an object of that present invention to provide a kind of glass fibre corrosion inhibiter coatings and systems
Preparation Method.
To realize goal of the invention, the invention adopts a technical scheme as:
A kind of glass fibre corrosion inhibiter coatings, overcoating layer is by glass fibre, corrosion inhibiter, organic resin and auxiliary agent group
At, wherein in parts by weight, 90-95 parts of organic resin, 0.3-0.8 parts of glass fibre, 0.3-0.7 parts of thiocarbamide corrosion inhibiter
With 1-4.5 parts of auxiliary agent.
The glass fibre accounts for the 0.3wt.%-0.8wt.% of organic resin, and corrosion inhibiter accounts for the 0.3wt.%- of organic resin
0.8wt.%；Wherein, it is preferably 0.5% that glass fibre, which accounts for organic resin, and it is preferably 0.5% that corrosion inhibiter, which accounts for organic resin,
30-60 μm of the glass fibre length, 2-6 μm of diameter；Length is preferably 40-50 μm, and diameter is preferably 2-4 μm；
The corrosion inhibiter is the one or more of thiocarbamide and/or thiourea derivative, and the organic resin is epoxy resin, polyurethane resin
Or the one of which of acrylic resin.
Thiourea derivative described in the thiourea derivative is thiocarbamide end linkage function group；The functionalization group is
Amino, acyl group or aldehyde groups it is one or more.Thiourea derivative is preferably thiosemicarbazides, different cigarette aldehyde thiosemicarbazones or acyl
Base thiocarbamide；
The organic resin is epoxy resin, polyurethane resin or acrylic resin, wherein in coating known to the prior art
Curing agent corresponding with organic resin will be added according to recording in the description of product while middle addition organic resin, in coating
In weight be included in organic resin in, specially epoxy resin corresponds to polyamide curing agent, polyurethane resin corresponds to polyurethane
Curing agent or acrylic resin correspond to propylene acid as curing agent；
The auxiliary agent is 0.5-1 parts of levelling agents according to parts by weight, 1-1.5 parts of defoaming agents and 1-2 parts of silane coupling agents.
Wherein, levelling agent BYK333, defoaming agent GPE10, silane coupling agent KH550.
A kind of preparation method of glass fibre corrosion inhibiter coatings:
(1) glass fibre is taken according to the above ratio, is added in organic solvent, and ultrasound fullys shake, then takes corrosion inhibiter
It is added into the above-mentioned organic solvent containing glass fibre, continues ultrasound and fully shake, so that it is uniformly dispersed, resulting dispersion waits for
With；Wherein, organic solvent is one or more compositions of ethyl alcohol, acetone and butyl acrylate；
(2) above-mentioned acquisition dispersion is added in organic resin in the ratio of 1:3-3:1, adds auxiliary agent later, fills
Divide and stirs evenly；
(3) curing agent is added in the organic resin dispersion liquid of step (2) again, is stirred, then drying is
Obtain coatings.
Above-mentioned acquisition coatings are sprayed or are scratched in metal surface, and then enable metal sustained release protection.
The metal is piling bar, oil pipeline, chemical industry equipment, ship or ocean platform metal equipment.
The present invention is had an advantage in that
Coating of the present invention includes glass fibre, corrosion inhibiter and organic resin.Corrosion inhibiter uniformly divides using glass fibre as carrier
It is scattered to film-forming in organic resin, making coating after disruption has good self-healing properties and corrosion resistance.The present invention
In glass fibre act not only as the carrier of corrosion inhibiter, cross-linked structure can also be formed in resin, improve coating
Toughness reduces coating damage probability.The present invention can extend coating stripping time 4- compared with other similar coating after film-forming
8 times, and its salt water penetration performance, simple process and low cost can be improved.
Detailed description of the invention
Fig. 1 is that glass fibre thiocarbamide provided in an embodiment of the present invention disperses film forming figure in resin；
Fig. 2 (a) is damaged blank epoxy coating natural immersion in 3.5% sodium chloride solution provided in an embodiment of the present invention
Surface topography photo after 1000 hours；
Fig. 2 (b) is that damaged selfreparing epoxy coating provided in an embodiment of the present invention soaks naturally in 3.5% sodium chloride solution
Surface topography photo of the bubble after 1000 hours；
Fig. 3 is that coatings provided in an embodiment of the present invention impregnate ac impedance spectroscopy variation in 3.5%NaCl solution
Figure；
Fig. 4 is blank coating provided in an embodiment of the present invention and the coatings polarization curve in 3.5%NaCl solution
Variation diagram；
Fig. 5 be different coating provided in an embodiment of the present invention coating resistance in the 3.5wt.%NaCl solution at any time
Variation diagram；
Fig. 6 be different coating provided in an embodiment of the present invention coating capacitor in the 3.5wt.%NaCl solution at any time
Variation diagram.
Specific embodiment
The present invention is the glass fibre corrosion inhibiter coatings of acquisition after extensive and in-depth study, made coating
Both can be used as priming paint, it is also possible to make intermediate coat, with metallic matrix binding force it is big, with finishing coat good compatibility, have both after film-forming
Good antistripping property and Anti-Chloride Ion Penetration, it is low in cost, technique letter is provided for the anti-corrosion of metal after coating damage
Single mode.
Coatings of the invention, after natural immersion 1000 hours, coating does not blister around breakdown point, breakdown point
Place's metallic corrosion products significantly reduces；By simulated seawater (3.5%NaCl solution) immersion test, using Solartron 1287
The test of+1260 electrochemical workstations, discovery corrosion inhibiter can extend about 4-8 times of resistance to splitting time of epoxy coating.
Substance provided by the present invention can be synthesized by marketable material or traditional chemical transform mode.Wherein, levelling agent
For BYK333, defoaming agent GPE10, silane coupling agent KH550.
Other aspects of the present invention are apparent to those skilled in the art due to this disclosure
's.
Below in conjunction with specific embodiment, the present invention is furture elucidated.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Unless otherwise defined or described herein, all professional and scientific terms used herein and the skilled people of art technology
Meaning known to member is identical.Furthermore any method similar to or equal to what is recorded and material all can be applied to the present invention
In method.
The preparation of 1 acylthioureas of embodiment
In 50ml hot acetone, 10g potassium rhodanate is added, 10g lauroyl chloride is heated to reflux to osmanthus acyl chlorides smell and disappears,
It is cooled to room temperature, is filtered to remove potassium chloride.The ammonium hydroxide of 15ml 28% is added in filtrate under stirring conditions, is evaporated, nothing
Water-ethanol extraction, obtains acylthioureas.
The preparation of 2 selfreparing epoxy coating of embodiment
It weighs that 0.5g is above-mentioned to prepare acylthioureas, 0.5g glass fibre is added and (is purchased from Ke Bangfu nanometers of skills of Beijing state
Art research institute), it is added to ultrasonic disperse 1 hour in dehydrated alcohol, content of the acylthioureas in dehydrated alcohol reaches after dispersion
0.01g/mL.The made dispersion liquid containing glass fibre and corrosion inhibiter is added in 45g epoxy resin (purchased from Jinan Tian Mao resin
Chemical company), it sequentially adds 0.6g levelling agent, 0.9g defoaming agent, 1.1g silane coupling agent and 45g polyamide curing agent and (is purchased from
Feicheng De Yuan Chemical Co., Ltd.), it stirs evenly, selfreparing epoxy coating can be obtained.
The preparation of 3 selfreparing polyurethane coating of embodiment
0.5g thiocarbamide (purchased from Sinopharm Chemical Reagent Co., Ltd.) is weighed, 0.5g glass fibre is added and (is purchased from Beijing
Ke Bangfu nanotechnology research institute, state), it is added to ultrasonic disperse 1 hour in acetone, the content of thiocarbamide in acetone reaches after dispersion
To 0.01g/mL.The made dispersion liquid containing glass fibre and corrosion inhibiter is added in 80g polyurethane resin (purchased from Ningbo flywheel
Zao Qi Co., Ltd), sequentially add 0.6g levelling agent, 1.0g defoaming agent, 1.1g silane coupling agent and 13.6g urethane cures
Agent stirs evenly, and selfreparing polyurethane coating can be obtained.The preparation of 4 selfreparing acrylic acid coatings of embodiment
0.5g thiosemicarbazides (purchased from Shanghai Jing Chun biochemical technology limited liability company) is weighed, 0.5g glass fibre is added
(being purchased from Beijing state Ke Bangfu nanotechnology research institute), is added to ultrasonic disperse 1 hour in butyl acrylate, amino sulphur after dispersion
Content of the urea in butyl acrylate reaches 0.01g/mL.The made dispersion liquid containing glass fibre and corrosion inhibiter is added to 80g
(Ningbo flywheel Zao Qi Co., Ltd is purchased from) in acrylic resin, sequentially adds 0.6g levelling agent, 0.9g defoaming agent, 1.1g silane
Coupling agent and 24g propylene acid as curing agent, stir evenly, selfreparing acrylic acid coatings can be obtained.
The preparation of 5 selfreparing polyurethane coating of embodiment
0.5g acylthioureas (purchased from Sinopharm Chemical Reagent Co., Ltd.) is weighed, 0.5g glass fibre is added and (is purchased from
Beijing state Ke Bangfu nanotechnology research institute), it is added to ultrasonic disperse 1 hour in acetone, thiocarbamide containing in acetone after dispersion
Amount reaches 0.01g/mL.The made dispersion liquid containing glass fibre and corrosion inhibiter is added in 80g polyurethane resin (purchased from Ningbo
Flywheel Zao Qi Co., Ltd), 1g levelling agent, 2g defoaming agent, 2.67g anti-settling agent and 13.6g polyurethane curing agent are sequentially added, is stirred
It mixes uniformly, selfreparing polyurethane coating can be obtained.
The preparation of 6 selfreparing acrylic acid coatings of embodiment
0.5g acylthioureas (purchased from Sinopharm Chemical Reagent Co., Ltd.) is weighed, 0.5g glass fibre is added and (is purchased from
Beijing state Ke Bangfu nanotechnology research institute), it is added to ultrasonic disperse 1 hour in butyl acrylate, thiocarbamide is in propylene after dispersion
Content in acid butyl ester reaches 0.01g/mL.The made dispersion liquid containing glass fibre and corrosion inhibiter is added to 80g acrylic acid tree
(purchased from Ningbo flywheel Zao Qi Co., Ltd is purchased from) in rouge, 1g levelling agent, 2g defoaming agent, 2.67g anti-settling agent and 24g are sequentially added
Propylene acid as curing agent, stirs evenly, and selfreparing acrylic acid coatings can be obtained.
Embodiment 7: the anti-corrosion effect of coatings compares
(1) salt water resistance of coatings
The selfreparing epoxy coating electrode and blank epoxy electrode that above-described embodiment is obtained, are immersed in 3.5% chlorination
1000h in sodium solution, taking-up are taken pictures (referring to fig. 2) after being dried at room temperature for, as seen from Figure 2 pure epoxy resin coating surface
There are a large amount of rusty stains, one is bubbled around breakdown point, and is not bubbled significantly around selfreparing epoxy coating electrode breakages point
Phenomenon occurs, and rusty stain is also less.
(2) antiseptic property of coatings
The corrosion resisting property of evaluation coatings in simulated seawater (3.5%NaCl solution).Using Solartron
1287+1260 electrochemical workstation, with AC impedance and dynamic potential polarization curve measuring technology analysis corrosion inhibiter and glass fibre
To the mechanism of action of epoxy coating.Using the saturated calomel electrode with Luggin capillary as reference electrode, platinum plate electrode is to electricity
Pole, selfreparing epoxy coating/carbon steel electrode are working electrode, and impregnating in simulated seawater solution stablizes open circuit potential (OCP)
Afterwards, with sine wave disturbance amplitude 20mV at OCP, frequency range is that 100000Hz-0.01Hz carries out EIS scanning.Polarization curve
Scanning speed be 0.5mV/s, scanning range be -200-200mV vs.OCP.Results of AC impedance is shown in Fig. 3, polarization curve knot
Fruit sees Fig. 4.0.5wt.% glass fibre and 0.5wt.% thiocarbamide are added in coating as seen from Figure 3, to 40 since impregnating the 5th day
It terminates, and impedance value is always more than initial impedance.The coating polarization for adding fiber and thiocarbamide as seen from Figure 4 is applied relative to blank
Layer, system anode and cathode polarizes to be deviated to low corrosion current direction, shows anode and cathode mistake of the addition to carbon steel of corrosion inhibiter and fiber
Journey all has apparent inhibiting effect.Meanwhile anode is tieed up blunt current density and is gradually reduced, passivation section increases, pitting potential to
Positive direction offset, shows the resistance to Cl of carbon steel-Erosiveness gradually increases, and fiber and corrosion inhibiter are to Cl-The local corrosion of induction has bright
Aobvious inhibiting effect.
(3) the surface self-repairing performance characterization of coating
The resistance to seepage of water of coating is to evaluate an important indicator of Performance of Epoxy Coatings, due to big in soaking process
The infiltration of dielectric constant hydrone, coating resistance are changed significantly (referring to figs. 5 and 6).Not by the visible expression of Fig. 5 and Fig. 6 difference
With the coating resistance R in the epoxy coating system of additive, obtained according to Equivalent Circuit FittingcWith coating capacitor QcWhen with impregnating
Between variation.In blank coating system, with the extension of soaking time, due to the gradually infiltration of hydrone, RcIt is gradually reduced,
QcIt is gradually increased, illustrates that the corrosion resisting property of coating gradually weakens, the protective performance of Q235 carbon steel is reduced.When being added in coating
When 0.5wt.% glass fibre and 0.5wt.% thiocarbamide, coating resistance can keep good continuity, when by the 40th day, value
About 8 times of blank coating resistance, illustrate that selfreparing works well.
Claims (8)
1. a kind of preparation method of glass fibre corrosion inhibiter coatings, it is characterised in that:
Overcoating layer is made of glass fibre, corrosion inhibiter, organic resin and auxiliary agent, wherein in parts by weight, organic resin
90-95 parts, 0.3-0.8 parts of glass fibre, 0.3-0.7 parts of thiocarbamide corrosion inhibiter and 1-4.5 parts of auxiliary agent；
(1) glass fibre is taken according to the above ratio, is added in organic solvent, and ultrasound fullys shake, then corrosion inhibiter is taken to add
Enter into the above-mentioned organic solvent containing glass fibre, continues ultrasound and fully shake, so that it is uniformly dispersed, resulting dispersion is stand-by；
Wherein, organic solvent is one or more compositions of ethyl alcohol, acetone and butyl acrylate；
(2) above-mentioned acquisition dispersion is added in organic resin in the ratio of 1:3-3:1, adds auxiliary agent later, sufficiently
It stirs evenly；
(3) curing agent is added in the organic resin dispersion liquid of step (2) again, is stirred, it is then obtained by drying
To coatings；
30-60 μm of the glass fibre length, 2-6 μm of diameter.
2. the preparation method of glass fibre corrosion inhibiter coatings according to claim 1, it is characterised in that: obtained above-mentioned
It sprays or is scratched in metal surface derived from reparation, and then enable metal sustained release protection.
3. the preparation method of glass fibre corrosion inhibiter coatings as described in claim 2, it is characterised in that: the metal
For piling bar, oil pipeline, chemical industry equipment, ship or ocean platform metal equipment.
4. a kind of glass fibre corrosion inhibiter coatings of any one of claim 1-3 preparation method preparation, it is characterised in that:
Overcoating layer is made of glass fibre, corrosion inhibiter, organic resin and auxiliary agent, wherein in parts by weight, organic resin 90-95
Part, 0.3-0.8 parts of glass fibre, 0.3-0.7 parts of thiocarbamide corrosion inhibiter and 1-4.5 parts of auxiliary agent.
5. by glass fibre corrosion inhibiter coatings described in claim 4, it is characterised in that: the glass fibre occupies machine tree
The 0.3wt%-0.8wt% of rouge, corrosion inhibiter account for 0.3 wt%-0.8 wt% of organic resin.
6. pressing claim 4 or the glass fibre corrosion inhibiter coatings, it is characterised in that: the glass fibre length
30-60 μm, 2-6 μm of diameter；The corrosion inhibiter is one or more, the organic resin of thiocarbamide and/or thiourea derivative
For epoxy resin, the one of which of polyurethane resin or acrylic resin.
7. by glass fibre corrosion inhibiter coatings described in claim 6, it is characterised in that: sulphur described in the thiourea derivative
Urea derivative is thiocarbamide end linkage function group；The functionalization group be amino, acyl group or aldehyde groups one kind or
It is a variety of.
8. by glass fibre corrosion inhibiter coatings described in claim 4, it is characterised in that: the organic resin is asphalt mixtures modified by epoxy resin
Rouge, polyurethane resin or acrylic resin；The auxiliary agent is 0.5-1 parts of levelling agents according to parts by weight, 1-1.5 parts of defoaming agents
With 1-2 parts of silane coupling agents.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215407A (en) * | 2008-01-18 | 2008-07-09 | 中山大学 | High temperature self-restoring fibre enhancement epoxy composite material and preparation method thereof |
| CN102505604A (en) * | 2011-11-18 | 2012-06-20 | 北京工业大学 | Anti-cracking interlayer for asphalt pavement |
| CN104312436A (en) * | 2014-09-28 | 2015-01-28 | 青岛高远光电测控技术有限公司 | Silencing coating for automobile exhaust pipe |
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| CN1092250C (en) * | 1998-04-08 | 2002-10-09 | 中国科学院福建物质结构研究所二部 | Novel corrosion inhibitor for inhibiting iron and steel corrosion in 10%-25% concentration celery salt solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215407A (en) * | 2008-01-18 | 2008-07-09 | 中山大学 | High temperature self-restoring fibre enhancement epoxy composite material and preparation method thereof |
| CN102505604A (en) * | 2011-11-18 | 2012-06-20 | 北京工业大学 | Anti-cracking interlayer for asphalt pavement |
| CN104312436A (en) * | 2014-09-28 | 2015-01-28 | 青岛高远光电测控技术有限公司 | Silencing coating for automobile exhaust pipe |
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