CN102634262A - Modified epoxy ballast tank paint - Google Patents
Modified epoxy ballast tank paint Download PDFInfo
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- CN102634262A CN102634262A CN2012101184412A CN201210118441A CN102634262A CN 102634262 A CN102634262 A CN 102634262A CN 2012101184412 A CN2012101184412 A CN 2012101184412A CN 201210118441 A CN201210118441 A CN 201210118441A CN 102634262 A CN102634262 A CN 102634262A
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Abstract
The invention relates to a modified epoxy ballast tank paint which is prepared from a component A and a component B in mass ratio of 100:20, wherein every 100 mass parts of component A comprises 20 parts of epoxy resin, 10 parts of modified resin, 50-55 parts of pigment and filler, 1-3 parts of assistant and the balance of organic solvent; the modified resin is the reaction product of hydroxyl-containing liquid C-9 resin and isocyanate-terminated polyether polyurethane in a mass ratio of 1/1; and the component B is prepared by the following steps: by using polyamide, 2-nitrogen-containing siloxane coupling agent and methyl isobutyl ketone as raw materials, dehydrating part of the polyamide, the 2-nitrogen-containing siloxane coupling agent and the methyl isobutyl ketone at 110-120 DEG C under reflux, continuing refluxing for 1 hour after finishing dehydrating, cooling to 40 DEG C, adding the rest of polyamide, and uniformly stirring to obtain the component B. The properties of the coated film of the modified epoxy ballast tank paint completely satisfy the requirements of Norsok M-501 for ballast tank paints.
Description
Technical field
The present invention relates to a kind of modified epoxy ballast tank coating.
Background technology
Ballast tank of ship is that in the cabin one type of quite special cabin in the boats and ships.Owing to be in the harsh corrosive environment of high temperature, high humidity and sea water immersion in the cabin; And between the usage period; The loading of seawater and discharge hocket repeatedly; Add the complicated structure in cabin, make that the erosion shield of ballast tank bubbles easy within a short period of time, crackle, early failure such as peel off, and then cause that the ballast tank hull structure is corroded to boats and ships and bring harm.What the supercoat of present 90% ballast tank adopted is the high-solid epoxy resin protective system.Generally be to prepare with liquid epoxies and low viscous solidifying agent; The degree of crosslinking of filming height, good, the strong adhesion of wear resistance; But bigger than normal, the poor impact resistance of the fragility of filming, for frequently the flexibility of loading-row's year alternate environment is bad in the ballast compartment, the easy of crack of filming is peeled off.Prepare coal tar-epoxy coating in the epoxy resin for the head it off employing adds coal-tar pitch, have excellent solidity to corrosion, reduction process external coating flexibility and high performance-price ratio, in the boats and ships protection against corrosion, be used widely owing to film.But because of coal tar pitch contains carcinogens, its use range is restricted, and particularly developed country has forbidden that it uses on boats and ships, thereby develops the modified epoxy coating that liquid petroleum resin substitutes coal tar in recent years again gradually.In order to obtain high-solid level or superelevation solids constituent modified epoxy coating, the liquid petroleum resin of being selected for use is low-molecular-weight carbon-9 resin.This liquid petroleum resin can reduce coated glass invert point (Tg) and increase free volume, thereby has improved the snappiness (for example publication number is the Chinese patent of CN101134867A and CN101133133A) of filming.Yet, to compare with the epoxy coating that does not have modification, the epoxy coating of liquid petroleum resin modification is found in condensation cabin test (40 ℃ water), films and bubbles easily, has influenced the protection effect of filming.In addition; In order significantly to improve coating efficiency; Economize on resources, the steel of intact shop primer get final product the application epoxy coating after slightly sweeping sand, and this just requires epoxy coating and shop primer that good wettability and extremely strong sticking power are arranged; Can peel off from shop primer otherwise film, influence the protection effect of epoxy coating.
Summary of the invention
The objective of the invention is: a kind of deficiency that can overcome liquid petroleum resin modified epoxy coating is provided, can improves epoxy coating sticking power again and the modified epoxy ballast tank coating of shop primer wettability.
The technical scheme that realizes the object of the invention is: a kind of modified epoxy ballast tank coating, constitute by A component and B component, and it is characterized in that; The A component is 100: 20 with the mass parts ratio of B component, wherein, and in the A component of per 100 mass parts; 20 parts of epoxy resin, 10 parts of modified resin, 50～55 parts of pigment and fillers; 1～3 part of auxiliary agent, surplus are organic solvent; Said modified resin is liquid carbon-9 resin and the reaction product that contains the Texin 5590 of isocyanate terminated base of hydroxyl; The mass parts ratio of the two consumption is 1/1; Wherein, the liquid carbon of hydroxyl-9 resin is the LA-300 of RUTRERS company or one or both the mixture among the LA-700, and its hydroxy radical content is 1.5～3.0wt%; The Texin 5590 that contains isocyanate terminated base is the DESMODUR E14 or the DESMODUR E15 of BAYER company, and the content of its NCO is 3～5wt%; Said epoxy resin is one or more the mixture among E51, E44, the F51;
Said B component is to be raw material with polymeric amide, the siloxanes coupling agent that contains 2 nitrogen, MIBK; With part polymeric amide and the siloxanes coupling agent and the MIBK that contain 2 nitrogen; Dewater for 110～120 ℃ at reflux temperature, dehydration finishes, after refluxing 1 hour again; Cool to 40 ℃ and add remaining polymeric amide, stirring makes; Wherein, polymeric amide is the Versmide v-140 of Cognis company or the Ancamide350A of Airproduct company; The siloxanes coupling agent that contains 2 nitrogen is the A-1122 of the KH-792 of Nanjing Dawning, GE company, the Z-6020 of Dow Corning Corporation or the KBM-603 of Japan XINYUE.
In the above-mentioned modified epoxy ballast tank coating; Said modified resin prepares as follows: liquid carbon-9 resin and the 0.1 mass parts dibutyl tin laurate of 50 mass parts hydroxyls are added stirring intensification in the reactor drum; The Texin 5590 drop that under 80 ℃ 50 mass parts is contained isocyanate terminated base is added in the reaction kettle; Dropwise back insulation 2 hours, cooling discharging is modification and attaches fat.
In the above-mentioned modified epoxy ballast tank coating, said B component prepares as follows: the siloxanes coupling agent and the 20 mass parts MIBKs that contain 2 nitrogen with 70～75 mass parts polymeric amide, 5～10 mass parts are raw material, get 40% of polymeric amide consumption and add in the reaction kettle; Add silane coupling agent, the MIBK that contains 2 nitrogen then; Be warmed up to reflux temperature and dewater for 110～120 ℃, in water trap, do not have the globule to deviate from basically, after continuing again to reflux 1 hour; Cool to 40 ℃ and add remaining polymeric amide; After stirring, filter, gained filtrating is the B component.
Technique effect of the present invention is: 1. in the A component of technical scheme of the present invention; Used modified resin is liquid carbon-9 resin and the reaction product that contains the Texin 5590 of isocyanate terminated base of hydroxyl, and the NCO at Texin 5590 two ends is connected with the hydroxyl of the liquid carbon of hydroxyl-9 resin.Compare with unmodified liquid petroleum resin, modified resin of the present invention has kept the hydrophobicity and the snappiness of liquid carbon-9 resin, and the ehter bond of the Texin 5590 of introducing can rotate freely the generation toughening effect, has improved the snappiness of resin; Simultaneously the hydrogen bond of the ammonia ester bond in the modified resin has strengthened the effect of the secondary valence bond of modified resin key, has improved anti-transport property, overcome the epoxy coating that uses unmodified liquid petroleum resin agglutination,cold test (40 ℃ of water) time the easy blistered shortcoming of filming; 2. the B component of technical scheme of the present invention is to be raw material with polymeric amide, the siloxanes coupling agent that contains 2 nitrogen, MIBK; With part polymeric amide and the siloxanes coupling agent and the MIBK that contain 2 nitrogen; Dewater for 110～120 ℃ at reflux temperature, dehydration finishes, after refluxing 1 hour again; Cool to 40 ℃ and add remaining polymeric amide, stirring makes.Between the reaction period, MIBK respectively with polymeric amide, contain 2 nitrogen the siloxanes coupling agent uncle ammonia hydrogen carry out ketoimineization.The nitrogenous siloxanes coupling agent of ketoimineization is active suitable; Having overcome nitrogenous siloxanes coupling agent hyperactivity can influence the shortcoming of solidifying agent stability; Test shows; B component normal temperature of the present invention is placed and still was transparence in 6 months, and MIBK, polymeric amide, the normal temperature that contains the siloxanes coupling agent of 2 nitrogen mix the solidifying agent of preparation, and normal temperature is placed and occurred March muddyly also separating out; Compare with other siloxanes coupling agents simultaneously, the siloxanes coupling agent that B component of the present invention has kept nitrogen atom again can obviously improve the advantage of film wet sticking power and stripper-resistance; Ketoimineization has also been sealed simultaneously the reactivity that uncle's ammonia on the polymeric amide has not only reduced solidifying agent, and the recoat that has prolonged coating improves the recoat performance of coating at interval, has also improved the perviousness at moist surface; Because of used polymeric amide is the dimeracid and the polyethylene polyamine reaction thing of low polymerization degree; The one of which end is the hydrophobic structure of the long carbochain of dimeracid; The other end is the hydrophilic-structure of polyamines, similar nonionic emulsifying agent, therefore; Mend the polymeric amide and the ketoimine polymeric amide of going into after the ketoimineization, many grounds are had good wetting action.Like this, polymeric amide and ketoimine polymeric amide are to ground wettability and the nitrogenous siloxanes coupling agent chemically bonded to ground, and synergy has improved the sticking power of coating on ground each other; 3. the consumption of the formation of determined A component of the present invention and B component and each composition cooperates appropriately, and making films has good penetration, wetting action, the firm person's of attaching power and excellent non-corrosibility to ground.
Filming of modified epoxy ballast tank coating of the present invention carried out correlated performance to be detected; Its result (seeing table 4) shows that the snappiness and the impact resistance of filming are good, and bubbling does not appear in the test of condensation cabin; The anti-cathodic disbonding property≤8mm of coating; The monolateral expansion erosion≤8mm of round-robin test performance, sea water resistance 4200h film and do not bubble, and meet the requirement of Norsok M-501 to ballast tank coating fully.
Embodiment
Below in conjunction with embodiment the present invention is made further specific descriptions, but be not limited to this.
Each embodiment and comparative example are raw materials used, unless otherwise indicated, are coating with the commercially available article of technical grade.
In the A component of per 100 mass parts of modified epoxy ballast tank coating of the present invention, 20 parts of epoxy resin, modified resin 10 minutes, 50～55 parts of pigment and fillers, 1～3 part of auxiliary agent, surplus is an organic solvent; Said modified resin is liquid carbon-9 resin and the reaction product that contains the Texin 5590 of isocyanate terminated base of hydroxyl; The mass parts ratio of the two consumption is 1/1; Wherein, the liquid carbon of hydroxyl-9 resin is the LA-300 of RUTRERS company or one or both the mixture among the LA-700, and its hydroxy radical content is 1.5～3.0wt%; The Texin 5590 that contains isocyanate terminated base is the DESMODUR E14 or the DESMODUR E15 of BAYER company, and the content of its NCO is 3～5wt%; Said epoxy resin is one or more the mixture among E51, E44, the F51;
Embodiment 1 preparation modified resin
1. prescription is seen table 1.
Table 1
2. prepare modified resin
Pressing table 1 prescription adds liquid carbon-9 resin of hydroxyl and stirs intensification in the reactor drum with dibutyl tin laurate; 80 ℃ of Texin 5590 drips of solution that will contain isocyanate terminated base down are added in the reaction kettle; Dropwise back insulation 2 hours, cooling discharging makes modified resin 1 and modified resin 2 respectively, preserves subsequent use; The modified resin outward appearance is yellowish transparence, and 50 ℃ store not gelling in 30 days;
The A component of embodiment 2 preparation modified epoxy ballast tank coating
1. the concrete prescription of A component is seen table 2.
Table 2
2. prepare the A component
In dispersion tank, add epoxy resin, modified resin, organic solvent, auxiliary agent, the back that stirs adds organobentonite; High-speed stirring 15min makes the fully wetting and dispersion of organobentonite, adds white titanium pigment, talcum powder, Feldspar Powder then; Stir, be ground to fineness 60 μ m through sand mill again, filter, pack; Make the A component 1 and A component 2 of modified epoxy ballast tank coating respectively, preserve subsequent use.
The B component of modified epoxy ballast tank coating of the present invention is to be raw material with polymeric amide, the siloxanes coupling agent that contains 2 nitrogen, MIBK; With part polymeric amide and the siloxanes coupling agent and the MIBK that contain 2 nitrogen; Dewater for 110～120 ℃ at reflux temperature, dehydration finishes, after refluxing 1 hour again; Cool to 40 ℃ and add remaining polymeric amide, stirring makes; Wherein, polymeric amide is the Versmide v-140 of Cognis company or the Ancamide350A of Airproduct company; The siloxanes coupling agent that contains 2 nitrogen is the A-1122 of the KH-792 of Nanjing Dawning, GE company, the Z-6020 of Dow Corning Corporation or the KBM-603 of Japan XINYUE.
The B component of embodiment 3 preparation modified epoxy ballast tank coating
1. prescription is seen table 3.
Table 3
2. prepare the B component
Get 30 mass parts polymeric amide and add in the reaction kettle, add silane coupling agent, the MIBK that contains 2 nitrogen then, be warmed up to reflux temperature and dewater for 110～120 ℃; In water trap, do not have the globule to deviate from basically, after continuing again to reflux 1 hour, cool to 40 ℃ of polymeric amide that add remaining 45 mass parts; After stirring, filter, gained filtrating is respectively B component 1 and B component 2; Its outward appearance initially is transparence, and sampling is sealed in the vial, and normal temperature is placed and still was transparence in 6 months.
Embodiment 4 preparation modified epoxy ballast tank coating
1. prepare modified epoxy ballast tank coating 1
Embodiment 2 A component 1 that makes and the B component 1 that embodiment 3 makes are stirred respectively; By the mass parts ratio of A component 1 and B component 1 is to mix at 100: 20; Make modified epoxy ballast tank coating 1, the coating for preparing can spray after placing 15～30min slaking;
2. prepare modified epoxy ballast tank coating 2
Embodiment 2 A component 2 that makes and the B component 2 that embodiment 3 makes are stirred respectively; By the mass parts ratio of A component 2 and B component 2 is to mix at 100: 20; Make modified epoxy ballast tank coating 2, the coating for preparing can spray after placing 15～30min slaking.
In order to show the following relatively coating 1～4 of coating characteristic preparation of the present invention
Compare coating 1
The A component is identical with the A component 1 of embodiment 2;
The B component is that 20 mass parts MIBKs stir with 80 mass parts polymeric amide Versmide v-140, filters and packages (not with the siloxanes coupling agent that contains 2 N) that make;
Compare coating 2
The A component replaces modified resin 1 with liquid carbon-9 resin LA300, and all the other are identical with the A component 1 of embodiment 2;
The B component is identical with the B component 1 of embodiment 3;
Compare coating 3
The A component replaces modified resin 2 with 8 mass parts liquid carbon-9 resin LA700, increases the siloxanes coupling agent KH560 that 2 mass parts contain epoxy group(ing), and all the other are identical with the A component 2 of embodiment 2;
The B component is identical with comparative example 1;
Compare coating 4
The A component is not used modified resin, does not use liquid carbon-9 resin yet, but adopts 28 mass parts epoxy resin E44, and 2 mass parts contain the siloxanes coupling agent KH560 of epoxy group(ing), and all the other are identical with the A component 1 of embodiment 2;
The B component is identical with comparative example 1;
The compound method of above-mentioned relatively coating 1～4 is all identical with embodiment 4.
The coating of embodiment 4 and the film performance of comparative example 1～4 coating are detected
Detect correlated performance as follows, the result is listed in table 4.
Snappiness is pressed GB/T 1731-1993, shock test is pressed GB/T 1732-1993, and test plate (panel) is tinplate, thickness 20 ± 3 μ m;
Draw back the method adhesion test by GB/T 5210-2006, sea water resistance by GB/T 9274-1988, condensation cabin test GB/T 6823-2008, round-robin test by norsok m-501 ballast tank system requirements, anti-cathodic disbonding property by GB/T 7790-2008; Test plate (panel) is the sandblast steel plate, thickness 320 ± 20 μ m.
Table 4
Can know by table 4 detected result:
1, the snappiness and the impact resistance of modified epoxy ballast tank coating of the present invention (embodiment 4 coating 1 and coating 2) coating are good, and bubbling does not appear in agglutination,cold test; The anti-cathodic disbonding property≤8mm of coating, the monolateral expansion erosion≤8mm of round-robin test, sea water resistance 4200h film and do not bubble, and meet the requirement of Norsok M-501 to ballast tank coating;
2, relatively coating 1 is basic identical with the coating 1 of embodiment 4; Difference is: do not use the siloxanes coupling agent that contains 2 nitrogen in the B component; It films bigger in the monolateral expansion erosion of round-robin test, and anti-cathodic disbonding property is relatively poor, has proved the effect of the siloxanes coupling agent that contains 2 nitrogen;
3, relatively coating 2 is basic identical with the coating 1 of embodiment 4; Difference is: do not use modified resin in the A component 1; And replace with liquid carbon-9 resin LA300; Snappiness that it is filmed and shock-resistant punching performance are good, but bubbling appears in the test of condensation cabin, proves that the condensation cabin experimental performance of modified resin is superior to unmodified liquid carbon-9 resin;
4, relatively coating 3 is basic identical with the coating 2 of embodiment 4, and difference is: A component 2 is not used modified resin, and replaces with liquid carbon-9 resin LA700, in the A component, adds the siloxanes coupling agent that contains epoxy group(ing), and the B component is with comparative example 1.Though snappiness and impact resistance that it is filmed are good, filming foaming occurred when testing in the condensation cabin, proves the effect of modified resin; It is bigger in the monolateral expansion erosion of round-robin test to film, and has surpassed 8mm, has proved that the effect of the siloxanes coupling agent that contains 2 nitrogen in the coating is superior to containing the siloxanes coupling agent of epoxy group(ing);
5, comparative example 4 coating are basic identical with existing pure epoxy coating; The A component does not add modified resin and only uses epoxy resin E44; It is single polymeric amide versmide v-140 that the B component does not add the siloxanes coupling agent that contains 2 nitrogen; The snappiness of filming, impact resistance, anti-cathodic disbonding property and round-robin test performance be all not as by modified epoxy ballast tank coating of the present invention (embodiment 4), proves that determined A component of the present invention and B component cooperatively interact and have good synergy.
Claims (3)
1. a modified epoxy ballast tank coating is made up of A component and B component, it is characterized in that; The A component is 100: 20 with the mass parts ratio of B component, wherein, and in the A component of per 100 mass parts; 20 parts of epoxy resin, 10 parts of modified resin, 50～55 parts of pigment and fillers; 1～3 part of auxiliary agent, surplus are organic solvent; Said modified resin is liquid carbon-9 resin and the reaction product that contains the Texin 5590 of isocyanate terminated base of hydroxyl; The mass parts ratio of the two consumption is 1/1; Wherein, the liquid carbon of hydroxyl-9 resin is the LA-300 of RUTRERS company or one or both the mixture among the LA-700, and its hydroxy radical content is 1.5～3.0wt%; The Texin 5590 that contains isocyanate terminated base is the DESMODUR E14 or the DESMODUR E15 of BAYER company, and the content of its NCO is 3～5wt%; Said epoxy resin is one or more the mixture among E51, E44, the F51;
Said B component is to be raw material with polymeric amide, the siloxanes coupling agent that contains 2 nitrogen, MIBK; With part polymeric amide and the siloxanes coupling agent and the MIBK that contain 2 nitrogen; Dewater for 110～120 ℃ at reflux temperature, dehydration finishes, after refluxing 1 hour again; Cool to 40 ℃ and add remaining polymeric amide, stirring makes; Wherein, polymeric amide is the Versmide v-140 of Cognis company or the Ancamide350A of Airproduct company; The siloxanes coupling agent that contains 2 nitrogen is the A-1122 of the KH-792 of Nanjing Dawning, GE company, the Z-6020 of Dow Corning Corporation or the KBM-603 of Japan XINYUE.
2. modified epoxy ballast tank coating according to claim 1; It is characterized in that; Said modified resin prepares as follows: liquid carbon-9 resin and the 0.1 mass parts dibutyl tin laurate of 50 mass parts hydroxyls are added stirring intensification in the reactor drum; The Texin 5590 drop that under 80 ℃ 50 mass parts is contained isocyanate terminated base is added in the reaction kettle, dropwises back insulation 2 hours, and cooling discharging is modified resin.
3. modified epoxy ballast tank coating according to claim 1 is characterized in that, said B component prepares as follows: the siloxanes coupling agent and the 20 mass parts MIBKs that contain 2 nitrogen with 70～75 mass parts polymeric amide, 5～10 mass parts are raw material; Get 40% of polymeric amide consumption and add in the reaction kettle, add silane coupling agent and the MIBK that contains 2 nitrogen then, be warmed up to reflux temperature and dewater for 110～120 ℃; In water trap, there is not the globule to deviate from basically; After continuing again to reflux 1 hour, cool to 40 ℃ and add remaining polymeric amide, after stirring; Filter, gained filtrating is the B component.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210118441.2A CN102634262B (en) | 2012-04-20 | 2012-04-20 | Modified epoxy ballast tank paint |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210118441.2A CN102634262B (en) | 2012-04-20 | 2012-04-20 | Modified epoxy ballast tank paint |
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| CN102634262A true CN102634262A (en) | 2012-08-15 |
| CN102634262B CN102634262B (en) | 2014-11-05 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602220A (en) * | 2013-11-14 | 2014-02-26 | 中国海洋石油总公司 | Siloxane hybrid anticorrosive paint |
| CN110564192A (en) * | 2019-08-29 | 2019-12-13 | 铜陵市永锐电器成套设备有限责任公司 | high-low voltage switch cabinet anticorrosion technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007129564A1 (en) * | 2006-05-10 | 2007-11-15 | Chugoku Marine Paints, Ltd. | Anticorrosive coating composition |
| CN101134867A (en) * | 2007-09-28 | 2008-03-05 | 中山大桥化工有限公司 | Shipping ballast cabin coating composition |
| CN101781508A (en) * | 2010-01-18 | 2010-07-21 | 中国海洋石油总公司 | Epoxy protective coating system for high-power nuclear power station |
-
2012
- 2012-04-20 CN CN201210118441.2A patent/CN102634262B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007129564A1 (en) * | 2006-05-10 | 2007-11-15 | Chugoku Marine Paints, Ltd. | Anticorrosive coating composition |
| CN101134867A (en) * | 2007-09-28 | 2008-03-05 | 中山大桥化工有限公司 | Shipping ballast cabin coating composition |
| CN101781508A (en) * | 2010-01-18 | 2010-07-21 | 中国海洋石油总公司 | Epoxy protective coating system for high-power nuclear power station |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602220A (en) * | 2013-11-14 | 2014-02-26 | 中国海洋石油总公司 | Siloxane hybrid anticorrosive paint |
| CN110564192A (en) * | 2019-08-29 | 2019-12-13 | 铜陵市永锐电器成套设备有限责任公司 | high-low voltage switch cabinet anticorrosion technology |
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