CN101781505A - Underwater coating heavy corrosion protection coating and preparation method thereof - Google Patents
Underwater coating heavy corrosion protection coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of coating, in particular to an underwater coating heavy corrosion protection coating and a preparation method thereof. The coating is prepared by taking modified epoxy resin and complex curing agent as main film-forming materials and adding pigment and fillers. The coating has high underwater bonding strength and excellent underwater brushing performance. The coating is an environment-friendly product which has low surface treatment, does not float and is not decomposed when underwater construction, has good levelling property, good adhesive force and good drying performance. The product is applicable to the protection of surfaces of buildings, structures, bridges, drilling platforms, piles and columns and the like in seawater and fresh water, saves energy, shortens the construction period and improves the efficiency.
Description
Technical field:
The present invention relates to paint field, be specially a kind of underwater coating heavy corrosion protection coating and preparation method thereof.
Background technology:
Along with marine oil, port and pier, the continuous development of hydropower station and shipping industry, many engineering structures that are in ocean environment, as drill winning apparatus, drilling unit, the offshore oil and gas storage tank, the bracing frame of line of pipes, trestle, piling bar, the interior cabin of hull bottom and boats and ships etc., owing to be immersed in the seawater throughout the year, or be subjected to the fluctuation of tidewater and splash, and the erosion that suffers marine biology and some mobiles, make the original preservative coat of structure wreck, keep in repair and these structures are difficult to move to land, this just presses for a kind of coating that can directly carry out application in seawater.In addition, Structural Engineering in the fresh water, as engineerings such as dyke, reservoir, sluice, underwater pipelines, and mine, tunnel, bathing pool, hot spring, swimming pool, tank, aqua storage tank, underground storehouse etc. are moist local, also all need curable coating in the water.In view of the above, developing heavy-duty coating a kind of environment-friendly type, can application in seawater and fresh water has great importance.
The eighties, all coating manufacture and the exploitations in being devoted to the water of practicability of each state.It is reported that Britain international standard does not have the underwater engineering rust proof paint that the erosion paint company is released epoxy-tar oil type, it is not water funk, can be directly at subaqueous work.The chemical stability of coating, water tolerance, hydrophobicity and toughness are all good.Resins, epoxy-polyamines curing system that SUMITOMO CHEMICAL chemical company releases, coating absorbs the water of substrate surface rapidly, and coating and ground are combined closely.Gradually the moisture content that absorbs is rejected to coatingsurface again in the solidification process, guarantees the integrity of coating system.
More original coating of " two component Wet-dry priming paint " life-span of domestic Wuhan Water Transporting Engineering College exploitation improves 3～5 times, can be at drying, humidity even subaqueous work.Sea rescue Salvage Bureau in Shanghai entrusts the subaqueous work protective system of Shanghai coating Research Institute to be tested and appraised March nineteen ninety.This coating has entered the practicability stage through on probation for many years, and its composition mainly is Resins, epoxy-polymeric amide system.The key problem in technology of coating is auxiliary agent and specific construction equipment.In a word, coating material solidified at the early-stage in the domestic water, with real practicability one segment distance is arranged still.
At present, the matured product of underwater coating heavy corrosion protection coating is the protective system under water of ES323 type 100% solid content of the excellent imperial company of Portugal production, and this coating is used in a lot of countries.The 9400 serial aqueous solidified epoxy coatings that the advanced paint company of U.S. AEGEON is produced not only can provide the erosion resistance protection for the equipment and the material of underwater operation, but also can be applied in the environment place of high humidity.Because the external product price is more expensive, is difficult in domestic big area and promotes.
So far, all kinds of coating of painting under water are base-material with Resins, epoxy all basically, are mixed with the coating of solvent-free or high solid, coating can discharge film and ground between moisture, solidify at normal temperatures rapidly, to reduce the impact of fluid filming.
Summary of the invention
The object of the invention is to provide a kind of underwater coating heavy corrosion protection coating and preparation method thereof, and this coating is environment-friendly type, cohesive strength height under water, and brushing excellent performance under water, preparation technology is simple, and cost is lower.
Technical scheme of the present invention is as follows:
A kind of underwater coating heavy corrosion protection coating by weight percentage, is made up of first component and component B two portions, and the first component accounts for 70～90%, and component B accounts for 10～30%.Wherein,
1, first component
The first component is the mill base that modified epoxy, pigment and filler are made, and counts by weight, and it is as follows to fill a prescription:
35～45 parts of modified epoxies;
15～25 parts of pigment;
25～50 parts of fillers;
Wherein, modified epoxy is made by epoxy amine affixture and the semiclosed thing reaction of tolylene diisocyanate, and the composition and the blending process of modified epoxy are as follows:
(1) count the prescription of epoxy amine affixture by weight:
1500～2000 parts of Resins, epoxy;
300～400 parts of diethylamides;
200～300 parts of dimethylbenzene.
(2) preparation technology of epoxy amine affixture:
1. Resins, epoxy and dimethylbenzene are added in the reactor heat temperature raising under constantly stirring, treat that temperature rises in the time of can flowing (60～80 ℃), begin to drip diethylamide, stir revolution 80～90 commentaries on classics/min, after dropwising, be incubated 1～3 hour down at 60～80 ℃;
2. under vacuum, deviate from xylene solvent, carry out sampling analysis after solvent has taken off;
3. analyzing oxirane value is between 0.23～0.25, and unhindered amina is 0, and is stand-by.
(3) count the prescription of the semiclosed thing of tolylene diisocyanate by weight:
800～900 parts of tolylene diisocyanates;
700～800 parts of 2 mercapto ethanols;
(4) preparation technology of the semiclosed thing of tolylene diisocyanate:
1. tolylene diisocyanate is added in the reactor, stir and be warming up to 40～60 ℃, begin to drip 2 mercapto ethanol, stir revolution 50～80 commentaries on classics/min, temperature is controlled at 50 ± 2 ℃, in 2～3 hours reaction times, is cooled to 20～25 ℃ naturally.
2. (weight percentage NCO), content are qualified, stand-by 25～27% to measure isocyanate group.
(5) count the prescription of modified epoxy by weight:
250～550 parts of epoxy amine affixtures;
150～350 parts of the semiclosed things of tolylene diisocyanate;
(6) preparation technology of modified epoxy:
Will the epoxy amine affixture and the semiclosed thing of tolylene diisocyanate add to stir in the reactor and heat up, insulation reaction is 1～3 hour when treating that temperature rises to 70～90 ℃, is cooled to 20～25 ℃ naturally, sampling and measuring-NCO content is 0 o'clock, i.e. salable product.
Among the present invention, pigment can be steady rust pigment, rust-stabilising pigment and inert pigment, as: one or more mixing in iron oxide red, zinc-chrome yellow, Stainless Steel Powder, zinc powder, aluminium powder, iron oxide black or the zinc phosphate etc., requiring granularity is 300～500 μ m.
Among the present invention, filler can for: one or more mixing in ground barium sulfate, composite iron-titanium powder or the mica powder etc., requiring granularity is 300～500 μ m.
(7) first component blending process:
Add modified epoxy earlier in joining paint can, start high speed dispersor, the revolution of dispersion machine is 800～1000 rev/mins, after 10～20 minutes, add pigment and filler, high speed dispersion is after 1～2 hour, grind on three-roller that to reach fineness be 60～80 μ m, get final product packing.
2, component B
Count by weight, component B is that the prescription of composite curing agent is as follows:
15～30 parts of solidifying agent I;
20～40 parts of solidifying agent II;
Wherein,
Solidifying agent I can be the solidifying agent of used for epoxy resin, as: one or more mixing in underwater curing agent 810 or the underwater curing agent 1085 etc.;
Solidifying agent II is a modified firming agent, counts the prescription of solidifying agent II by weight:
600～700 parts of oleic acid affixtures;
200～300 parts of diethylenetriamines;
(1) count the prescription of oleic acid affixture by weight:
300～700 parts of oleic acid;
200～600 parts in tung oil lipid acid;
0.2～1 part of calcium naphthenate;
Wherein, oleic acid can adopt the oleic acid in the cashew nut.
(2) preparation technology of oleic acid affixture:
In oleic acid and tung oil lipid acid and calcium naphthenate adding reactor, stir and be warming up to 200～300 ℃ of insulation reaction, to reaching 2.5～3.5 seconds, for salable product are continued to employ with Ge Shi pipe viscosimetric.
(3) preparation technology of solidifying agent II:
Oleic acid affixture and diethylenetriamine are added in the reactor, under constantly stirring, heat up, when reaching 270～280 ℃ etc. temperature of reaction, keep reaction 3～5 hours, sampling and measuring amine value reaches at 200～220 o'clock, is cooled to 200～220 ℃ again, starts vacuum pump and deviates from unhindered amina and reaction water, vacuum tightness reaches 0.89～0.92MPa, and it is salable product that resampling mensuration amine value reaches at 150～200 o'clock.Stop vacuum then, cooling, when temperature was reduced to 40～60 ℃, production process finished, and solidifying agent is stand-by.
(4) blending process of component B:
Solidifying agent I is joined among the solidifying agent II to scale, and stirring gets final product.
Among the present invention,, obtain underwater coating heavy corrosion protection coating, can use first component and component B two portions uniform mixing in proportion.
Design philosophy of the present invention is as follows:
1, resin choice
In the execution of coating process, the density of air and water and the greatest differences of viscosity number cause in air very easily the coating of the application very difficulty that becomes of constructing under water.In the film process of coating, the solvent evaporates membrane formation mechanism makes solvent evaporates become difficult in the static pressure that aqueous phase is subjected to water, and has only the ring-opening reaction mechanism of Resins, epoxy and the free radical reaction membrane formation mechanism of unsaturated polyester to be subjected to the influence of water less.Filming that the polyester system forms is thin and soft, is vulnerable to damage; Epoxy-resin systems contains polar hydroxyl and ehter bond etc., and there is certain wettability on wet surface, and good sticking power is arranged, and is widely used in anticorrosion under the severe rugged environment.Up to now, all kinds of coating of all underwater constructions, basically all be base-material with Resins, epoxy, can adopt low-molecular-weight liquid-state epoxy resin, the solvent-free system of preparation underwater curing, can also carry out modification or mix platform Resins, epoxy, to make the coating of excellent performance with other resins.
The present invention adopts low-molecular-weight epoxy resin, after introducing sulfydryl and ammonia ester bond carry out modification, increases the hydrophobic nature of coating and prevents the coating dispersiveness, and is good to wet wettability of the surface, more excellent sticking power arranged, the antiseptic property excellence.
2, the selection of solidifying agent
Underwater coating heavy corrosion protection coating needs special solidifying agent, and suitable viscosity and physical and mechanical properties and good construction performance and suitable curing speed under water be arranged.Epoxy curing agent commonly used, as: organic amine, organic acid anhydride, phenolic aldehyde amine etc. obtain good performance when being difficult to possess underwater construction.Realize resin at moist substrate even underwater curing, form and evenly to film continuously that key is that coating should have very big sticking power to ground, with discharge ground as much as possible and film between moisture, simultaneously a little water that can not discharge is transformed and utilizes.
Underwater coating heavy corrosion protection coating must be water insoluble and not by emulsifying water, and the comparison fast-curing epoxy resin, and the suitable construction time is arranged again.Through a large amount of experiment sievings, the present invention adopts two kinds of Compositional type solidifying agent, adopt underwater curing agent and solvent-free curing agent composite, solvent-free curing agent reacts with amine after adopting cashew nut oleic acid and the addition of tung oil lipid acid, increase hydrophobic nature, the Compositional type solidifying agent guarantees after two components are joined lacquer there is the suitable construction time, satisfies the requirement of underwater curing.
3, pigment and filler selection
In the underwater coating heavy corrosion protection coating pigment have shielding effect, increase paint film roughness, regulate the effect of the proportion of coating.Underwater coating heavy corrosion protection coating can adopt steady rust pigment, rust-stabilising pigment and inert pigment.Filler is based on inert material, and is bigger than important.Select heavy pigment and filler, make coating not floating.
Compare with coating in the prior art, the invention has the beneficial effects as follows:
1, underwater coating heavy corrosion protection coating of the present invention is that to be equipped with the Compositional type solidifying agent with modified epoxy be main film forming matter, dose pigment and filler is made, it is to enter the coating of anticorrosive construction under water, and coating is the cohesive strength height under water, under water the brushing excellent performance.
2, underwater coating heavy corrosion protection coating of the present invention can hang down surface treatment, and this coating has excellent hydrophobic nature, and underwater construction is met water and do not dissolved, under water construction not floating, do not decompose, belong to environmentally friendly machine.
3, underwater coating heavy corrosion protection coating chance water of the present invention does not disperse, and guarantees the quality of workmen's underwater construction.
4, underwater coating heavy corrosion protection coating of the present invention meet water do not produce floating, can be well attached to the coated article surface.
5, underwater coating heavy corrosion protection coating of the present invention has good levelling property and sticking power, paint film antiseptic property excellence.
6, underwater coating heavy corrosion protection coating of the present invention has good drying property (in 4～10 ℃ of water, surface drying was done solid work 24～48 hours less than 12 hours).
7, underwater coating heavy corrosion protection coating of the present invention is applicable to the protection on surfaces such as buildings in seawater, the fresh water, structures, bridge, drilling unit, stake, post, and save energy, is raised the efficiency at the reduction of erection time.
8, underwater coating heavy corrosion protection coating of the present invention can brush, blade coating, constructional method is simple, and the suitable construction time is arranged.
The present invention's protective system under water is as follows with the difference of general coating:
(1) general coating is coating decoration in air, without any resistance.The resistance that water is arranged during the underwater coating heavy corrosion protection coating construction, general coating is difficult for being coated onto body surface at subaqueous work and gets on, and underwater coating heavy corrosion protection coating of the present invention easily is coated onto body surface and gets on.
(2) because water has bigger buoyancy, general coating pollutes on being easy to coating climbed up on top of the water when application.Underwater coating heavy corrosion protection coating of the present invention does not have the problem that coating climbs up on top of the water when construction.
(3) general coating all contains certain amount of solvent and water-soluble material, and underwater coating heavy corrosion protection coating of the present invention does not then contain solvent and water-soluble substance.
(4) proportion of general coating is about 1.2～1.4g/cm
3, and the present invention under water the proportion of heavy-duty coating at 2.5～3.5g/cm
3, protective system is easy to overcome the surface tension of water so under water, and non-rising.
Embodiment:
Embodiment 1
Present embodiment is used for the protective system under water that the underground steel construction of water factory need be brushed, and by weight percentage, is made up of first component and component B two portions, and the first component accounts for 85%, and component B accounts for 15%.Wherein,
1, first component
The first component is the mill base that modified epoxy, pigment and filler are made, and counts by weight, and it is as follows to fill a prescription:
40 parts of modified epoxies;
25 parts of Stainless Steel Powders (granularity 400 μ m);
25 parts of composite iron-titanium powders (granularity 400 μ m);
10 parts of mica powders (granularity 400 μ m);
In the present embodiment, composite iron-titanium powder adopts the commercially available prod, as: can adopt Shijiazhuang evolve the forever composite iron-titanium powder 801 of worker company limited or composite iron-titanium powder 809 etc.
Wherein, modified epoxy is made by epoxy amine affixture and the semiclosed thing reaction of tolylene diisocyanate, and the composition and the blending process of modified epoxy are as follows:
(1) count the prescription of epoxy amine affixture by weight:
1960 parts of bisphenol A type epoxy resin E51;
365 parts of diethylamides;
250 parts of dimethylbenzene;
(2) preparation technology of epoxy amine affixture:
1. Resins, epoxy and dimethylbenzene are added in the reactor heat temperature raising under constantly stirring, when treating that temperature rises to Resins, epoxy and dimethylbenzene can flow (60 ℃), begin to drip diethylamide, stir revolution 84 commentaries on classics/min, the dropping time is 1 hour.After dropwising, be incubated 3 hours down at 60 ℃;
2. be that xylene solvent is deviate from distillation under 0.8～0.9MPa in vacuum tightness, carry out sampling analysis after solvent has taken off;
3. hydrochloric acid acetone method mensuration oxirane value is between 0.23～0.25, and it is 0 that acidimetry is measured unhindered amina content, is salable product, and it is stand-by to stay an operation.
(3) count the prescription of the semiclosed thing of tolylene diisocyanate by weight:
870 parts of tolylene diisocyanates;
760 parts of 2 mercapto ethanols;
(4) preparation technology of the semiclosed thing of tolylene diisocyanate:
1. tolylene diisocyanate is added in the reactor, stir and be warming up to 50 ℃, begin to drip 2 mercapto ethanol, stir revolution 60 commentaries on classics/min, temperature is controlled at 50 ± 2 ℃, in 2.5 hours reaction times, is cooled to 20 ℃ naturally.
2. (weight percentage NCO), content are qualified 25～27%, and it is stand-by to stay an operation to measure isocyanate group.
(5) count the prescription of modified epoxy by weight:
538 parts of epoxy amine affixtures;
326 parts of tolylene diisocyanate closures;
(6) preparation technology of modified epoxy:
Will the epoxy amine affixture and the semiclosed thing of tolylene diisocyanate add to stir in the reactor and heat up, insulation reaction is 2 hours when treating that temperature rises to 80 ℃, is cooled to 25 ℃ naturally, sampling and measuring-NCO content is 0 o'clock, i.e. salable product.
(7) first component blending process:
Add earlier modified epoxy in joining paint can, start high speed dispersor, the revolution of dispersion machine is 900 rev/mins, after 15 minutes, adds pigment and filler, and high speed dispersion is after 1.5 hours, grinds on three-roller that to reach fineness be 60～80 μ m, gets final product packing.
2, component B
Count by weight, component B is that the prescription of composite curing agent is as follows:
20 parts of solidifying agent I (underwater curing agent 810);
30 parts of solidifying agent II (modified epoxy solidifying agent);
Wherein,
Count the prescription of solidifying agent II by weight:
622 parts of oleic acid affixtures;
204 parts of diethylenetriamines;
(1) count the prescription of oleic acid affixture by weight:
342 parts of oleic acid;
280 parts in tung oil lipid acid;
0.5 part of calcium naphthenate;
Wherein, oleic acid can adopt the oleic acid in the cashew nut.
(2) preparation technology of oleic acid affixture:
In oleic acid and tung oil lipid acid and calcium naphthenate adding reactor, stir and be warming up to 260 ℃ of insulation reaction, to reaching 2.5～3.5 seconds, for salable product are continued to employ with Ge Shi pipe viscosimetric.
(3) preparation technology of solidifying agent II:
Oleic acid affixture and diethylenetriamine are added in the reactor, under constantly stirring, heat up, when reaching 270～280 ℃ etc. temperature of reaction, keep reaction 4 hours, sampling and measuring amine value reaches at 200～220 o'clock, is cooled to 210 ℃ again, starts vacuum pump and deviates from unhindered amina and reaction water, vacuum tightness reaches 0.89～0.92MPa, and it is salable product that resampling mensuration amine value reaches at 150～200 o'clock.Stop vacuum then, cooling, when temperature was reduced to 50 ℃, production process finished, and solidifying agent is stand-by.
(4) blending process of component B:
Solidifying agent I is joined among the solidifying agent II to scale, and stirring gets final product.
Among the present invention,, obtain underwater coating heavy corrosion protection coating, can use first component and component B two portions uniform mixing in proportion.
Technical indicator:
Fineness 60～80 μ m, viscosity 〉=100kU, proportion 2.8g/cm
3, blade coating is good under water.
This coating is constructed under water, manual earlier corrosion of removing the surface, and the brushing that will exert oneself during construction makes coating brush substrate surface, surface drying (10 ℃ of temperature) 6 hours, coating surface is smooth, and sticking power is good.
Embodiment 2
Present embodiment is used for underground fire well concrete surface rot-resistant protective system under water, by weight percentage, is made up of first component and component B two portions, and the first component accounts for 87%, and component B accounts for 13%.Wherein,
1, first component
The first component is the mill base that modified epoxy, pigment and filler are made, and counts by weight, and it is as follows to fill a prescription:
35 parts of modified epoxies;
15 parts of Stainless Steel Powders (granularity 300 μ m);
30 parts of composite iron-titanium powders (granularity 300 μ m);
20 parts of mica powders (granularity 300 μ m);
In the present embodiment, composite iron-titanium powder adopts the commercially available prod, as: can adopt Shijiazhuang evolve the forever composite iron-titanium powder 801 of worker company limited or composite iron-titanium powder 809 etc.
Wherein, modified epoxy is made by epoxy amine affixture and the semiclosed thing reaction of tolylene diisocyanate, and the composition and the blending process of modified epoxy are as follows:
(1) count the prescription of epoxy amine affixture by weight:
1500 parts of bisphenol A type epoxy resin E51;
300 parts of diethylamides;
200 parts of dimethylbenzene;
(2) preparation technology of epoxy amine affixture:
1. Resins, epoxy and dimethylbenzene are added in the reactor heat temperature raising under constantly stirring, when treating that temperature rises to Resins, epoxy and dimethylbenzene can flow (70 ℃), begin to drip diethylamide, stir revolution 84 commentaries on classics/min, the dropping time is 1 hour.After dropwising, be incubated 2 hours down at 70 ℃;
2. be that xylene solvent is deviate from distillation under 0.8～0.9MPa in vacuum tightness, carry out sampling analysis after solvent has taken off;
3. hydrochloric acid acetone method mensuration oxirane value is between 0.23～0.25, and it is 0 that acidimetry is measured unhindered amina content, is salable product, and it is stand-by to stay an operation.
(3) count the prescription of the semiclosed thing of tolylene diisocyanate by weight:
800 parts of tolylene diisocyanates;
700 parts of 2 mercapto ethanols;
(4) preparation technology of the semiclosed thing of tolylene diisocyanate:
1. tolylene diisocyanate is added in the reactor, stir and be warming up to 40 ℃, begin to drip 2 mercapto ethanol, stir revolution 50 commentaries on classics/min, temperature is controlled at 50 ± 2 ℃, in 2 hours reaction times, is cooled to 22 ℃ naturally.
2. (weight percentage NCO), content are qualified 25～27%, and it is stand-by to stay an operation to measure isocyanate group.
(5) count the prescription of modified epoxy by weight:
550 parts of epoxy amine affixtures;
350 parts of tolylene diisocyanate closures;
(6) preparation technology of modified epoxy:
Will the epoxy amine affixture and the semiclosed thing of tolylene diisocyanate add to stir in the reactor and heat up, insulation reaction is 3 hours when treating that temperature rises to 70 ℃, is cooled to 20 ℃ naturally, sampling and measuring-NCO content is 0 o'clock, i.e. salable product.
(7) first component blending process:
Add earlier modified epoxy in joining paint can, start high speed dispersor, the revolution of dispersion machine is 800 rev/mins, after 20 minutes, adds pigment and filler, and high speed dispersion is after 2 hours, grinds on three-roller that to reach fineness be 60～80 μ m, gets final product packing.
2, component B
Count by weight, component B is that the prescription of composite curing agent is as follows:
20 parts of solidifying agent I (underwater curing agent 1085);
30 parts of solidifying agent II (modified epoxy solidifying agent);
Wherein,
Count the prescription of solidifying agent II by weight:
600 parts of oleic acid affixtures;
200 parts of diethylenetriamines;
(1) count the prescription of oleic acid affixture by weight:
684 parts of oleic acid;
560 parts in tung oil lipid acid;
1 part of calcium naphthenate;
Wherein, oleic acid can adopt the oleic acid in the cashew nut.
(2) preparation technology of oleic acid affixture:
In oleic acid and tung oil lipid acid and calcium naphthenate adding reactor, stir and be warming up to 200 ℃ of insulation reaction, to reaching 2.5～3.5 seconds, for salable product are continued to employ with Ge Shi pipe viscosimetric.
(3) preparation technology of solidifying agent II:
Oleic acid affixture and diethylenetriamine are added in the reactor, under constantly stirring, heat up, when reaching 270～280 ℃ etc. temperature of reaction, keep reaction 4 hours, sampling and measuring amine value reaches at 200～220 o'clock, is cooled to 215 ℃ again, starts vacuum pump and deviates from unhindered amina and reaction water, vacuum tightness reaches 0.89～0.92MPa, and it is salable product that resampling mensuration amine value reaches at 150～200 o'clock.Stop vacuum then, cooling, when temperature was reduced to 40 ℃, production process finished, and solidifying agent is stand-by.
(4) blending process of component B:
Solidifying agent I is joined among the solidifying agent II to scale, and stirring gets final product.
Among the present invention,, obtain underwater coating heavy corrosion protection coating, can use first component and component B two portions uniform mixing in proportion.
Technical indicator:
Fineness 60～80 μ m, viscosity 〉=100kU, proportion 2.8g/cm
3, blade coating is good under water.
This coating is constructed under water, the manual earlier surperficial foreign material etc. of removing, and the brushing that will exert oneself during construction makes coating brush substrate surface, surface drying (15 ℃ of temperature) 4 hours, coating surface is smooth, and sticking power is good.
Embodiment 3
Present embodiment is used for the protective system under water of drilling unit surface anticorrosion, by weight percentage, is made up of first component and component B two portions, and the first component accounts for 85%, and component B accounts for 15%.Wherein,
1, first component
The first component is the mill base that modified epoxy, pigment and filler are made, and counts by weight, and it is as follows to fill a prescription:
45 parts of modified epoxies;
20 parts of Stainless Steel Powders (granularity 500 μ m);
35 parts of composite iron-titanium powders (granularity 500 μ m);
In the present embodiment, composite iron-titanium powder adopts the commercially available prod, as: can adopt Shijiazhuang evolve the forever composite iron-titanium powder 801 of worker company limited or composite iron-titanium powder 809 etc.
Wherein, modified epoxy is made by epoxy amine affixture and the semiclosed thing reaction of tolylene diisocyanate, and the composition and the blending process of modified epoxy are as follows:
(1) count the prescription of epoxy amine affixture by weight:
2000 parts of bisphenol A type epoxy resin E51;
400 parts of diethylamides;
300 parts of dimethylbenzene;
(2) preparation technology of epoxy amine affixture:
1. Resins, epoxy and dimethylbenzene are added in the reactor heat temperature raising under constantly stirring, when treating that temperature rises to Resins, epoxy and dimethylbenzene can flow (80 ℃), begin to drip diethylamide, stir revolution 90 commentaries on classics/min, the dropping time is 3 hours.After dropwising, be incubated 1 hour down at 80 ℃;
2. be that xylene solvent is deviate from distillation under 0.8～0.9MPa in vacuum tightness, carry out sampling analysis after solvent has taken off;
3. hydrochloric acid acetone method mensuration oxirane value is between 0.23～0.25, and it is 0 that acidimetry is measured unhindered amina content, is salable product, and it is stand-by to stay an operation.
(3) count the prescription of the semiclosed thing of tolylene diisocyanate by weight:
900 parts of tolylene diisocyanates;
800 parts of 2 mercapto ethanols;
(4) preparation technology of the semiclosed thing of tolylene diisocyanate:
1. tolylene diisocyanate is added in the reactor, stir and be warming up to 60 ℃, begin to drip 2 mercapto ethanol, stir revolution 80 commentaries on classics/min, temperature is controlled at 50 ± 2 ℃, in 3 hours reaction times, is cooled to 25 ℃ naturally.
2. (weight percentage NCO), content are qualified 25～27%, and it is stand-by to stay an operation to measure isocyanate group.
(5) count the prescription of modified epoxy by weight:
250 parts of epoxy amine affixtures;
150 parts of tolylene diisocyanate closures;
(6) preparation technology of modified epoxy:
Will the epoxy amine affixture and the semiclosed thing of tolylene diisocyanate add to stir in the reactor and heat up, insulation reaction is 1 hour when treating that temperature rises to 90 ℃, is cooled to 22 ℃ naturally, sampling and measuring-NCO content is 0 o'clock, i.e. salable product.
(7) first component blending process:
Add earlier modified epoxy in joining paint can, start high speed dispersor, the revolution of dispersion machine is 1000 rev/mins, after 10 minutes, adds pigment and filler, and high speed dispersion is after 1 hour, grinds on three-roller that to reach fineness be 60～80 μ m, gets final product packing.
2, component B
Count by weight, component B is that the prescription of composite curing agent is as follows:
20 parts of solidifying agent I (comprising: 10 parts of underwater curing agent 810 and 10 parts of underwater curing agent 1085);
40 parts of solidifying agent II (modified epoxy solidifying agent);
Wherein,
Count the prescription of solidifying agent II by weight:
700 parts of oleic acid affixtures;
300 parts of diethylenetriamines;
(1) count the prescription of oleic acid affixture by weight:
600 parts of oleic acid;
200 parts in tung oil lipid acid;
0.2 part of calcium naphthenate;
Wherein, oleic acid can adopt the oleic acid in the cashew nut.
(2) preparation technology of oleic acid affixture:
In oleic acid and tung oil lipid acid and calcium naphthenate adding reactor, stir and be warming up to 300 ℃ of insulation reaction, to reaching 2.5～3.5 seconds, for salable product are continued to employ with Ge Shi pipe viscosimetric.
(3) preparation technology of solidifying agent II:
Oleic acid affixture and diethylenetriamine are added in the reactor, under constantly stirring, heat up, when reaching 270～280 ℃ etc. temperature of reaction, keep reaction 4 hours, sampling and measuring amine value reaches at 200～220 o'clock, is cooled to 220 ℃ again, starts vacuum pump and deviates from unhindered amina and reaction water, vacuum tightness reaches 0.89～0.92MPa, and it is salable product that resampling mensuration amine value reaches at 150～200 o'clock.Stop vacuum then, cooling, when temperature was reduced to 60 ℃, production process finished, and solidifying agent is stand-by.
(4) blending process of component B:
Solidifying agent I is joined among the solidifying agent II to scale, and stirring gets final product.
Among the present invention,, obtain underwater coating heavy corrosion protection coating, can use first component and component B two portions uniform mixing in proportion.
Technical indicator:
Fineness 60～80 μ m, viscosity 〉=100kU, proportion 3.3g/cm
3, blade coating is good under water.
Construct in this coating seawater, earlier manual corrosion of removing the surface, the blade coating that will exert oneself with scraper during construction is to substrate surface, surface drying (10 ℃ of temperature) 6 hours, coating surface is smooth, and sticking power is good.
Embodiment 4
Present embodiment is used for underground fire well concrete surface rot-resistant protective system under water, by weight percentage, is made up of first component and component B two portions, and the first component accounts for 87%, and component B accounts for 13%.Wherein,
1, first component
The first component is the mill base that modified epoxy, pigment and filler are made, and counts by weight, and it is as follows to fill a prescription:
35 parts of modified epoxies;
5 parts of aluminium powders (granularity 300 μ m);
20 parts of Stainless Steel Powders (granularity 300 μ m);
20 parts in compound ferrophosphorus powder (granularity 300 μ m);
20 parts of ground barium sulfates (granularity 300 μ m);
Wherein, modified epoxy is made by epoxy amine affixture and the semiclosed thing reaction of tolylene diisocyanate, and the composition and the blending process of modified epoxy are as follows:
(1) count the prescription of epoxy amine affixture by weight:
1700 parts of bisphenol A type epoxy resin E51;
350 parts of diethylamides;
230 parts of dimethylbenzene;
(2) preparation technology of epoxy amine affixture:
1. Resins, epoxy and dimethylbenzene are added in the reactor heat temperature raising under constantly stirring, when treating that temperature rises to Resins, epoxy and dimethylbenzene can flow (70 ℃), begin to drip diethylamide, stir revolution 84 commentaries on classics/min, the dropping time is 1 hour.After dropwising, be incubated 2 hours down at 70 ℃;
2. be that xylene solvent is deviate from distillation under 0.8～0.9MPa in vacuum tightness, carry out sampling analysis after solvent has taken off;
3. hydrochloric acid acetone method mensuration oxirane value is between 0.23～0.25, and it is 0 that acidimetry is measured unhindered amina content, is salable product, and it is stand-by to stay an operation.
(3) count the prescription of the semiclosed thing of tolylene diisocyanate by weight:
850 parts of tolylene diisocyanates;
720 parts of 2 mercapto ethanols;
(4) preparation technology of the semiclosed thing of tolylene diisocyanate:
1. tolylene diisocyanate is added in the reactor, stir and be warming up to 40 ℃, begin to drip 2 mercapto ethanol, stir revolution 50 commentaries on classics/min, temperature is controlled at 50 ± 2 ℃, in 2 hours reaction times, is cooled to 22 ℃ naturally.
2. (weight percentage NCO), content are qualified 25～27%, and it is stand-by to stay an operation to measure isocyanate group.
(5) count the prescription of modified epoxy by weight:
350 parts of epoxy amine affixtures;
200 parts of tolylene diisocyanate closures;
(6) preparation technology of modified epoxy:
Will the epoxy amine affixture and the semiclosed thing of tolylene diisocyanate add to stir in the reactor and heat up, insulation reaction is 3 hours when treating that temperature rises to 70 ℃, is cooled to 20 ℃ naturally, sampling and measuring-NCO content is 0 o'clock, i.e. salable product.
(7) first component blending process:
Add earlier modified epoxy in joining paint can, start high speed dispersor, the revolution of dispersion machine is 800 rev/mins, after 20 minutes, adds pigment and filler, and high speed dispersion is after 2 hours, grinds on three-roller that to reach fineness be 60～80 μ m, gets final product packing.
2, component B
Count by weight, component B is that the prescription of composite curing agent is as follows:
15 parts of solidifying agent I (underwater curing agent 1085);
35 parts of solidifying agent II (modified epoxy solidifying agent);
Wherein,
Count the prescription of solidifying agent II by weight:
650 parts of oleic acid affixtures;
230 parts of diethylenetriamines;
(1) count the prescription of oleic acid affixture by weight:
450 parts of oleic acid;
260 parts in tung oil lipid acid;
0.4 part of calcium naphthenate;
Wherein, oleic acid can adopt the oleic acid in the cashew nut.
(2) preparation technology of oleic acid affixture:
In oleic acid and tung oil lipid acid and calcium naphthenate adding reactor, stir and be warming up to 200 ℃ of insulation reaction, to reaching 2.5～3.5 seconds, for salable product are continued to employ with Ge Shi pipe viscosimetric.
(3) preparation technology of solidifying agent II:
Oleic acid affixture and diethylenetriamine are added in the reactor, under constantly stirring, heat up, when reaching 270～280 ℃ etc. temperature of reaction, keep reaction 4 hours, sampling and measuring amine value reaches at 200～220 o'clock, is cooled to 215 ℃ again, starts vacuum pump and deviates from unhindered amina and reaction water, vacuum tightness reaches 0.89～0.92MPa, and it is salable product that resampling mensuration amine value reaches at 150～200 o'clock.Stop vacuum then, cooling, when temperature was reduced to 40 ℃, production process finished, and solidifying agent is stand-by.
(4) blending process of component B:
Solidifying agent I is joined among the solidifying agent II to scale, and stirring gets final product.
Among the present invention,, obtain underwater coating heavy corrosion protection coating, can use first component and component B two portions uniform mixing in proportion.
Technical indicator:
Fineness 60～80 μ m, viscosity 〉=100kU, proportion 2.8g/cm
3, blade coating is good under water.
This coating is constructed under water, the manual earlier surperficial foreign material etc. of removing, and the brushing that will exert oneself during construction makes coating brush substrate surface, surface drying (15 ℃ of temperature) 4 hours, coating surface is smooth, and sticking power is good.
Embodiment 5
Present embodiment is used for the protective system under water of drilling unit surface anticorrosion, by weight percentage, is made up of first component and component B two portions, and the first component accounts for 85%, and component B accounts for 15%.Wherein,
1, first component
The first component is the mill base that modified epoxy, pigment and filler are made, and counts by weight, and it is as follows to fill a prescription:
45 parts of modified epoxies;
10 parts of zinc powders (granularity 500 μ m);
15 parts of Stainless Steel Powders (granularity 500 μ m);
30 parts of composite iron-titanium powders (granularity 500 μ m).
Wherein, modified epoxy is made by epoxy amine affixture and the semiclosed thing reaction of tolylene diisocyanate, and the composition and the blending process of modified epoxy are as follows:
(1) count the prescription of epoxy amine affixture by weight:
1900 parts of bisphenol A type epoxy resin E51;
320 parts of diethylamides;
280 parts of dimethylbenzene;
(2) preparation technology of epoxy amine affixture:
1. Resins, epoxy and dimethylbenzene are added in the reactor heat temperature raising under constantly stirring, when treating that temperature rises to Resins, epoxy and dimethylbenzene can flow (80 ℃), begin to drip diethylamide, stir revolution 90 commentaries on classics/min, the dropping time is 3 hours.After dropwising, be incubated 1 hour down at 80 ℃;
2. be that xylene solvent is deviate from distillation under 0.8～0.9MPa in vacuum tightness, carry out sampling analysis after solvent has taken off;
3. hydrochloric acid acetone method mensuration oxirane value is between 0.23～0.25, and it is 0 that acidimetry is measured unhindered amina content, is salable product, and it is stand-by to stay an operation.
(3) count the prescription of the semiclosed thing of tolylene diisocyanate by weight:
820 parts of tolylene diisocyanates;
750 parts of 2 mercapto ethanols;
(4) preparation technology of the semiclosed thing of tolylene diisocyanate:
1. tolylene diisocyanate is added in the reactor, stir and be warming up to 60 ℃, begin to drip 2 mercapto ethanol, stir revolution 80 commentaries on classics/min, temperature is controlled at 50 ± 2 ℃, in 3 hours reaction times, is cooled to 25 ℃ naturally.
2. (weight percentage NCO), content are qualified 25～27%, and it is stand-by to stay an operation to measure isocyanate group.
(5) count the prescription of modified epoxy by weight:
400 parts of epoxy amine affixtures;
280 parts of tolylene diisocyanate closures;
(6) preparation technology of modified epoxy:
Will the epoxy amine affixture and the semiclosed thing of tolylene diisocyanate add to stir in the reactor and heat up, insulation reaction is 1 hour when treating that temperature rises to 90 ℃, is cooled to 22 ℃ naturally, sampling and measuring-NCO content is 0 o'clock, i.e. salable product.
(7) first component blending process:
Add earlier modified epoxy in joining paint can, start high speed dispersor, the revolution of dispersion machine is 1000 rev/mins, after 10 minutes, adds pigment and filler, and high speed dispersion is after 1 hour, grinds on three-roller that to reach fineness be 60～80 μ m, gets final product packing.
2, component B
Count by weight, component B is that the prescription of composite curing agent is as follows:
15 parts of solidifying agent I (comprising: 10 parts of underwater curing agent 810 and 5 parts of underwater curing agent 1085);
35 parts of solidifying agent II (modified epoxy solidifying agent);
Wherein,
Count the prescription of solidifying agent II by weight:
660 parts of oleic acid affixtures;
280 parts of diethylenetriamines;
(1) count the prescription of oleic acid affixture by weight:
650 parts of oleic acid;
400 parts in tung oil lipid acid;
0.8 part of calcium naphthenate;
Wherein, oleic acid can adopt the oleic acid in the cashew nut.
(2) preparation technology of oleic acid affixture:
In oleic acid and tung oil lipid acid and calcium naphthenate adding reactor, stir and be warming up to 300 ℃ of insulation reaction, to reaching 2.5～3.5 seconds, for salable product are continued to employ with Ge Shi pipe viscosimetric.
(3) preparation technology of solidifying agent II:
Oleic acid affixture and diethylenetriamine are added in the reactor, under constantly stirring, heat up, when reaching 270～280 ℃ etc. temperature of reaction, keep reaction 4 hours, sampling and measuring amine value reaches at 200～220 o'clock, is cooled to 220 ℃ again, starts vacuum pump and deviates from unhindered amina and reaction water, vacuum tightness reaches 0.89～0.92MPa, and it is salable product that resampling mensuration amine value reaches at 150～200 o'clock.Stop vacuum then, cooling, when temperature was reduced to 60 ℃, production process finished, and solidifying agent is stand-by.
(4) blending process of component B:
Solidifying agent I is joined among the solidifying agent II to scale, and stirring gets final product.
Among the present invention,, obtain underwater coating heavy corrosion protection coating, can use first component and component B two portions uniform mixing in proportion.
Technical indicator:
Fineness 60～80 μ m, viscosity 〉=100kU, proportion 3.3g/cm
3, blade coating is good under water.
Construct in this coating seawater, earlier manual corrosion of removing the surface, the blade coating that will exert oneself with scraper during construction is to substrate surface, surface drying (10 ℃ of temperature) 6 hours, coating surface is smooth, and sticking power is good.
Constructional method:
(1) surface treatment: substrate surface is removed surperficial rusty scale and old paint film etc. with wire brush, steel shovel etc., disposes and must set about application immediately.
(2) on the water, prepare coating to scale.During construction, being with Painting tool to enter underwater construction by the frogman, is main construction means with brushing and blade coating.
Construction embodiment:
Adopt the present invention, in seawater, 1 meter long steel pipe piling carried out hand cleaning after, by the frogman paint brush for preparing is coated onto on the steel pipe, coating no floating nothing in water is disperseed, and smooth coating has good sticking power on base material, surface drying time 6 hours is done solid work 30h.After 1 year, check test specimen, paint film do not have come off, do not have foaming, nothing is got rusty, the paint film antiseptic property is good.The technical indicator of underwater coating heavy corrosion protection coating following (table 1):
Table 1
| Classification | Index |
| Color | Of all kinds |
| Proportion | ??2.5～3.5g/cm 3 |
| Proportioning | Weight ratio first: second=4: 1 |
| The active phase | ??2h(25℃) |
| Time of drying (10 ℃) | Surface drying 6h |
| Do solid work 24h | |
| Theoretical consumption | ??500g/m 2, thickness 200 μ m |
| Envrionment temperature | ??5℃～40℃ |
The result shows that it is main film forming matter that underwater coating heavy corrosion protection coating of the present invention is equipped with the Compositional type solidifying agent with modified epoxy, doses pigment and filler is made.Coating is the cohesive strength height under water, under water the brushing excellent performance.This coating is to have a low surface treatment, under water construction not floating, do not decompose; Good levelling property, good sticking power, the environmentally friendly machine of good drying property.This product is applicable to the protection on surfaces such as buildings in seawater, the fresh water, structures, bridge, drilling unit, stake, post, and save energy, is raised the efficiency at the reduction of erection time.
Claims (7)
1. a underwater coating heavy corrosion protection coating is characterized in that, by weight percentage, is made up of first component and component B two portions, and the first component accounts for 70～90%, and component B accounts for 10～30%; Wherein,
(1) first component
The first component is the mill base that modified epoxy, pigment and filler are made, and counts by weight, and it is as follows to fill a prescription:
35～45 parts of modified epoxies;
15～25 parts of pigment;
25～50 parts of fillers;
Wherein, modified epoxy is made by epoxy amine affixture and the semiclosed thing reaction of tolylene diisocyanate, and the composition and the blending process of modified epoxy are as follows:
Count the prescription of epoxy amine affixture by weight:
1500～2000 parts of Resins, epoxy;
300～400 parts of diethylamides;
200～300 parts of dimethylbenzene;
Count the prescription of the semiclosed thing of tolylene diisocyanate by weight:
800～900 parts of tolylene diisocyanates;
700～800 parts of 2 mercapto ethanols;
Count the prescription of modified epoxy by weight:
250～550 parts of epoxy amine affixtures;
150～350 parts of the semiclosed things of tolylene diisocyanate;
(2) component B
Count by weight, component B is that the prescription of composite curing agent is as follows:
15～30 parts of solidifying agent I;
20～40 parts of solidifying agent II;
Wherein,
Solidifying agent I is the underwater curing agent of used for epoxy resin;
Solidifying agent II is a modified firming agent, counts the prescription of solidifying agent II by weight:
600～700 parts of oleic acid affixtures;
200～300 parts of diethylenetriamines;
Count the prescription of oleic acid affixture by weight:
300～700 parts of oleic acid;
200～600 parts in tung oil lipid acid;
0.2～1 part of calcium naphthenate.
2. according to the described underwater coating heavy corrosion protection coating of claim 1, it is characterized in that oleic acid adopts the oleic acid in the cashew nut.
3. according to the described underwater coating heavy corrosion protection coating of claim 1, it is characterized in that the underwater curing agent is one or more mixing in underwater curing agent 810 or the underwater curing agent 1085.
4. according to the described underwater coating heavy corrosion protection coating of claim 1, it is characterized in that pigment is steady rust pigment, rust-stabilising pigment and inert pigment.
5. according to the described underwater coating heavy corrosion protection coating of claim 1, it is characterized in that pigment is one or more mixing in iron oxide red, zinc-chrome yellow, Stainless Steel Powder, zinc powder, aluminium powder, iron oxide black or the zinc phosphate, requiring granularity is 300～500 μ m.
6. according to the described underwater coating heavy corrosion protection coating of claim 1, it is characterized in that filler is one or more mixing in ground barium sulfate, composite iron-titanium powder or the mica powder, requiring granularity is 300～500 μ m.
7. according to the preparation method of the described underwater coating heavy corrosion protection coating of claim 1, it is characterized in that,, obtain underwater coating heavy corrosion protection coating first component and component B two portions uniform mixing in proportion; Wherein:
(1) first component
The preparation technology of epoxy amine affixture:
1. Resins, epoxy and dimethylbenzene are added in the reactor heat temperature raising under constantly stirring, treat that temperature rises in the time of can flowing, begin to drip diethylamide, stir revolution 80～90 commentariess on classics/min, after dropwising, be incubated 1～3 hour down at 60～80 ℃;
2. under vacuum, deviate from xylene solvent, carry out sampling analysis after solvent has taken off;
3. analyzing oxirane value is between 0.23～0.25, and unhindered amina is 0, and is stand-by;
The preparation technology of the semiclosed thing of tolylene diisocyanate:
1. tolylene diisocyanate is added in the reactor, stir and be warming up to 40～60 ℃, begin to drip 2 mercapto ethanol, stir revolution 50～80 commentaries on classics/min, temperature is controlled at 50 ± 2 ℃, in 2～3 hours reaction times, is cooled to 20～25 ℃ naturally.
2. (weight percentage NCO), content are qualified, stand-by 25～27% to measure isocyanate group;
The preparation technology of modified epoxy:
Will the epoxy amine affixture and the semiclosed thing of tolylene diisocyanate add to stir in the reactor and heat up, insulation reaction is 1～3 hour when treating that temperature rises to 70～90 ℃, is cooled to 20～25 ℃ naturally, sampling and measuring-NCO content is 0 o'clock, i.e. salable product;
First component blending process:
Add modified epoxy earlier in joining paint can, start high speed dispersor, the revolution of dispersion machine is 800～1000 rev/mins, after 10～20 minutes, add pigment and filler, high speed dispersion is after 1～2 hour, grind on three-roller that to reach fineness be 60～80 μ m, get final product packing.
(2) component B
The preparation technology of oleic acid affixture:
In oleic acid and tung oil lipid acid and calcium naphthenate adding reactor, stir and be warming up to 200～300 ℃ of insulation reaction, to reaching 2.5～3.5 seconds, for salable product are continued to employ with Ge Shi pipe viscosimetric;
The preparation technology of solidifying agent II:
Oleic acid affixture and diethylenetriamine are added in the reactor, under constantly stirring, heat up, when reaching 270～280 ℃ etc. temperature of reaction, keep reaction 3～5 hours, sampling and measuring amine value reaches at 200～220 o'clock, is cooled to 200～220 ℃ again, starts vacuum pump and deviates from unhindered amina and reaction water, vacuum tightness reaches 0.89～0.92MPa, and it is salable product that resampling mensuration amine value reaches at 150～200 o'clock.Stop vacuum then, cooling, when temperature was reduced to 40～60 ℃, production process finished, and solidifying agent is stand-by;
The blending process of component B:
Solidifying agent I is joined among the solidifying agent II to scale, and stirring gets final product.
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| CN108148484B (en) * | 2017-12-26 | 2020-09-22 | 株洲市九华新材料涂装实业有限公司 | Water-based epoxy antirust coating for urban rails and motor cars and preparation method thereof |
| CN108487330A (en) * | 2018-02-13 | 2018-09-04 | 石狮华宝新材料工程有限公司 | Can underwater construction or submersible nano anti-corrosive, impervious layer and construction method |
| CN109897518A (en) * | 2019-02-01 | 2019-06-18 | 刘建卡 | A kind of painting under water solvent-free epoxy heavy-duty anticorrosive coating and preparation method thereof |
| CN113249012A (en) * | 2021-05-25 | 2021-08-13 | 成都扬华源动新材料科技有限公司 | Hydrophobic resin coating, preparation method thereof and drainage pipeline |
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