CN103382362B - A kind of polyurethane Composite Coating with antifouling property and preparation method thereof - Google Patents
A kind of polyurethane Composite Coating with antifouling property and preparation method thereof Download PDFInfo
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- CN103382362B CN103382362B CN201310340298.6A CN201310340298A CN103382362B CN 103382362 B CN103382362 B CN 103382362B CN 201310340298 A CN201310340298 A CN 201310340298A CN 103382362 B CN103382362 B CN 103382362B
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Abstract
The invention discloses a kind of polyurethane Composite Coating with antifouling property and preparation method thereof.This coating prepares by the following method: be distributed to by graphite oxide in water, ultrasonic, obtains graphite oxide uniform dispersion; Titanium dioxide is joined in step graphite oxide uniform dispersion, stirring, supersound process, centrifugal, dry and obtain the titania powder solid product of graphite oxide load; Solid product is added in deionized water, then adds the mixing solutions of hydrazine hydrate solution and strong aqua, stir, water-bath, reaction terminate rear cooling, through washing, centrifugal, dry after, obtain graphene modified composite titania material; The composite titania material of graphene modified is joined ultrasonic disperse in aqueous polyurethane.Polyurethane Composite Coating of the present invention, has good restraining effect to halobiontic attachment, can be applied to marine antifouling.
Description
Technical field
The present invention relates to a kind of polyurethane Composite Coating with antifouling property and preparation method thereof, belong to technical field of composite preparation.
Background technology
20 beginnings of the century, ship bottom antifouling paint is just successfully applied on marine antifouling, experienced by using poison material such as mercury, arsenic, Red copper oxide as stain control agent, then to being applied in antifouling varnish by organo-tin compound, the marine pollution matter caused thus also becomes increasingly conspicuous.In the historical progress developing ocean, along with the raising of social progress and human knowledge's level, environmental protection cry is more and more high, and research and development nontoxic pollution-free, the coating with specific function become lasting focus in global Coating Market.Urethane is a kind of important functional materials, has tempting application prospect in marine finish field, but urethane prevent marine organisms adhesive ability strong, this brings must limit to practical application, needs to utilize other means to improve its antifouling capacity.
Summary of the invention
The object of this invention is to provide and a kind of there is polyurethane Composite Coating of higher antifouling property and preparation method thereof.The present invention is matrix with urethane, utilizes the titanium dioxide of graphene modified to carry out modification, thus forms a kind of advanced composite material with high antifouling property.
Technical conceive of the present invention is such:
In anti-fouling ship paint, material suppresses the performance of marine organisms attachment particularly important, and nano-TiO
2there is photochemical catalytic oxidation bacteriostatic activity, thus reach the effect suppressing marine organisms attachment.But nano-TiO at present
2because its energy gap is wider, third contact of a total solar or lunar eclipse katalysis can only be issued in the irradiation of the shorter UV-light of wavelength, and proportion shared by natural light medium ultraviolet light is less, makes TiO
2the solar energy rate of photocatalyst is lower, and germ resistance can not be applied very well.And recent studies have found that the nano-TiO of graphene modified
2there is high absorption, high Photocatalytic oxidation activity, there is good photocatalytic activity, can well play its germ resistance.Therefore the nano-TiO of graphene modified is considered
2modified polyurethane paint, is applied to marine antifouling.
Technical scheme of the present invention is as follows:
There is a polyurethane Composite Coating for antifouling property, prepare as follows:
(1) graphite oxide is distributed in water, ultrasonic, obtain graphite oxide uniform dispersion;
(2) titanium dioxide is joined in the dispersion liquid of step (1), stirring, supersound process, centrifugal, dry and obtain the titania powder solid product of graphite oxide load;
(3) solid product is added in deionized water, then adds the mixing solutions of hydrazine hydrate solution and strong aqua, stir, forming reactions system, water-bath, reaction terminate rear cooling, through washing, centrifugal, dry after, obtain graphene modified composite titania material; In described matrix material, the mass ratio of graphite oxide and titanium dioxide is 0.5 ~ 5:100;
(4) graphene modified composite titania material is joined ultrasonic disperse in aqueous polyurethane;
Wherein, described graphite oxide adopts Hummer ' s chemical method to be oxidized by natural graphite to obtain.
In technical scheme of the present invention, in uniform dispersion described in step (1), the concentration of graphite oxide is preferably 0.002% ~ 1%, is more preferably 0.002% ~ 0.2%.
In technical scheme of the present invention, in the dispersion liquid described in step (2), the concentration of titanium dioxide is preferably 0.2% ~ 5%, is more preferably 0.2% ~ 3%.
In technical scheme of the present invention, the volumn concentration that the mixing solutions of the hydrazine hydrate solution described in step (3) and strong aqua is shared in reaction system is preferably 35%, in described mixing solutions, the volume ratio of hydrazine hydrate solution and strong aqua is preferably 1:4 ~ 10, is more preferably 1:5 ~ 7; In reaction system, the mass ratio of hydrazine hydrate and graphite oxide is 7:10.
In technical scheme of the present invention, the composite titania material of graphene modified described in step (4) and the mass ratio of aqueous polyurethane are preferably 1 ~ 10:100, are more preferably 1 ~ 3:100.
In the preferred technical solution of the present invention, the time ultrasonic described in step (2) is 0.5 ~ 1 hour, and the temperature of described oven dry is 80 DEG C.
In the preferred technical solution of the present invention, described in step (3), water-bath temperature is 90-95 DEG C, water-bath 1 ~ 2h, carries out in-situ reducing to load at the graphite oxide of titanium dioxide surface; The temperature of described oven dry is 80 DEG C.
In step of the present invention (1), graphite oxide is distributed in water, then graphite oxide is peeled off into graphite oxide sheet in 30 ~ 60 minutes by solution supersound process, obtain homodisperse graphite oxide dispersion liquid.
The invention has the beneficial effects as follows that providing a kind of has good inhibiting polyurethane Composite Coating to halobiontic attachment, composite coating of the present invention has good restraining effect than conventional polyurethanes coating to halobiontic attachment; There is provided a kind of and can obtain the method with higher antifouling property coating by simpler preparation technology.
Accompanying drawing explanation
The present invention has accompanying drawing 1 width;
Fig. 1 is that the titania modified polyurethane composite coating of graphene modified is to the restraining effect design sketch of benthic diatom.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Embodiment 1
(1) 10mg graphite oxide is distributed in 200mL water, then by ultrasonic for solution 30 ~ 60 minutes, graphite oxide is peeled off into graphite oxide sheet, obtain homodisperse graphite oxide dispersion liquid;
(2) join in the graphite oxide dispersion liquid of homogeneous dispersion by 990mg titanium dioxide, stirring, the ultrasonic titanium dioxide that makes are uniformly dispersed, after ultrasonic 0.5 hour, centrifugal, 80 DEG C of oven dry;
(3) titania powder by the load of step (2) gained graphite oxide is joined in deionized water, the hydrazine hydrate solution and the analytically pure ammoniacal liquor that add 35% percent by volume again mix in beaker, hydrazine hydrate solution and ammoniacal liquor volume ratio are 1:7, vigorous stirring is after 5 minutes, be placed in 95 DEG C of water-baths and react 1 hour, at the graphite oxide of titanium dioxide surface, in-situ reducing is carried out to load;
(4) after reaction terminates, product cooling deionized water rinsing, centrifugal, 80 DEG C of oven dry is treated, acquisition graphene modified composite titania material;
(5) aqueous polyurethane and graphene modified composite titania material are put into beaker, ultrasonic 30min by the mass ratio of 100:1, the polyurethane Composite Coating needed for final formation.
Embodiment 2
(1) 20mg graphite oxide is distributed in 200mL water, then by ultrasonic for solution 30 ~ 60 minutes, graphite oxide is peeled off into graphite oxide sheet, obtain homodisperse graphite oxide dispersion liquid;
(2) join in the graphite oxide dispersion liquid of homogeneous dispersion by 980mg titanium dioxide, stirring, the ultrasonic titanium dioxide that makes are uniformly dispersed, after ultrasonic 0.5 hour, centrifugal, 80 DEG C of oven dry;
(3) titania powder by the load of step (2) gained graphite oxide is joined in deionized water, the hydrazine hydrate solution and the analytically pure ammoniacal liquor that add 35% percent by volume again mix in beaker, hydrazine hydrate solution and ammoniacal liquor volume ratio are 1:7, vigorous stirring is after 5 minutes, be placed in 95 DEG C of water-baths and react 1 hour, at the graphite oxide of titanium dioxide surface, in-situ reducing is carried out to load;
(4) after reaction terminates, product cooling deionized water rinsing, centrifugal, 80 DEG C of oven dry is treated, acquisition graphene modified composite titania material;
(5) aqueous polyurethane and graphene modified composite titania material are put into beaker, ultrasonic 30min by the mass ratio of 100:1, the polyurethane Composite Coating needed for final formation.
Embodiment 3
(1) 30mg graphite oxide is distributed in 200mL water, then by ultrasonic for solution 30 ~ 60 minutes, graphite oxide is peeled off into graphite oxide sheet, obtain homodisperse graphite oxide dispersion liquid;
(2) join in the graphite oxide dispersion liquid of homogeneous dispersion by 970mg titanium dioxide, stirring, the ultrasonic titanium dioxide that makes are uniformly dispersed, after ultrasonic 0.5 hour, centrifugal, 80 DEG C of oven dry;
(3) titania powder by the load of step (2) gained graphite oxide is joined in deionized water, the hydrazine hydrate solution and the analytically pure ammoniacal liquor that add 35% percent by volume again mix in beaker, hydrazine hydrate solution and ammoniacal liquor volume ratio are 1:7, vigorous stirring is after 5 minutes, be placed in 95 DEG C of water-baths and react 1 hour, at the graphite oxide of titanium dioxide surface, in-situ reducing is carried out to load;
(4) after reaction terminates, product cooling deionized water rinsing, centrifugal, 80 DEG C of oven dry is treated, acquisition graphene modified composite titania material;
(5) aqueous polyurethane and graphene modified composite titania material are put into beaker, ultrasonic 30min by the mass ratio of 100:1, the polyurethane Composite Coating needed for final formation.
Embodiment 4
(1) 50mg graphite oxide is distributed in 200mL water, then by ultrasonic for solution 30 ~ 60 minutes, graphite oxide is peeled off into graphite oxide sheet, obtain homodisperse graphite oxide dispersion liquid;
(2) join in the graphite oxide dispersion liquid of homogeneous dispersion by 950mg titanium dioxide, stirring, the ultrasonic titanium dioxide that makes are uniformly dispersed, after ultrasonic 0.5 hour, centrifugal, 80 DEG C of oven dry;
(3) titania powder by the load of step (2) gained graphite oxide is joined in deionized water, the hydrazine hydrate solution and the analytically pure ammoniacal liquor that add 35% percent by volume again mix in beaker, hydrazine hydrate solution and ammoniacal liquor volume ratio are 1:7, vigorous stirring is after 5 minutes, be placed in 95 DEG C of water-baths and react 1 hour, at the graphite oxide of titanium dioxide surface, in-situ reducing is carried out to load;
(4) after reaction terminates, product cooling deionized water rinsing, centrifugal, 80 DEG C of oven dry is treated, acquisition graphene modified composite titania material;
(5) aqueous polyurethane and graphene modified composite titania material are put into beaker, ultrasonic 30min by the mass ratio of 100:1, the polyurethane Composite Coating needed for final formation.
Embodiment 5
The polyurethane Composite Coating that embodiment 1,2,3,4 obtains is numbered GT1, GT2, GT3, GT5 respectively, and only will be numbered GT0 with titania modified polyurethane coating, original polyurethane Finish code is PU, carries out the analysis of benthic diatom adhesion property to sample.
Namely coating sample (being respectively GT1, GT2, GT3, GT5, GT0, PU) brush is obtained required paint coatings sample on slide glass.The tack of coating sample surface benthic diatom can be measured by the chlorophyll test value measured in benthic diatom liquid, and concrete grammar is as follows:
(1) by paint coatings sample at 200mL, 0.3 μ g/ml
-1soak in benthic diatom liquid two days later, take out sample with tweezers, 6 samples are rocked in deionized water the priming paint diatom of removing surperficial non-attachment.
(2) brush respectively in the beaker filling 100ml deionized water with the diatom that specimen surface adheres to by small size hairbrush, drip 5ml, 10mgml simultaneously
-1magnesiumcarbonate solution, by the abundant dispersed with stirring of glass stick, obtains the benthic diatom algae liquid of coatingsurface attachment.
(3) vacuum pump suction filtration: install filter membrane on suction filter, the benthic diatom algae liquid obtained of suction filtration step (2) under 30kPa, when not having moisture on filter membrane, stops suction filtration.
(4) grind: after suction filtration terminates, immediately take out filter membrane put into agate mortar, and add 3ml volume fraction be 90% acetone soln grind.Be poured in tool plug plastic centrifuge tube again, and clean mortar 2 times with identical acetone soln, washing lotion is merged in centrifuge tube, and cumulative volume controls at 10ml.
(5) extract: centrifuge tube is placed in low temp biochemical incubator (low temperature is dark), at 5 DEG C, extracts 30min.
(6) centrifugal: centrifuge tube symmetry to be put into TDL-50C whizzer, 3000rmin
-1centrifugal 10min.Get supernatant liquor 4ml after centrifugal immediately to pour in disposable tool plug test tube, and fixed molten to 10ml with the acetone soln of 90%.
(7) measure: getting the good solution 2ml of constant volume in step (6), to be injected into light path be in the quartz colorimetric utensil of 1cm, and do blank with the acetone soln of identical 90%, adopt the solution extinction value of spectrophotometric determination wavelength at 750nm, 664nm, 647nm, 630nm place.
(8) calculate: the concentration of calculation sample solution Determination of Chlorophyll, method of calculation are as follows:
ρ
a(μg·ml
-1)=11.85×(D664-D750)-1.54×(D647-D750)-0.08×(D630-D750)
ρ
b(μg·ml
-1)=21.03×(D647-D750)-5.43×(D664-D750)-2.66×(D630-D750)
ρ
c(μg·ml
-1)=24.52×(D630-D750)-1.67×(D664-D750)-7.60×(D647-D750)
Wherein, D664, D750, D647 and D630 are respectively the solution extinction value at wavelength 664nm, 750nm, 647nm and 630nm place; Chlorophyllous concentration value contained by the benthic diatom that ρ adheres to for required coatingsurface, S is the surface-area of sheet glass coating.
Contained by the benthic diatom of paint coatings specimen surface attachment, chlorophyllous concentration value is higher, and the tack of benthic diatom is higher, the results are shown in Figure 1.
As can be seen from Figure 1, (1) graphene modified titanium dioxide polyurethane Composite Coating (GT1, GT2, GT3, GT5) of the present invention, relative to original polyurethane coating (PU) or only obviously reduce with the chlorophyllous content of coating of titania modified polyurethane coating (GT0), thus illustrate that benthic diatom adhesion amount obviously reduces, effectively inhibit the tack of benthic diatom.(2) result of GT1, GT2, GT3, GT5 represents, along with the increase of Graphene add-on, the rejection of the attachment of benthic diatom is presented to the trend improved gradually.These results suggest that, through the TiO of graphene modified
2the polyurethane coating of modification has better fungistatic effect, can be good at suppressing halobiontic attachment.
Claims (6)
1. have a polyurethane Composite Coating for antifouling property, it is characterized in that, this composite coating is prepared as follows:
(1) graphite oxide is distributed in water, ultrasonic, obtain graphite oxide uniform dispersion;
(2) titanium dioxide is joined in the graphite oxide uniform dispersion of step (1), stirring, supersound process, centrifugal, dry and obtain the titania powder solid product of graphite oxide load;
(3) solid product is added in deionized water, then adds the mixing solutions of hydrazine hydrate solution and strong aqua, stir, water-bath, reaction terminate rear cooling, through washing, centrifugal, dry after, obtain graphene modified composite titania material; In described matrix material, the mass ratio of graphite oxide and titanium dioxide is 0.5 ~ 5:100;
(4) graphene modified composite titania material is joined ultrasonic disperse in aqueous polyurethane;
Wherein, described graphite oxide adopts Hummer ' s chemical method to be oxidized by natural graphite to obtain;
Described in step (3), water-bath temperature is 90 ~ 95 DEG C, and the water-bath time is 1 ~ 2h, and the temperature of described oven dry is 80 DEG C.
2. composite coating according to claim 1, is characterized in that, in uniform dispersion described in step (1), the concentration of graphite oxide is 0.002% ~ 1%.
3. composite coating according to claim 1, is characterized in that, in the dispersion liquid described in step (2), the concentration of titanium dioxide is 0.2% ~ 5%.
4. composite coating according to claim 1, it is characterized in that, the volumn concentration that the mixing solutions of the hydrazine hydrate solution described in step (3) and strong aqua is shared in reaction system is 35%, in described mixing solutions, the volume ratio of hydrazine hydrate solution and strong aqua is 1:4 ~ 10, and in reaction system, the mass ratio of hydrazine hydrate and graphite oxide is 7:10.
5. composite coating according to claim 1, is characterized in that, the mass ratio of the graphene modified composite titania material described in step (4) and aqueous polyurethane is 1 ~ 10:100.
6. composite coating according to claim 1, is characterized in that, the time ultrasonic described in step (2) is 0.5 ~ 1 hour, and the temperature of described oven dry is 80 DEG C.
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| CN104629344A (en) * | 2015-03-03 | 2015-05-20 | 阿波罗（中国）有限公司 | Modified nano titanium dioxide polyurethane composite material and preparation technology thereof |
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