CN103382362A - Polyurethane composite coating with antifouling performance and preparation method thereof - Google Patents
Polyurethane composite coating with antifouling performance and preparation method thereof Download PDFInfo
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- CN103382362A CN103382362A CN2013103402986A CN201310340298A CN103382362A CN 103382362 A CN103382362 A CN 103382362A CN 2013103402986 A CN2013103402986 A CN 2013103402986A CN 201310340298 A CN201310340298 A CN 201310340298A CN 103382362 A CN103382362 A CN 103382362A
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- graphite oxide
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Abstract
The invention discloses a polyurethane composite coating with antifouling performance and a preparation method thereof. The coating is prepared through the following method which includes dispersing graphite oxide into water and conducting ultrasonic processing to obtain evenly dispersed liquid of graphite oxide; adding titanium dioxide into the evenly dispersed liquid of the graphite oxide and conducting stirring, ultrasonic processing, centrifuging and drying to obtain a titanium dioxide powder solid product loaded by the graphite oxide; adding the solid product into deionized water, then adding a mixed solution of a hydrazine hydrate solution and stronger ammonia water, evenly stirring, conducting water bath reaction, cooling after the reaction is finished and conducting washing, centrifuging and drying to obtain a graphene modified titanium dioxide composite material which is added into waterborne polyurethane to be dispersed in an ultrasonic mode. The polyurethane composite coating has good restraining effects on adhesion of marine organisms and can be applied to fouling prevention of ships.
Description
Technical field
The present invention relates to a kind of polyurethane Composite Coating with antifouling property and preparation method thereof, belong to the matrix material preparing technical field.
Background technology
20 beginnings of the century, ship bottom antifouling paint just successful Application to marine antifouling, experienced with poison material such as mercury, arsenic, Red copper oxide as stain control agent, then to organo-tin compound is applied in antifouling varnish, the marine pollution matter that causes thus also becomes increasingly conspicuous.In developing the historical progress of ocean, along with the raising of social progress and human knowledge's level, the 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, in the marine finish field, tempting application prospect is arranged, but urethane prevent that the marine organisms adhesive ability is not strong, this has brought and must limit to practical application, need to utilize other means to improve its antifouling ability.
Summary of the invention
The purpose of this invention is to provide a kind of polyurethane Composite Coating with higher antifouling property and preparation method thereof.The present invention utilizes the titanium dioxide of graphene modified to carry out modification take urethane as matrix, thereby consists of a kind of advanced composite material with high antifouling property.
Technical conceive of the present invention is such:
The performance that material inhibition marine organisms adhere in anti-fouling ship paint is particularly important, and nano-TiO
2Have the photochemical catalytic oxidation bacteriostatic activity, suppress thereby reach the effect that marine organisms adhere to.But present nano-TiO
2Because its energy gap is wider, can only issue third contact of a total solar or lunar eclipse katalysis in the irradiation of the shorter UV-light of wavelength, and less at the shared proportion of natural light medium ultraviolet light, make TiO
2The solar energy of photocatalyst is lower with rate, and germ resistance can not finely be applied.And recent research is found the nano-TiO of graphene modified
2Have high absorption, high Photocatalytic oxidation activity, have good photocatalytic activity, can well bring into play its germ resistance.Therefore consider the nano-TiO of graphene modified
2Modified polyurethane paint is applied to marine antifouling.
Technical scheme of the present invention is as follows:
A kind of polyurethane Composite Coating with antifouling property, preparation as follows:
(1) graphite oxide is distributed in water, ultrasonic, obtain the graphite oxide uniform dispersion;
(2) titanium dioxide is joined in the dispersion liquid of step (1) stirring, supersound process, the titania powder solid product that centrifugal, oven dry obtains the graphite oxide load;
(3) solid product is added in deionized water, then add the mixing solutions of hydrazine hydrate solution and strong aqua, stir, form reaction system, water-bath, cooling after reaction finishes, after washing, centrifugal, oven dry, obtain the graphene modified composite titania material; In described matrix material, the mass ratio of graphite oxide and titanium dioxide is 0.5～5:100;
(4) the graphene modified composite titania material is joined in aqueous polyurethane, ultra-sonic dispersion gets final product;
Wherein, described graphite oxide is to adopt the oxidation of Hummer ' s chemical method to make by natural graphite.
In technical scheme of the present invention, described in step (1) in uniform dispersion the concentration of graphite oxide be preferably 0.002%～1%, 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%, and more preferably 0.2%～3%.
In technical scheme of the present invention, the mixing solutions of the hydrazine hydrate solution described in step (3) and strong aqua shared volumn concentration 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, 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 the graphene modified described in step (4) and the mass ratio of aqueous polyurethane are preferably 1～10:100, more preferably 1～3:100.
In the preferred technical solution of the present invention, the ultrasonic time described in step (2) is 0.5～1 hour, and the temperature of described oven dry is 80 ℃.
In the preferred technical solution of the present invention, described in step (3), the water-bath temperature is 90-95 ℃, and water-bath 1～2h carries out in-situ reducing to the graphite oxide that loads on titanium dioxide surface; The temperature of described oven dry is 80 ℃.
In step of the present invention (1), graphite oxide is distributed in water, then the solution supersound process was peeled off into the graphite oxide sheet with graphite oxide in 30～60 minutes, obtain homodisperse graphite oxide dispersion liquid.
The invention has the beneficial effects as follows provides a kind of to halobiontic adhering to inhibiting polyurethane Composite Coating preferably being arranged, and composite coating of the present invention has restraining effect preferably than conventional polyurethanes coating to halobiontic adhering to; Provide a kind of and can obtain to have by simpler preparation technology the method for higher antifouling property coating.
Description of drawings
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) the 10mg graphite oxide is distributed in 200mL water, then solution was peeled off into the graphite oxide sheet with graphite oxide in ultrasonic 30～60 minutes, obtain homodisperse graphite oxide dispersion liquid;
(2) 990mg titanium dioxide is joined in the graphite oxide dispersion liquid of homogeneous dispersion, stirring, the ultrasonic titanium dioxide that makes are uniformly dispersed, and is centrifugal after ultrasonic 0.5 hour, 80 ℃ of oven dry;
(3) will join in deionized water by the titania powder of step (2) gained graphite oxide load, add again hydrazine hydrate solution and the analytically pure ammoniacal liquor of 35% percent by volume to mix in beaker, hydrazine hydrate solution and ammoniacal liquor volume ratio are 1:7, after vigorous stirring 5 minutes, be placed in 95 ℃ of water-baths and reacted 1 hour, the graphite oxide that loads on titanium dioxide surface is carried out in-situ reducing;
(4) after reaction finishes, treat that product is cooling with deionized water rinsing, centrifugal, 80 ℃ of oven dry obtain the graphene modified composite titania material;
(5) by the mass ratio of 100:1, aqueous polyurethane and graphene modified composite titania material are put into beaker, ultrasonic 30min finally forms required polyurethane Composite Coating.
Embodiment 2
(1) the 20mg graphite oxide is distributed in 200mL water, then solution was peeled off into the graphite oxide sheet with graphite oxide in ultrasonic 30～60 minutes, obtain homodisperse graphite oxide dispersion liquid;
(2) 980mg titanium dioxide is joined in the graphite oxide dispersion liquid of homogeneous dispersion, stirring, the ultrasonic titanium dioxide that makes are uniformly dispersed, and is centrifugal after ultrasonic 0.5 hour, 80 ℃ of oven dry;
(3) will join in deionized water by the titania powder of step (2) gained graphite oxide load, add again hydrazine hydrate solution and the analytically pure ammoniacal liquor of 35% percent by volume to mix in beaker, hydrazine hydrate solution and ammoniacal liquor volume ratio are 1:7, after vigorous stirring 5 minutes, be placed in 95 ℃ of water-baths and reacted 1 hour, the graphite oxide that loads on titanium dioxide surface is carried out in-situ reducing;
(4) after reaction finishes, treat that product is cooling with deionized water rinsing, centrifugal, 80 ℃ of oven dry obtain the graphene modified composite titania material;
(5) by the mass ratio of 100:1, aqueous polyurethane and graphene modified composite titania material are put into beaker, ultrasonic 30min finally forms required polyurethane Composite Coating.
Embodiment 3
(1) the 30mg graphite oxide is distributed in 200mL water, then solution was peeled off into the graphite oxide sheet with graphite oxide in ultrasonic 30～60 minutes, obtain homodisperse graphite oxide dispersion liquid;
(2) 970mg titanium dioxide is joined in the graphite oxide dispersion liquid of homogeneous dispersion, stirring, the ultrasonic titanium dioxide that makes are uniformly dispersed, and is centrifugal after ultrasonic 0.5 hour, 80 ℃ of oven dry;
(3) will join in deionized water by the titania powder of step (2) gained graphite oxide load, add again hydrazine hydrate solution and the analytically pure ammoniacal liquor of 35% percent by volume to mix in beaker, hydrazine hydrate solution and ammoniacal liquor volume ratio are 1:7, after vigorous stirring 5 minutes, be placed in 95 ℃ of water-baths and reacted 1 hour, the graphite oxide that loads on titanium dioxide surface is carried out in-situ reducing;
(4) after reaction finishes, treat that product is cooling with deionized water rinsing, centrifugal, 80 ℃ of oven dry obtain the graphene modified composite titania material;
(5) by the mass ratio of 100:1, aqueous polyurethane and graphene modified composite titania material are put into beaker, ultrasonic 30min finally forms required polyurethane Composite Coating.
Embodiment 4
(1) the 50mg graphite oxide is distributed in 200mL water, then solution was peeled off into the graphite oxide sheet with graphite oxide in ultrasonic 30～60 minutes, obtain homodisperse graphite oxide dispersion liquid;
(2) 950mg titanium dioxide is joined in the graphite oxide dispersion liquid of homogeneous dispersion, stirring, the ultrasonic titanium dioxide that makes are uniformly dispersed, and is centrifugal after ultrasonic 0.5 hour, 80 ℃ of oven dry;
(3) will join in deionized water by the titania powder of step (2) gained graphite oxide load, add again hydrazine hydrate solution and the analytically pure ammoniacal liquor of 35% percent by volume to mix in beaker, hydrazine hydrate solution and ammoniacal liquor volume ratio are 1:7, after vigorous stirring 5 minutes, be placed in 95 ℃ of water-baths and reacted 1 hour, the graphite oxide that loads on titanium dioxide surface is carried out in-situ reducing;
(4) after reaction finishes, treat that product is cooling with deionized water rinsing, centrifugal, 80 ℃ of oven dry obtain the graphene modified composite titania material;
(5) by the mass ratio of 100:1, aqueous polyurethane and graphene modified composite titania material are put into beaker, ultrasonic 30min finally forms required polyurethane Composite Coating.
Embodiment 5
The polyurethane Composite Coating that embodiment 1,2,3,4 is obtained is numbered respectively GT1, GT2, and GT3, GT5 will only be numbered GT0 with titania modified polyurethane coating, and original polyurethane coating is numbered PU, and sample is carried out the analysis of benthic diatom adhesion property.
Coating sample (being respectively GT1, GT2, GT3, GT5, GT0, PU) brush is namely made required paint coatings sample on slide glass.The tack of coating specimen surface benthic diatom can be measured by the chlorophyll test value of measuring in benthic diatom liquid, and concrete grammar is as follows:
(1) with the paint coatings sample at 200mL, 0.3 μ g/ml
-1Soak two days later in benthic diatom liquid, take out sample with tweezers, 6 samples are rocked in deionized water remove the non-priming paint diatom that adheres in surface.
(2) diatom that with small size hairbrush, specimen surface is adhered to is brushed respectively to the beaker that fills the 100ml deionized water, drips simultaneously 5ml, 10mgml
-1Magnesiumcarbonate solution with the abundant dispersed with stirring of glass stick, obtains the benthic diatom algae liquid that coatingsurface adheres to.
(3) vacuum pump suction filtration: install filter membrane on suction filter, the benthic diatom algae liquid that obtains of suction filtration step (2), when there is no moisture on filter membrane, stop suction filtration under 30kPa.
(4) grind: suction filtration takes out immediately filter membrane and puts into agate mortar after finishing, and to add the 3ml volume fraction be that 90% acetone soln grinds.Be poured in tool plug plastic centrifuge tube again, and clean mortar 2 times with identical acetone soln, washing lotion merges in centrifuge tube, and cumulative volume is controlled at 10ml.
(5) extract: centrifuge tube is placed in low temp biochemical incubator (low temperature is dark), extracts 30min under 5 ℃.
(6) centrifugal: that the centrifuge tube symmetry is put into TDL-50C whizzer, 3000rmin
-1Centrifugal 10min.Get immediately supernatant liquor 4ml after centrifugal and pour in disposable tool plug test tube, and fixed molten to 10ml with 90% acetone soln.
(7) measure: get the middle good solution 2ml of constant volume of step (6) and be injected in the quartz colorimetric utensil that light path is 1cm, and do blank with identical 90% acetone soln, adopt the spectrophotometric determination wavelength in the solution extinction value 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; ρ is the contained chlorophyllous concentration value of benthic diatom that required coatingsurface adheres to, and S is the surface-area of sheet glass coating.
The contained chlorophyllous concentration value of the benthic diatom that the paint coatings specimen surface adheres to 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 of the present invention (GT1, GT2, GT3, GT5), with respect to original polyurethane coating (PU) or only use the chlorophyllous content of coating of titania modified polyurethane coating (GT0) obviously to reduce, thereby illustrate that the benthic diatom adhesion amount obviously reduces, and has effectively suppressed the tack of benthic diatom.(2) result of GT1, GT2, GT3, GT5 represents, along with the increase of Graphene add-on, the rejection that adheres to of benthic diatom is presented the trend that improves 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 adhering to.
Claims (7)
1. the polyurethane Composite Coating with antifouling property, is characterized in that, this composite coating prepares as follows:
(1) graphite oxide is distributed in water, ultrasonic, obtain the graphite oxide uniform dispersion;
(2) titanium dioxide is joined in the graphite oxide uniform dispersion of step (1) stirring, supersound process, the titania powder solid product that centrifugal, oven dry obtains the graphite oxide load;
(3) solid product is added in deionized water, then add the mixing solutions of hydrazine hydrate solution and strong aqua, stir, water-bath, reaction is cooling after finishing, and after washing, centrifugal, oven dry, obtains the graphene modified composite titania material; In described matrix material, the mass ratio of graphite oxide and titanium dioxide is 0.5～5:100;
(4) the graphene modified composite titania material is joined in aqueous polyurethane, ultra-sonic dispersion gets final product;
Wherein, described graphite oxide is to adopt the oxidation of Hummer ' s chemical method to make by natural graphite.
2. preparation method according to claim 1, is characterized in that, described in step (1) in uniform dispersion the concentration of graphite oxide be 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 mixing solutions of the hydrazine hydrate solution described in step (3) and strong aqua shared volumn concentration 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 ultrasonic time described in step (2) is 0.5～1 hour, and the temperature of described oven dry is 80 ℃.
7. composite coating according to claim 1, is characterized in that, described in step (3), the water-bath temperature is 90～95 ℃, and the water-bath time is 1～2h, and the temperature of described oven dry is 80 ℃.
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| CN104231815A (en) * | 2014-09-30 | 2014-12-24 | 济宁利特纳米技术有限责任公司 | Functionalized antifouling anticorrosive graphene paint as well as preparation method and painting method thereof |
| 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 |
| CN104817930A (en) * | 2015-05-05 | 2015-08-05 | 济宁利特纳米技术有限责任公司 | Heat-conductive and anti-corrosion coating based on graphene functional material and preparation method of same |
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| CN106752834A (en) * | 2017-01-19 | 2017-05-31 | 青岛大学 | A kind of preparation method of graphene oxide/titania/silica composite coating |
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| CN110982359A (en) * | 2019-11-13 | 2020-04-10 | 湖北航天化学技术研究所 | Marine antifouling paint |
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| CN104231815A (en) * | 2014-09-30 | 2014-12-24 | 济宁利特纳米技术有限责任公司 | Functionalized antifouling anticorrosive graphene paint as well as preparation method and painting method thereof |
| 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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| CN106752833A (en) * | 2017-01-19 | 2017-05-31 | 青岛大学 | A kind of preparation method of graphene oxide/silica composite coating |
| CN108624203A (en) * | 2017-03-16 | 2018-10-09 | 青岛大学 | A kind of preparation method of graphene oxide/titanium dioxide composite coating |
| CN108047911A (en) * | 2017-12-15 | 2018-05-18 | 苏州赛斯德工程设备有限公司 | A kind of preparation method of environment-friendly type antifouling of ship's hull coating |
| CN108310539A (en) * | 2018-05-03 | 2018-07-24 | 常州市第人民医院 | A kind of fast alarm system of drop and device |
| CN108525060A (en) * | 2018-05-03 | 2018-09-14 | 常州市第人民医院 | A kind of children's infusion support |
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| CN108525060B (en) * | 2018-05-03 | 2020-09-01 | 常州市第一人民医院 | Infusion support for children |
| CN110982359A (en) * | 2019-11-13 | 2020-04-10 | 湖北航天化学技术研究所 | Marine antifouling paint |
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