CN106189784A - The preparation method of the polyurethane coating that a kind of corrosion resistance is high - Google Patents

The preparation method of the polyurethane coating that a kind of corrosion resistance is high Download PDF

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CN106189784A
CN106189784A CN201610669299.9A CN201610669299A CN106189784A CN 106189784 A CN106189784 A CN 106189784A CN 201610669299 A CN201610669299 A CN 201610669299A CN 106189784 A CN106189784 A CN 106189784A
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tio
nano
coating
polyurethane
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庞宇
刘建萍
符策锐
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Foshan Polytechnic
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The preparation method of the polyurethane coating that a kind of corrosion resistance is high, comprises the steps: that (1) is to nano-TiO2Middle addition deionized water moistening, ultrasonic vibration obtains nano-TiO2Aqueous solution；(2) silane coupler KH 570 is dissolved in dehydrated alcohol, instills pH value regulator and adjust acid-base value, obtain modifying agent mixed solution；(3) modifying agent mixed solution is slowly dropped into nano-TiO2Aqueous solution, stirring mixes, is dried, mill to obtain modified Nano TiO2；(4) by modified Nano TiO2Mass fraction by 1%～5% adds in polyurethane resin, and ball milling obtains nano-TiO2Polyurethane Composite Coating, is coated on metal interface, solidify to form the polyurethane coating that corrosion resistance is high；The present invention is by modified Nano TiO2Mass fraction with 1%～5% adds in polyurethane resin, can soak for a long time and high impedance behavior occur in 3.5%NaCl electrolyte solution, nano-TiO in coating2The effective filling pore of polymolecularity, improve the compactness of coating structure, make the transmission difficulty of corrosive medium bigger, improve the corrosion resistance of polyurethane coating.

Description

The preparation method of the polyurethane coating that a kind of corrosion resistance is high
Technical field
The present invention relates to nanometer titanic oxide material field, particularly relate to the system of the high polyurethane coating of a kind of corrosion resistance Preparation Method.
Background technology
Nano-TiO2There is the distinctive skin effect of nanoparticle, bulk effect, quantum size effect and macroscopic quantum tunnel Channel effect, and unique performance such as higher photocatalytic activity, ultraviolet screening ability is strong, thermal conductance good, good dispersion, but Due to nano-TiO2Specific surface area is big, surface hydrophilic oleophobic, and nano-particle is easily reunited in resin matrix, had a strong impact on it The performance of body performance, limits application in some aspects.
Utilize nano-TiO2Prepare polyurethane coating, be typically at present to utilize unmodified nano-TiO2As material, but due to Unmodified nano-TiO2Reuniting in bulky grain in the coating, cause coating porosity to become big, the coating structure prepared loosens, for electrolysis Matter solution provides passage to coating penetration, can reduce the corrosion resistance of polyurethane coating on the contrary；And at present for polyurethane In the preparation process of coating, due to nano-TiO2Specific surface area is big, surface hydrophilic oleophobic, and nano-particle is easily rolled into a ball in resin matrix Poly-, it is difficult to control polyurethane resin and nano-TiO2Reaction ratio, thus cause the complicated process of preparation of polyurethane coating, electricity The service life of pole is short, and anti-corrosion capability is low, be difficult to reach high-quality requirement.
Summary of the invention
It is an object of the invention to propose the high polyurethane of the simple and easily controllable corrosion resistance of a kind of preparation technology be coated with The preparation method of layer, the coating prepared has high resistant resistance, and decay resistance is greatly enhanced.
For reaching this purpose, the present invention by the following technical solutions:
The preparation method of the polyurethane coating that a kind of corrosion resistance is high, comprises the steps:
(1) nano-TiO2The preparation of aqueous solution: to nano-TiO2Middle addition deionized water carries out moistening, to receiving after moistening Rice TiO2Carry out ultrasonic vibration 25～35min, it is thus achieved that nano-TiO2Aqueous solution；
(2) preparation of modifying agent mixed solution: Silane coupling reagent KH-570 is dissolved in dehydrated alcohol, and instill pH value tune Joint agent, adjusts acidity-basicity ph=4, obtains modifying agent mixed solution；
(3) modified: described modifying agent mixed solution is slowly dropped into described nano-TiO2Aqueous solution, stirs at 60～80 DEG C After mixing hybrid reaction, be dried by mixed liquor, milling obtains modified Nano TiO2；
(4) by described modified Nano TiO2Mass fraction by 1%～5% adds in polyurethane resin, ball milling 4～6h, Obtain nano-TiO2Polyurethane Composite Coating, by described nano-TiO2Polyurethane Composite Coating is coated on metal interface, after solidification The polyurethane coating that corrosion resistance is high can be formed.
Further illustrating, also carry out washing procedure after stirring hybrid reaction described in step (3), described washing procedure is for adopting With the remaining modifying agent mixed solution of absolute ethanol washing.
Further illustrate, the described nano-TiO in step (1)2It is 6:300 with the ratio of deionized water.
Further illustrating, pH value regulator described in step (2) is any one in glacial acetic acid, hydrochloric acid, sulphuric acid or oxalic acid Kind.
Further illustrating, described in step (3), the stirring hybrid reaction time is 4.5～5.5h.
Further illustrating, also include the treatment process of metal interface in step (4), described treatment process is to be respectively adopted Metal interface is polished by 120#, 400#, 800# and 1200# sand paper step by step, with deionized water rinsing after polishing, subsequently with third Ketone and ethanol carry out oil removing, except water, be dried, the metal interface after processing is working electrode.
Further illustrate, nano-TiO described in step (4)2Polyurethane Composite Coating room temperature be 24～26 DEG C, the wettest Degree is 25～solidifies for 35% time, and described hardening time is 70～75h.
Further illustrating, the thickness of described polyurethane coating is 65～75 μm.
Further illustrate, modified Nano TiO in described polyurethane coating2Content be 3%.
Beneficial effects of the present invention: by modified Nano TiO2Mass fraction with 1%～5% adds in polyurethane resin, Finer and close by the coating structure that ultimately forms after ball milling, solidification, coating resistance can up to 2.6 × 108 Ω cm2, and can In 3.5%NaCl electrolyte solution, long-time immersion embodies higher impedance behavior；Nano-TiO in coating2High dispersive Property, make modified Nano TiO2Can effective filling pore, improve the compactness of coating structure so that corrosive medium is at coat inside Transmission difficulty is bigger, and electrolyte solution is difficult to penetrate the metallic matrix interface within coating arrival, improves the resistance to of polyurethane coating Corrosivity, the metallic matrix interface for coat inside has good protective effect.
Accompanying drawing explanation
Fig. 1 is to be not added with nano-TiO2The Bode figure of polyurethane coating EIS in 3.5%NaCl solution；
Fig. 2 is unmodified nano-TiO2Content is the Bode of the polyurethane coating of 1% EIS in 3.5%NaCl solution Figure；
Fig. 3 is unmodified nano-TiO2Content is the Bode of the polyurethane coating of 3% EIS in 3.5%NaCl solution Figure；
Fig. 4 is unmodified nano-TiO2Content is the Bode of the polyurethane coating of 5% EIS in 3.5%NaCl solution Figure；
Fig. 5 is modified Nano TiO2Content is the Bode figure of the polyurethane coating of 1% EIS in 3.5%NaCl solution；
Fig. 6 modified Nano TiO2Content is the Bode figure of the polyurethane coating of 3% EIS in 3.5%NaCl solution；
Fig. 7 modified Nano TiO2Content is the Bode figure of the polyurethane coating of 5% EIS in 3.5%NaCl solution.
Detailed description of the invention
Further illustrate technical scheme below in conjunction with the accompanying drawings and by detailed description of the invention.
The preparation method of the polyurethane coating that a kind of corrosion resistance is high, comprises the steps:
(1) nano-TiO2The preparation of aqueous solution: to nano-TiO2Middle addition deionized water carries out moistening, to receiving after moistening Rice TiO2Carry out ultrasonic vibration 25～35min, it is thus achieved that nano-TiO2Aqueous solution；
(2) preparation of modifying agent mixed solution: Silane coupling reagent KH-570 is dissolved in dehydrated alcohol, and instill pH value tune Joint agent, adjusts acidity-basicity ph=4, obtains modifying agent mixed solution；
(3) modified: described modifying agent mixed solution is slowly dropped into described nano-TiO2Aqueous solution, stirs at 60～80 DEG C After mixing hybrid reaction, be dried by mixed liquor, milling obtains modified Nano TiO2；
(4) by described modified Nano TiO2Mass fraction by 1%～5% adds in polyurethane resin, ball milling 4～6h, Obtain nano-TiO2Polyurethane Composite Coating, by described nano-TiO2Polyurethane Composite Coating is coated on metal interface, after solidification The polyurethane coating that corrosion resistance is high can be formed.
The present invention proposes the preparation method of the high polyurethane coating of a kind of corrosion resistance, by first by nano-TiO2First pass through After deionized water is sufficiently humidified so as to, then the acid modification agent mixed solution of pH=4 is slowly added into described nano-TiO2 Aqueous solution mixes, is dried, milling obtains modified Nano TiO2；Its feature is: (1) nano-TiO after moistening2 Though a small amount of cohesion can occur in water, but find through experiment, the nano-TiO after moistening2Can be with described acid modification After agent mixed solution quickly mixes so that described Silane coupling reagent KH-570 is the most quickly grafted under conditions of acidity is moistening On the surface of nano titanium oxide, improve the efficiency of whole moistening and modifying process, make nano-TiO2Surface property is by parent Aqueous is changed into hydrophobicity, thus improves the affinity of inorganic particle and organic matrix, and Silane coupling reagent KH-570 exists Nano-TiO2Surface forms protective layer, creates space steric effect, hinders the gathering between nanoparticle, thus improve and receive Rice TiO2Dispersibility；(2) described acid modification agent mixed solution is slowly dropped into the nano-TiO after moistening2Mix, keep away Exempt to cause nano-TiO owing to substantial amounts of heat can be produced2Too high and affect the stability of its modification by temperature, therefore maintain Temperature, in the range of 60～80 DEG C, is effectively improved nano-TiO2Stablizing of surface modification effect；(3) without in each dissolving During carry out the effect of external work of ultrasonic vibration, not only ensure modified Nano TiO2Possesses uniform, stable good dispersion Performance, and simplify operation sequence, efficiently solve described Silane coupling reagent KH-570 to described nano-TiO2Carry out surface The time of modified process is long, complicated process of preparation, unmanageable problem.
By described modified Nano TiO2Mass fraction with 1%～5% adds in polyurethane resin, by ball milling, solidification After the coating structure that ultimately forms finer and close, coating resistance can up to 2.6 × 108 Ω cm2, can be electrolysed at 3.5%NaCl In matter solution, long-time immersion embodies higher impedance behavior, although the infiltration of electrolyte solution can make the resistance value of coating Reduce, but nano-TiO in coating2Polymolecularity, make modified Nano TiO2Can effectively filling pore, the cause of raising coating structure Close property, then make corrosive medium bigger in the transmission difficulty of coat inside, and electrolyte solution is difficult to penetrate within coating arrival Metallic matrix interface, the most described modified Nano TiO2The corrosion resistance of polyurethane coating can be significantly improved, for coat inside Metallic matrix interface there is good protective effect.
Further illustrating, also carry out washing procedure after stirring hybrid reaction described in step (3), described washing procedure is for adopting With the remaining modifying agent mixed solution of absolute ethanol washing.By described washing procedure, to described nano-TiO2It is modified After hybrid reaction, remove the modifying agent mixed solution under reaction residual by dehydrated alcohol, thus reduce impurity to modified Nano TiO2The interference of dispersibility.
Further illustrate, the described nano-TiO in step (1)2It is 6:300 with the ratio of deionized water.By controlling institute State nano-TiO2And the ratio between deionized water, if ratio is excessive, the most described nano-TiO2Carry out dissolving moistening same Time, intermolecular cohesion can be produced and increase follow-up described acidity state Silane coupling reagent KH-570 to nano-TiO2Surface Modified effect, the most described nano-TiO2Be ratio 6:300 and in lasting ultrasonic vibration with deionized water, make described in change Property nano-TiO2The suspended state kept in balance.
Further illustrating, pH value regulator described in step (2) is any one in glacial acetic acid, hydrochloric acid, sulphuric acid or oxalic acid Kind.By utilizing described pH value regulator to reduce the pH value that described Silane coupling reagent KH-570 is dissolved in dehydrated alcohol, make institute State Silane coupling reagent KH-570 in sour environment, be more beneficial for and nano-TiO2The hydroxyl phase coupling of particle surface or link, It is combined in nano-titania particle surface with the form of chemical bond, forms rock-steady structure.
Further illustrating, described in step (3), the stirring hybrid reaction time is 4.5～5.5h.Due to described silane coupled Agent KH-570 be under conditions of the middle temperature of 60～80 DEG C with nano-TiO2It is stirred hybrid reaction, along with silane coupler KH-570 is linked to described nano-TiO2On the hydroxyl of particle surface, stirring the hybrid reaction time in the range of 4.5～5.5h, The most not only ensure that and make dehydration complete, improve modified Nano TiO2Dispersibility, and the external work effect of appropriate stirring Improve modified Nano TiO further2Scattered stability.
Further illustrating, also include the treatment process of metal interface in step (4), described treatment process is to be respectively adopted Metal interface is polished by 120#, 400#, 800# and 1200# sand paper step by step, with deionized water rinsing after polishing, subsequently with third Ketone and ethanol carry out oil removing, except water, be dried, the metal interface after processing is working electrode.By to described metal interface Polish step by step, oil removing and except water so that it is the impurity of its surface residual is opened, eliminated to the metal oxide film on surface so that Described modified Nano TiO2Polyurethane Composite Coating is more evenly distributed in surface, after overcuring, improves polyurethane coating and causes Density and the uniformity；When described metal interface is as working electrode, described polyurethane coating can protect described work electricity effectively Pole corrosion resistance in electrolyte solution, improves its service life.
Further illustrate, nano-TiO described in step (4)2Polyurethane Composite Coating room temperature be 24～26 DEG C, the wettest Degree is 25～solidifies for 35% time, and described hardening time is 70～75h.If described nano-TiO2Polyurethane Composite Coating is in mistake Under conditions of height or excessively low temperature, fast setting then can cause described modified Nano TiO2Slight reunion can be produced between particle, If the relative humidity of solidification is excessive, then can make described modified Nano TiO2And the ratio between described polyurethane resin reduces, institute State modified Nano TiO2Cannot be fully filled space, therefore room temperature and 25～35% relative humidity under conditions of solidify one The fixed time, thus the polyurethane coating that compactness is high can be formed, improve the corrosion resistance of polyurethane coating.
Further illustrating, the thickness of described polyurethane coating is 65～75 μm.Owing to described polyurethane coating soaks for a long time Steep in electrolyte solution, therefore the thickness of described polyurethane coating is kept 65～75 μm, improve modified Nano TiO2Point Cloth density and thickness, such that it is able to effectively suppress the infiltration of electrolyte solution, improve the corrosion resistance of described polyurethane coating, prolong Its experimental lifetime long, reduces production cost.
Further illustrate, modified Nano TiO in described polyurethane coating2Content be 3%.Use electrochemical impedance technology Test to the immersion corrosion of described polyurethane coating finds, modified Nano TiO2Dispersibility in resin improves and crosslinking Effect so that coating structure is stable, and compactness is also improved, it is provided that the inhibition of Korrosionsmedium transmission bigger, Make modified Nano TiO2The polyurethane coating filled has higher Rpo value in immersion process；And as described modified Nano TiO2? When content in described polyurethane coating is 3%, its decay resistance is best, and after soaking 2880h, its coating resistance is still protected Hold at 108 more than Ω cm2.
The preparation method of an embodiment 1-polyurethane coating:
Use existing known polyurethane resin material to be prepared into polyurethane Composite Coating, with spraying process, coating is coated in On metal interface, and being 26 DEG C in room temperature, relative humidity is to carry out for 35% time solidifying 75h, and the thickness preparing polyurethane coating is 75μm。
The preparation method of a comparative example 1-polyurethane coating:
Respectively by described unmodified nano-TiO2Mass fraction by 1%, 3%, 5% adds in polyurethane resin, ball milling 6h, obtains three kinds of different nano-TiOs2Polyurethane Composite Coating, is coated in coating on metal interface with spraying process, and in room Temperature is 26 DEG C, and relative humidity is to carry out for 35% time solidifying 75h, and the thickness forming polyurethane coating is 75 μm.
The preparation method of a comparative example 2-polyurethane coating, comprises the steps:
(1) nano-TiO2The preparation of aqueous solution: by 6g nano-TiO2Add in there-necked flask with 300ml deionized water and carry out Moistening, to the nano-TiO after moistening2Carry out ultrasonic vibration 35min, it is thus achieved that nano-TiO2Aqueous solution；
(2) preparation of modifying agent mixed solution: weigh 1.8g Silane coupling reagent KH-570 and be dissolved in 15ml dehydrated alcohol, and Instill pH value regulator glacial acetic acid and adjust acidity-basicity ph=4, obtain modifying agent mixed solution；
(3) modified: the described nano-TiO that described modifying agent mixed solution is slowly dropped in there-necked flask2In aqueous solution, After stirring hybrid reaction 5.5h at 80 DEG C, use the modifying agent mixed solution that absolute ethanol washing is remaining, mixed liquor is dried, Mill and obtain modified Nano TiO2；
(4) respectively by described modified Nano TiO2It is separately added in polyurethane resin by the mass fraction of 1%, 3%, 5%, Ball milling 6h, obtains three kinds of different nano-TiOs2Polyurethane Composite Coating, by described nano-TiO2Polyurethane Composite Coating is coated on On metal interface, and being 26 DEG C in room temperature, relative humidity is to carry out for 35% time solidifying 75h, can form the thickness of polyurethane coating Degree is 75 μm.
Above-mentioned enforcement 1, contrast enforcement 1 and the prepared polyurethane coating obtained of comparative example 2 are carried out electrochemical impedance Spectrum experiment, studies nano-TiO2Polyurethane composite coating soaks the impedance behavior of different time, and described electrochemical impedance spectroscopy is tested Using AUTOLAB PGSTAT 30 electrochemical workstation of Eco Chemistry company of Holland, sample is soaked in mass fraction and is In the NaCl solution of 3.5%, carry out testing impedance in different time points sampling.Test is carried out at ambient temperature, uses three electricity Polar body system, reference electrode is saturated calomel electrode, and auxiliary electrode is platinum electrode.First measure open circuit position, after OCP is stable Starting to measure, the frequency range of measurement is 105-10-2Hz, and measuring signal is the sine wave of amplitude 20mV；Liquid nitrogen is utilized to solidify After composite coating sample quench disconnected, fracture surface after vacuum metal spraying, use Quanta 200F type field emission microscope see Examine nano-TiO2Deployment conditions in coating.
As it is shown in figure 1, for being not added with nano-TiO2The Bode figure of polyurethane coating EIS in 3.5%NaCl solution. As seen from the figure, coating is soaked after 2h, log (Z)～log (f) in an oblique line, and phase angle the most close- 90 °, illustrate that coating now is equivalent to the isolation layer that a resistance value is very big, capacitance is the least；Along with the prolongation of soak time, The curve of log (Z)～log (f) moves towards low frequency direction, and the curve at phase angle declines, and impedance magnitude is all constantly reducing, and this says The infiltration of bright electrolyte solution makes the resistance value of coating reduce, but coating still presents a time constant feature, illustrates to be coated with Layer has not expired, and also has preferably protection for base material, and when being dipped to 2880h, coating presents two time constant features, electricity Solving matter and arrive parent metal interface, parent metal there occurs corrosion.
As shown in figs. 2 to 4, the most unmodified nano-TiO2Content be 1%, 3% and 5% polyurethane coating exist The Bode figure of the EIS in 3.5%NaCl solution.As seen from the figure, three kinds of coatings present a time constant feature at the immersion initial stage, Illustrate that coating has not expired.After soaking 1680h, three kinds of coatings all present two time constant features, the big amplitude variation of coating resistance Little, high frequency capacity reactance arc constantly shrinks, and shows that electrolyte solution has reached saturated to the infiltration of coating, and base metal occurs corruption , there is the electrode reaction resistance at substrate/solution interface, the wherein impedance of high band circular arc correspondence coating self in erosion, and low frequency The electrode reaction resistance of section circular arc correspondence metal/solution interface.When soak time is 2880h, coating impedance spectrum is one Time constant and the impedance spectrum in Warburg impedance characteristic, the appearance of this impedance spectrum represents, the phase after steeping, organic coating The porosity on surface and the bubble domain of coating/substrate metal interface are the biggest, and organic coating has lost stop protective effect, At this moment electrode surface can be observed many corrosions and bubbling, and under coating, metal erosion is serious.Shown by EIS test result, not Modified Nano TiO2Introducing can reduce the corrosion resistance of coating, unmodified nano-TiO on the contrary2Reunite in bulky grain in the coating, Causing coating porosity to become big, coating structure loosens, and provides passage for electrolyte solution to coating penetration.
As shown in Fig. 5～7, for modified Nano TiO2Content is that the polyurethane coating of 1%, 3% and 5% is at 3.5%NaCl The Bode figure of the EIS in solution.As seen from the figure, modified Nano TiO2Content is that the coating of 1% and 3% is in whole immersion process phase Parallactic angle curve only one of which peak value all the time, presents a time constant feature, illustrates that base material is had very well by both coatings Protective effect.This is due to modified Nano TiO2Can effectively be filled with the hole of varnish, make coating structure fine and close, electrolyte is molten Liquid is difficult to penetrate coating and arrives coating/metallic matrix interface, can play a very good protection base material.And modified Nano TiO2Content be 5% coating soaking after 2880h, occur in that unconspicuous two time constant features, corrosive medium be described Although reaching the surface of base material, but the further destruction to coating is suppressed, and this is due to the nano-TiO of excess2 Cause slight reunion, provide duct for Korrosionsmedium permeation coating, but nano-TiO in coating2Stable crosslinking Structure prevents again the Korrosionsmedium further destruction to coating.
The coating resistance of the different coating in table 1 immersion process
As shown in table 1, different coating coating resistance Rpo in immersion process, as seen from table, add the most commensurability before modified Rear nano-TiO2Polyurethane resin matching after the coating resistance Rpo size order when soaking 2880h be: modified containing 3% Nano-TiO2> containing 1% modified Nano TiO2 > containing 5% modified Nano TiO2> it is not added with nano-TiO2> containing 1% unmodified nanometer TiO2> containing 3% unmodified nano-TiO2> containing 5% unmodified nano-TiO2, this shows to add modified Nano TiO2Coating resistance to Corrosive power is significantly better than adding unmodified nano-TiO2, wherein add 3% modified Nano TiO2The decay resistance of coating Preferably, after soaking 2880h, its coating resistance is still maintained at 108 more than Ω cm2；Nano-TiO2Through silane coupler Modified, its dispersibility in polyurethane resin improves and crosslinking effect so that coating structure is stable, and compactness also obtains Improve, it is provided that the inhibition of Korrosionsmedium transmission bigger, make modified nano-TiO2The polyurethane coating filled exists Immersion process has higher Rpo value.
The preparation method of an embodiment 2-polyurethane coating, comprises the steps:
(1) nano-TiO2The preparation of aqueous solution: by 6g nano-TiO2Add in there-necked flask with 300ml deionized water and carry out Moistening, to the nano-TiO after moistening2Carry out ultrasonic vibration 25min, it is thus achieved that nano-TiO2Aqueous solution；
(2) preparation of modifying agent mixed solution: weigh 1.8g Silane coupling reagent KH-570 and be dissolved in 15ml dehydrated alcohol, and Instill pH value regulator hydrochloric acid and adjust acidity-basicity ph=4, obtain modifying agent mixed solution；
(3) modified: the described nano-TiO that described modifying agent mixed solution is slowly dropped in there-necked flask2In aqueous solution, After stirring hybrid reaction 4.5h at 60 DEG C, use the modifying agent mixed solution that absolute ethanol washing is remaining, mixed liquor is dried, Mill and obtain modified Nano TiO2；
(4) by described modified Nano TiO2It is separately added in polyurethane resin by the mass fraction of 1%, ball milling 4h, obtains Nano-TiO2Polyurethane Composite Coating, uses 120#, 400#, 800# and 1200# sand paper to polish metal interface step by step, and After deionized water rinsing, with acetone and ethanol carry out oil removing, except water, be dried, the metal interface after processing is as work Make electrode, by described nano-TiO2Polyurethane Composite Coating is coated on metal interface, and is 24 DEG C in room temperature, and relative humidity is Carrying out for 25% time solidifying 70h, the thickness that can form polyurethane coating is 65 μm.
The preparation method of an embodiment 3-polyurethane coating, comprises the steps:
(1) nano-TiO2The preparation of aqueous solution: by 6g nano-TiO2Add in there-necked flask with 300ml deionized water and carry out Moistening, to the nano-TiO after moistening2Carry out ultrasonic vibration 30min, it is thus achieved that nano-TiO2Aqueous solution；
(2) preparation of modifying agent mixed solution: weigh 1.8g Silane coupling reagent KH-570 and be dissolved in 15ml dehydrated alcohol, and Instill pH value regulator sulphuric acid and adjust acidity-basicity ph=4, obtain modifying agent mixed solution；
(3) modified: the described nano-TiO that described modifying agent mixed solution is slowly dropped in there-necked flask2In aqueous solution, After stirring hybrid reaction 5h at 70 DEG C, use the modifying agent mixed solution that absolute ethanol washing is remaining, mixed liquor is dried, grinds Mill obtains modified Nano TiO2；
(4) by described modified Nano TiO2It is separately added in polyurethane resin by the mass fraction of 3%, ball milling 5h, obtains Nano-TiO2Polyurethane Composite Coating, uses 120#, 400#, 800# and 1200# sand paper to polish metal interface step by step, and After deionized water rinsing, with acetone and ethanol carry out oil removing, except water, be dried, the metal interface after processing is as work Make electrode, by described nano-TiO2Polyurethane Composite Coating is coated on metal interface, and is 25 DEG C in room temperature, and relative humidity is Carrying out for 30% time solidifying 73h, the thickness that can form polyurethane coating is 70 μm.
Test result indicate that interpolation modified Nano TiO2The corrosion resistance of polyurethane coating can be significantly improved, wherein containing 3% The coating of modified Nano TiO2, in immersion process, presents a time constant feature, after being dipped to 2880h, coating all the time Resistance remains as 2.6 × 108 Ω cm2, hence it is evident that higher than the coating resistance of other components, shows that this coating has best corrosion resistant Erosion property.
The know-why of the present invention is described above in association with specific embodiment.These describe and are intended merely to explain the present invention's Principle, and limiting the scope of the invention can not be construed to by any way.Based on explanation herein, the technology of this area Personnel need not pay performing creative labour can associate other detailed description of the invention of the present invention, and these modes fall within Within protection scope of the present invention.

Claims (9)

1. the preparation method of the polyurethane coating that a corrosion resistance is high, it is characterised in that: comprise the steps:
(1) nano-TiO2The preparation of aqueous solution: to nano-TiO2Middle addition deionized water carries out moistening, to the nanometer after moistening TiO2Carry out ultrasonic vibration 25～35min, it is thus achieved that nano-TiO2Aqueous solution；
(2) preparation of modifying agent mixed solution: Silane coupling reagent KH-570 is dissolved in dehydrated alcohol, and instill pH value regulation Agent, adjusts acidity-basicity ph=4, obtains modifying agent mixed solution；
(3) modified: described modifying agent mixed solution is slowly dropped into described nano-TiO2Aqueous solution, at 60～80 DEG C, stirring is mixed After closing reaction, be dried by mixed liquor, milling obtains modified Nano TiO2；
(4) by described modified Nano TiO2Mass fraction by 1%～5% adds in polyurethane resin, and ball milling 4～6h is received Rice TiO2Polyurethane Composite Coating, by described nano-TiO2Polyurethane Composite Coating is coated on metal interface, gets final product shape after solidification Become the polyurethane coating that corrosion resistance is high.
The preparation method of the polyurethane coating that a kind of corrosion resistance is high, it is characterised in that: step (3) also carrying out washing procedure after stirring hybrid reaction described in, described washing procedure is to use remaining the changing of absolute ethanol washing Property agent mixed solution.
The preparation method of the polyurethane coating that a kind of corrosion resistance is high, it is characterised in that: step (1) the described nano-TiO in2It is 6:300 with the ratio of deionized water.
The preparation method of the polyurethane coating that a kind of corrosion resistance is high, it is characterised in that: step (2) pH value regulator described in is any one in glacial acetic acid, hydrochloric acid, sulphuric acid or oxalic acid.
The preparation method of the polyurethane coating that a kind of corrosion resistance is high, it is characterised in that: step (3) described in, the stirring hybrid reaction time is 4.5～5.5h.
The preparation method of the polyurethane coating that a kind of corrosion resistance is high, it is characterised in that: step (4) also including the treatment process of metal interface in, described treatment process is to be respectively adopted 120#, 400#, 800# and 1200# sand paper Metal interface is polished step by step, with deionized water rinsing after polishing, carries out oil removing, except water, dry with acetone and ethanol subsequently Dry, the metal interface after processing is working electrode.
The preparation method of the polyurethane coating that a kind of corrosion resistance is high, it is characterised in that: step (4) nano-TiO described in2Polyurethane Composite Coating room temperature be 24～26 DEG C, relative humidity be 25～solidify for 35% time, Described hardening time is 70～75h.
The preparation method of the polyurethane coating that a kind of corrosion resistance is high, it is characterised in that: described poly- The thickness of urethane coating is 65～75 μm.
The preparation method of the polyurethane coating that a kind of corrosion resistance is high, it is characterised in that: described poly- Modified Nano TiO in urethane coating2Content be 3%.
CN201610669299.9A 2016-08-15 2016-08-15 The preparation method of the polyurethane coating that a kind of corrosion resistance is high Pending CN106189784A (en)

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