CN107446387B - The dedicated titanium dioxide process of marine paint - Google Patents

The dedicated titanium dioxide process of marine paint Download PDF

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Publication number
CN107446387B
CN107446387B CN201710573594.9A CN201710573594A CN107446387B CN 107446387 B CN107446387 B CN 107446387B CN 201710573594 A CN201710573594 A CN 201710573594A CN 107446387 B CN107446387 B CN 107446387B
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titanium dioxide
marine paint
iron
valve
pipeline
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CN107446387A (en
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徐英杰
徐英豪
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China Ti Group Yusheng Titanium Industry Co ltd
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Xizang Tooker Trade Ltd Co
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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
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon 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
    • 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
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • 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
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers

Abstract

The present invention proposes the dedicated titanium dioxide process of marine paint, and industrial titanium dioxide is carried out two-stage except being reacted under high pressure and high temperature condition after iron with lye, titania nanotube is made；Successively to titania nanotube carry silver processing, it is amido modified after, graphene oxide is coated on titania nanotube, the load silver titania nanotube of the graphene oxide cladding with amino is made；To get the dedicated titanium dioxide of marine paint after the load silver titania nanotube progress surface organic process coated to the graphene oxide with amino.The present invention carries out second level to industrial titanium dioxide excessively and removes iron, it solves because iron content is excessively high in titanium dioxide, so that being introduced into the problem of ferro element excessive in marine paint causes marine paint corrosion resistance and mechanical performance to decline, dispersion performance of the titanium dioxide in marine paint production is improved simultaneously, improves the corrosion resistance and mechanical performance of marine paint.

Description

The dedicated titanium dioxide process of marine paint
Technical field
The present invention relates to the dedicated titanium dioxide process of marine paint.
Background technique
Marine paint is to be coated on each position inside and outside ship, required with extending Ship Life and meeting the extraordinary of ship The general designation of various paint wants used marine paint as ship hull bottom, waterline, deck, shell etc. apply the difference of holding position The performance asked is also different.Wherein, specific as at ship waterline, i.e., hull bottom is lightly loaded the position between heavy duty, while by seawater Leaching with daylight is shone, and the impact and friction of wave and the parasitism of marine organisms etc. influence, and this requires the ship waterlines of coating Paint should have good corrosion resistance, mechanical performance and anti-pollution.
In the actual production process of marine paint, industrial titanium dioxide leads to as a kind of cheap, function admirable filler Often it is widely used.And industrial titanium dioxide is since product quality is very different, especially when the ferro element in industrial titanium dioxide contains When measuring excessively high, iron content in marine paint can be made higher accordingly, this application in marine paint, especially marine paint for boot toppings In, since coating is chronically at bloom according under the saltwater environment of high humidity, excessively high iron content can aggravate environment to marine paint Corrosion function, be unfavorable for improve marine paint corrosion resistance and mechanical performance；Additionally, due to industrial titanium dioxide as nothing Machine powder, during the processing of marine paint, dispersion performance is poor, reunion is easy to happen inside marine paint, not only The filling capacity of titanium dioxide is influenced, and is unfavorable for improving the mechanical performance and corrosion resistance of marine paint, influences marine paint Product quality.
Application No. is the patent documents of CN201110099500.1 to disclose a kind of preparation side of titanium pigment used in ship paint Method, comprising the following steps: a, calcine the metatitanic acid to obtain titanium dioxide crude product TiO is made2Calgon is added in slurry；B, add Silicon-containing compound is added after heat, is homogenized；c,TiO2The pH value of slurry is adjusted to 0.8~4；D, organic dispersing agent is added after curing, Aluminum contained compound is added, is then homogenized；E, by TiO2The pH value of slurry is adjusted to 4~8；F, make TiO2Slurry curing；G, will TiO2Slurry filtration makes resistivity >=100 Ω M of filter cake；Then it dries, then is heat-treated；H, it is added at organic surface Reason agent crushed to get.But this application does not contain ferro element in titanium dioxide crude product during to titania modified Amount is limited, and is unfavorable for reducing the content of ferro element in marine paint, be declined so as to cause the mechanical performance of marine paint, while not Conducive to raising marine paint to the corrosion resistance of seawater；This application is not directed to influence of the marine organisms to marine paint simultaneously, from And it is unfavorable for improving the anti-pollution of marine paint.
Application No. is the patent documents of CN201610703524.6 to disclose a kind of Heavy-Duty Marine Paints, by component A and Component B composition, by weight, the weight ratio of the component A and component B are 15: 5~1；Each component prepares raw material by weight Meter, it is as follows: component A: 15~20 parts of zinc powder, 10~15 parts of titanium dioxide, 10~15 parts of molybdenum sesquioxide, the poly- sesquialter of octaphenyl cage modle 15~30 parts of silicone-modified sulfonated polyimide, 0.5~3 part of polyoxyethylene polyoxy propyl alcohol amidogen ether, N, N- lupetazin 1~ 5 parts, 1~10 part of KH-550,1~5 part of graphene oxide, 30~50 parts of ethyl orthosilicate and 10~20 parts of dimethyl sulfoxide； Component B: beta-cyclodextrin modified amido blocks sulfonate polybenzimidazole 5-10 parts, 30~50 parts of nano-titanium dioxide, silica flour 15 ~20,40~50 parts of epoxy resin E51,1~10 part of KH-560,5~10 parts of 1,12- dibromo-dodecane, 5~10 parts of ethylene glycol And 1~10 part of pentaerythrite.But titanium dioxide is not performed corresponding processing in this application, so that titanium dioxide is being answered For still remaining the problems such as titanium dioxide iron content is higher, dispersion performance is poor in the production process of marine paint, from And be unfavorable for improving the mechanical performance and corrosion resistance of marine paint, influence the product quality of marine paint.
Application No. is the patent documents of CN201611066511.9 to disclose a kind of wear-resistant weather-proof conductive anticorrosion of elastomer Naval vessel rudder ceramic coating composition, uses bisphenol F epoxy resin for base-material, cooperates a variety of compound additives, comprising: toughener, Solvent, conductive agent, curing agent, auxiliary agent, levelling agent, ceramic powder filler, wherein ceramic powder filler contains titanium dioxide, silicon nitride, oxygen Change cerium and brown diamond spar.But titanium dioxide is not performed corresponding processing in this application, so that titanium dioxide is being applied to ship In the production process of oceangoing ship coating, the problems such as titanium dioxide iron content is higher, dispersion performance is poor is still remained, thus unfavorable In the mechanical performance and corrosion resistance that improve marine paint, the product quality of marine paint is influenced.
Summary of the invention
The present invention is particularly applied to ship waterline to solve industrial titanium dioxide applied in the production process of marine paint In the production process of paint, because iron content is higher in industrial titanium dioxide, dispersion performance is poor, caused marine paint is corrosion-resistant The problems such as performance and poor mechanical performance, while improving the anti-pollution of marine paint.
In order to solve the above technical problems, technical scheme is as follows:
The dedicated titanium dioxide process of marine paint, after industrial titanium dioxide progress two-stage removes iron, with lye in high pressure-temperature Under the conditions of react, be made titania nanotube；Successively to titania nanotube carry silver processing, it is amido modified after, will Graphene oxide is coated on titania nanotube, and the load silver nano titania of the graphene oxide cladding with amino is made Pipe；To get marine paint after the load silver titania nanotube progress surface organic process coated to the graphene oxide with amino Dedicated titanium dioxide.
Further, comprising the following steps:
S1, industrial titanium dioxide is added in deironing apparatus, is carried out once except iron and grinding screening, the titanium white qualified to screening Powder carries out secondary except iron；
S2, the secondary titanium dioxide except after iron and aqueous slkali are added in reaction kettle, it is right under hyperbaric environment after mixing dispersion Mixed liquor heating, carries out hydro-thermal reaction；Product after hydro-thermal reaction is centrifuged, neutrality is washed to, obtains dioxy after filtering Change titanium nanotube；
S3, titania nanotube is added in silver nitrate solution, regulation system pH value is 6.8~7.3, stirring to dioxy It after change titanium nanotube is evenly dispersed, is centrifuged, washing filtering, and low temperature drying processing is carried out to filter cake, obtain carrying silver-colored Titania nanotube；
S4, silver-colored titania nanotube will be carried and excess of ammonia propyl trimethoxy silicane mixes and after the 3-5h that flows back, mistake Filter after filter cake is aged 2-3h, is obtained with amido modified load silver titania nanotube；
S5, it graphene oxide is placed in organic solvent is stirred, Ultrasonic Pulverization obtains graphene oxide solution；
S6, the graphene oxide solution in the titania nanotube and step S5 in step S4 is sufficiently stirred, is filtered, Low temperature drying processing is carried out to filter cake, obtains the load silver titania nanotube of the graphene oxide cladding with amino；
S7, using ethyl alcohol as solvent, zinc pyrithione, stearic acid are mixed to prepare emulsion, step is added into emulsion Titanium dioxide made from S6 filters after being uniformly dispersed, filter cake is dried, up to the dedicated titanium dioxide of marine paint after crushing.
Preferably, in step sl, the median of the qualified titanium dioxide of the screening is secondary to remove between 70-90nm Iron content≤10ppm of titanium dioxide after iron.
Preferably, in step s 2, it is 15-25g/L that the ratio between the quality of titanium dioxide and the volume of aqueous slkali, which is added,；It is described Aqueous slkali is sodium hydroxide solution or potassium hydroxide solution, and the alkaline concentration is 3.0-4.0mol/L；The hydro-thermal reaction Pressure be 0.36-0.50MPa, temperature be 132-140 DEG C.
Further, in step s 5, the organic solvent include dimethylformamide, in dimethyl acetamide at least It is a kind of.
Preferably, in step s 6, the mass ratio of titania nanotube and graphene oxide is 100-150:1.
Further, the deironing apparatus includes: in step sl
Level-one removes iron still, removes iron for carrying out level-one to industrial titanium dioxide；
Planetary ball mill, with level-one except the discharge nozzle of iron still is connect；
Vibrating screen connects respectively at the feed inlet of the discharge port of planetary ball mill, the feed inlet of planetary ball mill, collecting bin It connects；
Second level removes iron still, is internally provided with agitating device, the second level except iron still respectively with collecting bin, dilute acid bath, diafiltration Device connection；
Diafiltration device is connect with waste liquid tank, dilute acid bath, water tank respectively.
Preferably, the level-one includes: except iron still
Level-one is arranged in except on the shell of iron still, the feed inlet is connect with feeder pipe in feed inlet；
Transport mechanism, the transport mechanism include driving device, drive roll, driven voller, conveyer belt, the driving device with Drive roll or driven voller connection, provide power for transport mechanism, by transmission band connection between drive roll and driven voller, in institute It states and is provided with permanent magnetism set on the axial outer of driven voller, the permanent magnetism tackling is magnetic；
The transport mechanism is feed end in the side close to drive roll, positioned at the lower section of feeder pipe, and passes through conveyer belt Material is accepted, the transport mechanism is discharge end in the side close to driven voller, ash can and discharge port are set below driven voller, Ash can is located at driven voller central axis close to the side of drive roll, and discharge port is located at driven voller central axis far from drive roll Side, the discharge port are connect with discharge nozzle；
Deironing mechanism, the Deironing mechanism include electromagnet, between the feed end and discharge end of transport mechanism, electromagnet Side, the electromagnet have magnetism in the case where energization on a moving belt for setting.
Preferably, diafiltration area is arranged in diafiltration device top, collecting tank is arranged in diafiltration device lower part；
The collecting tank includes filtrate receiver, abacus, material collection slot；
The filtrate receiver and spent acid piping connection are provided with spent acid valve on spent acid pipeline；
It is connected with diluted acid pipeline on the filtrate receiver top, filtrate receiver is connect by diluted acid pipeline with dilute acid bath, diluted acid pipe Road is provided with diluted acid valve；
The discharge end of material pipeline is provided with above filtrate receiver, materail tube road is provided with material valve, material pipeline Feed end is with second level except iron still is connect；
The abacus bottom is provided with flushing liquor pipeline, and flushing-liquid pipe road is provided with flushing liquor valve, flushing liquor Pipeline and spent acid piping connection；
Spray thrower, the discharge end connection of the spray thrower and clear water pipeline, water pipe are provided with above the abacus Road is provided with Clean water valve, and the feed end of clear water pipeline is connect with water tank；
Diafiltration area top is provided with slideway；
Electronic sliding block is mounted in slideway, and is slid into above filtrate receiver in the horizontal direction along slideway, on abacus Any position in above side, material collection slot；
Extension sleeve stretches in vertical direction, is mounted on electronic sliding block；
Connecting rod is connect with extension sleeve and filter frame respectively；
Filter frame carries out the movement in vertical direction under the drive of extension sleeve, and water is carried out under the drive of electronic sliding block Square upward movement, the filter frame are internally provided with filter plate.
Further, diafiltration device further includes central controller, the Clean water valve, material valve, diluted acid valve, spent acid Valve, flushing liquor valve are Perfected electromagnetic metering valve, are connect with central controller, and valve is executed under the control of central controller and is opened Movement is closed, electronic sliding block, extension sleeve are connect with central controller respectively, are moved under the control of central controller；
Specific control process the following steps are included:
A, central controller successively controls electronic sliding block, extension sleeve movement, is in filter frame above filtrate receiver, material The lower section of pipeline discharge end；
B, central controller opens material valve and spent acid valve, by filter plate to the mixture of acid pickle and titanium dioxide into Row filtering, acid pickle enter waste liquid tank through spent acid pipeline, and titanium dioxide stays on filter plate；
C, central controller closes spent acid valve, opens diluted acid valve, makes the diluted acid that storage is quantitative in filtrate receiver, center control Device control extension sleeve movement processed, is in filter frame in filtrate receiver, is immersed in titanium dioxide in diluted acid；
D, after immersion, central controller controls extension sleeve and electronic slide block movement make filter frame be in flushing liquor Above slot, below spray thrower；
E, central controller opens Clean water valve, is rinsed with quantitative clear water to titanium dioxide；
F, after flushing, the movement of central controller controls extension sleeve is in filter frame in abacus, makes titanium white Powder is immersed in flushing liquor；
G, after immersion, the movement of central controller controls extension sleeve is in filter frame above abacus, simultaneously Central controller opens flushing liquor valve and closes flushing liquor valve after liquid discharge to be rinsed；
H, diafiltration device successively carries out step e, step f and step g, after repeating 1-2 times, central controller controls telescopic Cylinder and electronic slide block movement, are in filter frame in material collection slot, to collect the secondary titanium dioxide except after iron.
Compared with prior art, the present invention proposes the dedicated titanium dioxide process of marine paint, by industrial titanium dioxide It carries out second level and removes iron, solve because iron content is excessively high in titanium dioxide, so that excessive ferro element problem is introduced into marine paint, Improve the corrosion resistance and mechanical performance of marine paint.
Simultaneously by the present invention in that using at least one of dimethylformamide, dimethyl acetamide as solvent, by band Amido modified load silver titania nanotube enhances between titanium dioxide and graphene oxide in conjunction with graphene oxide Binding force makes collective effect between the two to enhance the corrosion resistance and mechanical performance of marine paint.
In addition in the present invention, the stearic acid of coated by titanium dioxide provides corresponding modification for titanium dioxide, not only Dispersion performance of the titanium dioxide in marine paint production process is improved, the generation of titanium dioxide reunion phenomenon is avoided, makes two Titanium oxide disperses more uniformly in marine paint, enhances the compatibility of titanium dioxide Yu coating organic substrate, effectively presses down The sedimentation phenomenon in marine paint storage process is made, and in the coating process of marine paint, has been conducive to improve coating thickness, from And protective effect of the marine paint to hull is enhanced, improve the corrosion resistance and mechanical performance of marine paint.
The present invention carries silver during the cladding of titanium dioxide, through titania nanotube, improves the anti-of marine paint Bacterium, anti-mildew ability, reduce the attachment of marine organisms, reduce influence of the marine organisms to marine paint；Simultaneously because dioxy The zinc pyrithione for changing titanium cladding can be effectively prevented crust biology, seaweed and aquatic organism and be attached on hull, thus greatly The anti-pollution of marine paint is improved greatly.
Detailed description of the invention
In order to illustrate more clearly of the technical solution in the present invention, attached drawing needed in the embodiment will be made below Simply introduce, it should be apparent that, drawings in the following description are only some embodiments of the invention, for the general of this field For logical technical staff, without creative efforts, it is also possible to obtain other drawings based on these drawings.
Fig. 1 is the structural schematic diagram of the deironing apparatus of the dedicated titanium dioxide process of marine paint of the present invention；
Fig. 2 is that the level-one of the dedicated titanium dioxide process of marine paint of the present invention removes the structural schematic diagram of iron still；
Fig. 3 is the structural schematic diagram of the diafiltration device of the dedicated titanium dioxide process of marine paint of the present invention.
Appended drawing reference
1, level-one removes iron still；101, feed inlet；102, feeder pipe；103, electromagnet；104, drive roll；105, driving dress It sets；106, conveyer belt；107, driven voller；1071, permanent magnetism set；108, discharge port；109, ash can；110, discharge nozzle；2, planet Ball mill；3, vibrating screen；4, collecting bin；5, second level removes iron still；6, diafiltration device；600, central controller；61, diafiltration area； 611, slideway；612, electronic sliding block；613, extension sleeve；614, connecting rod；615, filter frame；616, filter plate；62, collecting tank； 621, filtrate receiver；622, abacus；623, material collection slot；63, clear water pipeline；631, Clean water valve；632, spray thrower； 64, material pipeline；641, material valve；65, diluted acid pipeline；651, diluted acid valve；66, spent acid pipeline；661, spent acid valve； 67, flushing liquor pipeline；671, flushing liquor valve；7, waste liquid tank；8, dilute acid bath；9, water tank.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention is further described, Obviously, described embodiment is only a part of the embodiments of the present invention, rather than whole embodiments.Based in the present invention Embodiment, those of ordinary skill in the art's every other embodiment obtained under the premise of not making the creative labor, It shall fall within the protection scope of the present invention.
The dedicated titanium dioxide process of marine paint, comprising the following steps:
S1, industrial titanium dioxide is added in deironing apparatus, is carried out once except iron and grinding screening, the titanium white qualified to screening Powder carries out secondary except iron；
S2, the secondary titanium dioxide except after iron and aqueous slkali are added in reaction kettle, it is right under hyperbaric environment after mixing dispersion Mixed liquor heating, carries out hydro-thermal reaction；Product after hydro-thermal reaction is centrifuged, neutrality is washed to, obtains dioxy after filtering Change titanium nanotube；
S3, titania nanotube is added in silver nitrate solution, regulation system pH value is 6.8~7.3, stirring to dioxy It after change titanium nanotube is evenly dispersed, is centrifuged, washing filtering, and low temperature drying processing is carried out to filter cake, obtain carrying silver-colored Titania nanotube；
S4, silver-colored titania nanotube will be carried and excess of ammonia propyl trimethoxy silicane mixes and after the 3-5h that flows back, mistake Filter after filter cake is aged 2-3h, is obtained with amido modified load silver titania nanotube；
S5, it graphene oxide is placed in organic solvent is stirred, Ultrasonic Pulverization obtains graphene oxide solution；
S6, the graphene oxide solution in the titania nanotube and step S5 in step S4 is sufficiently stirred, is filtered, Low temperature drying processing is carried out to filter cake, obtains the load silver titania nanotube of the graphene oxide cladding with amino；
S7, using ethyl alcohol as solvent, zinc pyrithione, stearic acid are mixed to prepare emulsion, step is added into emulsion Titanium dioxide made from S6 filters after being uniformly dispersed, filter cake is dried, up to the dedicated titanium dioxide of marine paint after crushing.
Raw material is used as using industrial titanium dioxide in the present invention, and industry titanium dioxide is since product quality is very different, especially It is to make that iron content is higher in marine paint accordingly when the iron content in industrial titanium dioxide is excessively high, this is in ship In the application of oceangoing ship paint, especially marine paint for boot toppings, since coating is chronically at bloom according under the saltwater environment of high humidity, excessively high iron Constituent content can aggravate corrosion function of the environment to marine paint, be unfavorable for improving the corrosion resistance and mechanicalness of marine paint Can, so must carry out operating except iron to industrial titanium dioxide.
In step sl, successively industrial titanium dioxide is carried out once except iron-grinding-screening-is secondary except iron is handled, wherein for Improve the size distribution situation of industrial titanium dioxide, convenient for the progress of the subsequent wet treatment process of titanium dioxide, improves secondary removes Iron efficiency sieves the median of qualified titanium dioxide in step S1 between 70-90nm.
Simultaneously in the two-stage iron removal by step S1, so that the secondary iron content except titanium dioxide after iron≤ 10ppm, to solve the problems, such as that iron content is excessively high in industrial titanium dioxide, improves ship in the production process of marine paint Oceangoing ship paint corrosion resistance and mechanical performance.
Industry titanium dioxide employed in the present invention includes: plate titanium-type titanium dioxide, rutile titanium dioxide, anatase titanium dioxide Any one of titanium dioxide.
In step s 2, it is 15-25g/L that the ratio between the quality of titanium dioxide and the volume of aqueous slkali, which is added, is particularly utilized The characteristic that titanium dioxide is reacted with aqueous slkali is handled the particle structure of titanium dioxide, with titanium dioxide and sodium hydroxide For, specific reaction equation is TiO2+ 2NaOH=Na2TiO3+H2O；But titanium dioxide needs and high concentration in the process Lye could preferably be reacted, and the present invention is to be made titania nanotube, if using the lye of high concentration, not only Whether there are some potential safety problemss, and its extent of reaction is difficult to control, cannot ensure titanium dioxide finally is made to have and receive The uniformity coefficient of nanotube structures and its nano tube structure；
In view of problem above, researcher of the invention passes through the study found that under hyperbaric environment, low concentration in utilization Lye can with titanium dioxide carry out hydro-thermal reaction.Since under high temperature and high pressure environment, lye and titanium dioxide have well Reactivity, by control hydro-thermal reaction temperature, pressure, can conveniently realize and react between titanium dioxide and lye The control of degree makes titania nanotube obtained have more uniform regular nano tube structure, specifically in step S2 In, the aqueous slkali is sodium hydroxide solution or potassium hydroxide solution, and the alkaline concentration is middle low concentration, preferably 3.0- 4.0mol/L；The pressure of the hydro-thermal reaction is 0.36-0.50MPa, and temperature is 132-140 DEG C.
In step s3, it using the good adsorption properties of titania nanotube, is adsorbed in titania nanotube Silver ion is made and carries silver-colored titania nanotube, and since titanium dioxide has good photocatalytic activity, silver ion has good Fungistatic effect, while titania nanotube have biggish specific surface area, enable titanium dioxide and silver ion efficiently It plays and cooperates with antibacterial effect, improve the antifouling and antibiosis of marine paint, anti-mildew ability, reduce the attachment of marine organisms, drop Low influences of the marine organisms to marine paint.Silver ion is formd additionally, due to the silver-colored titania nanotube of load produced by the present invention Slow-release carrier, in the long-term use process of marine paint, silver ion is gradually released in marine paint for this, so that ship Oceangoing ship paint has long-acting antifouling and antibiosis ability, is conducive to the service life for improving marine paint.
In step S4-S6, specially graphene oxide coats the process for carrying silver-colored titania nanotube；Firstly, utilizing Methoxy group in aminopropyl trimethoxysilane is coupled with silver-colored titania nanotube is carried, and is formed with amido modified Carry silver-colored titania nanotube；Then it is coupled using amino group and graphene oxide, graphene oxide is made to be coated on two Titania surface, to form the load silver titania nanotube of the graphene oxide cladding with amino；Due to graphene oxide Good stability and weatherability are all had with titanium dioxide, the two is combined and is applied to by aminopropyl trimethoxysilane In marine paint, be conducive to the corrosion resistance for improving marine paint.
Be simply mixed difference with by titanium dioxide and graphene oxide, utilizes aminopropyl trimethoxy silicon in the present invention Alkane is coupled titanium dioxide and graphene oxide, not only enhances the binding force between titanium dioxide and graphene oxide, makes The two collective effect is to enhance the corrosion resistance of marine paint, and in the production process of marine paint, aminopropyl trimethoxy Silane improves the crosslinked action between ship raw materials for varnish as crosslinking accelerator, to improve the mechanical performance of marine paint.
In step s 5, organic solvent includes at least one of dimethylformamide, dimethyl acetamide；Simultaneously in step In rapid S6, the cladding process of graphene oxide and titanium dioxide is also to carry out in the organic solvent.Used by step S5 Organic solvent is due to not only contributing to disperse graphene oxide with stronger polarity, so that graphene oxide is having What is be distributed in solvent is more uniform, improves graphene oxide to the uniformity coefficient of coated by titanium dioxide；And step S5 is used Organic solvent can form the electronics of solvation on graphene oxide surface layer, enhance the knot between amino group and graphene oxide Cooperation is used, to enhance the comprehensive profit between titanium dioxide and graphene oxide, collective effect between the two is made to enhance ship The mechanical performance and corrosion resistance of oceangoing ship paint；In addition, the organic solvent also promotes between amino group and graphene oxide Coupling process, improve the reaction efficiency in production process.
In the step s 7, the process that organic coating is specially carried out to titanium dioxide made from step S6, makes through this hair The bright dedicated titanium dioxide powder of marine paint obtained switchs to lipophilicity by hydrophily, produces to solve titanium dioxide in marine paint The problem of existing dispersion performance difference in the process.Specifically, handling using stearic acid titanium dioxide, dioxy is not only improved Change dispersion performance of the titanium in marine paint production process, avoids the generation of titanium dioxide reunion phenomenon, make titanium dioxide in ship Disperse more uniformly in oceangoing ship paint, enhances the compatibility of titanium dioxide Yu coating organic substrate, restrained effectively marine paint Sedimentation phenomenon in storage process；And titanium dioxide is handled using stearic acid, it is advantageous in the coating process of marine paint The corrosion resistance and machine of marine paint are improved to enhance protective effect of the marine paint to hull in improving coating thickness Tool performance.
The present invention is not under the premise of influencing to carry out organic coating effect to titanium dioxide simultaneously, in order to further increase ship The anti-pollution of oceangoing ship paint after emulsion is made in stearic acid and zinc pyrithione premixing, then carries out at cladding titanium dioxide Reason, this make zinc pyrithione with stearic acid cladding on the titanium dioxide, this marine paint in actual use, can be with It is effectively prevented crust biology, seaweed and aquatic organism to be attached on hull, to substantially increase the anti-pollution of marine paint.
For the iron compound being effectively removed in industrial titanium dioxide, reduces and introduce marine paint because using industrial titanium dioxide Internal iron compound, to improve the corrosion resistance and mechanical performance of marine paint.In view of the magnetization property of iron compound, room temperature Titanium dioxide is not reacted with diluted acid under normal pressure, and the characteristic of acidolysis then occurs for iron compound, and the present invention except iron in step sl by filling It sets and carries out two-stage except iron, removed including the level-one iron removal with magnetic method except iron, and using the second level that diluted acid acid hydrolyzation carries out Iron process.Specifically, by magnetic method remove iron level-one iron removal, to the magnetic iron compound in industrial titanium dioxide into Row removal；The second level iron removal carried out by diluted acid acid hydrolyzation, iron compound acidolysis remaining in industrial titanium dioxide is laggard Row is separated by solid-liquid separation, so that remaining iron compound be separated from industrial titanium dioxide, realizes that second level removes iron.
The deironing apparatus includes:
Level-one removes iron still 1, removes iron for carrying out level-one to industrial titanium dioxide；
Planetary ball mill 2, with level-one except the discharge nozzle 110 of iron still 1 is connect；
Vibrating screen 3, respectively at the discharge port of planetary ball mill 2, the feed inlet of planetary ball mill 2, the feed inlet of collecting bin 4 Connection；
Second level removes iron still 5, for the acidolysis kettle with cavity structure, and agitating device is internally provided with, to industrial titanium dioxide It carries out second level and removes iron, the second level is connect with collecting bin 4, dilute acid bath 8, diafiltration device 6 respectively except iron still 5；
Diafiltration device 6 is connect with waste liquid tank 7, dilute acid bath 8, water tank 9 respectively.
In order to ensure level-one except 1 pair of iron still industrial titanium dioxide carries out efficiently removing iron, is removed in iron still 1 in level-one and two-stage is set Magnetize iron removal, specifically, level-one includes: except iron still 1
Level-one is arranged in except on the shell of iron still 1, the feed inlet 101 is connect with feeder pipe 102 in feed inlet 101；
Transport mechanism, the transport mechanism include driving device 105, drive roll 104, driven voller 107, conveyer belt 106, institute State driving device 105 to connect with drive roll 104 or driven voller 107, provide power for transport mechanism, drive roll 104 with it is driven Connected between roller 107 by conveyer belt 106, be provided with permanent magnetism set 1071 on the axial outer of the driven voller 107, it is described forever Magnetosheath 1071 has magnetism；
The transport mechanism is feed end in the side close to drive roll 104, positioned at the lower section of feeder pipe 102, and is passed through Conveyer belt 106 accepts material, and the transport mechanism is discharge end in the side close to driven voller 107, is arranged below driven voller 107 Ash can 109 and discharge port 108, ash can 109 are located at 107 central axis of driven voller close to the side of drive roll 104, discharge port 108 are located at side of 107 central axis of driven voller far from drive roll 104, and the discharge port 108 is connect with discharge nozzle 110；
Deironing mechanism, the Deironing mechanism include electromagnet 103, between the feed end and discharge end of transport mechanism, electricity Magnet 103 is arranged above conveyer belt 106, and the electromagnet 103 has magnetism in the case where energization.
And after second level carries out acidolysis except iron except iron still, the acid pickle containing titanium dioxide need to be separated by solid-liquid separation, in order to true The efficiency being separated by solid-liquid separation is protected, Ying Jinliang avoids the iron ion doping after acidolysis in titanium dioxide, this is just necessary to ensure that diafiltration device 6 There should be efficient diafiltration performance, while in view of the convenience of entire diafiltration operation, to improve production efficiency.
Specifically, diafiltration area 61 is arranged in 6 top of diafiltration device, collecting tank 62 is arranged in 6 lower part of diafiltration device；
The collecting tank 62 includes filtrate receiver 621, abacus 622, material collection slot 623；
The filtrate receiver 621 is connect with spent acid pipeline 66, and spent acid valve 661 is provided on spent acid pipeline 66；
It is connected with diluted acid pipeline 65 on 621 top of filtrate receiver, filtrate receiver 621 passes through diluted acid pipeline 65 and dilute acid bath 8 It connects, is provided with diluted acid valve 651 on diluted acid pipeline 65；
It is provided with the discharge end of material pipeline 64 above filtrate receiver 621, material valve 641 is provided on material pipeline 64, The feed end of material pipeline 64 is with second level except iron still 5 is connect；
622 bottom of abacus is provided with flushing liquor pipeline 67, and flushing liquor valve is provided on flushing liquor pipeline 67 671, flushing liquor pipeline 67 is connect with spent acid pipeline 66；
Spray thrower 632, the discharge end of the spray thrower 632 and clear water pipeline 63 are provided with above the abacus 622 It connects, is provided with Clean water valve 631 on clear water pipeline 63, the feed end of clear water pipeline 63 is connect with water tank 9；
61 top of diafiltration area is provided with slideway 611；
Electronic sliding block 612 is mounted in slideway 611, and is slid on filtrate receiver 621 in the horizontal direction along slideway 611 Any position above side, abacus 622, in 623 top of material collection slot；
Extension sleeve 613 stretches in vertical direction, is mounted on electronic sliding block 612；
Connecting rod 614 is connect with extension sleeve 613 and filter frame 615 respectively；
Filter frame 615 carries out the movement in vertical direction under the drive of extension sleeve 613, in the band of electronic sliding block 612 The dynamic lower movement carried out in horizontal direction, the filter frame 615 are internally provided with filter plate 616.
Further, in order to realize automation control of the diafiltration device 6 in operation, reduce manpower in production at This, improve production efficiency, the diafiltration device 6 further includes central controller 600, the Clean water valve 631, material valve 641, Diluted acid valve 651, spent acid valve 661, flushing liquor valve 671 are Perfected electromagnetic metering valve, are connect with central controller 600, in Entreat controller 600 control under execute valve opening and closing movement, electronic sliding block 612, extension sleeve 613 respectively with central controller 600 connections, are moved under the control of central controller 600；
Specific control process the following steps are included:
A, central controller 600 successively controls electronic sliding block 612, extension sleeve 613 moves, and filter frame 615 is made to be in filter 621 top of liquid bath, the lower section of 64 discharge end of material pipeline；
B, central controller 600 opens material valve 641 and spent acid valve 661, by filter plate 616 to acid pickle and titanium white The mixture of powder is filtered, and acid pickle enters waste liquid tank 7 through spent acid pipeline 66, and titanium dioxide stays on filter plate 616；
C, central controller 600 closes spent acid valve 661, opens diluted acid valve 651, keeps storage in filtrate receiver 621 certain The diluted acid of amount, central controller 600 control extension sleeve 613 and move, be in filter frame 615 in filtrate receiver 621, make titanium dioxide It is immersed in diluted acid；
D, after immersion, central controller 600 controls extension sleeve 613 and electronic sliding block 612 moves, and makes filter frame 615 in 622 top of abacus, 632 lower section of spray thrower；Central controller 600 opens spent acid valve 661 simultaneously, by filtrate Diluted acid discharge in slot 621；
E, central controller 600 opens Clean water valve 631, is rinsed with quantitative clear water to titanium dioxide；
F, after flushing, central controller 600 controls extension sleeve 613 and moves, and filter frame 615 is made to be in abacus In 622, it is immersed in titanium dioxide in flushing liquor；
G, after immersion, central controller 600 controls extension sleeve 613 and moves, and filter frame 615 is made to be in abacus 622 tops, while central controller 600 opens flushing liquor valve 671 and closes flushing liquor valve 671 after liquid discharge to be rinsed；
H, diafiltration device 6 successively carries out step e, step f and step g, and after repeating 1-2 times, the control of central controller 600 is stretched Contracting sleeve 613 and electronic sliding block 612 move, and are in filter frame 615 in material collection slot 623, secondary except after iron to collect Titanium dioxide.
A specific embodiment of the invention is further described with reference to embodiments, is not therefore limited the present invention System is within the scope of the embodiment described.
Embodiment 1
The dedicated titanium dioxide process of marine paint, comprising the following steps:
S1, industrial titanium dioxide is added in deironing apparatus, is carried out once except iron and grinding screening, to the titanium dioxide after screening It is sampled, and measuring the median of titanium dioxide in Malvern laser particle analyzer is 73nm, by the qualified titanium dioxide of screening It carries out secondary except iron, then samples to titanium dioxide, carry out iron content analysis and measures iron content to be 8ppm；
S2, the sodium hydroxide solution of the secondary titanium dioxide except after iron and 3.0mol/L is added in reaction kettle, wherein titanium white The ratio between quality and the volume of sodium hydroxide solution of powder are 18g/L, are 0.36MPa, temperature 132 in pressure after mixing dispersion Hydro-thermal reaction is carried out under conditions of DEG C；Product after hydro-thermal reaction is centrifuged, neutrality is washed to, obtains titanium dioxide after filtering Titanium nanotube；
S3, titania nanotube is added in silver nitrate solution, regulation system pH value is 7.3, stirring to titanium dioxide It after nanotube is evenly dispersed, is centrifuged, filter cake is dried under the conditions of 75 DEG C 5h, obtains carrying silver-colored dioxy by washing filtering Change titanium nanotube；
S4, silver-colored titania nanotube will be carried and excess of ammonia propyl trimethoxy silicane mix and after the 3h that flows back, filtered, After filter cake is aged 2h, obtain with amido modified load silver titania nanotube；
S5, it graphene oxide is placed in solvent dimethylformamide is stirred, Ultrasonic Pulverization obtains graphene oxide Solution；
S6, the graphene oxide solution in the titania nanotube and step S5 in step S4 is mixed, wherein dioxy The mass ratio for changing titanium nanotube and graphene oxide is 120:1, is filtered after being sufficiently stirred, and filter cake is dry under the conditions of 90 DEG C 7h obtains the load silver titania nanotube of the graphene oxide cladding with amino；
S7, using ethyl alcohol as solvent, zinc pyrithione, stearic acid are mixed to prepare emulsion, step is added into emulsion Titanium dioxide made from S6, wherein zinc pyrithione: stearic acid: titanium dioxide 1:2:4 is uniformly dispersed in terms of mass fraction After filter, filter cake is dried, up to the dedicated titanium dioxide of marine paint after crushing.
Embodiment 2
The dedicated titanium dioxide process of marine paint, comprising the following steps:
S1, industrial titanium dioxide is added in deironing apparatus, is carried out once except iron and grinding screening, to the titanium dioxide after screening It is sampled, and measuring the median of titanium dioxide in Malvern laser particle analyzer is 90nm, by the qualified titanium dioxide of screening It carries out secondary except iron, then samples to titanium dioxide, carry out iron content analysis and measures iron content to be 10ppm；
S2, the potassium hydroxide solution of the secondary titanium dioxide except after iron and 3.2mol/L is added in reaction kettle, wherein titanium white The ratio between quality and the volume of potassium hydroxide solution of powder are 15g/L, are 0.40MPa, temperature 138 in pressure after mixing dispersion Hydro-thermal reaction is carried out under conditions of DEG C；Product after hydro-thermal reaction is centrifuged, neutrality is washed to, obtains titanium dioxide after filtering Titanium nanotube；
S3, titania nanotube is added in silver nitrate solution, regulation system pH value is 7.0, stirring to titanium dioxide It after nanotube is evenly dispersed, is centrifuged, filter cake is dried under the conditions of 70 DEG C 6h, obtains carrying silver-colored dioxy by washing filtering Change titanium nanotube；
S4, silver-colored titania nanotube will be carried and excess of ammonia propyl trimethoxy silicane mixes and after the 4.5h that flows back, mistake Filter after filter cake is aged 3h, is obtained with amido modified load silver titania nanotube；
S5, it graphene oxide is placed in dimethylacetamide solvent is stirred, Ultrasonic Pulverization obtains graphene oxide Solution；
S6, the graphene oxide solution in the titania nanotube and step S5 in step S4 is mixed, wherein dioxy The mass ratio for changing titanium nanotube and graphene oxide is 100:1, is filtered after being sufficiently stirred, and filter cake is dry under the conditions of 85 DEG C 8h obtains the load silver titania nanotube of the graphene oxide cladding with amino；
S7, using ethyl alcohol as solvent, zinc pyrithione, stearic acid are mixed to prepare emulsion, step is added into emulsion Titanium dioxide made from S6, wherein zinc pyrithione: stearic acid: titanium dioxide 1:2:5 is uniformly dispersed in terms of mass fraction After filter, filter cake is dried, up to the dedicated titanium dioxide of marine paint after crushing.
Embodiment 3
The dedicated titanium dioxide process of marine paint, comprising the following steps:
S1, industrial titanium dioxide is added in deironing apparatus, is carried out once except iron and grinding screening, to the titanium dioxide after screening It is sampled, and measuring the median of titanium dioxide in Malvern laser particle analyzer is 70nm, by the qualified titanium dioxide of screening It carries out secondary except iron, then samples to titanium dioxide, carry out iron content analysis and measures iron content to be 9ppm；
S2, the potassium hydroxide solution of the secondary titanium dioxide except after iron and 4.0mol/L is added in reaction kettle, wherein titanium white The ratio between quality and the volume of potassium hydroxide solution of powder are 25g/L, are 0.45MPa, temperature 140 in pressure after mixing dispersion Hydro-thermal reaction is carried out under conditions of DEG C；Product after hydro-thermal reaction is centrifuged, neutrality is washed to, obtains titanium dioxide after filtering Titanium nanotube；
S3, titania nanotube is added in silver nitrate solution, regulation system pH value is 6.8, stirring to titanium dioxide It after nanotube is evenly dispersed, is centrifuged, filter cake is dried under the conditions of 80 DEG C 3h, obtains carrying silver-colored dioxy by washing filtering Change titanium nanotube；
S4, silver-colored titania nanotube will be carried and excess of ammonia propyl trimethoxy silicane mix and after the 5h that flows back, filtered, After filter cake is aged 2.5h, obtain with amido modified load silver titania nanotube；
S5, it graphene oxide is placed in solvent dimethylformamide is stirred, Ultrasonic Pulverization obtains graphene oxide Solution；
S6, the graphene oxide solution in the titania nanotube and step S5 in step S4 is mixed, wherein dioxy The mass ratio for changing titanium nanotube and graphene oxide is 150:1, is filtered after being sufficiently stirred, and filter cake is dry under the conditions of 70 DEG C 8h obtains the load silver titania nanotube of the graphene oxide cladding with amino；
S7, using ethyl alcohol as solvent, zinc pyrithione, stearic acid are mixed to prepare emulsion, step is added into emulsion Titanium dioxide made from S6, wherein zinc pyrithione: stearic acid: titanium dioxide 1:3:7 is uniformly dispersed in terms of mass fraction After filter, filter cake is dried, up to the dedicated titanium dioxide of marine paint after crushing.
Embodiment 4
The dedicated titanium dioxide process of marine paint, comprising the following steps:
S1, industrial titanium dioxide is added in deironing apparatus, is carried out once except iron and grinding screening, to the titanium dioxide after screening It is sampled, and measuring the median of titanium dioxide in Malvern laser particle analyzer is 82nm, by the qualified titanium dioxide of screening It carries out secondary except iron, then samples to titanium dioxide, carry out iron content analysis and measures iron content to be 6ppm；
S2, the sodium hydroxide solution of the secondary titanium dioxide except after iron and 3.6mol/L is added in reaction kettle, wherein titanium white The ratio between quality and the volume of sodium hydroxide solution of powder are 20g/L, are 0.50MPa, temperature 136 in pressure after mixing dispersion Hydro-thermal reaction is carried out under conditions of DEG C；Product after hydro-thermal reaction is centrifuged, neutrality is washed to, obtains titanium dioxide after filtering Titanium nanotube；
S3, titania nanotube is added in silver nitrate solution, regulation system pH value is 6.9, stirring to titanium dioxide It after nanotube is evenly dispersed, is centrifuged, filter cake is dried under the conditions of 90 DEG C 3h, obtains carrying silver-colored dioxy by washing filtering Change titanium nanotube；
S4, silver-colored titania nanotube will be carried and excess of ammonia propyl trimethoxy silicane mix and after the 5h that flows back, filtered, After filter cake is aged 3h, obtain with amido modified load silver titania nanotube；
S5, it graphene oxide is placed in solvent dimethylformamide is stirred, Ultrasonic Pulverization obtains graphene oxide Solution；
S6, the graphene oxide solution in the titania nanotube and step S5 in step S4 is mixed, wherein dioxy The mass ratio for changing titanium nanotube and graphene oxide is 130:1, is filtered after being sufficiently stirred, and filter cake is dry under the conditions of 90 DEG C 8h obtains the load silver titania nanotube of the graphene oxide cladding with amino；
S7, using ethyl alcohol as solvent, zinc pyrithione, stearic acid are mixed to prepare emulsion, step is added into emulsion Titanium dioxide made from S6, wherein zinc pyrithione: stearic acid: titanium dioxide 1:2.5:6, dispersion are equal in terms of mass fraction Filtering, is dried filter cake after even, up to the dedicated titanium dioxide of marine paint after crushing.
Comparative example 1
It is comparative example with the embodiment 1 of patent application document CN106336802A, the specific method is as follows:
A kind of Heavy-Duty Marine Paints gather 20 parts of zinc powder, 15 parts of titanium dioxide, 15 parts of molybdenum sesquioxide, octaphenyl cage modle 30 parts of silsesquioxane modification sulphonation polyimides, 3 parts of polyoxyethylene polyoxy propyl alcohol amidogen ether, N, 3 parts of N- lupetazin, KH- 550 8 parts, 4 parts of graphene oxide, 40 parts of ethyl orthosilicate and 15 parts of dimethyl sulfoxide pour into pill tank, are stirred by dispersion Machine is stirred, and at 400 revs/min, mixing time is 15 minutes for mixing speed control, obtains component A；
Beta-cyclodextrin modified amido is blocked 8 parts of sulfonate polybenzimidazole, 40 parts of nano-titanium dioxide, silica flour 18, ring 45 parts of oxygen resin E51,8 parts of KH-560,8 parts of 1,12- dibromo-dodecane, 8 parts of ethylene glycol and 8 parts of pentaerythrite pour into ingredient It in cylinder, is stirred by dispersator, at 1000 revs/min, mixing time is 30 minutes for mixing speed control, obtains component B； It is by weight to mix to get Heavy-Duty Marine Paints at 15: 3 by the component A and component B；
Based on the raw material proportioning of the marine paint in comparative example 1 and preparation method, by the titanium dioxide in comparative example 1 with And nano-titanium dioxide, the dedicated titanium dioxide of marine paint obtained in 1-4 of the embodiment of the present invention is replaced with, respectively as embodiment 5-8, and mechanical performance and corrosion resistance detection are carried out to marine paint made from embodiment 5-8, comparative example 1, specifically such as 1 institute of table Show.
The mechanical performance and corrosion resistance table of 1 marine paint of table
From table 1 it follows that solving since the application has carried out second level iron removal to industrial titanium dioxide because of titanium white Iron content is excessively high in powder, so that being introduced into ferro element excessive in marine paint leads to marine paint corrosion resistance and mechanicalness The problem of capable of declining；The surface treatment carried out simultaneously by the application to titanium dioxide, not only improves titanium dioxide in ship The dispersion performance in production process is painted, the generation of titanium dioxide reunion phenomenon is avoided, disperses titanium dioxide in marine paint It obtains more uniformly, enhances the compatibility of titanium dioxide Yu coating organic substrate, restrained effectively in marine paint storage process Sedimentation phenomenon be conducive to improve coating thickness, to enhance marine paint to hull and in the coating process of marine paint Protective effect, improve the corrosion resistance and mechanical performance of marine paint；In addition, using aminopropyl trimethoxysilane to two Titanium oxide is coupled with graphene oxide, not only enhances the binding force between titanium dioxide and graphene oxide, makes the two altogether Same-action to enhance the corrosion resistance of marine paint, and in the production process of marine paint, make by aminopropyl trimethoxysilane For crosslinking accelerator, the crosslinked action between ship raw materials for varnish is improved, to improve the mechanical performance of marine paint.I.e. such as table Shown in data in 1, in mechanical performance and corrosion resistance, ship made from the dedicated titanium dioxide of the marine paint of the application is utilized Oceangoing ship paint is better than marine paint obtained by comparative example 1, and its data has statistical significance (p < 0.01).
Meanwhile in the step S5 of the method for the present invention solvent service condition, be specifically described by following embodiment:
Embodiment 9-12, comparative example 2-6 embodiment with it is substantially same as Example 8 with condition, except that During preparing the dedicated titanium dioxide of marine paint, solvent used in the step S5 is different, concrete condition and result such as table 2 It is shown.
Table 2
The organic solvent that the present invention uses in step s 5 includes dimethylformamide, at least one in dimethyl acetamide Kind, compared to other conventional organic solvents, present invention organic solvent used by step S5 is due to stronger polarity, no Only be conducive to disperse graphene oxide, so that graphene oxide is distributed more uniform, raising oxygen in organic solvent Uniformity coefficient of the graphite alkene to coated by titanium dioxide；And the organic solvent that step S5 is used can be in graphene oxide surface layer shape At the electronics of solvation, enhance the combination between amino group and graphene oxide, to enhance titanium dioxide and oxidation Comprehensive profit between graphene makes collective effect between the two enhance the mechanical performance and corrosion resistance of marine paint.Cause This includes dimethylformamide, diformazan by the organic solvent that the data in table 2 can be seen that the present invention uses in step s 5 At least one of yl acetamide, for other organic solvents, final marine paint obtained all has better machinery Performance and corrosion resistance, and its data has statistical significance (p < 0.01).
In addition, in the case where temporary indefinite specific mechanism, the researcher of the application process through a large number of experiments It was unexpectedly observed that when dimethylformamide and dimethyl acetamide are applied in combination, compared to any single solvent is used, finally Obtained marine paint has preferable mechanical performance and corrosion resistance, and its data has statistical significance (p < 0.05).
Compared with prior art, the present invention proposes the dedicated titanium dioxide process of marine paint, by industrial titanium dioxide It carries out second level and removes iron, solve because iron content is excessively high in titanium dioxide, led so that being introduced into ferro element excessive in marine paint The problem of causing marine paint corrosion resistance and mechanical performance to decline, to improve the corrosion resistance and mechanicalness of marine paint Energy.
Simultaneously by the present invention in that using at least one of dimethylformamide, dimethyl acetamide as solvent, by band Amido modified load silver titania nanotube enhances between titanium dioxide and graphene oxide in conjunction with graphene oxide Binding force makes collective effect between the two to enhance the corrosion resistance and mechanical performance of marine paint.
In addition in the present invention, the stearic acid of coated by titanium dioxide provides corresponding modification for titanium dioxide, not only Dispersion performance of the titanium dioxide in marine paint production process is improved, the generation of titanium dioxide reunion phenomenon is avoided, makes two Titanium oxide disperses more uniformly in marine paint, enhances the compatibility of titanium dioxide Yu coating organic substrate, effectively presses down The sedimentation phenomenon in marine paint storage process is made, and in the coating process of marine paint, has been conducive to improve coating thickness, from And protective effect of the marine paint to hull is enhanced, improve the corrosion resistance and mechanical performance of marine paint.
The present invention carries silver during the cladding of titanium dioxide, through titania nanotube, improves the anti-of marine paint Bacterium, anti-mildew ability, reduce the attachment of marine organisms, reduce influence of the marine organisms to marine paint；Simultaneously because dioxy The zinc pyrithione for changing titanium cladding can be effectively prevented crust biology, seaweed and aquatic organism and be attached on hull, thus greatly The anti-pollution of marine paint is improved greatly.
The foregoing is merely the preferred embodiments of the application, not to limit the application, all essences in the application Within mind and principle, any modification, equivalent substitution, improvement and etc. done be should be included within the scope of the application protection.

Claims (8)

1. the dedicated titanium dioxide process of marine paint, which is characterized in that after industrial titanium dioxide progress two-stage removes iron, exist with lye Pressure is 0.36-0.50MPa, and temperature is reacted under conditions of being 132-140 DEG C, and titania nanotube is made；Successively to dioxy Change titanium nanotube carry silver processing, it is amido modified after, graphene oxide is coated on titania nanotube, band ammonia is made The load silver titania nanotube of the graphene oxide cladding of base；To the load silver titanium dioxide of the graphene oxide cladding with amino To get the dedicated titanium dioxide of marine paint after nanotube progress surface organic process；
The method specifically includes the following steps:
S1, industrial titanium dioxide is added in deironing apparatus, is carried out once except iron and grinding screening, the titanium dioxide qualified to screening into Row is secondary to remove iron；
S2, secondary titanium dioxide and aqueous slkali except after iron is added in reaction kettle, in pressure is 0.36- after mixing dispersion Mixed liquor is heated under conditions of 0.50MPa, carries out hydro-thermal reaction；Product after hydro-thermal reaction is centrifuged, is washed to Property, titania nanotube is obtained after filtering；
S3, titania nanotube is added in silver nitrate solution, regulation system pH value is 6.8~7.3, stirring to titanium dioxide It after nanotube is evenly dispersed, is centrifuged, washing filtering, and filter cake is dried under the conditions of 70-90 DEG C of temperature Processing, obtains carrying silver-colored titania nanotube；
S4, silver-colored titania nanotube will be carried and excess of ammonia propyl trimethoxy silicane mix and after the 3-5h that flows back, filtering, general After filter cake is aged 2-3h, obtain with amido modified load silver titania nanotube；
S5, it graphene oxide is placed in organic solvent is stirred, Ultrasonic Pulverization obtains graphene oxide solution；
S6, the graphene oxide solution in the titania nanotube and step S5 in step S4 is sufficiently stirred, is filtered, to filter Cake carries out drying and processing under the conditions of 70-90 DEG C of temperature, obtains the load silver titanium dioxide of the graphene oxide cladding with amino Nanotube；
S7, using ethyl alcohol as solvent, zinc pyrithione, stearic acid are mixed to prepare emulsion, into emulsion be added step S6 system The titanium dioxide obtained, filters after being uniformly dispersed, filter cake is dried, up to the dedicated titanium dioxide of marine paint after crushing；
The organic solvent includes at least one of dimethylformamide, dimethyl acetamide.
2. the dedicated titanium dioxide process of marine paint as described in claim 1, which is characterized in that in step sl, described The median of qualified titanium dioxide is sieved between 70-90nm, secondary iron content≤10ppm except titanium dioxide after iron.
3. the dedicated titanium dioxide process of marine paint as described in claim 1, which is characterized in that in step s 2, be added The ratio between quality and the volume of aqueous slkali of titanium dioxide are 15-25g/L；The aqueous slkali is that sodium hydroxide solution or potassium hydroxide are molten Liquid, the alkaline concentration are 3.0-4.0mol/L；The pressure of the hydro-thermal reaction is 0.36-0.50MPa, temperature 132- 140℃。
4. the dedicated titanium dioxide process of marine paint as described in any one of claims 1-3, which is characterized in that in step S6 In, the mass ratio of titania nanotube and graphene oxide is 100-150:1.
5. the dedicated titanium dioxide process of marine paint as described in claim 1, which is characterized in that described in step sl Deironing apparatus includes:
Level-one removes iron still (1), removes iron for carrying out level-one to industrial titanium dioxide；
Planetary ball mill (2), with level-one except the discharge nozzle (110) of iron still (1) is connect；
Vibrating screen (3), the discharge port respectively at planetary ball mill (2), the feed inlet of planetary ball mill (2), collecting bin (4) into Material mouth connection；
Second level removes iron still (5), and the second level is connect with collecting bin (4), dilute acid bath (8), diafiltration device (6) respectively except iron still (5)；
Diafiltration device (6) is connect with waste liquid tank (7), dilute acid bath (8), water tank (9) respectively.
6. the dedicated titanium dioxide process of marine paint as claimed in claim 5, which is characterized in that the level-one removes iron still (1) include:
Feed inlet (101) is arranged on shell of the level-one except iron still (1), and the feed inlet (101) connect with feeder pipe (102)；
Transport mechanism, the transport mechanism include driving device (105), drive roll (104), driven voller (107), conveyer belt (106)；The driving device (105) connect with drive roll (104) or driven voller (107), provides power for transport mechanism, main It is connect between dynamic roller (104) and driven voller (107) by conveyer belt (106), is set on the axial outer of the driven voller (107) It is equipped with permanent magnetism set (1071), the permanent magnetism set (1071) has magnetism；
The transport mechanism is feed end in the side close to drive roll (104), is located at the lower section of feeder pipe (102), and is passed through Conveyer belt (106) accepts material, and the transport mechanism is discharge end in the side close to driven voller (107), under driven voller (107) Side's setting ash can (109) and discharge port (108), ash can (109) are located at driven voller (107) central axis close to drive roll (104) side, discharge port (108) are located at side of driven voller (107) central axis far from drive roll (104), the discharging Mouth (108) is connect with discharge nozzle (110)；
Deironing mechanism, the Deironing mechanism includes electromagnet (103), between the feed end and discharge end of transport mechanism, electromagnetism Above conveyer belt (106), the electromagnet (103) has magnetism in the case where energization for body (103) setting.
7. the dedicated titanium dioxide process of marine paint as claimed in claim 5, which is characterized in that the diafiltration device (6) Diafiltration area (61) are arranged in top, and collecting tank (62) are arranged in diafiltration device (6) lower part；
The collecting tank (62) includes filtrate receiver (621), abacus (622), material collection slot (623)；
The filtrate receiver (621) connect with spent acid pipeline (66), and spent acid valve (661) are provided on spent acid pipeline (66)；
It is connected with diluted acid pipeline (65) on the filtrate receiver (621) top, filtrate receiver (621) passes through diluted acid pipeline (65) and diluted acid Slot (8) connects, and is provided with diluted acid valve (651) on diluted acid pipeline (65)；
The discharge end of material pipeline (64) is provided with above filtrate receiver (621), material pipeline is provided with material valve on (64) (641), the feed end of material pipeline (64) is connect with second level except iron still (5)；
Abacus (622) bottom is provided with flushing liquor pipeline (67), and flushing liquor pipeline is provided with rinse fluid valve on (67) Door (671), flushing liquor pipeline (67) are connect with spent acid pipeline (66)；
It is provided with spray thrower (632) above the abacus (622), the spray thrower (632) goes out with clear water pipeline (63) Expect end connection, is provided with Clean water valve (631) on clear water pipeline (63), the feed end of clear water pipeline (63) is connect with water tank (9)；
Diafiltration area (61) top is provided with slideway (611)；
Electronic sliding block (612) is mounted in slideway (611), and slides into filtrate receiver (621) in the horizontal direction along slideway (611) Any position above top, abacus (622), in material collection slot (623) top；
Extension sleeve (613) stretches in vertical direction, is mounted on electronic sliding block (612)；
Connecting rod (614) is connect with extension sleeve (613) and filter frame (615) respectively；
Filter frame (615) carries out the movement in vertical direction under the drive of extension sleeve (613), in electronic sliding block (612) The lower movement carried out in horizontal direction is driven, the filter frame (615) is internally provided with filter plate (616).
8. the dedicated titanium dioxide process of marine paint as claimed in claim 7, which is characterized in that diafiltration device (6) includes Central controller (600), Clean water valve (631), diluted acid valve (651), spent acid valve (661), rinse material valve (641) Fluid valve (671) is Perfected electromagnetic metering valve, connect with central controller (600), executes under the control of central controller (600) Valve opening and closing movement, electronic sliding block (612), extension sleeve (613) are connect with central controller (600) respectively, are controlled in center It is moved under the control of device (600)；
Specific control process the following steps are included:
A, central controller (600) successively controls electronic sliding block (612), extension sleeve (613) movement, makes at filter frame (615) Above filtrate receiver (621), the lower section of material pipeline (64) discharge end；
B, central controller (600) opens material valve (641) and spent acid valve (661), by filter plate (616) to acid pickle with The mixture of titanium dioxide is filtered, and acid pickle enters waste liquid tank (7) through spent acid pipeline (66), and titanium dioxide stays in filter plate (616) On；
C, central controller (600) closes spent acid valve (661), opens diluted acid valve (651), makes storage in filtrate receiver (621) A certain amount of diluted acid, central controller (600) control extension sleeve (613) movement, filter frame (615) are made to be in filtrate receiver (621) in, it is immersed in titanium dioxide in diluted acid；
D, after immersion, central controller (600) controls extension sleeve (613) and electronic sliding block (612) movement, makes filter frame (615) above abacus (622), below spray thrower (632)；
E, central controller (600) opens Clean water valve (631), is rinsed with quantitative clear water to titanium dioxide；
F, after flushing, central controller (600) controls extension sleeve (613) movement, and filter frame (615) is made to be in flushing liquor In slot (622), it is immersed in titanium dioxide in flushing liquor；
G, after immersion, central controller (600) controls extension sleeve (613) movement, and filter frame (615) is made to be in flushing liquor Above slot (622), while central controller (600) opens flushing liquor valve (671), after liquid discharge to be rinsed, closes flushing liquor Valve (671)；
H, diafiltration device (6) successively carries out step e, step f and step g, and after repeating 1-2 times, central controller (600) control is stretched Contracting sleeve (613) and electronic sliding block (612) movement, are in filter frame (615) in material collection slot (623), secondary to collect Except the titanium dioxide after iron.
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