CN110041807A - A kind of preparation method of marine anticorrosion composite coating - Google Patents
A kind of preparation method of marine anticorrosion composite coating Download PDFInfo
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The present invention relates to a kind of preparation methods of marine anticorrosion composite coating, belong to technical field of coatings.The present invention is using bisphenol-A phenolic epoxy resin as raw material, prepare marine anticorrosion composite coating, novolac epoxy resin is a kind of polyfunctional group tetraglycidel ether epoxy resin, existing phenolic structure in its molecular structure, there is epoxy group again, the main polymer chain of bisphenol-A phenolic epoxy resin contains diphenol propane type structure, make it have very strong mechanical strength and wearability, the cure shrinkage of coating is low, toughness is high, contain a large amount of epoxy group in bisphenol-A phenolic epoxy resin, to form extremely strong adhesion strength with substrate, especially the introducing of organosilicon is so that the hydrophobic and lyophobic property of bisphenol-A phenolic epoxy resin improves, with especially excellent corrosion resistance and resistance to ultraviolet, chemicals energy, to keep high marine anticorrosion composite coating flexible smooth, with self-cleaning performance, improve the toughness and corrosion resistance of coating.
Description
Technical field
The present invention relates to a kind of preparation methods of marine anticorrosion composite coating, belong to technical field of coatings.
Background technique
Ocean accounts for about the 70% of earth surface product, and in world commerce, sea transport is leaned in 90% or more shipping, marine resources with
Marine vessel industry has become mainstay indispensable in development of world economy.However, as sea stormy waves etc. is to metal
The reciprocating impact that component generates；The corrosion to metal material such as seawater, marine organisms and its metabolite, marine environment have become
Extremely harsh corrosive environment.No matter submarine, the ship etc. in seawater or on sea, require using high-strength, corrosion-resistant material
Material manufacture, and brushing corrosion-inhibiting coating is protected.Therefore, the extensive pass that most suitable Marine Antifouling Paint has caused people is found
Note.
Marine Antifouling Paint refers in marine environment, can play the role of one kind of anti-corrosion protection to ocean engineering matrix
Functional paint is one of most important research object in ocean engineering coating for a long time.In marine environment in seawater and sea wind
All contain a large amount of salts substances, have serious corrosiveness to the ocean engineering based on steel,
In addition there are the marine animals such as algae, fish and microorganism in seawater, offshore engineering equipment surface in the seawater can be adhered to,
Accelerate the corrosiveness of metallic matrix.Marine environment has the spy of duration and chronicity to the corrosiveness of offshore engineering equipment
Point, offshore engineering equipment are recycled from coming into operation to scrapping, will the continual corrosiveness by marine environment, therefore
Anticorrosive work is the key that ocean engineering.Marine Antifouling Paint can be divided into two major classes according to the property of matrix, and one kind is steel knot
Structure anticorrosive paint, another kind of is non-steel structure anti-corrosion paint.The former effective object is ship, bridge, seabed steel pipe etc. with steel
Equipment and foundation engineering based on material;The effective object of the latter is that bridge pier, harbour etc. are with other materials such as concrete, rubber
Main equipment and foundation engineering.Since marine environment has, corrosivity is strong, etching time is long, the particularity more than burst factor,
It is required that Marine Antifouling Paint has the features such as heavy antisepsis, performance stabilization, long service life, simple coating operation ].With the epoch
Development, people will be more and more in the activity that marine field is carried out, and the construction of ocean engineering will show fast development
The impetus.And since marine environment has certain destructiveness to ocean engineering facility, it be easy to cause big safety accident, research sea
Foreign anticorrosive paint is significant.Ocean engineering can be effectively protected in Marine Antifouling Paint with outstanding anti-corrosion protection performance,
Phenomena such as avoiding the occurrence of run-down steel construction, fracture, will greatly improve the safety of ocean working environment.
The Corrosion style multiplicity of steel construction in ocean engineering: galvanic corrosion, cavitation phenomenon, erosion corrosion and impingment corrosion,
Gas-evolving electrodes, oxygen uptake corrosion etc..Mainly have using more anticorrosive paint: epoxies anticorrosive paint, gathers fluorine carbon anticorrosive paint
Urethane class anticorrosive paint, rubber anti-corrosive coating, organic (inorganic) silicon resinoid coating, polyurea elastomer anticorrosive paint, glass
Scale class anticorrosive paint and organic (inorganic) zinc-rich paint.Protection for marine metal substrate, mainly by using resistance to
The methods of corrosion material, addition corrosion inhibiter, metal surface modification, coating protection and electrochemical protection.The protection of its floating coat is one
The traditional marine anti corrosion technology of kind: being coated in metal substrate surface using corrosion resistant coating, form a film through high temperature or normal temperature cure, right
It carries out guarantor's protection.The anticorrosion mechanism of anticorrosive coating film includes: shielding action, passivation, the protective effect of antirust filler, cathode
Protective effect etc..Coating protection has many advantages, such as that easy construction, anticorrosion ability be obvious, high financial profit, in marine anticorrosion neck
Domain obtains large-scale application.Coating property determines that the protection effect of coating is answered in the protective coating that ocean heavy antisepsis field uses
Have following advantages: good mechanical property, resistance to rainwater, seawater scouring collision even rub；Stability is good, acidproof alkali salt, chemically-resistant
Product, oil resistant, ageing-resistant and UV resistant performance；Adhesive force is strong, has stronger adhesive force and adhesive property with substrate；Easily apply
It is work, environmentally protective.In addition, also having certain requirement to the shielding of coating, hydrophobicity, resistance to soiling and service life etc..Coating
Each performance be not it is independent, interact, close association, develop while the corrosion-inhibiting coating having the above advantages is current
One of most important work.With the fast development of marine economy, marine anticorrosion increasingly obtains the attention of people, marine anticorrosion
Designing and developing for coating is with high content of technology, capital investment is big, the R&D cycle is long.Must from the corrodible property of marine environment, with
Some or multiple mechanism of corrosion are point of penetration, issue different anticorrosive paint or have the coating system of synergistic effect, with suitable
Answer different corrosive environments.
Traditional anticorrosive paint is because of the reasons such as solvent contamination is big, anti-corrosion life is short, corrosion-resistant, weatherability is not strong, in the application
It is restricted, the performance of resin is improved from structure, modified coating property is attended to one thing and lose sight of another, and the synthesis for having excellent is difficult
Property.From now on, the research and development of Marine Antifouling Paint are mainly towards environmentally protective, long-life, thick-film, low prepared surface, easily construction
Direction develop, according to the corrodible property of different field, develop different types of anticorrosive paint and rationally utilize a variety of modifications
Means are effectively to contain the basic Research Thinking of marine anticorrosion from now on.
Summary of the invention
The technical problems to be solved by the invention: it is short, corrosion-resistant and resistance to that the present invention is directed to traditional anticorrosive paint anti-corrosion life
The not strong problem of time property, provides a kind of preparation method of marine anticorrosion composite coating.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
(1) dimethylbenzene is added in n-butanol, 10 ~ 20min is stirred with 200 ~ 300r/min revolving speed under room temperature, obtains organic solution；
(2) modified nano zinc oxide powder is added in organic solution, with 1000 ~ 1200r/min revolving speed high-speed stirred under room temperature
20 ~ 30min, then it is placed in 20 ~ 30min of ultrasonic disperse in supersonic wave cleaning machine, obtain modified nano zinc oxide slurry；
(3) organic-silicon-modified bisphenol-A phenolic epoxy resin, polyether sulfone mixed slurry are added in modified nano zinc oxide slurry,
20 ~ 30min is stirred with 300 ~ 400r/min revolving speed under room temperature, obtains mixed slurry；
(4) polyamide is added in mixed slurry, 4 ~ 6min is stirred with 400 ~ 600r/min revolving speed at 40 ~ 60 DEG C, obtains ocean
Anti-corrosion composite coating.
The modified nano zinc oxide powder, organic-silicon-modified bisphenol-A phenolic epoxy resin, polyether sulfone mixed slurry,
Polyamide, 3 dimethylbenzene, n-butanol parts by weight be 10 ~ 20 parts of modified nano zinc oxide powder, 20 ~ 40 parts it is organic-silicon-modified double
Phenol A novolac epoxy resin, 20 ~ 40 parts of polyether sulfone mixed slurries, 5 ~ 10 parts of polyamide, 30 ~ 60 parts of dimethylbenzene, 60 ~ 80 parts of positive fourths
Alcohol.
The condition of ultrasonic disperse described in step (2) is 200 ~ 250W, 30 ~ 40 DEG C.
The specific preparation step of modified nano zinc oxide powder described in step (2) are as follows:
(1) titanate coupling agent is added in isopropanol, 10 ~ 20min is stirred with 200 ~ 240r/min revolving speed under room temperature, obtains modification
Liquid；
(2), nano zine oxide is added in modification liquid, is placed under room temperature in magnetic stirring apparatus and is stirred with 300 ~ 400 r/min revolving speeds
1 ~ 3h is mixed, filters, obtains solid；
(3) solid is placed in baking oven, dry 1 ~ 3h under conditions of 70 ~ 80 DEG C, then is placed in 10 ~ 20min of grinding in grinder,
Obtain modified nano zinc oxide powder.
The isopropanol, titanate coupling agent, nano zine oxide parts by weight be 60 ~ 70 parts of isopropanols, 0.3 ~ 0.5 part
The nano zine oxide of titanate coupling agent, 10 ~ 20 parts of 20 ~ 30nm of partial size.
The specific preparation step of organic-silicon-modified bisphenol-A phenolic epoxy resin described in step (3) are as follows:
(1) by dimethyl polysiloxane, N- β-aminoethyl-γ-aminopropyltrimethoxysilane adding into acetone, under room temperature with
200 ~ 300r/min revolving speed stirs 20 ~ 30min, obtains silane acetone soln；
(2) bisphenol-A phenolic epoxy resin, dibutyl tin dilaurate are added in silane acetone soln, in 100 ~ 120 DEG C of item
4 ~ 5h is stirred to react with 200 ~ 300r/min revolving speed under part, obtains reaction solution；
(3) reaction solution is evaporated under reduced pressure 1 ~ 2h, obtains organic-silicon-modified bisphenol-A phenolic epoxy resin.
The bisphenol-A phenolic epoxy resin, dimethyl polysiloxane, acetone, N- β-aminoethyl-γ-aminopropyl front three
Oxysilane, the parts by weight of dibutyl tin dilaurate are 20 ~ 30 parts of bisphenol-A phenolic epoxy resin, the poly- silicon oxygen of 6 ~ 8 parts of dimethyl
Alkane, 60 ~ 80 parts of acetone, 1 ~ 3 part of N- β-aminoethyl-γ-aminopropyltrimethoxysilane, 0.3 ~ 0.5 part of dibutyl tin cinnamic acid
Tin.
The condition of vacuum distillation described in step (3) is 0.01 ~ 0.03MPa, 60 ~ 80 DEG C.
The specific preparation step of polyether sulfone mixed slurry described in step (3) are as follows:
(1) polyether sulfone polyethersulfone resin is placed in ball mill, with 150 ~ 200r/min revolving speed 1 ~ 2h of ball milling under room temperature, obtains polyethers
Sulphone resin powder；
(2) polytetrafluoroethylene (PTFE) is placed in sand mill, with 3000 ~ 3500r/min revolving speed 2 ~ 4h of high speed grinding under room temperature, obtains poly- four
Vinyl fluoride powder；
(3) by dehydrated alcohol adding into acetone, 20 ~ 30min is stirred with 200 ~ 300r/min revolving speed under room temperature, it is molten to obtain ethyl alcohol acetone
Liquid；
(4) polyethersulfone resin powder, teflon resin powder are added in ethyl alcohol acetone soln, under room temperature with 400 ~
600r/min revolving speed stirs 1 ~ 2h, obtains polyether sulfone mixed slurry.
The polyethersulfone resin, polytetrafluoroethylene (PTFE), dehydrated alcohol, acetone parts by weight be 40 ~ 60 parts of polyethersulfone resins,
20 ~ 30 parts of polytetrafluoroethylene (PTFE), 40 ~ 60 parts of dehydrated alcohols, 60 ~ 80 parts of acetone.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention prepares marine anticorrosion composite coating, novolac epoxy resin is one using bisphenol-A phenolic epoxy resin as raw material
Polyfunctional group tetraglycidel ether epoxy resin, existing phenolic structure in molecular structure are planted, and has epoxy group, is had more excellent
Thermal stability, mechanical strength, electric insulating quality and higher glass transition temperature, bisphenol-A phenolic epoxy resin it is poly-
It closes owner's chain and contains diphenol propane type structure, make it have very strong mechanical strength and wearability, the cure shrinkage of coating
Low, toughness is high, and a large amount of epoxy group is contained in bisphenol-A phenolic epoxy resin, so that extremely strong adhesion strength is formed with substrate, it is special
It is not the introducing of organosilicon so that the hydrophobic and lyophobic property of bisphenol-A phenolic epoxy resin improves, there is especially excellent corrosion resistance
To keep high marine anticorrosion composite coating flexible smooth, there can be self-cleaning performance with resistance to ultraviolet, chemicals energy, improve and apply
The toughness and corrosion resistance of material；
(2) present invention prepares marine anticorrosion composite coating, organosilicon tool by organosilicon to bisphenol-A phenolic epoxy resin modification
Have the advantages that low temperature flexibility, hydrophobic, dielectric strength are high, there is good complementarity with the performance of novolac epoxy resin, pass through
The active end group of polysiloxane molecule such as hydroxyl, amino, alkoxy and the epoxy group and hydroxyl in novolac epoxy resin molecule
To introduce silicone segments, organosilicon and silane coupling agent with active group are modified novolac epoxy resin, have for reaction
The compatibility of machine silicon and novolac epoxy resin, and the degree of cross linking of solidfied material can be effectively increased, therefore the modification of organosilicon can make phenol
Formaldehyde epoxy resin toughness increases, and improves the performances such as its weatherability, impact strength, to effectively improve the compound painting of marine anticorrosion
The durability and corrosion resistance of material；
(3) present invention prepares marine anticorrosion composite coating by addition polyethersulfone resin and polytetrafluoroethylene (PTFE), polyethersulfone resin
Containing the phenyl ring of rigid radical in strand, the ehter bond of flexible group, the big conjugated structure of the sulfuryl on main chain and formation in addition,
Good stability and corrosion resistance are made it have, the flexible group of main chain has resin flexible well in polyether sulfone structure
Property and impact resistance, and rigid radical makes resin have very strong hardness, and big conjugated structure keeps resin stability very strong, simultaneously
Also improve its mechanical strength, the strand two sides of polytetrafluoroethylene (PTFE) are all fluorine atoms, and be serrated arrangement, C-F bond energy compared with
Greatly, the characteristics such as fluorine atom electronegativity is larger make it have preferable heat-resisting quantity, hydro-oleophobicity, wearability, solvent resistance, anti-
The advantages that rotten performance, the corrosion-resistant, resistance to of marine anticorrosion composite coating can be effectively improved by adding polyethersulfone resin and polytetrafluoroethylene (PTFE)
Time property and service life.
Specific embodiment
According to parts by weight, 60 ~ 70 parts of isopropanols, 0.3 ~ 0.5 part of titanate coupling agent, 10 ~ 20 parts of partial sizes are weighed respectively
Titanate coupling agent is added in isopropanol the nano zine oxide of 20 ~ 30nm, with 200 ~ 240r/min revolving speed stirring 10 under room temperature
~ 20min, obtains modification liquid, and nano zine oxide is added in modification liquid, is placed in magnetic stirring apparatus under room temperature with 300 ~ 400 r/
Min revolving speed stirs 1 ~ 3h, filters, obtains solid, solid is placed in baking oven, dry 1 ~ 3h under conditions of 70 ~ 80 DEG C, then is placed in
10 ~ 20min is ground in grinder, obtains modified nano zinc oxide powder, then according to parts by weight, weighs 20 ~ 30 parts of bisphenol-As respectively
Novolac epoxy resin, 6 ~ 8 parts of dimethyl polysiloxanes, 60 ~ 80 parts of acetone, 1 ~ 3 part of N- β-aminoethyl-γ-aminopropyl trimethoxy
Base silane, 0.3 ~ 0.5 part of dibutyl tin dilaurate, by dimethyl polysiloxane, N- β-aminoethyl-γ-aminopropyl trimethoxy
Base silane adding into acetone stirs 20 ~ 30min with 200 ~ 300r/min revolving speed under room temperature, silane acetone soln is obtained, by bisphenol-A
Novolac epoxy resin, dibutyl tin dilaurate are added in silane acetone soln, under conditions of 100 ~ 120 DEG C with 200 ~
300r/min revolving speed is stirred to react 4 ~ 5h, obtains reaction solution, places reaction liquid into 0.01 ~ 0.03MPa, subtracts under conditions of 60 ~ 80 DEG C
Pressure 1 ~ 2h of distillation, obtains organic-silicon-modified bisphenol-A phenolic epoxy resin, then according to parts by weight, weighs 40 ~ 60 parts of polyether sulfones respectively
Resin, 20 ~ 30 parts of polytetrafluoroethylene (PTFE), 40 ~ 60 parts of dehydrated alcohols, 60 ~ 80 parts of acetone, are placed in ball milling for polyether sulfone polyethersulfone resin
In machine, with 150 ~ 200r/min revolving speed 1 ~ 2h of ball milling under room temperature, polyethersulfone resin powder is obtained, polytetrafluoroethylene (PTFE) is placed in sand mill
In, with 3000 ~ 3500r/min revolving speed 2 ~ 4h of high speed grinding under room temperature, polytetrafluorethylepowder powder is obtained, acetone is added in dehydrated alcohol
In, 20 ~ 30min is stirred with 200 ~ 300r/min revolving speed under room temperature, ethyl alcohol acetone soln is obtained, by polyethersulfone resin powder, poly- four
Fluoroethylene resin powder is added in ethyl alcohol acetone soln, stirs 1 ~ 2h under room temperature with 400 ~ 600r/min revolving speed, and it is mixed to obtain polyether sulfone
Slurry is closed, then according to parts by weight, weighs 10 ~ 20 parts of modified nano zinc oxide powder, 20 ~ 40 parts of organic-silicon-modified bis-phenols respectively
A novolac epoxy resin, 20 ~ 40 parts of polyether sulfone mixed slurries, 5 ~ 10 parts of polyamide, 30 ~ 60 parts of dimethylbenzene, 60 ~ 80 parts of n-butanols,
Dimethylbenzene is added in n-butanol, 10 ~ 20min is stirred with 200 ~ 300r/min revolving speed under room temperature, obtains organic solution, modification is received
Rice Zinc oxide powder is added in organic solution, with 1000 ~ 1200r/min revolving speed 20 ~ 30min of high-speed stirred under room temperature, then is placed in
In supersonic wave cleaning machine, 20 ~ 30min of ultrasonic disperse under conditions of 200 ~ 250W, 30 ~ 40 DEG C obtains modified nano zinc oxide slurry
Material organic-silicon-modified bisphenol-A phenolic epoxy resin, polyether sulfone mixed slurry is added in modified nano zinc oxide slurry, room temperature
Under with 300 ~ 400r/min revolving speed stir 20 ~ 30min, obtain mixed slurry, by polyamide be added mixed slurry in, at 40 ~ 60 DEG C
Under with 400 ~ 600r/min revolving speed stir 4 ~ 6min, obtain marine anticorrosion composite coating.
According to parts by weight, the nanometer of 60 parts of isopropanols, 0.3 part of titanate coupling agent, 10 parts of partial size 20nm are weighed respectively
Titanate coupling agent is added in isopropanol zinc oxide, stirs 10min under room temperature with 200r/min revolving speed, obtains modification liquid, will receive
Rice zinc oxide is added in modification liquid, is placed in magnetic stirring apparatus under room temperature and stirs 1h with 300 r/min revolving speeds, filters, obtains solid,
Solid is placed in baking oven, dry 1h under conditions of 70 DEG C, then is placed in grinder and grinds 10min, obtains modified Nano oxidation
Zinc powder, then according to parts by weight, 20 parts of bisphenol-A phenolic epoxy resin, 6 parts of dimethyl polysiloxanes, 60 part third are weighed respectively
Ketone, 1 part of N- β-aminoethyl-γ-aminopropyltrimethoxysilane, 0.3 part of dibutyl tin dilaurate, by the poly- silicon oxygen of dimethyl
Alkane, N- β-aminoethyl-γ-aminopropyltrimethoxysilane adding into acetone, under room temperature with 200 ~ 300r/min revolving speed stirring 20 ~
30min obtains silane acetone soln, and bisphenol-A phenolic epoxy resin, dibutyl tin dilaurate are added in silane acetone soln,
4h is stirred to react with 200r/min revolving speed under conditions of 100 DEG C, obtains reaction solution, places reaction liquid into the item of 0.01MPa, 60 DEG C
It is evaporated under reduced pressure 1h under part, obtains organic-silicon-modified bisphenol-A phenolic epoxy resin, then according to parts by weight, weighs 40 parts of polyethers respectively
Sulphone resin, 20 parts of polytetrafluoroethylene (PTFE), 40 parts of dehydrated alcohols, 60 parts of acetone, polyether sulfone polyethersulfone resin are placed in ball mill, often
With 150r/min revolving speed ball milling 1h under temperature, obtain polyethersulfone resin powder, polytetrafluoroethylene (PTFE) be placed in sand mill, under room temperature with
3000r/min revolving speed high speed grinding 2h, obtains polytetrafluorethylepowder powder, by dehydrated alcohol adding into acetone, with 200r/ under room temperature
Min revolving speed stirs 20min, obtains ethyl alcohol acetone soln, and ethyl alcohol third is added in polyethersulfone resin powder, teflon resin powder
In ketone solution, 1h is stirred with 400r/min revolving speed under room temperature, obtains polyether sulfone mixed slurry, then according to parts by weight, weigh respectively
10 parts of modified nano zinc oxide powder, 20 parts of organic-silicon-modified bisphenol-A phenolic epoxy resin, 20 parts of polyether sulfone mixed slurries, 5 parts
Dimethylbenzene is added in n-butanol for polyamide, 30 parts of dimethylbenzene, 60 parts of n-butanols, with the stirring of 200r/min revolving speed under room temperature
10min obtains organic solution, and modified nano zinc oxide powder is added in organic solution, with 1000r/min revolving speed high speed under room temperature
20min is stirred, then is placed in supersonic wave cleaning machine, ultrasonic disperse 20min under conditions of 200W, 30 DEG C obtains modified Nano oxygen
Change zinc slurry, modified nano zinc oxide slurry is added in organic-silicon-modified bisphenol-A phenolic epoxy resin, polyether sulfone mixed slurry
In, under room temperature with 300r/min revolving speed stir 20min, obtain mixed slurry, by polyamide be added mixed slurry in, at 40 DEG C with
400r/min revolving speed stirs 4min, obtains marine anticorrosion composite coating.
According to parts by weight, the nanometer of 65 parts of isopropanols, 0.4 part of titanate coupling agent, 15 parts of partial size 25nm are weighed respectively
Titanate coupling agent is added in isopropanol zinc oxide, stirs 15min under room temperature with 220r/min revolving speed, obtains modification liquid, will receive
Rice zinc oxide is added in modification liquid, is placed in magnetic stirring apparatus under room temperature and stirs 2h with 350 r/min revolving speeds, filters, obtains solid,
Solid is placed in baking oven, dry 2h under conditions of 75 DEG C, then is placed in grinder and grinds 15min, obtains modified Nano oxidation
Zinc powder, then according to parts by weight, 25 parts of bisphenol-A phenolic epoxy resin, 7 parts of dimethyl polysiloxanes, 70 part third are weighed respectively
Ketone, 2 parts of N- β-aminoethyl-γ-aminopropyltrimethoxysilanes, 0.4 part of dibutyl tin dilaurate, by the poly- silicon oxygen of dimethyl
Alkane, N- β-aminoethyl-γ-aminopropyltrimethoxysilane adding into acetone stir 25min with 250r/min revolving speed under room temperature,
Silane acetone soln is obtained, bisphenol-A phenolic epoxy resin, dibutyl tin dilaurate are added in silane acetone soln, at 110 DEG C
Under conditions of 4.5h is stirred to react with 250r/min revolving speed, obtain reaction solution, place reaction liquid into 0.02MPa, under conditions of 70 DEG C
It is evaporated under reduced pressure 1.5h, obtains organic-silicon-modified bisphenol-A phenolic epoxy resin, then according to parts by weight, weighs 50 parts of polyether sulfones respectively
Resin, 25 parts of polytetrafluoroethylene (PTFE), 50 parts of dehydrated alcohols, 70 parts of acetone, polyether sulfone polyethersulfone resin are placed in ball mill, room temperature
Under with 170r/min revolving speed ball milling 1.5h, obtain polyethersulfone resin powder, polytetrafluoroethylene (PTFE) be placed in sand mill, under room temperature with
3250r/min revolving speed high speed grinding 3h, obtains polytetrafluorethylepowder powder, by dehydrated alcohol adding into acetone, with 250r/ under room temperature
Min revolving speed stirs 25min, obtains ethyl alcohol acetone soln, and ethyl alcohol third is added in polyethersulfone resin powder, teflon resin powder
In ketone solution, 1.5h is stirred with 500r/min revolving speed under room temperature, obtains polyether sulfone mixed slurry, then according to parts by weight, claim respectively
Measure 15 parts of modified nano zinc oxide powder, 30 parts of organic-silicon-modified bisphenol-A phenolic epoxy resin, 30 parts of polyether sulfone mixed slurries, 7
Part polyamide, 45 parts of dimethylbenzene, 70 parts of n-butanols, dimethylbenzene is added in n-butanol, with the stirring of 250r/min revolving speed under room temperature
15min obtains organic solution, and modified nano zinc oxide powder is added in organic solution, with 1100r/min revolving speed high speed under room temperature
25min is stirred, then is placed in supersonic wave cleaning machine, ultrasonic disperse 25min under conditions of 225W, 35 DEG C obtains modified Nano oxygen
Change zinc slurry, modified nano zinc oxide slurry is added in organic-silicon-modified bisphenol-A phenolic epoxy resin, polyether sulfone mixed slurry
In, under room temperature with 350r/min revolving speed stir 25min, obtain mixed slurry, by polyamide be added mixed slurry in, at 50 DEG C with
500r/min revolving speed stirs 5min, obtains marine anticorrosion composite coating.
According to parts by weight, the nanometer of 70 parts of isopropanols, 0.5 part of titanate coupling agent, 20 parts of partial size 30nm are weighed respectively
Titanate coupling agent is added in isopropanol zinc oxide, stirs 20min under room temperature with 240r/min revolving speed, obtains modification liquid, will receive
Rice zinc oxide is added in modification liquid, is placed in magnetic stirring apparatus under room temperature and stirs 3h with 400 r/min revolving speeds, filters, obtains solid,
Solid is placed in baking oven, dry 3h under conditions of 80 DEG C, then is placed in grinder and grinds 20min, obtains modified Nano oxidation
Zinc powder, then according to parts by weight, 30 parts of bisphenol-A phenolic epoxy resin, 8 parts of dimethyl polysiloxanes, 80 part third are weighed respectively
Ketone, 3 parts of N- β-aminoethyl-γ-aminopropyltrimethoxysilanes, 0.5 part of dibutyl tin dilaurate, by the poly- silicon oxygen of dimethyl
Alkane, N- β-aminoethyl-γ-aminopropyltrimethoxysilane adding into acetone stir 30min with 300r/min revolving speed under room temperature,
Silane acetone soln is obtained, bisphenol-A phenolic epoxy resin, dibutyl tin dilaurate are added in silane acetone soln, at 120 DEG C
Under conditions of 5h is stirred to react with 300r/min revolving speed, obtain reaction solution, place reaction liquid into 0.03MPa, subtract under conditions of 80 DEG C
Pressure distillation 2h, obtain organic-silicon-modified bisphenol-A phenolic epoxy resin, then according to parts by weight, respectively weigh 60 parts of polyethersulfone resins,
30 parts of polytetrafluoroethylene (PTFE), 60 parts of dehydrated alcohols, 80 parts of acetone, polyether sulfone polyethersulfone resin is placed in ball mill, under room temperature with
200r/min revolving speed ball milling 2h, obtains polyethersulfone resin powder, polytetrafluoroethylene (PTFE) is placed in sand mill, with 3500r/ under room temperature
Min revolving speed high speed grinding 4h, obtains polytetrafluorethylepowder powder, by dehydrated alcohol adding into acetone, with 300r/min revolving speed under room temperature
30min is stirred, ethyl alcohol acetone soln is obtained, ethyl alcohol acetone soln is added in polyethersulfone resin powder, teflon resin powder
In, 2h is stirred with 600r/min revolving speed under room temperature, obtains polyether sulfone mixed slurry, then according to parts by weight, 20 parts is weighed respectively and changes
Property nano-zinc oxide powder, 40 parts of organic-silicon-modified bisphenol-A phenolic epoxy resin, 40 parts of polyether sulfone mixed slurries, 10 parts of polyamides
Dimethylbenzene is added in n-butanol for amine, 60 parts of dimethylbenzene, 80 parts of n-butanols, stirs 20min under room temperature with 300r/min revolving speed,
Organic solution is obtained, modified nano zinc oxide powder is added in organic solution, with 1200r/min revolving speed high-speed stirred under room temperature
30min, then be placed in supersonic wave cleaning machine, ultrasonic disperse 30min under conditions of 250W, 40 DEG C obtains modified nano zinc oxide
Slurry organic-silicon-modified bisphenol-A phenolic epoxy resin, polyether sulfone mixed slurry is added in modified nano zinc oxide slurry, often
30min is stirred with 400r/min revolving speed under temperature, obtains mixed slurry, polyamide is added in mixed slurry, with 600r/ at 60 DEG C
Min revolving speed stirs 6min, obtains marine anticorrosion composite coating.
The Marine Antifouling Paint that marine anticorrosion composite coating prepared by the present invention and Fujian company produce is detected,
Detection method: film prepared by foreign anti-corrosion composite coating is adhered to according to GB9286 " cross cut test of paint and varnish paint film "
The grade of power is measured, and is carried out according to standard GB/T/T 1732 " paint film impact resistance measuring method " to foreign anti-corrosion composite coating
The impact resistance of coating is tested, specific testing result such as following table table 1:
Table 1
| Performance characterization | Example 1 | Example 2 | Example 3 | Comparative example |
| Adhere to grade | 0A | 1A | 0A | 5B |
| Impact strength (kgcm) | 50 | 50 | 50 | 35 |
The film strong shock resistance of marine anticorrosion composite coating preparation prepared by the present invention as shown in Table 1, adhesive ability is good, is
A kind of excellent marine anticorrosion composite coating has fabulous market prospects and application prospect.
Claims (10)
1. a kind of preparation method of marine anticorrosion composite coating, which is characterized in that specific preparation step are as follows:
(1) dimethylbenzene is added in n-butanol, 10 ~ 20min is stirred with 200 ~ 300r/min revolving speed under room temperature, obtains organic solution；
(2) modified nano zinc oxide powder is added in organic solution, with 1000 ~ 1200r/min revolving speed high-speed stirred under room temperature
20 ~ 30min, then it is placed in 20 ~ 30min of ultrasonic disperse in supersonic wave cleaning machine, obtain modified nano zinc oxide slurry；
(3) organic-silicon-modified bisphenol-A phenolic epoxy resin, polyether sulfone mixed slurry are added in modified nano zinc oxide slurry,
20 ~ 30min is stirred with 300 ~ 400r/min revolving speed under room temperature, obtains mixed slurry；
(4) polyamide is added in mixed slurry, 4 ~ 6min is stirred with 400 ~ 600r/min revolving speed at 40 ~ 60 DEG C, obtains ocean
Anti-corrosion composite coating.
2. a kind of preparation method of marine anticorrosion composite coating according to claim 1, which is characterized in that the modification
Nano-zinc oxide powder, organic-silicon-modified bisphenol-A phenolic epoxy resin, polyether sulfone mixed slurry, polyamide, 3 dimethylbenzene, positive fourth
The parts by weight of alcohol be 10 ~ 20 parts of modified nano zinc oxide powder, 20 ~ 40 parts of organic-silicon-modified bisphenol-A phenolic epoxy resin, 20 ~
40 parts of polyether sulfone mixed slurries, 5 ~ 10 parts of polyamide, 30 ~ 60 parts of dimethylbenzene, 60 ~ 80 parts of n-butanols.
3. a kind of preparation method of marine anticorrosion composite coating according to claim 1, which is characterized in that step (2) institute
The condition for the ultrasonic disperse stated is 200 ~ 250W, 30 ~ 40 DEG C.
4. a kind of preparation method of marine anticorrosion composite coating according to claim 1, which is characterized in that step (2) institute
The specific preparation step for the modified nano zinc oxide powder stated are as follows:
(1) titanate coupling agent is added in isopropanol, 10 ~ 20min is stirred with 200 ~ 240r/min revolving speed under room temperature, obtains modification
Liquid；
(2), nano zine oxide is added in modification liquid, is placed under room temperature in magnetic stirring apparatus and is stirred with 300 ~ 400 r/min revolving speeds
1 ~ 3h is mixed, filters, obtains solid；
(3) solid is placed in baking oven, dry 1 ~ 3h under conditions of 70 ~ 80 DEG C, then is placed in 10 ~ 20min of grinding in grinder,
Obtain modified nano zinc oxide powder.
5. a kind of preparation method of marine anticorrosion composite coating according to claim 4, which is characterized in that the isopropyl
Alcohol, titanate coupling agent, nano zine oxide parts by weight be 60 ~ 70 parts of isopropanols, 0.3 ~ 0.5 part of titanate coupling agent, 10 ~ 20
The nano zine oxide of 20 ~ 30nm of part partial size.
6. a kind of preparation method of marine anticorrosion composite coating according to claim 1, which is characterized in that step (3) institute
The specific preparation step for the organic-silicon-modified bisphenol-A phenolic epoxy resin stated are as follows:
(1) by dimethyl polysiloxane, N- β-aminoethyl-γ-aminopropyltrimethoxysilane adding into acetone, under room temperature with
200 ~ 300r/min revolving speed stirs 20 ~ 30min, obtains silane acetone soln；
(2) bisphenol-A phenolic epoxy resin, dibutyl tin dilaurate are added in silane acetone soln, in 100 ~ 120 DEG C of item
4 ~ 5h is stirred to react with 200 ~ 300r/min revolving speed under part, obtains reaction solution；
(3) reaction solution is evaporated under reduced pressure 1 ~ 2h, obtains organic-silicon-modified bisphenol-A phenolic epoxy resin.
7. a kind of preparation method of marine anticorrosion composite coating according to claim 6, which is characterized in that the bis-phenol
A novolac epoxy resin, dimethyl polysiloxane, acetone, N- β-aminoethyl-γ-aminopropyltrimethoxysilane, dibutyl tin
The parts by weight of cinnamic acid tin are 20 ~ 30 parts of bisphenol-A phenolic epoxy resin, 6 ~ 8 parts of dimethyl polysiloxanes, 60 ~ 80 parts of acetone, 1 ~ 3
Part N- β-aminoethyl-γ-aminopropyltrimethoxysilane, 0.3 ~ 0.5 part of dibutyl tin dilaurate.
8. a kind of preparation method of marine anticorrosion composite coating according to claim 6, which is characterized in that step (3) institute
The condition for the vacuum distillation stated is 0.01 ~ 0.03MPa, 60 ~ 80 DEG C.
9. a kind of preparation method of marine anticorrosion composite coating according to claim 1, which is characterized in that step (3) institute
The specific preparation step for the polyether sulfone mixed slurry stated are as follows:
(1) polyether sulfone polyethersulfone resin is placed in ball mill, with 150 ~ 200r/min revolving speed 1 ~ 2h of ball milling under room temperature, obtains polyethers
Sulphone resin powder；
(2) polytetrafluoroethylene (PTFE) is placed in sand mill, with 3000 ~ 3500r/min revolving speed 2 ~ 4h of high speed grinding under room temperature, obtains poly- four
Vinyl fluoride powder；
(3) by dehydrated alcohol adding into acetone, 20 ~ 30min is stirred with 200 ~ 300r/min revolving speed under room temperature, it is molten to obtain ethyl alcohol acetone
Liquid；
(4) polyethersulfone resin powder, teflon resin powder are added in ethyl alcohol acetone soln, under room temperature with 400 ~
600r/min revolving speed stirs 1 ~ 2h, obtains polyether sulfone mixed slurry.
10. a kind of preparation method of marine anticorrosion composite coating according to claim 9, which is characterized in that described is poly-
Ether sulfone resin, polytetrafluoroethylene (PTFE), dehydrated alcohol, acetone parts by weight be 40 ~ 60 parts of polyethersulfone resins, 20 ~ 30 parts of polytetrafluoroethyl-nes
Alkene, 40 ~ 60 parts of dehydrated alcohols, 60 ~ 80 parts of acetone.
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| CN110540788A (en) * | 2019-08-29 | 2019-12-06 | 洛阳双瑞防腐工程技术有限公司 | Heat-resistant epoxy anticorrosive paint and preparation method thereof |
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Application publication date: 20190723 |