CN109609029A - It is a kind of with the low surface energy antifouling coating for seas and preparation method thereof for delaying low molecular weight lubricant release action - Google Patents
It is a kind of with the low surface energy antifouling coating for seas and preparation method thereof for delaying low molecular weight lubricant release action Download PDFInfo
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- CN109609029A CN109609029A CN201811479496.XA CN201811479496A CN109609029A CN 109609029 A CN109609029 A CN 109609029A CN 201811479496 A CN201811479496 A CN 201811479496A CN 109609029 A CN109609029 A CN 109609029A
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- surface energy
- antifouling coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention belongs to environment-friendly type marine antifouling coating technical fields, it specifically discloses a kind of with the low surface energy antifouling coating for seas and preparation method thereof for delaying low molecular weight lubricant release action, the low surface energy antifouling coating for seas, by weight, including following raw material: 40~80 parts of hydroxyl endblocked polydimethylsiloxanes, 5~15 parts of compound porous polystyrene microspheres, 2~5 parts of curing agent, 0.5~1 part of catalyst, 15~25 parts of solvents；The composite porous polymer microballoon sufficiently adsorbs low molecular weight lubricant for expanded polystyrene microballoon and is made.Good antifouling effect, the long service life for the low surface energy antifouling coating for seas that the present invention obtains have extremely strong application value in actual production use.
Description
Technical field
The invention belongs to environment-friendly type marine antifouling coating technical fields, and in particular to one kind, which has, delays low molecular weight to lubricate
The low surface energy antifouling coating for seas and preparation method thereof of agent release action.
Background technique
The ship navigated by water in ocean for a long time is often subject to the attachment such as marine microorganism, animals and plants, causes serious biology
It is stained, biodeterioration can accelerate the corrosion of hull surface, and energy consumption increases, shortens the working life, and increase operation and maintenance cost etc..It is anti-
Only the method for sea marine organism pollution mainly has: coating marine antifouling coating, electrochemical method, electrolytic seawater method and submarine mechanical are clear
It washes, wherein coating marine antifouling coating is current most effective, most convenient, most economical method.
Traditional marine antifouling coating mainly discharged with poison it is antifouling, mainly by discharge some copper, tin, mercury, lead come
It carries out antifouling, although anti-fouling effect is obvious, there are problems that endangering environment, Marine Pollution.As law of marine environmental protection is advised
It is increasingly strict, traditional marine antifouling coating is gradually eliminated, in order to meet the needs of environmental protection, the low surface of organosilicon
Energy marine antifouling coating has become an important kind in antifouling paint.This kind of antifouling paint utilizes the characteristic of its low-surface-energy
Make marine organisms be difficult to adhere to or adhere to it is insecure, the effect in ship's navigation using water flow be easy to remove fouling organism,
It is close by researcher's extensive concern since its is nontoxic and pollution-free.
Patent Application Publication CN103748157 A discloses a kind of antifouling composition containing sterol and/or its derivative, should
Anti-pollution combined elastic body is the organic siloxane polymer resin of a kind of " softer ", provides the characteristic of low-surface-energy, is included
Sterol/or derivatives thereof, biodegradable, the influence for seawater and aquatic environment is smaller.But above-mentioned antifouling composition is only
Be rely on low-surface-energy characteristic carry out it is antifouling, for the complex situations in marine environment, single antifouling means have certain
Limitation.
In organic silicon substrate resin, the silicone oil of low molecular weight is added as anti-fouling agent, can further increase coating
Anti-pollution (Wong T S, Kang S H, Tang S K, et al.Bioinspired self-repairing slippery
surfaces with pressure-stable omniphobicity[J].Nature, 2011,477(7365):443-
447.).By injecting lubricant on the surface with certain roughness, makes lubricant full of entire coating, form one on surface
Determine the lubricant coating of thickness, the slickness of coating surface can be increased, the lubricant Autonomic Migration Framework of storage inside is tieed up to surface
The smooth of surface is held, is on the other hand easier to take away fouling organism under the souring of water flow, plays surface self-cleaning
Effect, so that the anti-fouling effect of low surface energy coatings is more significant.
The antifouling paint of this kind of injection lubricant, anti-pollution greatly improves, and has been carried out in marine anti-pollution side
Application (Amini S, Kolle S, Petrone L, the et al.Preventing mussel adhesion using in face
Lubricant-infused materials [J] .Science, 2017,357 (6352): 668-673.), by this type
The antifouling paint of type carries out real sea test, it is found that this coating still has good anti-pollution in complicated marine environment.
But the condition for limiting this kind of antifouling paint development is the performance of coating after the lubricant of addition releases
It can all be substantially reduced including mechanical performance, anti-pollution etc., or even lose antifouling effect, keep the service life of this kind of antifouling paint big
It is big to shorten, for the problem existing in the prior art, need further improved.
Summary of the invention
The object of the present invention is to provide a kind of with the low-surface-energy sea for delaying low molecular weight lubricant release action
Foreign antifouling paint, the coating can slow down the speed that low molecular weight lubricant discharges in low surface energy anti-fouling paint, prolong to realize
The service life of long antifouling paint.
The purpose of the present invention is achieved through the following technical solutions:
It is a kind of with the low surface energy antifouling coating for seas for delaying low molecular weight lubricant release action, which is characterized in that
By weight, including following raw material: 40~80 parts of hydroxyl endblocked polydimethylsiloxanes, 5~15 parts of compound porous polyphenyl second
Alkene microballoon, 2~5 parts of curing agent, 0.5~1 part of catalyst, 15~25 parts of solvents, wherein the compound porous polystyrene is micro-
Ball sufficiently adsorbs low molecular weight lubricant for expanded polystyrene microballoon and is made.
The present invention slows down low point by adding the realization of porous polymer microsphere porous material in low surface energy anti-fouling paint
The speed of son amount lubricant release, extends antifouling paint service life to realize, the basic principle is that expanded polystyrene is micro-
The cellular structure of ball has delayed the rate of release of low molecular weight lubricant, and expanded polystyrene microballoon plays similar medicine carrier,
The effect of medicament slow release.
The amount ratio of the low molecular weight lubricant and expanded polystyrene microballoon is 1:1~2, preferably 1:1.5~
1.8, the present invention needs the additional amount strict control to low molecule lubricant, in this preferred scope, can make porous polyphenyl second
Alkene microballoon sufficiently adsorbs low molecular weight lubricant, and lubricant additional amount will not be made excessive, has both saved resource in this way, also not shadow
Ring subsequent preparation process.
Preferably, the antifouling paint of the low surface energy for marine includes 50~70 parts of hydroxy-end capped poly dimethyls of following raw material
Siloxanes, 10~15 parts of compound porous polystyrene microspheres, 2~5 parts of curing agent, 0.5~1 part of catalyst, 15~25 parts it is molten
The slow release effect of agent, the low surface energy antifouling coating for seas obtained in this preferred scope is more preferable.
Preferably, the expanded polystyrene microballoon anergy functional group, this is because porous polymer microsphere be
It is added in low surface energy anti-fouling paint presoma, therefore the functional group above polymer microballoon needs that low-surface-energy cannot be interfered
Antifouling paint film forming reaction, therefore using not can reactive functionality expanded polystyrene microballoon, can to avoid its interference
Coating film forming procedure has better retarding action for the rate of release of lubricant, in addition, this without it is specific can reactive functionality
Expanded polystyrene microballoon be easier synthesize.
The low molecular weight lubricant is methyl-silicone oil (PDMS) or perfluor silicone oil, it is therefore preferable to methyl-silicone oil, methyl silicon
Oil is monomer and polymer, therefore it can make low with different molecular weight using methyl-silicone oil as lubricant
The anti-fouling effect of surface energy antifouling coating for seas is more preferable, methyl-silicone oil it is spontaneous be diffused into surface, build more smooth surface,
Pollutant is difficult to adhere to, and lubricant can take away some of the contaminants, plays the role of from polishing.
The curing agent is tetraethyl orthosilicate.
The catalyst is dibutyl tin dilaurate or two sad dibutyl tins.
The above-mentioned preparation method with the low surface energy antifouling coating for seas for delaying low molecular weight lubricant release action, packet
Include following steps:
(1) expanded polystyrene microballoon is immersed in low molecular weight lubricant, is obtained after sufficiently adsorbing compound porous poly-
Phenylethylene micro ball, then compound porous polystyrene microsphere, hydroxyl endblocked polydimethylsiloxane and solvent are mixed, substrate is made
Film forming matter；
(2) curing agent is dissolved in solvent and obtains component A, catalyst is dissolved in solvent and obtains B component, finally by component A and B
Component sequentially adds in substrate film forming matter made from step (1), stirs 1~3h, the low surface energy antifouling coating for seas is made.
Preferably, the preparation method of above-mentioned low surface energy antifouling coating for seas, comprising the following steps:
(1) expanded polystyrene microballoon is immersed in methyl-silicone oil, compound porous polystyrene is obtained after sufficiently adsorbing
Microballoon, then compound porous polystyrene microsphere, hydroxyl endblocked polydimethylsiloxane and dimethylbenzene are mixed, substrate film forming is made
Object；
(2) tetraethyl orthosilicate is dissolved in dimethylbenzene and obtains component A, dilaurate dibutyl is dissolved in acetylacetone,2,4-pentanedione and is obtained
B component finally sequentially adds component A and B component in substrate film forming matter made from step (1), stirs 1~2h, is made described
Low surface energy antifouling coating for seas.
Compared with the prior art, the present invention has the following beneficial effects:
(1) present invention may be implemented to subtract by adding porous polymer microsphere porous material in low surface energy anti-fouling paint
The speed of slow low molecular weight lubricant release, to realize the purpose for extending antifouling paint service life, obtained low-surface-energy
Good antifouling effect, the long service life of marine antifouling coating have extremely strong application value in actual production use；
(2) preparation process of the invention is simple and easy to control, and raw material used is simple and easy to get, is very suitable for industrializing extensive life
It produces.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of the present invention and comparative example 1；
Fig. 2 is the result figure for the anti-protein adsorption of coating that embodiment 1, embodiment 2 and comparative example 1 obtain；
Low molecular weight lubricant elongated release at any time in the coating that Fig. 3 obtains for embodiment 1, embodiment 2 and comparative example 1
The variation diagram of amount.
Specific embodiment
Embodiment 1
(1) preparation of the expanded polystyrene microballoon (PSD) without functional group: (Lei Jinhua described in specific method reference literature
Porous polymer microsphere load alkene catalyst catalysis in olefine polymerization Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences, 2010.)；
(2) 7g PSD is immersed in 4g lubricant PDMS, makes the abundant adsorpting lubrication agent of PSD, form the PSD of lubricant infiltration
Porous microsphere is named as i-PSD, then 6g i-PSD, 30g hydroxyl endblocked polydimethylsiloxane and 5g dimethylbenzene is mixed
It closes, substrate film forming matter is made；
(3) 1.5g curing agent tetraethyl orthosilicate is dissolved in 5g dimethylbenzene and obtains component A, by 0.25g catalyst dibutyltin silicon
Sour dibutyl, which is dissolved in 2.5g acetylacetone,2,4-pentanedione, obtains B component, finally sequentially adds in substrate film forming matter component A and B component, stirs
Reaction 2h is mixed, low surface energy antifouling coating for seas is made, finally on a glass by the coating of obtained coating, is solidified at room temperature
Film forming, obtains low surface energy for marine nonpolluting coating.
Embodiment 2
(1) preparation of the expanded polystyrene microballoon (PSDA) of cyano-functional: (Lei Jin described in specific method reference literature
Change porous polymer microsphere and load alkene catalyst catalysis in olefine polymerization Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences,
2010.)；
(2) 7g PSDA is immersed in 4g PDMS, makes the abundant adsorpting lubrication agent of PSDA, the PSDA for forming lubricant infiltration is more
Hole microballoon is named as i-PSDA, then 6g i-PSDA, 30g hydroxyl endblocked polydimethylsiloxane and 5g dimethylbenzene is mixed
It closes, substrate film forming matter is made；
(3) 1.5g curing agent tetraethyl orthosilicate is dissolved in 5g dimethylbenzene and obtains component A, by 0.25g catalyst dibutyltin silicon
Sour dibutyl, which is dissolved in 2.5g acetylacetone,2,4-pentanedione, obtains B component, finally sequentially adds in substrate film forming matter component A and B component, stirs
Reaction 2h is mixed, low surface energy antifouling coating for seas is made, finally on a glass by the coating of obtained coating, is solidified at room temperature
Film forming, obtains low surface energy for marine nonpolluting coating.
Comparative example 1
(1) 4g PDMS, 30g hydroxyl endblocked polydimethylsiloxane and 5g dimethylbenzene are mixed, substrate film forming matter is made；
(2) 1.5g curing agent tetraethyl orthosilicate is dissolved in 5g dimethylbenzene and obtains component A, by 0.25g catalyst dibutyltin silicon
Sour dibutyl, which is dissolved in 2.5g acetylacetone,2,4-pentanedione, obtains B component, finally sequentially adds in substrate film forming matter component A and B component, stirs
Reaction 2h is mixed, low surface energy antifouling coating for seas is made, finally on a glass by the coating of obtained coating, is solidified at room temperature
Film forming, obtains low surface energy for marine nonpolluting coating.
Effect measuring is carried out to the low surface energy for marine nonpolluting coating that embodiment 1, embodiment 2 and comparative example 1 obtain, specifically
As a result as follows:
Anti-fouling effect: anti-protein adsorption test is carried out to later coating is solidified, by testing coating embodiment 1, embodiment 2
And comparative example 1 is separately immersed in the PBS (phosphate-buffered of the BSA (bovine serum albumin(BSA)) and Lys (lysozyme) of normal concentration
Solution) in, and be in isothermal vibration environment 5 hours, then, test sample is taken out from protein solution, test specimens
The Strength Changes of ultraviolet characteristic absorption peak of the product before and after impregnating protein solution characterize protein adsorption quantity such as Fig. 2 institute of sample
Show.
As shown in Figure 2, after the added PSD microballoon of the embodiment of the present invention, it will not influence the anti-fouling effect of coating.
Slow release effect: the release experiment of low molecular weight lubricant is simulated, wherein first in order to accelerate releasing for added lubricant
Speed is put, the method that we use ultrasonic extraction is placed in quantitative solvent the film coating after solidification and carries out ultrasound, makes to lubricate
Agent rapidly extracting carries out quantitative analysis to the low molecular weight lubricant in solvent later into solvent, when by ultrasonic difference
Between obtained lubricant extracted amount be compared, obtain result as shown in Figure 3.
From the figure 3, it may be seen that the low molecular weight lubricant in the low surface energy antifouling coating for seas that the embodiment of the present invention obtains is released
It puts rate obviously to slow down, has reached expected purpose.Early period specifically is discharged in lubricant, embodiment 1 and embodiment 2 have to be connect very much
Close rate of release, and in the later period, low molecular weight lubricant release in low surface energy antifouling coating for seas obtained in embodiment 1
Speed more tends to gently, this explanation, the scheme of embodiment 1 has more obvious retarding action for the rate of release of lubricant.
Generally, i-PSD system delays lubricant releasing effect more obvious.
Claims (8)
1. a kind of with the low surface energy antifouling coating for seas for delaying low molecular weight lubricant release action, which is characterized in that press
Parts by weight meter, including following raw material: 40~80 parts of hydroxyl endblocked polydimethylsiloxanes, 5~15 parts of compound porous polystyrene
Microballoon, 2~5 parts of curing agent, 0.5~1 part of catalyst, 15~25 parts of solvents, wherein the compound porous polystyrene microsphere by
Expanded polystyrene microballoon sufficiently adsorbs low molecular weight lubricant and is made.
2. low surface energy antifouling coating for seas according to claim 1, which is characterized in that the low molecular weight lubricant
Amount ratio with expanded polystyrene microballoon is 1:1~2.
3. low surface energy antifouling coating for seas according to claim 1, which is characterized in that by weight, including with
Lower raw material: 50~70 parts of hydroxyl endblocked polydimethylsiloxanes, 10~15 parts of compound porous polystyrene microspheres, 2~5 parts of solidifications
Agent, 0.5~1 part of catalyst, 15~25 parts of solvents.
4. low surface energy antifouling coating for seas according to claim 1, which is characterized in that the expanded polystyrene is micro-
Ball anergy functional group.
5. low surface energy antifouling coating for seas according to claim 1, which is characterized in that the low molecular weight lubricant
For methyl-silicone oil or perfluor silicone oil.
6. low surface energy antifouling coating for seas according to claim 1, which is characterized in that the curing agent is positive silicic acid
Tetra-ethyl ester.
7. low surface energy antifouling coating for seas according to claim 1, which is characterized in that the catalyst is silicon in February
Sour dibutyl tin or two sad dibutyl tins.
8. the preparation method of described in any item low surface energy antifouling coating for seas according to claim 1~7, including following step
It is rapid:
(1) expanded polystyrene microballoon is immersed in low molecular weight lubricant, compound porous polyphenyl second is obtained after sufficiently adsorbing
Alkene microballoon, then compound porous polystyrene microsphere, hydroxyl endblocked polydimethylsiloxane and solvent are mixed, substrate film forming is made
Object；
(2) curing agent is dissolved in solvent and obtains component A, catalyst is dissolved in solvent and obtains B component, finally by component A and B component
It sequentially adds in substrate film forming matter made from step (1), stirs 1~3h, the low surface energy antifouling coating for seas is made.
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Cited By (5)
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| CN110628287A (en) * | 2019-09-05 | 2019-12-31 | 哈尔滨工程大学 | Preparation method of fluorine-containing self-polishing resin-based super-smooth coating material |
| CN111825984A (en) * | 2020-06-30 | 2020-10-27 | 苏州天澜生物材料科技有限公司 | Solid-liquid filled low-surface-energy smooth functional material and preparation method thereof |
| CN113278360A (en) * | 2021-05-31 | 2021-08-20 | 大连海事大学 | Preparation method of slow-release antifouling composite coating with bionic structure |
| CN114907766A (en) * | 2022-03-14 | 2022-08-16 | 中海石油(中国)有限公司 | Novel marine antifouling material based on biochar micro-nano structure and preparation method and application thereof |
| CN115819816A (en) * | 2022-12-01 | 2023-03-21 | 常州大学 | Preparation method of autocrine type silicone rubber membrane super-smooth material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110628287A (en) * | 2019-09-05 | 2019-12-31 | 哈尔滨工程大学 | Preparation method of fluorine-containing self-polishing resin-based super-smooth coating material |
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| CN111825984A (en) * | 2020-06-30 | 2020-10-27 | 苏州天澜生物材料科技有限公司 | Solid-liquid filled low-surface-energy smooth functional material and preparation method thereof |
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| CN113278360A (en) * | 2021-05-31 | 2021-08-20 | 大连海事大学 | Preparation method of slow-release antifouling composite coating with bionic structure |
| CN114907766A (en) * | 2022-03-14 | 2022-08-16 | 中海石油(中国)有限公司 | Novel marine antifouling material based on biochar micro-nano structure and preparation method and application thereof |
| CN115819816A (en) * | 2022-12-01 | 2023-03-21 | 常州大学 | Preparation method of autocrine type silicone rubber membrane super-smooth material |
| CN115819816B (en) * | 2022-12-01 | 2023-09-26 | 常州大学 | Preparation method of autocrine type silicon rubber membrane super-smooth material |
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Application publication date: 20190412 |