CN109749616A - A kind of anti-fouling coating and preparation method thereof that can discharge anti-fouling agent - Google Patents
A kind of anti-fouling coating and preparation method thereof that can discharge anti-fouling agent Download PDFInfo
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Abstract
A kind of anti-fouling coating and preparation method thereof that can discharge anti-fouling agent, the coating include 4,4 '-diphenylmethane diisocyanate rouge, polyether polyol polyethylene glycol, polytetramethylene ether diol, polyester polyol polycaprolactone, 1,4-butanediol, bisphenol A type epoxy resin and PU defoaming agent；Component two includes mesoporous silica particles and anti-fouling composition；Component one is pressed (20~50) with component two: 1 mass ratio mixes, and obtains the anti-fouling coating that can discharge anti-fouling agent.Under the premise of introducing oligomer polyol and more cyanate esters can guarantee that anti-fouling agent release performance is controllable in the present invention, the excellent mechanical property of polyurethane and adhesion strength etc. are not influenced.Mesoporous silicon oxide has high-wear resistance simultaneously, and the wearability of coating can be improved, prolong the service life.The problem of this method simple process, cost is relatively low, is suitble to industrialized production, and there is no poisonous substance releases, therefore the coating has a good application prospect in marine anti-pollution field.
Description
Technical field
The present invention relates to a kind of synthesis fields of marine antifouling coating, and in particular to a kind of to discharge the antifouling of anti-fouling agent
Damage coating and preparation method thereof.
Background technique
The development of marine settings such as naval vessel, submarine, offshore platform etc. will directly facilitate various countries' sea-freight and sea power mentions
It rises, but complicated marine environment seriously restricts the performance performance of marine settings, especially brought by marine biofouling
It seriously endangers.Biodeterioration is actually forming process of the biocoene in marine settings material surface.The generation of biodeterioration
Influence very serious can be caused on the military service equipment in marine environment, major embodiment: 1) causing ship resistance to be significantly increased, boat
The decline of scanning frequency degree；2) oil consumption increases severely；3) the corrosion rate quickening etc. of steel.Thus reduce marine settings service life and
The problems such as causing navigation energy consumption to be aggravated.
Existing guard technology such as surface soiling coating technology acts the operation energy consumption that uses and reduce for extending marine settings
Preferable effect is arrived, but it is long to still remain maintenance period, costly, the antifouling disadvantages such as low with drag reduction efficiency.Such as tradition is anti-
The destruction that dirty coating (organotin) balances marine ecology is also by more and more focus of attention.But once this painting
Layer by physical injury, need promptly to suspend and repaired and safeguarded, be unfavorable for marine settings military service flexibility with it is motor-driven
Property.
To the Nature study for reference, realize efficient dirty the protection in surface and drag reduction be marine settings future development must be by
Road.Have by adding the antibiont attached component extracted out of organism in nonpolluting coating, realizes to marine settings
Surface is stained the report of protection to a certain degree, while such coating also has both environmental protection and nontoxic advantage.However the antibiont
Activity be not easy to keep and be not easy to secrete for a long time, cause that its anti-fouling effect is not good enough, limit the development of marine anti-pollution coating
With application.
Summary of the invention
In order to solve the deficiency of above-mentioned existing technology, the anti-of anti-fouling agent can be discharged the purpose of the present invention is to provide a kind of
It is stained coating and preparation method thereof.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of anti-fouling coating that can discharge anti-fouling agent, including following two parts:
Component one by mass percentage, is formulated by following component and quality proportioning:
Component two includes mesoporous silica particles and anti-fouling composition, and mesoporous silica particles and anti-fouling composition
Mass ratio is (0.001~0.04): (0.01~0.1)；
Component one is pressed (20~50) with component two: 1 mass ratio mixes, and obtains the anti-fouling painting that can discharge anti-fouling agent
Layer.
A further improvement of the present invention lies in that mesoporous silica particles by mass percentage, are prepared by following components
It forms:
A further improvement of the present invention lies in that 1,3,5- trimethylbenzene of expanding agent.
A further improvement of the present invention lies in that regulator is hydrochloric acid or sodium hydroxide.
A further improvement of the present invention lies in that anti-fouling composition is copper pyrithione, capsaicine, 4,5- dichloro- -2- just pungent
Base -4- isothiazoline -3- ketone, N- cyclopropyl-N '-(1,1- dimethyl ethyl) -6- (methyl thio) -1,3,5- triazine -2,4-
The one or more of diamines.
A kind of preparation method for the anti-fouling coating that can discharge anti-fouling agent, by component one and component two in mass ratio (20~
50): 1 mixing is coated in substrate, and solidification obtains the anti-fouling coating that can discharge anti-fouling agent；Wherein, the preparation of component one
Process is as follows:
1) by mass percentage, the polyether polyol of 3~55% polytetramethylene ether diol and 15~65% is gathered
Ethylene glycol (PEG) is added in container, is heated to 100~120 DEG C of vacuum dehydrations；
2) 4~60% 4,4 '-diphenylmethane diisocyanate rouge and 4~60% bisphenol type epoxy are added after cooling down
Resin；
3) after reacting 30min~50min, the 1,4-butanediol for being added 1~20% carries out chain extension；
4) after reacting 1~2h, 0.5~10% PU defrother is added and quickly stirs, after bubble elimination, terminate anti-
It answers, obtains component one；
The preparation process of component two is as follows:
Mesoporous silica particles are added to the water, ultrasonic disperse is uniform, then be added anti-fouling composition and under stiring instead
After answering 2-3h, after centrifugation, washing, drying, component two is obtained；Wherein, the ratio of mesoporous silica particles, water and anti-fouling composition is
(0.001~0.04) g:1mL:(0.01~0.1) g.
A further improvement of the present invention lies in that the pressure of vacuum dehydration is 0.667kPa in step 1), the time is 1~4h.
A further improvement of the present invention lies in that 4~60% 4,4 '-diphenyl are added in step 2), after being cooled to 65 DEG C
Methane diisocyanate resin；Anti-fouling composition is copper pyrithione, capsaicine, 4,5- dichloro- -2- n-octyl -4- isothiazoline -3-
The one or more of ketone, N- cyclopropyl-N '-(1,1- dimethyl ethyl) -6- (methyl thio) -1,3,5- triazine -2,4- diamines.
A further improvement of the present invention lies in that the preparation process of mesoporous silica particles is as follows:
(1) by mass percentage, 30~60% cetyl trimethylammonium bromide is added in container, then plus
Enter distilled water, after heating dissolves cetyl trimethylammonium bromide, 1~20% regulator is added while stirring；Stirring is equal
After even, be added 5~20% ethyl orthosilicate, 4~30% sodium metasilicate and 5~30% expanding agent and stirring, 40~60
24~36h is reacted at DEG C；
(2) it is then stored at room temperature 6~8 days, filters, dry 1~4h, obtains mesoporous silica particles at 110 DEG C.
A further improvement of the present invention lies in that in step (1), the ratio of cetyl trimethylammonium bromide and distilled water is
1g:10mL；In step (1), the temperature of heating is 40~60 DEG C；In step (2), expanding agent 1,3,5- trimethylbenzene, regulator
For hydrochloric acid or sodium hydroxide.
Compared with prior art, the invention has the following advantages:
The present invention uses mesoporous silica particles, has the characteristics that its surface area greatly using it and has that hole is adjustable, can
It adjusts absorption in the synthesis process or the ability of anti-fouling composition is received in hiding, make micropore of the anti-fouling composition from mesoporous silica particles
In release, the marine organisms for playing the role of adherency fall off.The behavior of this process such as marine organisms secreting mucus or enzyme,
Speed of the ship in metres per second is faster or its higher rate of release of water temperature is faster.And it can also be by adjusting in polyether polyols (i.e. component one)
Ratio, reaction condition etc., and adjust the ratio of component one and component two, realize its mechanical property and anti-fouling performance.
Under the premise of introducing oligomer polyol and more cyanate esters can guarantee that anti-fouling agent release performance is controllable in the present invention, do not influence to gather
The excellent mechanical property of urethane and adhesion strength etc..Mesoporous silicon oxide has high-wear resistance simultaneously, and the resistance to of coating can be improved
Mill property, prolongs the service life.This method simple process, cost is relatively low, is suitble to industrialized production, and there is no asking for poisonous substance release
Topic, therefore the coating has a good application prospect in marine anti-pollution field.
Mesoporous silica particles in the present invention have many advantages, such as, such as big specific surface area, high diffusivity and storage
Property and adjustable aperture etc., wherein the size in aperture can by adjusting expanding agent 1 in synthesis process, what 3,5- trimethylbenzenes were added
Amount is regulated and controled, and pore size adjustable extent is 20nm~600nm.
Mesoporous silica particles in the present invention are to anti-fouling composition absorption carriage mainly by electrostatic interaction, hydrogen bond phase interaction
With or weak Van der Waals force etc., anti-fouling composition primary attachment is in its outer surface or is supported in mesoporous.
The release of antifouling molecule and release rate in the present invention is related with locating briny environment, since diffusion etc. makes
Anti-fouling composition is released from the micropore of mesoporous silica particles, and the marine organisms for playing the role of adherency fall off.This mistake
The behavior of journey such as marine organisms secreting mucus or enzyme, speed of the ship in metres per second is faster or its higher rate of release of water temperature is faster.
Under the premise of introducing oligomer polyol and more cyanate esters can guarantee that anti-fouling agent release performance is controllable in the present invention,
The excellent mechanical property of polyurethane and adhesion strength etc. are not influenced.Mesoporous silicon oxide has high-wear resistance simultaneously, can be improved
The wearability of coating, prolongs the service life.This method simple process, cost is relatively low, is suitble to industrialized production, there is no poisonous substances to release
The problem of putting, therefore the coating has a good application prospect in marine anti-pollution field.
Specific embodiment
The present invention can be explained in more detail by following example, the invention is not limited to the following examples.
The anti-fouling coating that can discharge anti-fouling agent of the invention, including two two parts of following components one and component:
Component one by mass percentage, is formulated by following component and quality proportioning:
Component two includes mesoporous silica particles and anti-fouling composition, and mesoporous silica particles and anti-fouling composition
Mass ratio is (0.001~0.04): (0.01~0.1).
Wherein, mesoporous silica particles by mass percentage, are formulated by following components:
Component one is pressed (20~50) with component two: 1 mass ratio mixes, and obtains the anti-fouling painting that can discharge anti-fouling agent
Layer.
The anti-fouling coating that can discharge anti-fouling agent of the invention the preparation method comprises the following steps: in mass ratio by component one and component two
(20~50): 1 mixing is coated in substrate, and solidification obtains the anti-fouling coating that can discharge anti-fouling agent；Wherein, component one
Preparation process is as follows:
1) by mass percentage, that 3~55% polytetramethylene ether diol (PTMG) and 15~65% polyethers is more
First alcohol polyethylene glycol (PEG) is added in the three-necked flask equipped with thermometer and blender (500ml), is heated to 100~120
DEG C, 1~4h of vacuum dehydration at 0.667kPa；
2) 65 DEG C are cooled to, 4~60% 4,4 '-diphenylmethane diisocyanate rouge (MDI) and 4~60% pair are added
Phenol A type epoxy resin；
3) after reacting 30min~50min, the 1,4-butanediol for being added 1~20% carries out chain extension；
4) after reacting 1~2h, 0.5~10% PU defrother is added and quickly stirs, after bubble elimination, terminate anti-
It answers, obtains component one.
The preparation process of component two is as follows:
Mesoporous silica particles are first prepared, detailed process is as follows:
1) by mass percentage, 30~60% cetyl trimethylammonium bromide is added in container, then plus
Enter distilled water, be heated to 40~60 DEG C make cetyl trimethylammonium bromide dissolve after, while stirring be added 1~20% adjusting
Agent；
2) stir 10min after, be added 5~20% ethyl orthosilicate, 4~30% sodium metasilicate and 5~30% reaming
Agent is simultaneously stirred, 24~36h of isothermal reaction at 40~60 DEG C；
3) it is stored at room temperature 6~8 days, filters, dry 1~4h at 110 DEG C, obtaining white powder is mesoporous silicon oxide
Grain；
Again using the component two of mesoporous silica particles preparation, detailed process is as follows:
Mesoporous silica particles are added to the water, ultrasonic disperse is uniform, and anti-fouling composition is then added and is stirred continuously anti-
After answering 2-3h, after mixture centrifugation, washing, drying at room temperature, the mesoporous silica particles of load anti-fouling composition are obtained, i.e.,
Component two.Wherein, the ratio of mesoporous silica particles, water and anti-fouling composition is (0.001~0.04) g:1mL:(0.01~0.1)
g。
In step 1), the ratio of cetyl trimethylammonium bromide and distilled water is 1g:10mL.
In step 1), the temperature of heating is 40~60 DEG C.
In step 2), expanding agent 1,3,5- trimethylbenzene；Regulator is hydrochloric acid (11.6~12.4mol/L) or sodium hydroxide
(sodium hydroxide is first soluble in water by sodium hydroxide when being actually added into, and obtains the sodium hydroxide solution of 1~10mol/L, then will
Sodium hydroxide solution is added)；Anti-fouling composition is copper pyrithione, capsaicine, 4,5- dichloro- -2- n-octyl -4- isothiazoline -
One kind or several of 3- ketone, N- cyclopropyl-N '-(1,1- dimethyl ethyl) -6- (methyl thio) -1,3,5- triazine -2,4- diamines
Kind.
The synthetic material of a kind of marine antifouling coating of the invention: by polyurethane, mesoporous silica particles and antifouling
Ingredient etc. is copolymerized, and structure is that mesoporous silicon oxide has large surface area and mesoporous can hide to receive absorbing anti-fouling molecule.
Mesoporous silica particles prepared by the present invention have many advantages, such as, such as big specific surface area, high diffusivity and storage
Sustainability and adjustable aperture etc., wherein the size in aperture can be added by adjusting 1,3,5- trimethylbenzene of expanding agent in synthesis process
Amount regulated and controled, pore size adjustable extent be 20nm~600nm.
Intermediary hole silica dioxide granule of the present invention is to anti-fouling composition absorption carriage mainly by electrostatic interaction, interaction of hydrogen bond
Or weak Van der Waals force etc., anti-fouling composition primary attachment is in its outer surface or is supported in mesoporous.
Antifouling molecule release of the invention and release rate are related with locating briny environment, since diffusion etc. makes to prevent
Dirty ingredient is released from the micropore of mesoporous silica particles, and the marine organisms for playing the role of adherency fall off.This process
Such as the behavior of marine organisms secreting mucus or enzyme, speed of the ship in metres per second is faster or its higher rate of release of water temperature is faster.
The above-mentioned anti-fouling coating that can discharge anti-fouling agent is preparing the application in marine anti-pollution coating.
Embodiment 1
The anti-fouling coating that can discharge anti-fouling agent of hydrophobically modified is prepared according to the following steps:
The preparation process of component one is as follows:
1) by mass percentage, by 3% polytetramethylene ether diol (PTMG) and the 65% poly- second of polyether polyol
Glycol (PEG) is added in the three-necked flask equipped with thermometer and blender (500ml), is heated to 100 DEG C, at 0.667kPa
Vacuum dehydration 4h；
2) 65 DEG C are cooled to, is added the 4 of 4%, 4 '-diphenylmethane diisocyanate rouge (MDI) and 4% bisphenol-A type ring
Oxygen resin；
3) after reacting 30min, the 1,4-butanediol for being added 20% carries out chain extension；
4) after reacting 1h, 4% PU defrother is added and quickly stirs, after bubble elimination, terminate reaction, obtain component
One.
The preparation process of component two is as follows:
The mesoporous silica particles of load anti-fouling composition are first prepared, process is as follows:
1) by mass percentage, 30% cetyl trimethylammonium bromide CTAB is added in 250mL three-necked flask
100mL distilled water dissolves, constant temperature in 60 DEG C of water-baths, and 20% hydrochloric acid is added while stirring；
2) ten minutes later, it is slowly added into 10% 1,3,5- front three of ethyl orthosilicate, 30% sodium metasilicate and 10% expanding agent
Benzo is stirred continuously, and constant temperature is for 24 hours at 60 DEG C；
3) it is stored at room temperature 6 days, filters, dry 1h, obtains white powder mesoporous silica particles at 110 DEG C；
Component two is prepared using the mesoporous silica particles of the load anti-fouling composition of above-mentioned preparation, process is as follows:
0.2g mesoporous silica particles are added in 5ml water, ultrasonic disperse is uniform, and 0.1g anti-fouling composition then is added simultaneously
After being stirred continuously reaction 2-3h, after mixture centrifugation, washing, drying at room temperature, the mesoporous dioxy of load anti-fouling composition is obtained
Silicon carbide particle, i.e. component two.
Component two is added in component one by 20:1 in mass ratio, quickly after mixing evenly, is coated in A3 steel test piece (mould
Quasi- marine surface), 25~40 DEG C of solidification 1h~3h of Yu Wendu obtain the anti-fouling coating that can discharge anti-fouling agent.
Embodiment 2
The preparation process of component one is as follows:
1) by mass percentage, by 4% polytetramethylene ether diol (PTMG) and the 15% poly- second of polyether polyol
Glycol (PEG) is added in the three-necked flask equipped with thermometer and blender (500ml), is heated to 105 DEG C, at 0.667kPa
Vacuum dehydration 3h；
2) 65 DEG C are cooled to, is added the 4 of 10%, 4 '-diphenylmethane diisocyanate rouge (MDI) and 60% bisphenol A-type
Epoxy resin；
3) after reacting 40min, the 1,4-butanediol for being added 1% carries out chain extension；
4) after reacting 2h, 10% PU defrother is added and quickly stirs, after bubble elimination, terminate reaction, obtain group
Divide one.
The preparation process of component two is as follows:
Mesoporous silica particles are first prepared, process is as follows:
(1) by mass percentage, 40% cetyl trimethylammonium bromide is added in container, is then added and steams
After 50 DEG C of heating dissolves cetyl trimethylammonium bromide, 5% regulator is added in distilled water while stirring；After mixing evenly,
Be added 20% ethyl orthosilicate, 10% sodium metasilicate and 25% expanding agent and stirring, react 30h at 50 DEG C；Wherein, ten
The ratio of six alkyl trimethyl ammonium bromides and distilled water is 1g:10mL；Regulator is hydrochloric acid；Expanding agent is 1,3,5- trimethylbenzene.
(2) it is then stored at room temperature 7 days, filters, dry 2h, obtains mesoporous silica particles at 110 DEG C.
Component two is prepared using the mesoporous silica particles of the load anti-fouling composition of above-mentioned preparation, process is as follows:
Mesoporous silica particles are added to the water, ultrasonic disperse is uniform, then be added anti-fouling composition and under stiring instead
After answering 3h, after centrifugation, washing, drying, component two is obtained；Wherein, the ratio of mesoporous silica particles, water and anti-fouling composition is
0.04g:1mL:0.05g.Anti-fouling composition is capsaicine.
Finally, component one and the mixing of 30:1 in mass ratio of component two are coated in substrate, solidification obtains to discharge
The anti-fouling coating of anti-fouling agent.
Embodiment 3
The preparation process of component one is as follows:
1) by mass percentage, by 55% polytetramethylene ether diol (PTMG) and the 15% poly- second of polyether polyol
Glycol (PEG) is added in the three-necked flask equipped with thermometer and blender (500ml), is heated to 110 DEG C, at 0.667kPa
Vacuum dehydration 2h；
2) 65 DEG C are cooled to, is added the 4 of 20%, 4 '-diphenylmethane diisocyanate rouge (MDI) and 4.5% bisphenol A-type
Epoxy resin；
3) after reacting 50min, the 1,4-butanediol for being added 5% carries out chain extension；
4) after reacting 2h, 0.5% PU defrother is added and quickly stirs, after bubble elimination, terminate reaction, obtain group
Divide one.
The preparation process of component two is as follows:
Mesoporous silica particles are first prepared, process is as follows:
(1) by mass percentage, 50% cetyl trimethylammonium bromide is added in container, is then added and steams
After 40 DEG C of heating dissolves cetyl trimethylammonium bromide, 10% regulator is added in distilled water while stirring；It stirs evenly
Afterwards, be added 5% ethyl orthosilicate, 30% sodium metasilicate and 5% expanding agent and stirring, react 36h at 40 DEG C；Wherein,
The ratio of cetyl trimethylammonium bromide and distilled water is 1g:10mL；Regulator is sodium hydroxide；Expanding agent is 1,3,5- front three
Benzene.
(2) it is then stored at room temperature 8 days, filters, dry 3h, obtains mesoporous silica particles at 110 DEG C.
Component two is prepared using the mesoporous silica particles of the load anti-fouling composition of above-mentioned preparation, process is as follows:
Mesoporous silica particles are added to the water, ultrasonic disperse is uniform, then be added anti-fouling composition and under stiring instead
After answering 3h, after centrifugation, washing, drying, component two is obtained；Wherein, the ratio of mesoporous silica particles, water and anti-fouling composition is
0.005g:1mL:0.01g.Anti-fouling composition is 4,5- dichloro--Kathon and N- cyclopropyl-N '-
The mixture of (1,1- dimethyl ethyl) -6- (methyl thio) -1,3,5- triazine -2,4- diamines.
Finally, component one and the mixing of 40:1 in mass ratio of component two are coated in substrate, solidification obtains to discharge
The anti-fouling coating of anti-fouling agent.
Embodiment 4
The preparation process of component one is as follows:
1) by mass percentage, by 3% polytetramethylene ether diol (PTMG) and the 15% poly- second of polyether polyol
Glycol (PEG) is added in the three-necked flask equipped with thermometer and blender (500ml), is heated to 120 DEG C, at 0.667kPa
Vacuum dehydration 1h；
2) 65 DEG C are cooled to, is added the 4 of 60%, 4 '-diphenylmethane diisocyanate rouge (MDI) and 10% bisphenol A-type
Epoxy resin；
3) after reacting 30min, the 1,4-butanediol for being added 10% carries out chain extension；
4) after reacting 1h, 2% PU defrother is added and quickly stirs, after bubble elimination, terminate reaction, obtain component
One.
The preparation process of component two is as follows:
Mesoporous silica particles are first prepared, process is as follows:
(1) by mass percentage, 60% cetyl trimethylammonium bromide is added in container, is then added and steams
After 45 DEG C of heating dissolves cetyl trimethylammonium bromide, 1% regulator is added in distilled water while stirring；After mixing evenly,
Be added 5% ethyl orthosilicate, 4% sodium metasilicate and 30% expanding agent and stirring, react 32h at 45 DEG C；Wherein, ten six
The ratio of alkyl trimethyl ammonium bromide and distilled water is 1g:10mL；Regulator is sodium hydroxide；Expanding agent is 1,3,5- trimethylbenzene.
(2) it is then stored at room temperature 6 days, filters, dry 4h, obtains mesoporous silica particles at 110 DEG C.
Component two is prepared using the mesoporous silica particles of the load anti-fouling composition of above-mentioned preparation, process is as follows:
Mesoporous silica particles are added to the water, ultrasonic disperse is uniform, then be added anti-fouling composition and under stiring instead
After answering 3h, after centrifugation, washing, drying, component two is obtained；Wherein, the ratio of mesoporous silica particles, water and anti-fouling composition is
0.02g:1mL:0.03g.Anti-fouling composition is the mixture of copper pyrithione and capsaicine.
Finally, component one and the mixing of 50:1 in mass ratio of component two are coated in substrate, solidification obtains to discharge
The anti-fouling coating of anti-fouling agent.
Coating prepared by the present invention is mainly used for the antifouling of ship.The coating is mainly synthesized by component one and component two, group
Divide the one flexible chain of raw material, rigid chain and the chain extender of preparation etc., wherein flexible chain is by polytetramethylene ether diol (PTMG)
It is obtained with the reaction of 4,4 '-diphenylmethane diisocyanate rouge (MDI).By several objects such as surfactant, water, silicon source, acid or alkali
Phase anti-fouling composition synthesis component two is adulterated or loaded again to matter, and component two (mesoporous silicon oxide for being mounted with anti-fouling composition) is added
In component one (polyurethane), it is coated in substrate surface, in 25~40 DEG C of solidification 1h~3h, obtaining a kind of can discharge anti-fouling agent
Anti-fouling coating.Present invention combination mesoporous silica particles have the characteristics that its surface area is big and have that hole is adjustable, can close
At adjusting absorption in the process or the ability of anti-fouling composition is received in hiding, and mainly by electrostatic interaction, interaction of hydrogen bond or weak model
Anti-fouling composition is adsorbed on its outer surface or is supported in mesoporous by De Huali etc..In the seawater, due to diffusion make it is antifouling
Ingredient is released from the micropore of mesoporous silica particles, and the marine organisms for playing the role of adherency fall off.This process is such as
The behavior of marine organisms secreting mucus or enzyme, speed of the ship in metres per second is faster or its higher rate of release of water temperature is faster.And can also it lead to
Ratio, the reaction condition etc. between polymer (i.e. component one) are overregulated, realizes its mechanical property and anti-fouling performance.It is mesoporous
Silica dioxide granule mainly by electrostatic interaction, interaction of hydrogen bond or weak Van der Waals force etc., prevents anti-fouling composition absorption carriage
Dirty ingredient primary attachment is in its outer surface or is supported in mesoporous.Oligomer polyol and more cyanate esters are introduced in invention can be with
Under the premise of guaranteeing that anti-fouling agent release performance is controllable, the excellent mechanical property of polyurethane and adhesion strength etc. are not influenced.It is mesoporous simultaneously
Silica has high-wear resistance, and the wearability of coating can be improved, prolong the service life.This method simple process, cost
It is lower, it is suitble to industrialized production, the problem of there is no poisonous substance releases, therefore the coating has in marine anti-pollution field and well answers
Use prospect.
Claims (10)
1. a kind of anti-fouling coating that can discharge anti-fouling agent, which is characterized in that including following two parts:
Component one by mass percentage, is formulated by following component and quality proportioning:
Component two includes mesoporous silica particles and anti-fouling composition, and the quality of mesoporous silica particles and anti-fouling composition
Than for (0.001~0.04): (0.01~0.1)；
Component one is pressed (20~50) with component two: 1 mass ratio mixes, and obtains the anti-fouling coating that can discharge anti-fouling agent.
2. a kind of anti-fouling coating that can discharge anti-fouling agent according to claim 1, which is characterized in that mesoporous silicon oxide
Particle by mass percentage, is formulated by following components:
3. a kind of anti-fouling coating that can discharge anti-fouling agent according to claim 2, which is characterized in that expanding agent 1,3,
5- trimethylbenzene.
4. a kind of anti-fouling coating that can discharge anti-fouling agent according to claim 1, which is characterized in that regulator is hydrochloric acid
Or sodium hydroxide.
5. a kind of anti-fouling coating that can discharge anti-fouling agent according to claim 1, which is characterized in that anti-fouling composition is pyrrole
Pyridine thioketones copper, capsaicine, 4,5- dichloro--Kathon, N- cyclopropyl-N '-(1,1- dimethyl second
Base) -6- (methyl thio) -1,3,5- triazine -2,4- diamines one or more.
6. a kind of preparation method for the anti-fouling coating that can discharge anti-fouling agent, which is characterized in that component one and component two are pressed matter
Amount is than (20~50): 1 mixing is coated in substrate, and solidification obtains the anti-fouling coating that can discharge anti-fouling agent；Wherein, component
One preparation process is as follows:
1) by mass percentage, by the poly- second two of the polyether polyol of 3~55% polytetramethylene ether diol and 15~65%
Alcohol (PEG) is added in container, is heated to 100~120 DEG C of vacuum dehydrations；
2) 4~60% 4,4 '-diphenylmethane diisocyanate rouge and 4~60% bisphenol A type epoxy resin are added after cooling down；
3) after reacting 30min~50min, the 1,4-butanediol for being added 1~20% carries out chain extension；
4) after reacting 1~2h, 0.5~10% PU defrother is added and quickly stirs, after bubble elimination, terminate reaction, obtain
To component one；
The preparation process of component two is as follows:
Mesoporous silica particles are added to the water, ultrasonic disperse is uniform, and anti-fouling composition is then added and reacts 2- under stiring
After 3h, after centrifugation, washing, drying, component two is obtained；Wherein, the ratio of mesoporous silica particles, water and anti-fouling composition is
(0.001~0.04) g:1mL:(0.01~0.1) g.
7. a kind of preparation method of anti-fouling coating that can discharge anti-fouling agent according to claim 6, which is characterized in that step
It is rapid 1) in, the pressure of vacuum dehydration is 0.667kPa, and the time is 1~4h.
8. a kind of preparation method of anti-fouling coating that can discharge anti-fouling agent according to claim 6, which is characterized in that step
It is rapid 2) in, after being cooled to 65 DEG C be added 4~60% 4,4 '-diphenylmethane diisocyanate rouge；Anti-fouling composition is pyrithione
Copper, capsaicine, 4,5- dichloro--Kathon, N- cyclopropyl-N '-(1,1- dimethyl ethyl) -6-
The one or more of (methyl thio) -1,3,5- triazine -2,4- diamines.
9. a kind of preparation method of anti-fouling coating that can discharge anti-fouling agent according to claim 6, which is characterized in that be situated between
The preparation process of hole silica dioxide granule is as follows:
(1) by mass percentage, 30~60% cetyl trimethylammonium bromide is added in container, is then added and steams
After heating dissolves cetyl trimethylammonium bromide, 1~20% regulator is added in distilled water while stirring；After mixing evenly,
Be added 5~20% ethyl orthosilicate, 4~30% sodium metasilicate and 5~30% expanding agent and stirring, it is anti-at 40~60 DEG C
Answer 24~36h；
(2) it is then stored at room temperature 6~8 days, filters, dry 1~4h, obtains mesoporous silica particles at 110 DEG C.
10. a kind of preparation method of anti-fouling coating that can discharge anti-fouling agent according to claim 9, which is characterized in that
In step (1), the ratio of cetyl trimethylammonium bromide and distilled water is 1g:10mL；In step (1), the temperature of heating is 40
~60 DEG C；In step (2), expanding agent 1,3,5- trimethylbenzene, regulator is hydrochloric acid or sodium hydroxide.
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| CN110835495A (en) * | 2019-11-29 | 2020-02-25 | 厦门双瑞船舶涂料有限公司 | Moisture-curing polyurethane antifouling paint for fishing net and preparation method thereof |
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| CN112048047A (en) * | 2020-08-24 | 2020-12-08 | 郑州大学 | Transparent yellowing-resistant high-toughness self-repairing polyurethane elastomer based on hydrogen bonding pyridine |
| CN112048047B (en) * | 2020-08-24 | 2022-05-10 | 郑州大学 | Transparent yellowing-resistant high-toughness self-repairing polyurethane elastomer based on hydrogen bonding pyridine |
| CN114106663A (en) * | 2021-12-25 | 2022-03-01 | 烟台恒诺新材料有限公司 | Anti-adhesion nano ceramic coating and preparation method thereof |
| CN116376394A (en) * | 2023-03-20 | 2023-07-04 | 广东美涂士建材股份有限公司 | Environment-friendly marine microorganism fouling prevention coating and preparation method thereof |
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