CN110003765A - A kind of aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint and the preparation method and application thereof - Google Patents
A kind of aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint and the preparation method and application thereof Download PDFInfo
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- CN110003765A CN110003765A CN201910195064.4A CN201910195064A CN110003765A CN 110003765 A CN110003765 A CN 110003765A CN 201910195064 A CN201910195064 A CN 201910195064A CN 110003765 A CN110003765 A CN 110003765A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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Abstract
The present invention relates to a kind of aqueous non-toxic permanent seal cooling fluorine silicon antifouling paints and the preparation method and application thereof, preparation method is as follows: 1) preparing modifying epoxy resin by organosilicon: organosilicon is mixed with epoxy resin, catalyst reaction is added and obtains modifying epoxy resin by organosilicon EP-Si；2) it prepares emulsifier: polyethylene glycol is mixed with epoxy resin, catalyst reaction is added and obtains emulsifier EP-PEG；3) it prepares aqueous epoxy emulsion: emulsifier EP-PEG is mixed with modifying epoxy resin by organosilicon EP-Si, be warming up to 50~100 DEG C, cosolvent and deionized water is added, obtains aqueous epoxy emulsion after fully emulsified；4) aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint is prepared.Aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint adhesive force provided by the invention is high, durability and anti-pollution are good.
Description
Technical field
The invention belongs to Environmental Protective Water-paint technical fields, and in particular to one kind can be used for that marine ship is antifouling and ocean work
The aqueous non-toxic fluorine silicon antifouling paint of journey.
Background technique
Contain various metals salt in seawater, there is corrosivity to ocean engineering such as deep sea fishing ground steel frame construction coating, pass through
The seawater of a period of time impregnates, and coating can generate mostly to fall off and crack, and exposes the steel frame construction of bottom, seawater and steel frame construction
Primary battery layer is formed, the corrosion in surface layer steel face is accelerated, if things go on like this, the safety of the ocean engineerings such as deep sea fishing ground can be caused very big
Threat.
In addition, the pollution that marine organisms attachment generates is that a very headache is asked for ship and ocean engineering building
Topic, the biological pollution that can cause large area biological attachment are usually because of macros such as barnacle, diatom, mussel and primary
Animal individual is attached to marine surface, it is difficult to such large area ocean attachment is washed out with ship's speed promotion, marine organisms attachment increases
The weight of ship and deep sea fishing ground is added, so that marine fuel oil be caused to expend increase, a large amount of manpower of deep sea fishing ground needs and object
Power carries out decontamination work.
The superpower wear-resistant paint that deep sea fishing ground uses during construction at present, main purpose are to improve it in the seawater
Corrosion resistance and crocking resistance, and do not have anti-pollution, it needs to configure corresponding cleaning equipment and personnel carries out self
Cleaning, wastes a large amount of manpower and material resources.Commercially available anti-fouling ship paint is all based on oiliness, and effect preferably has Aksu promise
Intelsleek1100SR, the high-end antifouling paint of marine rainbow old man Hempaguard and the Atlantic+ middle-end antifouling paint of Bell,
The principle that wherein 1100SR and Atlantic+ is all made of low-surface-energy carries out antifouling, i.e. attachment of the reduction protein on coating
Power, antifouling to achieve the effect that, Hempaguard melts using by silicone hydrogels and controllable biocide release tech
Together in surface energy in a kind of coating, had both been reduced, the biology that adherency is killed further through insecticide is antifouling to achieve the purpose that,
And insecticide can damage marine ecology.
The above valuable product, average price are well beyond much engaged in ocean Construction Company in 800 yuan/kilogram or more
Expection, increase construction cost, and these three products are oil products, are sprayed using toluene as diluent, greatly
The organic matter volatilization of amount causes health threat to constructor and brings a large amount of environmental pollution.Three kinds of coating are made with low-surface-energy
Anti-pollution relies primarily on, however while improving surface depolluting properties, the adhesive force of antifouling paint is also reduced, is needed
The good epoxy bottom of adsorption capacity is sprayed, the cost of entire hull is substantially increased.In addition, three kinds of antifouling paints are contained with fluorine-containing
Silene hydrocarbon causes free radical polymerization as main crosslinking component, using peroxide, and obtained coating has certain brittleness,
Edge location, which is prone to wear, during practical sea-freight falls off.
Summary of the invention
The technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide a kind of adhesive force
High, durability and the good aqueous non-toxic fluorine silicon antifouling paint and its preparation method and application of anti-pollution.
In order to solve the above technical problems, present invention provide the technical scheme that
A kind of aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint is provided, preparation method is as follows:
1) modifying epoxy resin by organosilicon is prepared: by the organosilicon with following formula I with epoxy resin by group molar ratio X:
Epoxy group=1~2:1 mixing, is added catalyst reaction (contained by the hydroxyl and organosilicon in hydroxyl and epoxy group or epoxy
Amine propyl reaction) obtain modifying epoxy resin by organosilicon EP-Si；
Wherein X is-OH ,-NH2Or-COOH, R1, R2And R3General formula is-O- (CH2)m- H, R4General formula is-O- (CH2)m, m is
The integer of 0-20, R1, R2And R3In m can be identical or different；
2) prepare emulsifier: by polyethylene glycol with epoxy resin by group molar ratio hydroxyl: epoxy group=1~2:1 is mixed,
Addition catalyst is reacted (hydroxyl and epoxy group chain extending reaction) and obtains emulsifier EP-PEG；
3) aqueous epoxy emulsion is prepared: by silicon-modified epoxy obtained by emulsifier EP-PEG obtained by step 2) and step 1)
Resin EP-Si 1~20:100 in mass ratio mixing, is warming up to 50~100 DEG C, and cosolvent and deionized water is added, fully emulsified
After obtain aqueous epoxy emulsion；
4) aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint is prepared:
First, second, the third three kinds of components are prepared first:
Component A is mixed to get by the component of following mass percentage: aqueous epoxy emulsion 10 obtained by step 3)~
40%, contain silicon emulsion 10~30%, organic additive 10~20%, surfactant 5~10%, cosolvent 5~10%, nano powder
Body 0.5~1%, remaining is deionized water, and first component solid content is 40~60%；
Second component: curing agent, catalyst, the two quality is than curing agent: catalyst=1~9:1；
Third component: fluorine-containing latex；
By the first, second, the third three kinds of component first in mass ratio: second: the third=5~9:2~4:1 is uniformly mixed, and is obtained aqueous
Nontoxic permanent seal cooling fluorine silicon antifouling paint.
According to the above scheme, the step 1) catalyst is selected from triethylamine, triethanolamine, N, N- dimethylethanolamine, diethyl
Hydramine, triphenylphosphine, alchlor, additional amount are organosilicon and the 1~5% of epoxy resin gross mass in step 1).
According to the above scheme, the step 1) reaction condition are as follows: 100~150 DEG C of 4~6h of reaction are warming up under inert atmosphere.
According to the above scheme, the step 1) epoxy resin be one of epoxy resin E20, E35, E42, E44, E51 or
It is a variety of.
According to the above scheme, the step 1) organosilicon includes Xing Feilong hydroxy silicon oil 209 (Mn=2000~3000), 3- ammonia
Propyl-triethoxysilicane.
According to the above scheme, step 2) the polyethylene glycol structures formula are as follows:
Wherein a is the integer of 2-25.
According to the above scheme, the step 2) epoxy resin is identical as epoxy resin described in step 1).
According to the above scheme, the step 2) catalyst is selected from triethylamine, triethanolamine, N, N- dimethylethanolamine, diethyl
Hydramine, triphenylphosphine, alchlor, additional amount are the 1-10% of epoxy resin and polyethylene glycol gross mass in step 2).
According to the above scheme, the step 2) reaction condition are as follows: 100~150 DEG C are warming up under inert atmosphere protection, reaction 4
~6h.
According to the above scheme, the step 3) cosolvent is propylene glycol monomethyl ether, 1,4-butanediol, butyl glycol ether, n-butanol
In any two or more mixture, the additional amount of cosolvent accounts for the 5~10% of aqueous epoxy emulsion quality.
According to the above scheme, step 3) emulsification condition are as follows: emulsification revolving speed be 500~1500r/min, emulsification times be 15~
30min。
Preferably, step 3) the aqueous epoxy emulsion solid content is 50 ± 2%.
According to the above scheme, step 4) is described contains silicon emulsion containing silicon emulsion or aqueous polyurethane for waterborne polyester containing silicon emulsion,
Wherein waterborne polyester includes wide tree GS335, Guangzhou cobalt general one of 7509 or two kind containing silicon emulsion, and aqueous polyurethane is siliceous
Lotion includes Bayer U54.
According to the above scheme, the step 4) organic additive is ethylene glycol or 1,4-butanediol.
According to the above scheme, the step 4) surfactant is selected from fatty alcohol polyoxyethylene ether ammonium sulfate (AESA), laurel
Alcohol sodium sulphate (K12 or SDS), Nonyl pheno (10) ether (TX-10), diglycollic amide (6501) glycerol stearate list
Ester, alkyl, polyether (PO-EO copolymer), dispersing agent NNO, aliphatic alcohol polyethenoxy (3) ether (AEO-3).
According to the above scheme, the step 4) cosolvent is selected from propylene glycol monomethyl ether, 1,4-butanediol, butyl glycol ether, positive fourth
Alcohol.
According to the above scheme, the step 4) nano-powder is selected from nano aluminium oxide, nano zine oxide, nano-titanium oxide.
According to the above scheme, the step 4) curing agent is that polyether-modified Isocyanates curing agent or fatty amines epoxy are solid
Agent, polyether-modified Isocyanates curing agent include polyether-modified isophorone diisocyanate, polyether-modified hexa-methylene
Diisocyanate, polyether-modified toluene di-isocyanate(TDI) and their trimer derivatives, specifically include Bayer 3100, Bayer
2655, Tosoh AQ100R5, Luo Diya EasaquaTM803, ten thousand China chemistry Aquolin 270 and Asahi Chemical Industry WT30-100 of XD
One of or it is several；Fatty amines epoxy hardener includes joining solid BANCO 901, celestial being nation SG-6801, double phoenix QG-628
One of or it is several.
According to the above scheme, the step 4) catalyst is selected from triethylene tetramine, diethylenetriamine, dibutyl tin cinnamic acid
One of tin.
According to the above scheme, the step 4) fluorine-containing latex be fluorine-containing aqueous acrylic emulsion or ptfe emulsion,
Middle fluorine-containing aqueous acrylic emulsion includes instruction to rise abruptly one or more of, polytetrafluoroethyl-ne in G9010, love jade-like stone Ma DF-01 up to HD8327, state
Alkene lotion includes Du Pont TE3859, one of Du Pont DISP 30LX, 3M TF5032 or several.
Step 1) prepares modifying epoxy resin by organosilicon in the present invention, and reaction equation is as follows:
, n=2~20.
Step 2) prepares emulsifier in the present invention, and reaction equation is as follows:
Here n=2~20 are same epoxy resin with step 1).
M=5~15, the polyethylene glycol of corresponding different molecular quality select to correspond to according to the chain length of step 1) epoxy resin
Polyethylene glycol be modified, this step obtain the emulsifying effectiveness of emulsifier with the modified organosilicon epoxy resin of step 1)
Molecular weight is identical or close to most preferably.
The invention also includes the preparation method of above-mentioned aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint, preparation method is as follows:
1) modifying epoxy resin by organosilicon is prepared: by the organosilicon with following formula I with epoxy resin by group molar ratio X:
Epoxy group=1~2:1 mixing, is added catalyst reaction (contained by the hydroxyl and organosilicon in hydroxyl and epoxy group or epoxy
Amine propyl reaction) obtain modifying epoxy resin by organosilicon EP-Si；
Wherein X is-OH ,-NH2Or-COOH, R1, R2And R3General formula is-O- (CH2)m- H, R4General formula is-O- (CH2)m, m is
The integer of 0-20, R1, R2And R3In m can be identical or different；
2) prepare emulsifier: by polyethylene glycol with epoxy resin by group molar ratio hydroxyl: epoxy group=1~2:1 is mixed,
Addition catalyst is reacted (hydroxyl and epoxy group chain extending reaction) and obtains emulsifier EP-PEG；
3) aqueous epoxy emulsion is prepared: by silicon-modified epoxy obtained by emulsifier EP-PEG obtained by step 2) and step 1)
Resin EP-Si 1~20:100 in mass ratio mixing, is warming up to 50~100 DEG C, and cosolvent and deionized water is added, fully emulsified
After obtain aqueous epoxy emulsion；
4) aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint is prepared:
First, second, the third three kinds of components are prepared first:
Component A is mixed to get by the component of following mass percentage: aqueous epoxy emulsion 10 obtained by step 3)~
40%, contain silicon emulsion 10~30%, organic additive 10~20%, surfactant 5~10%, cosolvent 5~10%, nano powder
Body 0.5~1%, remaining is deionized water, and first component solid content is 40~60%；
Second component: curing agent, catalyst, the two quality is than curing agent: catalyst=1~9:1；
Third component: fluorine-containing latex；
By the first, second, the third three kinds of component first in mass ratio: second: the third=5~9:2~4:1 is uniformly mixed, and is obtained aqueous
Nontoxic permanent seal cooling fluorine silicon antifouling paint.
The invention also includes above-mentioned aqueous non-toxic permanent seal cooling fluorine silicon antifouling paints in marine antifouling and the antifouling side of ocean engineering
The application in face.
The present invention obtains organosilicon epoxy resin, then by epoxy water first by epoxy resin with after organic-silicon-modified
With containing hydrophilic radical it is modified after obtain emulsifier, then obtained with the epoxy emulsifier organosilicon epoxy resin prepared aqueous
Epoxy emulsion, using epoxy emulsion as matrix resin lotion, because of itself adhesive force with higher, have after solidification compared with
High crosslink density and smooth surface, can guarantee in seawater durability；Then siliceous aqueous polyurethane emulsion, which is added, reduces ratio
Surface energy, reduces the adhesive force of marine organisms, achievees the purpose that attachment；MP50E is added and contains silicon emulsion, siliceous soft segment is provided and is increased
The glossiness of blooming, the phenyl silanes contained can reduce surface energy；Fluorine-containing lotion and polytetrafluoroethyl-ne is added
Alkene lotion, because it is capable of providing CF3Group, CF3With excellent reduction surface energy properties；And the mixing of other reinforcing agents is added
Obtain nontoxic durable antifouling paint.
The beneficial effects of the present invention are: 1, provided by the invention aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint adhesive force
High, durability and anti-pollution are good.2, preparation method provided by the invention is environmentally protective, does not generate debirs, with conventional original
Material is prepared, and cost is relatively low.
Detailed description of the invention
Fig. 1 is 1 day, placement after aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint brushing prepared by the embodiment of the present invention 1
3 months in seawater, place 6 months photos in seawater；
Fig. 2 is 1 day after aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint brushing prepared by embodiment 2,3 in placement seawater
A month, place 6 months photos in seawater；
Fig. 3 is 1 day after aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint brushing prepared by embodiment 3,3 in placement seawater
A month, place 6 months photos in seawater；
Fig. 4 is 1 day after aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint brushing prepared by embodiment 4,3 in placement seawater
A month, place 6 months photos in seawater；
Fig. 5 is anti-fouling agent additional amount detection figure in the plate of embodiment 1-4 brushing；
Fig. 6 is the plate resistance to distilled water that embodiment 1-4 is brushed, the solution min of resistance to 3.5%NaCl figure；
Fig. 7 is the plate salt-fog resistant time figure that embodiment 1-4 is brushed.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, with reference to the accompanying drawing to the present invention make into
One step detailed description.
Nano-powder nano aluminium oxide (30nm) used in the embodiment of the present invention, nano zine oxide (50 ± 10nm), nano oxygen
Change titanium (60nm), graphene oxide, graphene, former three is purchased from Aladdin company, after be both using Hummers method system
Standby to obtain, partial size is 75~120nm.
Embodiment 1
A kind of aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint, it is specific the preparation method is as follows:
1) modifying epoxy resin by organosilicon is prepared: by n (NH2): n (epoxy group)=1:1 ratio weighs 2.2g 3- ammonia third
Ethyl triethoxy silicane alkane and 3.91 epoxy resin E-51, are added in four-hole boiling flask, and 1g triethanolamine is added and makees catalyst, anhydrous
Anaerobic, N2It is warming up to 120 DEG C of reaction 5h under atmosphere protection, obtains modifying epoxy resin by organosilicon EP-Si；
2) prepare emulsifier: by PEG-1000 and E-51 in n (hydroxyl): n (epoxy group)=1:1 ratio is fed to four necks
In flask (3.27g E-51 and 20gPEG-1000), in N2Protection under be heated to 80~85 DEG C dissolution, be added tri- ethyl alcohol of 1g
Amine, is warming up to 120 DEG C and is reacted, and constant temperature 5h obtains emulsifier EP-PEG；
3) it prepares aqueous epoxy emulsion: 40g EP-Si and 2.4gEP-PEG mixture is added into three-neck flask, is heated to
86 DEG C stir evenly, and the mixture (quality is than propylene glycol monomethyl ether: n-butanol=2:3) of 10g propylene glycol monomethyl ether and n-butanol is added,
It is slowly dropped into distilled water, until the viscosity of system declines suddenly, 1200r/min stirs 15min, solid content is adjusted according to demand,
Water is added to dilute to obtain the aqueous epoxy emulsion that solid content is 50 ± 2%；
4) aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint is prepared:
First, second, the third three kinds of components are prepared first:
Component A: aqueous epoxy emulsion 48mL, MP50E containing silicon emulsion 38mL, propylene glycol 7mL, 440 tables obtained by step 3)
Face activating agent 3mL, propylene glycol monomethyl ether 2mL, nano aluminium oxide 1g, deionized water 15mL；
Second component: join solid 901 30mL of BANCO, triethylene diamine 5mL；
Third component: 3M TF5032 15mL；
By the first, second, the third three kinds of component first in mass ratio: second: third=9:2:1 is uniformly mixed, and it is resistance to obtain aqueous non-toxic
Long type fluorine silicon antifouling paint.
By aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint film spary manufactured in the present embodiment in 200mm × 100mm steel plate
On.
The left, center, right Fig. 1 is respectively 1 day after aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint brushing prepared by the present embodiment,
The photo placed in seawater 3 months, place 6 months in seawater, the non-brushing antifouling paint of top half is as control, it can be seen that on
The part of the non-brushing antifouling paint of layer gradually appears marine organisms attachment in 3 months, and until 6 months, large area was adhered to,
Illustrate that antifouling paint anti-fouling effect manufactured in the present embodiment is significant.
Embodiment 2
A kind of aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint, it is specific the preparation method is as follows:
1) modifying epoxy resin by organosilicon is prepared: by n (NH2): n (epoxy group)=1:1 ratio weighs 2.2g3- ammonia third
Ethyl triethoxy silicane alkane and 4.54 epoxy resin E-44s, are added in four-hole boiling flask, and 1g triethanolamine is added and makees catalyst, anhydrous
Anaerobic, N2It is warming up to 140 DEG C of reaction 4.5h under atmosphere protection, obtains modifying epoxy resin by organosilicon；
2) prepare emulsifier: by PEG-2000 and E-44 in n (hydroxyl): n (epoxy group)=1:1 ratio is fed to four necks
In flask (3.27g E-20 and 10.68gPEG-1000), in N2Protection under be heated to 80~85 DEG C dissolution, be added tri- second of 1g
Hydramine, is warming up to 120 DEG C and is reacted, and constant temperature 5h obtains emulsifier EP-PEG；
3) it prepares aqueous epoxy emulsion: 40g E-44 and 2.8gEP-PEG mixture is added into three-neck flask, is heated to
86 DEG C stir evenly, and the mixture (2:3) of 10g propylene glycol monomethyl ether and n-butanol is added, distilled water is slowly dropped into, until system
Viscosity declines suddenly, and 1200r/min stirs 15min, and water is added and dilutes to obtain the aqueous epoxy emulsion that solid content is 50 ± 2%；
4) aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint is prepared:
First, second, the third three kinds of components are prepared first:
Component A: aqueous epoxy emulsion 48mL, MP50E containing silicon emulsion 38mL, propylene glycol 7mL, 440 tables obtained by step 3)
Face activating agent 3mL, propylene glycol monomethyl ether 2mL, nano aluminium oxide 1g, deionized water 15mL；
Second component: 2655 30mL of Bayer, dibutyl tin dilaurylate 5mL；
Third component: Du Pont TE3859 15mL；
By the first, second, the third three kinds of component first in mass ratio: second: third=9:2:1 is uniformly mixed, and it is resistance to obtain aqueous non-toxic
Long type fluorine silicon antifouling paint.
By aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint film spary manufactured in the present embodiment in 200mm × 100mm steel plate
On.
The left, center, right Fig. 2 is respectively 1 day after aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint brushing prepared by the present embodiment,
The photo placed in seawater 3 months, place 6 months in seawater, the non-brushing antifouling paint of top half is as control, it can be seen that on
The part of the non-brushing antifouling paint of layer gradually appears marine organisms attachment in 3 months, and until 6 months, large area was adhered to,
Illustrate that antifouling paint anti-fouling effect manufactured in the present embodiment is significant.
Embodiment 3
A kind of aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint, it is specific the preparation method is as follows:
1) it prepares modifying epoxy resin by organosilicon: weighing 20g Xing Feilong hydroxyl in n (OH): n (epoxy group)=1:1 ratio
Base silicone oil 209 and 3.91g epoxy resin E-51, are added in four-hole boiling flask, and 1g triphenylphosphine is added and does catalyst, anhydrous nothing
Oxygen, N2It is warming up to 150 DEG C of reaction 4h under atmosphere protection, obtains modifying epoxy resin by organosilicon；
2) prepare emulsifier: by PEG-4000 and E-51 in n (hydroxyl): n (epoxy group)=1:1 ratio is fed to four necks
3.91g E-51 and 40gPEG-4000 in flask), in N2Protection under be heated to 80~85 DEG C dissolution, be added 1g triethanolamine,
It is warming up to 150 DEG C to be reacted, constant temperature 4h obtains emulsifier EP-PEG；
3) it prepares aqueous epoxy emulsion: 40g E-44 and 3.2g EP-PEG mixture is added into three-neck flask, is heated to
86 DEG C stir evenly, and the mixture (2:3) of 10g propylene glycol monomethyl ether and n-butanol is added, distilled water is slowly dropped into, until system
Viscosity declines suddenly, and 1200r/min stirs 15min, and water is added and dilutes to obtain the aqueous epoxy emulsion that solid content is 50 ± 2%；
4) aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint is prepared:
First, second, the third three kinds of components are prepared first:
Component A: aqueous epoxy emulsion 48mL, MP50E containing silicon emulsion 25mL obtained by step 3), it is wide to set GS335 36mL,
Propylene glycol 7mL, 440 surfactant 3mL, propylene glycol monomethyl ether 2mL, nano aluminium oxide 1g, deionized water 15mL；
Second component: 3100 30mL of Bayer, dibutyl tin dilaurylate 5mL；
Third component: Du Pont DISP 30LX 15mL；
By the first, second, the third three kinds of component first in mass ratio: second: third=9:2:1 is uniformly mixed, and it is resistance to obtain aqueous non-toxic
Long type fluorine silicon antifouling paint.
By aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint film spary manufactured in the present embodiment in 200mm × 100mm steel plate
On.
The left, center, right Fig. 3 is respectively 1 day after aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint brushing prepared by the present embodiment,
The photo placed in seawater 3 months, place 6 months in seawater, the non-brushing antifouling paint of top half is as control, it can be seen that on
The part of the non-brushing antifouling paint of layer gradually appears marine organisms attachment in 3 months, and until 6 months, large area was adhered to,
Illustrate that antifouling paint anti-fouling effect manufactured in the present embodiment is significant.
Embodiment 4
A kind of aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint, it is specific the preparation method is as follows:
1) it prepares modifying epoxy resin by organosilicon: weighing 20g Xing Feilong in n (OH): n (epoxy group)=1.25:1 ratio
Hydroxy silicon oil 209 and 5.67g epoxy resin E-44, are added in four-hole boiling flask, and 1g alchlor is added and does catalyst, anhydrous nothing
Oxygen, N2It is warming up to 150 DEG C of reaction 4h under atmosphere protection, obtains modifying epoxy resin by organosilicon EP-Si；
2) prepare emulsifier: by PEG-4000 and E-44 in n (hydroxyl): n (epoxy group)=1:1 ratio is fed to four necks
In flask (3.27g E-44 and 21.36gPEG-4000), in N2Protection under be heated to 80~85 DEG C dissolution, be added tri- second of 1g
Hydramine, is warming up to 150 DEG C and is reacted, and constant temperature 4h obtains emulsifier EP-PEG；
3) it prepares aqueous epoxy emulsion: 40g EP-Si and 2.8g EP-PEG mixture is added into three-neck flask, heating
It is stirred evenly to 86 DEG C, the mixture (2:3) of 10g propylene glycol monomethyl ether and n-butanol is added, distilled water is slowly dropped into, until system
Viscosity decline suddenly, 1200r/min stirs 15min, and water is added and dilutes to obtain the water-base epoxy cream that solid content is 50 ± 2%
Liquid；
4) aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint is prepared:
First, second, the third three kinds of components are prepared first:
Component A: aqueous epoxy emulsion 48mL, MP50E containing silicon emulsion 25mL, Bayer U54 36mL obtained by step 3), third
Glycol 7mL, 440 surfactant 3mL, propylene glycol monomethyl ether 2mL, nano aluminium oxide 1g, deionized water 15mL；
Second component: 3100 30mL of Bayer, catalyst 5mL dibutyl tin dilaurate；
Third component: 3M TF5032 7mL, Du Pont DISP 30LX 8mL；
By the first, second, the third three kinds of component first in mass ratio: second: third=9:2:1 is uniformly mixed, and it is resistance to obtain aqueous non-toxic
Long type fluorine silicon antifouling paint.
By aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint film spary manufactured in the present embodiment in 200mm × 100mm steel plate
On.
The left, center, right Fig. 4 is respectively 1 day after aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint brushing prepared by the present embodiment,
The photo placed in seawater 3 months, place 6 months in seawater, the non-brushing antifouling paint of top half is as control, it can be seen that on
The part of the non-brushing antifouling paint of layer gradually appears marine organisms attachment in 3 months, and until 6 months, large area was adhered to,
Illustrate that antifouling paint anti-fouling effect manufactured in the present embodiment is significant.
After embodiment 1-4 is brushed finish completely, the applicant has carried out the test of anti-pollution to the plate of brushing, has prevented
The test of test, resistance to 3.5%NaCl that dirty dosage is added and test four tests of salt spray resistance, Fig. 5 is what embodiment 1-4 was brushed
Anti-fouling agent additional amount detection figure in plate, as seen from the figure, the additional amount of four embodiment anti-fouling agents of the invention is below national marine
Standard as defined in standard.The plate resistance to distilled water that Fig. 6 brushes for embodiment 1-4, the solution min of resistance to 3.5%NaCl figure, as seen from the figure,
The present embodiment antifouling paint can be more than 300 days of national regulation, therefore have excellent durability in the seawater.Fig. 7 is real
The plate salt-fog resistant time figure that a 1-4 is brushed is applied, as seen from the figure, the present embodiment antifouling paint can be more than the salt spray resistance of national regulation
Time 2500h, therefore there is excellent durability in the seawater.The above test result demonstrates antifouling painting prepared by the present invention
Material has excellent anti-pollution, green non-poisonous pollution-free, and has good durability.
Claims (10)
1. a kind of aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint, which is characterized in that preparation method is as follows:
1) modifying epoxy resin by organosilicon is prepared: by the organosilicon with following formula I with epoxy resin by group molar ratio X: epoxy
Base=1~2:1 mixing, is added catalyst reaction and obtains modifying epoxy resin by organosilicon EP-Si；
Wherein X is-OH ,-NH2Or-COOH, R1, R2And R3General formula is-O- (CH2)m- H, R4General formula is-O- (CH2)m, m 0-20
Integer, R1, R2And R3In m can be identical or different；
2) prepare emulsifier: by polyethylene glycol with epoxy resin by group molar ratio hydroxyl: epoxy group=1~2:1 is mixed, and is added
Catalyst is reacted to obtain emulsifier EP-PEG；
3) aqueous epoxy emulsion is prepared: by modifying epoxy resin by organosilicon obtained by emulsifier EP-PEG obtained by step 2) and step 1)
EP-Si 1~20:100 in mass ratio mixing, is warming up to 50~100 DEG C, and cosolvent and deionized water is added, obtains after fully emulsified
To aqueous epoxy emulsion；
4) aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint is prepared:
First, second, the third three kinds of components are prepared first:
Component A is mixed to get by the component of following mass percentage: aqueous epoxy emulsion 10~40% obtained by step 3) contains
Silicon emulsion 10~30%, organic additive 10~20%, surfactant 5~10%, cosolvent 5~10%, nano-powder 0.5~
1%, remaining is deionized water, and first component solid content is 40~60%；
Second component: curing agent, catalyst, the two quality is than curing agent: catalyst=1~9:1；
Third component: fluorine-containing latex；
By the first, second, the third three kinds of component first in mass ratio: second: the third=5~9:2~4:1 is uniformly mixed, and obtains aqueous non-toxic
Permanent seal cooling fluorine silicon antifouling paint.
2. aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint according to claim 1, which is characterized in that the step 1) catalysis
Agent is selected from triethylamine, and triethanolamine, N, N- dimethylethanolamine, diethanol amine, triphenylphosphine, alchlor, additional amount is
Organosilicon and the 1~5% of epoxy resin gross mass in step 1)；Step 1) the reaction condition are as follows: be warming up under inert atmosphere
100~150 DEG C of 4~6h of reaction；Step 1) the epoxy resin be one of epoxy resin E20, E35, E42, E44, E51 or
It is a variety of；Step 1) the organosilicon includes Xing Feilong hydroxy silicon oil 209,3- aminopropyl triethoxysilane.
3. aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint according to claim 1, which is characterized in that step 2) the poly- second
Diol structure formula are as follows:
Wherein a is the integer of 2-25；
Step 2) the epoxy resin is identical as epoxy resin described in step 1)；
Step 2) the catalyst be selected from triethylamine, triethanolamine, N, N- dimethylethanolamine, diethanol amine, triphenylphosphine, three
Aluminium chloride, additional amount are the 1-10% of epoxy resin and polyethylene glycol gross mass in step 2)；
Step 2) the reaction condition are as follows: be warming up to 100~150 DEG C under inert atmosphere protection, react 4~6h.
4. aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint according to claim 1, which is characterized in that the step 3) hydrotropy
Agent is propylene glycol monomethyl ether, 1,4-butanediol, butyl glycol ether, any two or more mixture in n-butanol, cosolvent plus
Enter amount accounts for aqueous epoxy emulsion quality 5~10%；Step 3) emulsification condition are as follows: emulsification revolving speed is 500~1500r/min, cream
The change time is 15~30min；Step 3) the aqueous epoxy emulsion solid content is 50 ± 2%.
5. aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint according to claim 1, which is characterized in that step 4) is described siliceous
Lotion is that waterborne polyester containing silicon emulsion or aqueous polyurethane contains silicon emulsion, wherein waterborne polyester containing silicon emulsion include wide tree GS335,
Guangzhou cobalt general one of 7509 or two kind, aqueous polyurethane include Bayer U54 containing silicon emulsion；Step 4) the organic additive
For ethylene glycol or 1,4- butanediol；Step 4) the surfactant is selected from fatty alcohol polyoxyethylene ether ammonium sulfate, laruyl alcohol sulphur
Sour sodium, nonylphenol polyoxyethylene ether, diglycollic amide glycerol stearate monoesters, alkyl, polyether, dispersing agent NNO, fatty alcohol polyoxy
Vinethene.
6. aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint according to claim 1, which is characterized in that the step 4) hydrotropy
Agent is selected from propylene glycol monomethyl ether, 1,4-butanediol, butyl glycol ether, n-butanol；Step 4) the nano-powder is selected from nano oxidized
Aluminium, nano zine oxide, nano-titanium oxide.
7. aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint according to claim 1, which is characterized in that the step 4) solidification
Agent is polyether-modified Isocyanates curing agent or fatty amines epoxy hardener, and polyether-modified Isocyanates curing agent includes
Polyether-modified isophorone diisocyanate, polyether-modified hexamethylene diisocyanate, polyether-modified toluene di-isocyanate(TDI)
And their trimer derivatives；Fatty amines epoxy hardener includes joining solid BANCO 901, celestial being nation SG-6801, double phoenix
One of QG-628 is several；Step 4) the catalyst is selected from triethylene tetramine, diethylenetriamine, dibutyl tin
One of cinnamic acid tin.
8. aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint according to claim 1, which is characterized in that step 4) is described fluorine-containing
Lotion is fluorine-containing aqueous acrylic emulsion or ptfe emulsion, and wherein fluorine-containing aqueous acrylic emulsion includes that instruction reaches
HD8327, state rise abruptly one or more of in G9010, love jade-like stone Ma DF-01, and ptfe emulsion includes Du Pont TE3859, Du Pont
One of DISP 30LX, 3M TF5032 are several.
9. a kind of preparation method of any aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint of claim 1-8, feature exist
In preparation method is as follows:
1) modifying epoxy resin by organosilicon is prepared: by the organosilicon with following formula I with epoxy resin by group molar ratio X: epoxy
Base=1~2:1 mixing, is added the catalyst reaction (amine contained by hydroxyl and organosilicon in hydroxyl and epoxy group or epoxy
Propyl reaction) obtain modifying epoxy resin by organosilicon EP-Si；
Wherein X is-OH ,-NH2Or-COOH, R1, R2And R3General formula is-O- (CH2)m- H, R4General formula is-O- (CH2)m, m 0-20
Integer, R1, R2And R3In m can be identical or different；
2) prepare emulsifier: by polyethylene glycol with epoxy resin by group molar ratio hydroxyl: epoxy group=1~2:1 is mixed, and is added
Catalyst is reacted (hydroxyl and epoxy group chain extending reaction) and obtains emulsifier EP-PEG；
3) aqueous epoxy emulsion is prepared: by modifying epoxy resin by organosilicon obtained by emulsifier EP-PEG obtained by step 2) and step 1)
EP-Si 1~20:100 in mass ratio mixing, is warming up to 50~100 DEG C, and cosolvent and deionized water is added, obtains after fully emulsified
To aqueous epoxy emulsion；
4) aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint is prepared:
First, second, the third three kinds of components are prepared first:
Component A is mixed to get by the component of following mass percentage: aqueous epoxy emulsion 10~40% obtained by step 3) contains
Silicon emulsion 10~30%, organic additive 10~20%, surfactant 5~10%, cosolvent 5~10%, nano-powder 0.5~
1%, remaining is deionized water, and first component solid content is 40~60%；
Second component: curing agent, catalyst, the two quality is than curing agent: catalyst=1~9:1；
Third component: fluorine-containing latex；
By the first, second, the third three kinds of component first in mass ratio: second: the third=5~9:2~4:1 is uniformly mixed, and obtains aqueous non-toxic
Permanent seal cooling fluorine silicon antifouling paint.
10. a kind of any aqueous non-toxic permanent seal cooling fluorine silicon antifouling paint of claim 1-8 is in marine antifouling and ocean work
The application of the antifouling aspect of journey.
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