CN107652887A - Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent - Google Patents

Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent Download PDF

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CN107652887A
CN107652887A CN201710809362.9A CN201710809362A CN107652887A CN 107652887 A CN107652887 A CN 107652887A CN 201710809362 A CN201710809362 A CN 201710809362A CN 107652887 A CN107652887 A CN 107652887A
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component
mass ratio
reaction
silicone oil
fouling
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CN107652887B (en
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胡建坤
陆阿定
沈思哲
张海春
孙宝库
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Zhejiang Marine Development Research Institute
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Zhejiang Marine Development Research Institute
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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
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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    • 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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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    • C09D5/1618—Non-macromolecular compounds inorganic
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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    • C09D5/1625—Non-macromolecular compounds organic
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
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    • C08L2205/00—Polymer mixtures characterised by other features
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    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses a kind of preparation method of the environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, using allyl polyglycol ether or ethylene glycol monoallyl ether and containing hydrogen silicone oil as initiation material, heating carries out hydrogen silicification reaction, then the fully butyl rubber of swelling dissolving is incorporated in dimethylbenzene, continues reaction and silicon hydrogel resin is made；Keep reaction temperature constant, thixotropic agent, hydroxy silicon oil, 3 hydroxybutyric acid β lactones, the ketone of 4,5 dichloro, 2 n-octyl, 4 isothiazoline 3, artificial camphor and cage modle polysilsesquioxane, stirring reaction are added into gained silicon hydrogel resin, component A is obtained, it is standby；Tetraethyl orthosilicate is well mixed with di-n-butyltin dilaurate, MTES, cyclohexanone, acetylacetone,2,4-pentanedione and dimethylbenzene, obtains B component；By component A and B component according to mass ratio 7~9：1 is well mixed, solidifies 5~8 hours, produces anti-fouling material.

Description

Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent
Technical field
The present invention relates to a kind of anti-fouling material, and in particular to a kind of ring based on silicon hydrogel resin and natural anti-fouling agent Border friendly anti-fouling material.Belong to technical field.
Background technology
Marine biofouling refers to marine microorganism, plant and animal in ship, marine facility adsorption, growth and numerous The biofouling grown and formed, it to the mankind be engaged in Activities of Ocean bring it is many unfavorable.Brushing antifouling paint is as main antifouling Means are worldwide widely used, wherein, it is the most notable with tributyl tin (TBT) and cupric antifouling paint.However, apply Anti-fouling agent in layer can be enriched with by food chain influences human health and ecological safety.In recent years, Marine Environmental Problems are compeled Cutting concern promotes people constantly to study new environmentally friendly antifouling paint.
Hydrogel is a kind of environment-friendly new function high polymer material, it have crosslinking three-dimensional net structure, It can be swelled and not dissolve in water, and large quantity of moisture can be kept.More and more results of study about hydrogel show, Hydrogel is effective against the absorption of protein, is a kind of potential efficient and environmentally friendly novel sea antifouling paint.And it is current, Research on hydrogel is mostly also in theoretical research stage, although having, experimental results demonstrate hydrogel has excellent antiplastering Property and anti-fouling effect, but in the multifarious marine environment of complex biological, the defects of certain is still suffered from, for example, after swelling Mechanical property is poor, with the poor adhesion of coating surface, it is easy to aging the shortcomings of limit the development of hydrogel nonpolluting coating.
The content of the invention
The purpose of the present invention is to overcome above-mentioned the deficiencies in the prior art, there is provided one kind is based on silicon hydrogel resin and day The environmentally friendly anti-fouling material of right anti-fouling agent.
To achieve the above object, the present invention uses following technical proposals：
The preparation method of environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, including it is following Step：
(1) using allyl polyglycol ether or ethylene glycol monoallyl ether and containing hydrogen silicone oil as initiation material, 70 are heated to ~90 DEG C of progress hydrogen silicification reactions, the fully butyl rubber of swelling dissolving is then incorporated in dimethylbenzene, continues reaction 50~70 Minute, silicon hydrogel resin is made；
(2) keep reaction temperature constant, added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acids-β-lactone, DCOIT, artificial camphor and the poly- sesquialter silicon of cage modle Oxygen alkane, stirring reaction 1~2 hour, obtains component A, standby；
(3) by tetraethyl orthosilicate and di-n-butyltin dilaurate, MTES, cyclohexanone, acetylacetone,2,4-pentanedione It is well mixed with dimethylbenzene, obtains B component；
(4) by component A and B component according to mass ratio 7~9：1 is well mixed, solidifies 5~8 hours, produces anti-fouling material；
Wherein, in component A, allyl polyglycol ether or ethylene glycol monoallyl ether, containing hydrogen silicone oil, dimethylbenzene, butyl Rubber, thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acids-β-lactone, DCOIT, conjunction It is 25~75 into the mass ratio of camphor and cage modle polysilsesquioxane：20~30：8~10：4~5：0.5~1.5：18~22：3 ~5：4~6：4~6：0.4~0.6；In B component, tetraethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxy silane Alkane, cyclohexanone, the mass ratio of acetylacetone,2,4-pentanedione and dimethylbenzene are 20~21：0.008~0.012：2~2.2：2.1~2.3：5.7~ 6：27~30.
Preferably, in step (1), the specific method of hydrogen silicification reaction is：By allyl polyglycol ether or ethylene glycol list Allyl ether is configured to mixed liquor with Karstedt catalyst, is slowly added dropwise by constant pressure funnel through 1 hour to 70~90 DEG C containing hydrogen silicone oil in, continue after being added dropwise reaction 3 hours, be down to room temperature.
Preferably, in step (1), the specific method of hydrogen silicification reaction is：By allyl polyglycol ether and Karstedt Catalyst is configured to mixed liquor, is slowly added dropwise by constant pressure funnel through 1 hour into 70~90 DEG C of containing hydrogen silicone oil, is added dropwise After continue reaction 2 hours, add VTES, continue reaction 2 hours, be down to room temperature；Vinyl three The mass ratio of Ethoxysilane and containing hydrogen silicone oil is 9：25.
It is further preferred that the Karstedt catalyst is the xylene solution of mass concentration 2%, the dimethylbenzene is molten The volume mass of liquid and containing hydrogen silicone oil ratio is 10~20 μm of L：25g.
It is further preferred that the hydrogen content of containing hydrogen silicone oil is 0.18% or >=0.6%.
Preferably, in step (2), allyl polyglycol ether or ethylene glycol monoallyl ether, containing hydrogen silicone oil, dimethylbenzene, Butyl rubber, thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acids-β-lactone, the chloro- 2- n-octyls -4- isothiazolines -3- of 4,5- bis- The mass ratio of ketone, artificial camphor and cage modle polysilsesquioxane is 25~75：25：9：4.5：0.5~1.5：20：4：5：5：0.5.
Preferably, iron oxide is also added into step (2) as pigment, the mass ratio of itself and hydroxy silicon oil is 5~6：20.
Preferably, larch extract, nanometer capsaicine and oyster shell powder are also added into step (2), they are with hydroxyl silicon The mass ratio of oil is 3~4：1~2：4~5：20.
Clean, dry, 50~80nm powder obtained by grinding it is further preferred that the oyster shell powder is oyster shell.
Preferably, in step (2), the thixotropic agent is aerosil and polyamide wax, they and hydroxy silicon oil Mass ratio is 15：0.5~1.5：20.
Preferably, in step (2), the viscosity of hydroxy silicon oil is 5000cSt.
Preferably, in step (2), the cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, its molecular formula For (i-Bu)8Si8O12。
Preferably, in step (3), tetraethyl orthosilicate and di-n-butyltin dilaurate, MTES, hexamethylene The mass ratio of ketone, acetylacetone,2,4-pentanedione and dimethylbenzene is 20.4：0.01：2.1：2.2：5.8：28.
Preferably, in step (4), by component A and B component according to mass ratio 8：1 is well mixed.
Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, is prepared by the above method Obtain.
Beneficial effects of the present invention：
The present invention synthesized a kind of silicon hydrogel resin with self-reparing capability, and by being answered with natural anti-fouling agent Close, be prepared into a kind of environment-friendly novel sea antifouling paint.It is specific as follows：
1st, the present invention uses allyl polyglycol ether or ethylene glycol monoallyl ether and containing hydrogen silicone oil, butyl rubber as original Material, using Karstedt catalyst, gradient hydrogen silicification reaction is carried out, improves the adhesive force and weather resisteant of resin.The resin soaks After entering water, the hydrophily flexible chain of pectination can be formed, is advantageous to the lifting of resin antifouling property.
2nd, the present invention uses traditional hydroxy silicon oil and tetraethyl orthosilicate, silica silicon crosslinked action is made full use of, in silicone In hydrogel resin system, a kind of resin network structure of three dimensions crosslinking is constructed.Meanwhile two bays that B component introduces Sour di-n-butyl tin catalyst can also be catalyzed the double-bond polymerization of butyl rubber system remaining, build deeper cross-linked structure. So as to it ensure that hydrogel resin immersion after, while there is extremely strong adhesive force, preferable water-retaining property and lasting stability.
3rd, it is additive using enclosed cage-type silsesquioxane (T8), reduces the surface energy of organic siliconresin, together When assign silicon hydrogel resin certain self-reparing capability, after hydrogel resin inner surface breakage, free T8 can be migrated To damaged face, under the catalytic action of seawater alkaline matter, Si-O-Si enclosed constructions are automatically opened up, silicon occurs with damaged surface Alcohol condensation reaction, new Si-O-Si backbones are formed, so as to be repaired to damaged surface.
4th, it is anti-fouling agent using natural products such as artificial camphor, 3- hydroxybutyric acids-β-lactones, and anti-fouling agent is in hydrogel In resin system, do not discharge substantially, so as to greatly reduce harm of the anti-fouling agent to the marine eco-environment.
5th, present invention further introduces larch extract, nanometer capsaicine and oyster shell powder, they and artificial camphor and 3- hydroxyls The natural anti-fouling agents such as base butenoic acid-β-lactone act synergistically, and improve antifouling property.
Embodiment
With reference to embodiment, the present invention will be further elaborated, it should explanation, the description below merely to The present invention is explained, its content is not defined.
The syntheti c route of embodiment 1 and embodiment 3~5 is as follows：
Wherein, x, y, z and n are >=1 integer.
Embodiment 1：
The preparation method of environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, including it is following Step：
(1) using allyl polyglycol ether and containing hydrogen silicone oil as initiation material, 70 DEG C of progress hydrogen silicification reactions are heated to, so The fully butyl rubber of swelling dissolving is incorporated in dimethylbenzene afterwards, continues reaction 50 minutes, silicon hydrogel resin is made；
(2) keep reaction temperature constant, added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acids-β-lactone, DCOIT, artificial camphor and the poly- sesquialter silicon of cage modle Oxygen alkane, stirring reaction 1 hour, obtains component A, standby；
(3) by tetraethyl orthosilicate and di-n-butyltin dilaurate, MTES, cyclohexanone, acetylacetone,2,4-pentanedione It is well mixed with dimethylbenzene, obtains B component；
(4) by component A and B component according to mass ratio 7：1 is well mixed, solidifies 5 hours, produces anti-fouling material；
Wherein, in component A, allyl polyglycol ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxyl silicon Oil, 3- hydroxybutyric acids-β-lactone, DCOIT, artificial camphor and the poly- sesquialter of cage modle The mass ratio of siloxanes is 25：20：8：4：0.5：18：3：4：4：0.4；In B component, tetraethyl orthosilicate and two positive fourth of tin dilaurate Ji Xi, MTES, cyclohexanone, the mass ratio of acetylacetone,2,4-pentanedione and dimethylbenzene are 20：0.008：2：2.1：5.7：27.
In step (1), the specific method of hydrogen silicification reaction is：Allyl polyglycol ether and Karstedt catalyst are matched somebody with somebody Mixed liquor is set to, was slowly added dropwise by constant pressure funnel through 1 hour into 70 DEG C of containing hydrogen silicone oil, is continued after being added dropwise anti- Answer 3 hours, be down to room temperature.
Karstedt catalyst be mass concentration 2% xylene solution, the body of the xylene solution and containing hydrogen silicone oil Product mass ratio is 10 μm of L：25g.
The hydrogen content of containing hydrogen silicone oil is 0.18%.
Iron oxide is also added into step (2) as pigment, the mass ratio of itself and hydroxy silicon oil is 5：20.
Thixotropic agent is aerosil and polyamide wax, and the mass ratio of they and hydroxy silicon oil is 15：0.5：20.
The viscosity of hydroxy silicon oil is 5000cSt.
Cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, and its molecular formula is (i-Bu)8Si8O12。
In step (4), by component A and B component according to mass ratio 8：1 is well mixed.
Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, is prepared by the above method Obtain.
Embodiment 2：
The preparation method of environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, including it is following Step：
(1) using ethylene glycol monoallyl ether and containing hydrogen silicone oil as initiation material, 90 DEG C of progress hydrogen silicification reactions are heated to, so The fully butyl rubber of swelling dissolving is incorporated in dimethylbenzene afterwards, continues reaction 70 minutes, silicon hydrogel resin is made；
(2) keep reaction temperature constant, added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acids-β-lactone, DCOIT, artificial camphor and the poly- sesquialter silicon of cage modle Oxygen alkane, stirring reaction 2 hours, obtains component A, standby；
(3) by tetraethyl orthosilicate and di-n-butyltin dilaurate, MTES, cyclohexanone, acetylacetone,2,4-pentanedione It is well mixed with dimethylbenzene, obtains B component；
(4) by component A and B component according to mass ratio 9：1 is well mixed, solidifies 8 hours, produces anti-fouling material；
Wherein, in component A, ethylene glycol monoallyl ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxyl silicon Oil, 3- hydroxybutyric acids-β-lactone, DCOIT, artificial camphor and the poly- sesquialter of cage modle The mass ratio of siloxanes is 75：30：10：5：1.5：22：5：6：6：0.6；In B component, tetraethyl orthosilicate and tin dilaurate two are just Butyl tin, MTES, cyclohexanone, the mass ratio of acetylacetone,2,4-pentanedione and dimethylbenzene are 21：0.012：2.2：2.3：6： 30。
In step (1), the specific method of hydrogen silicification reaction is：Ethylene glycol monoallyl ether and Karstedt catalyst are matched somebody with somebody Mixed liquor is set to, was slowly added dropwise into 70~90 DEG C of containing hydrogen silicone oil, is added dropwise follow-up through 1 hour by constant pressure funnel Continuous reaction 3 hours, is down to room temperature.
Karstedt catalyst be mass concentration 2% xylene solution, the body of the xylene solution and containing hydrogen silicone oil Product mass ratio is 10~20 μm of L：25g.
The hydrogen content of containing hydrogen silicone oil is 0.18% or >=0.6%.
Iron oxide is also added into step (2) as pigment, the mass ratio of itself and hydroxy silicon oil is 6：20.
Thixotropic agent is aerosil and polyamide wax, and the mass ratio of they and hydroxy silicon oil is 15：1.5：20.
The viscosity of hydroxy silicon oil is 5000cSt.
Cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, and its molecular formula is (i-Bu)8Si8O12。
In step (3), tetraethyl orthosilicate and di-n-butyltin dilaurate, MTES, cyclohexanone, acetyl The mass ratio of acetone and dimethylbenzene is 20.4：0.01：2.1：2.2：5.8：28.
In step (4), by component A and B component according to mass ratio 8：1 is well mixed.
Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, is prepared by the above method Obtain.
Embodiment 3：
The preparation method of environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, including it is following Step：
(1) using allyl polyglycol ether and containing hydrogen silicone oil as initiation material, 80 DEG C of progress hydrogen silicification reactions are heated to, so The fully butyl rubber of swelling dissolving is incorporated in dimethylbenzene afterwards, continues reaction 60 minutes, silicon hydrogel resin is made；
(2) keep reaction temperature constant, added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acids-β-lactone, DCOIT, artificial camphor and the poly- sesquialter silicon of cage modle Oxygen alkane, stirring reaction 1 hour, obtains component A, standby；
(3) by tetraethyl orthosilicate and di-n-butyltin dilaurate, MTES, cyclohexanone, acetylacetone,2,4-pentanedione It is well mixed with dimethylbenzene, obtains B component；
(4) by component A and B component according to mass ratio 8：1 is well mixed, solidifies 7 hours, produces anti-fouling material；
Wherein, in component A, allyl polyglycol ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxyl silicon Oil, 3- hydroxybutyric acids-β-lactone, DCOIT, artificial camphor and the poly- sesquialter of cage modle The mass ratio of siloxanes is 50：25：9：4.5：1：20：4：5：5：0.5；In B component, tetraethyl orthosilicate and two positive fourth of tin dilaurate Ji Xi, MTES, cyclohexanone, the mass ratio of acetylacetone,2,4-pentanedione and dimethylbenzene are 20.4：0.01：2.1：2.2：5.8： 28。
In step (1), the specific method of hydrogen silicification reaction is：Allyl polyglycol ether and Karstedt catalyst are matched somebody with somebody Mixed liquor is set to, was slowly added dropwise by constant pressure funnel through 1 hour into 80 DEG C of containing hydrogen silicone oil, is continued after being added dropwise anti- Answer 2 hours, add VTES, continue reaction 2 hours, be down to room temperature；VTES with The mass ratio of containing hydrogen silicone oil is 9：25.
Karstedt catalyst be mass concentration 2% xylene solution, the body of the xylene solution and containing hydrogen silicone oil Product mass ratio is 15 μm of L：25g.
Hydrogen content >=0.6% of containing hydrogen silicone oil.
Iron oxide is also added into step (2) as pigment, the mass ratio of itself and hydroxy silicon oil is 5.5：20.
Thixotropic agent is aerosil and polyamide wax, and the mass ratio of they and hydroxy silicon oil is 15：1：20.
The viscosity of hydroxy silicon oil is 5000cSt.
Cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, and its molecular formula is (i-Bu)8Si8O12。
In step (4), by component A and B component according to mass ratio 8：1 is well mixed.
Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, is prepared by the above method Obtain.
Embodiment 4：
The preparation method of environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, including it is following Step：
(1) using allyl polyglycol ether and containing hydrogen silicone oil as initiation material, 80 DEG C of progress hydrogen silicification reactions are heated to, so The fully butyl rubber of swelling dissolving is incorporated in dimethylbenzene afterwards, continues reaction 60 minutes, silicon hydrogel resin is made；
(2) keep reaction temperature constant, added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acids-β-lactone, DCOIT, artificial camphor and the poly- sesquialter silicon of cage modle Oxygen alkane, stirring reaction 1 hour, obtains component A, standby；
(3) by tetraethyl orthosilicate and di-n-butyltin dilaurate, MTES, cyclohexanone, acetylacetone,2,4-pentanedione It is well mixed with dimethylbenzene, obtains B component；
(4) by component A and B component according to mass ratio 8：1 is well mixed, solidifies 7 hours, produces anti-fouling material；
Wherein, in component A, allyl polyglycol ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxyl silicon Oil, 3- hydroxybutyric acids-β-lactone, DCOIT, artificial camphor and the poly- sesquialter of cage modle The mass ratio of siloxanes is 50：25：9：4.5：1：20：4：5：5：0.5；In B component, tetraethyl orthosilicate and two positive fourth of tin dilaurate Ji Xi, MTES, cyclohexanone, the mass ratio of acetylacetone,2,4-pentanedione and dimethylbenzene are 20.4：0.01：2.1：2.2：5.8： 28。
In step (1), the specific method of hydrogen silicification reaction is：Allyl polyglycol ether and Karstedt catalyst are matched somebody with somebody Mixed liquor is set to, was slowly added dropwise by constant pressure funnel through 1 hour into 80 DEG C of containing hydrogen silicone oil, is continued after being added dropwise anti- Answer 2 hours, add VTES, continue reaction 2 hours, be down to room temperature；VTES with The mass ratio of containing hydrogen silicone oil is 9：25.
Karstedt catalyst be mass concentration 2% xylene solution, the body of the xylene solution and containing hydrogen silicone oil Product mass ratio is 15 μm of L：25g.
Hydrogen content >=0.6% of containing hydrogen silicone oil.
Iron oxide is also added into step (2) as pigment, the mass ratio of itself and hydroxy silicon oil is 5.5：20.
Larch extract, nanometer capsaicine and oyster shell powder are also added into step (2), their quality with hydroxy silicon oil Than for 3：1：4：20.Oyster shell powder is that oyster shell is cleaned, dried, 50nm powder obtained by grinding.
Thixotropic agent is aerosil and polyamide wax, and the mass ratio of they and hydroxy silicon oil is 15：1：20.
The viscosity of hydroxy silicon oil is 5000cSt.
Cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, and its molecular formula is (i-Bu)8Si8O12。
In step (4), by component A and B component according to mass ratio 8：1 is well mixed.
Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, is prepared by the above method Obtain.
Embodiment 5：
The preparation method of environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, including it is following Step：
(1) using allyl polyglycol ether and containing hydrogen silicone oil as initiation material, 80 DEG C of progress hydrogen silicification reactions are heated to, so The fully butyl rubber of swelling dissolving is incorporated in dimethylbenzene afterwards, continues reaction 60 minutes, silicon hydrogel resin is made；
(2) keep reaction temperature constant, added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acids-β-lactone, DCOIT, artificial camphor and the poly- sesquialter silicon of cage modle Oxygen alkane, stirring reaction 1 hour, obtains component A, standby；
(3) by tetraethyl orthosilicate and di-n-butyltin dilaurate, MTES, cyclohexanone, acetylacetone,2,4-pentanedione It is well mixed with dimethylbenzene, obtains B component；
(4) by component A and B component according to mass ratio 8：1 is well mixed, solidifies 7 hours, produces anti-fouling material；
Wherein, in component A, allyl polyglycol ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxyl silicon Oil, 3- hydroxybutyric acids-β-lactone, DCOIT, artificial camphor and the poly- sesquialter of cage modle The mass ratio of siloxanes is 50：25：9：4.5：1：20：4：5：5：0.5；In B component, tetraethyl orthosilicate and two positive fourth of tin dilaurate Ji Xi, MTES, cyclohexanone, the mass ratio of acetylacetone,2,4-pentanedione and dimethylbenzene are 20.4：0.01：2.1：2.2：5.8： 28。
In step (1), the specific method of hydrogen silicification reaction is：Allyl polyglycol ether and Karstedt catalyst are matched somebody with somebody Mixed liquor is set to, was slowly added dropwise by constant pressure funnel through 1 hour into 80 DEG C of containing hydrogen silicone oil, is continued after being added dropwise anti- Answer 2 hours, add VTES, continue reaction 2 hours, be down to room temperature；VTES with The mass ratio of containing hydrogen silicone oil is 9：25.
Karstedt catalyst be mass concentration 2% xylene solution, the body of the xylene solution and containing hydrogen silicone oil Product mass ratio is 15 μm of L：25g.
Hydrogen content >=0.6% of containing hydrogen silicone oil.
Iron oxide is also added into step (2) as pigment, the mass ratio of itself and hydroxy silicon oil is 5.5：20.
Larch extract, nanometer capsaicine and oyster shell powder are also added into step (2), their quality with hydroxy silicon oil Than for 4：2：5：20.Oyster shell powder is that oyster shell is cleaned, dried, 80nm powder obtained by grinding.
Thixotropic agent is aerosil and polyamide wax, and the mass ratio of they and hydroxy silicon oil is 15：1：20.
The viscosity of hydroxy silicon oil is 5000cSt.
Cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, and its molecular formula is (i-Bu)8Si8O12。
In step (4), by component A and B component according to mass ratio 8：1 is well mixed.
Environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, is prepared by the above method Obtain.
Comparative example 1
A kind of preparation method of anti-fouling material, comprises the following steps：
(1) using allyl polyglycol ether and containing hydrogen silicone oil as initiation material, 80 DEG C of progress hydrogen silicification reactions are heated to, so The fully butyl rubber of swelling dissolving is incorporated in dimethylbenzene afterwards, continues reaction 60 minutes, silicon hydrogel resin is made；
(2) keep reaction temperature constant, added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil, 4,5- bis- chloro- Kathons, artificial camphor and cage modle polysilsesquioxane, stirring reaction 1 hour, are obtained It is standby to component A；
(3) by tetraethyl orthosilicate and di-n-butyltin dilaurate, MTES, cyclohexanone, acetylacetone,2,4-pentanedione It is well mixed with dimethylbenzene, obtains B component；
(4) by component A and B component according to mass ratio 8：1 is well mixed, solidifies 7 hours, produces anti-fouling material；
Wherein, in component A, allyl polyglycol ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxyl silicon Oil, DCOIT, the mass ratio of artificial camphor and cage modle polysilsesquioxane are 50： 25：9：4.5：1：20：5：5：0.5；In B component, tetraethyl orthosilicate and di-n-butyltin dilaurate, methyltriethoxy silane Alkane, cyclohexanone, the mass ratio of acetylacetone,2,4-pentanedione and dimethylbenzene are 20.4：0.01：2.1：2.2：5.8：28.
In step (1), the specific method of hydrogen silicification reaction is：Allyl polyglycol ether and Karstedt catalyst are matched somebody with somebody Mixed liquor is set to, was slowly added dropwise by constant pressure funnel through 1 hour into 80 DEG C of containing hydrogen silicone oil, is continued after being added dropwise anti- Answer 2 hours, add VTES, continue reaction 2 hours, be down to room temperature；VTES with The mass ratio of containing hydrogen silicone oil is 9：25.
Karstedt catalyst be mass concentration 2% xylene solution, the body of the xylene solution and containing hydrogen silicone oil Product mass ratio is 15 μm of L：25g.
Hydrogen content >=0.6% of containing hydrogen silicone oil.
Iron oxide is also added into step (2) as pigment, the mass ratio of itself and hydroxy silicon oil is 5.5：20.
Thixotropic agent is aerosil and polyamide wax, and the mass ratio of they and hydroxy silicon oil is 15：1：20.
The viscosity of hydroxy silicon oil is 5000cSt.
Cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, and its molecular formula is (i-Bu)8Si8O12。
In step (4), by component A and B component according to mass ratio 8：1 is well mixed.
A kind of anti-fouling material, is prepared by the above method.
Comparative example 2
A kind of preparation method of anti-fouling material, comprises the following steps：
(1) using allyl polyglycol ether and containing hydrogen silicone oil as initiation material, 80 DEG C of progress hydrogen silicification reactions are heated to, so The fully butyl rubber of swelling dissolving is incorporated in dimethylbenzene afterwards, continues reaction 60 minutes, silicon hydrogel resin is made；
(2) keep reaction temperature constant, added into silicon hydrogel resin obtained by step (1) thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acids-β-lactone, 4,5-, bis- chloro- Kathons and cage modle polysilsesquioxane, stirring Reaction 1 hour, obtains component A, standby；
(3) by tetraethyl orthosilicate and di-n-butyltin dilaurate, MTES, cyclohexanone, acetylacetone,2,4-pentanedione It is well mixed with dimethylbenzene, obtains B component；
(4) by component A and B component according to mass ratio 8：1 is well mixed, solidifies 7 hours, produces anti-fouling material；
Wherein, in component A, allyl polyglycol ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxyl silicon Oil, 3- hydroxybutyric acids-β-lactone, DCOIT and cage modle polysilsesquioxane Mass ratio is 50：25：9：4.5：1：20：4：5：0.5；In B component, tetraethyl orthosilicate and di-n-butyltin dilaurate, methyl Triethoxysilane, cyclohexanone, the mass ratio of acetylacetone,2,4-pentanedione and dimethylbenzene are 20.4：0.01：2.1：2.2：5.8：28.
In step (1), the specific method of hydrogen silicification reaction is：Allyl polyglycol ether and Karstedt catalyst are matched somebody with somebody Mixed liquor is set to, was slowly added dropwise by constant pressure funnel through 1 hour into 80 DEG C of containing hydrogen silicone oil, is continued after being added dropwise anti- Answer 2 hours, add VTES, continue reaction 2 hours, be down to room temperature；VTES with The mass ratio of containing hydrogen silicone oil is 9：25.
Karstedt catalyst be mass concentration 2% xylene solution, the body of the xylene solution and containing hydrogen silicone oil Product mass ratio is 15 μm of L：25g.
Hydrogen content >=0.6% of containing hydrogen silicone oil.
Iron oxide is also added into step (2) as pigment, the mass ratio of itself and hydroxy silicon oil is 5.5：20.
Thixotropic agent is aerosil and polyamide wax, and the mass ratio of they and hydroxy silicon oil is 15：1：20.
The viscosity of hydroxy silicon oil is 5000cSt.
Cage modle polysilsesquioxane is isobutyl group cage-type silsesquioxane, and its molecular formula is (i-Bu)8Si8O12。
In step (4), by component A and B component according to mass ratio 8：1 is well mixed.
A kind of anti-fouling material, is prepared by the above method.
Test example
1st, the coating property that the anti-fouling material of embodiment 1~5 or comparative example 1~2 is sprayed to tinplate is investigated, as a result It is shown in Table 1.
The coating property of table 1. compares
As shown in Table 1, the paint film that is formed has good mechanical property and resistance to after the anti-fouling material spraying of embodiment 1~5 Corrosive nature, wearability and adhesive force are also relatively good, and property indices are far superior to comparative example 1 and comparative example 2.
2nd, according to GB/T21805-2008, the extra large hanging plate test of reality of 6 months has been carried out in Zhoushan spiral shell sea of gates domain, the results are shown in Table 2。
The real extra large hanging plate test result of table 2.
From table 2 it can be seen that comparative example 1 omits 3- hydroxybutyric acids-β-lactone, comparative example 2 omits artificial camphor, antifouling Positive effect is deteriorated, and the anti-fouling material of embodiment 1~5 has obvious preferable antifouling property.
Although the above-mentioned embodiment to the present invention is described, not to the limit of the scope of the present invention System, on the basis of technical scheme, those skilled in the art need not pay creative work can make it is each Kind modification is deformed still within protection scope of the present invention.

Claims (10)

1. a kind of preparation method of the environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, its feature It is, comprises the following steps：
（1）Using allyl polyglycol ether or ethylene glycol monoallyl ether and containing hydrogen silicone oil as initiation material, 70~90 are heated to DEG C hydrogen silicification reaction is carried out, is then incorporated in dimethylbenzene the butyl rubber of fully swelling dissolving, continues reaction 50~70 minutes, Silicon hydrogel resin is made；
（2）Keep reaction temperature constant, to step（1）Thixotropic agent, hydroxy silicon oil, 3- hydroxyls are added in gained silicon hydrogel resin Base butenoic acid-β-lactone, 4,5-, bis- chloro- Kathons, artificial camphor and cage modle polysilsesquioxane, Stirring reaction 1~2 hour, obtains component A, standby；
（3）By tetraethyl orthosilicate and di-n-butyltin dilaurate, MTES, cyclohexanone, acetylacetone,2,4-pentanedione and two Toluene is well mixed, and obtains B component；
（4）By component A and B component according to mass ratio 7~9：1 is well mixed, solidifies 5~8 hours, produces anti-fouling material；
Wherein, in component A, allyl polyglycol ether or ethylene glycol monoallyl ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, Thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acids-β-lactone, DCOIT, synthesis camphor tree The mass ratio of brain and cage modle polysilsesquioxane is 25~75：20~30：8~10：4~5：0.5~1.5：18~22：3~5：4 ~6：4~6：0.4~0.6；In B component, tetraethyl orthosilicate and di-n-butyltin dilaurate, MTES, ring The mass ratio of hexanone, acetylacetone,2,4-pentanedione and dimethylbenzene is 20~21：0.008~0.012：2~2.2：2.1~2.3：5.7~6：27 ~30.
2. preparation method according to claim 1, it is characterised in that step（1）In, the specific method of hydrogen silicification reaction It is：Allyl polyglycol ether or ethylene glycol monoallyl ether are configured to mixed liquor with Karstedt catalyst, pass through constant pressure Dropping funel was slowly added dropwise into 70~90 DEG C of containing hydrogen silicone oil through 1 hour, is continued reaction 3 hours after being added dropwise, is down to room Temperature.
3. preparation method according to claim 1, it is characterised in that step（1）In, the specific method of hydrogen silicification reaction It is：Allyl polyglycol ether and Karstedt catalyst are configured to mixed liquor, it is slow through 1 hour by constant pressure funnel It is added dropwise in 70~90 DEG C of containing hydrogen silicone oil, continues reaction 2 hours after being added dropwise, add VTES, Continue reaction 2 hours, be down to room temperature；The mass ratio of VTES and containing hydrogen silicone oil is 9：25.
4. the preparation method according to Claims 2 or 3, it is characterised in that the Karstedt catalyst is mass concentration 2% xylene solution, the volume mass ratio of the xylene solution and containing hydrogen silicone oil is 10~20 μm of L：25g.
5. preparation method according to claim 1, it is characterised in that step（2）In, allyl polyglycol ether or second two Alcohol mono allyl ether, containing hydrogen silicone oil, dimethylbenzene, butyl rubber, thixotropic agent, hydroxy silicon oil, 3- hydroxybutyric acids-β-lactone, 4, The mass ratio of bis- chloro- Kathons of 5-, artificial camphor and cage modle polysilsesquioxane is 25~75： 25：9：4.5：0.5~1.5：20：4：5：5：0.5.
6. preparation method according to claim 1, it is characterised in that step（2）In be also added into iron oxide as pigment, The mass ratio of itself and hydroxy silicon oil is 5~6：20.
7. preparation method according to claim 1, it is characterised in that step（2）In, the thixotropic agent is gas phase titanium dioxide Silicon and polyamide wax, their mass ratioes with hydroxy silicon oil are 15：0.5~1.5：20.
8. preparation method according to claim 1, it is characterised in that step（3）In, tetraethyl orthosilicate and tin dilaurate two Normal-butyl tin, MTES, cyclohexanone, the mass ratio of acetylacetone,2,4-pentanedione and dimethylbenzene are 20.4：0.01：2.1：2.2： 5.8：28.
9. preparation method according to claim 1, it is characterised in that step（4）In, by component A and B component according to quality Than 8：1 is well mixed.
10. a kind of environmentally friendly anti-fouling material based on silicon hydrogel resin and natural anti-fouling agent, is by claim 1 What described method was prepared.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109021629A (en) * 2018-07-12 2018-12-18 中国科学院海洋研究所 A kind of environmentally friendly selfreparing hydrogel anticorrosive paint and its synthetic method
CN109401228A (en) * 2018-11-07 2019-03-01 长沙浩然医疗科技有限公司 A kind of plastic additive and production technology
CN109988445A (en) * 2019-04-09 2019-07-09 浙江国能科技有限公司 A kind of super water paint for going water decontamination to go stain
CN111268959A (en) * 2019-12-02 2020-06-12 哈尔滨工程大学 Concrete for inducing adhesion of marine periphyton and promoting growth and preparation method thereof
CN111718486A (en) * 2020-06-22 2020-09-29 湖北回天新材料股份有限公司 Thixotropic agent and two-component silicone sealant containing same
CN112940610A (en) * 2021-01-17 2021-06-11 浙江大学 Bromo-pyrrole-nitrile grafted silicone hydrogel super-lubricating non-adhesion antifouling coating
CN114716913A (en) * 2022-03-17 2022-07-08 中国船舶重工集团公司第七二五研究所 Amphiphilic antifouling active agent and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4144806A1 (en) * 2021-09-06 2023-03-08 SWISS KRONO Tec AG Composition having antimicrobial properties, especially biocidal properties, for surface coatings on wooden panels

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3470336B2 (en) * 1995-02-20 2003-11-25 ダイキン工業株式会社 Antifouling agent and composition for non-aqueous paint containing the same
CN102344747A (en) * 2010-07-30 2012-02-08 雍飞 Low surface energy organosilicon coating material composition, preparation method, updating method and application thereof
US20150223450A1 (en) * 2012-08-09 2015-08-13 Rohm And Haas Company Coating composition with biocide
CN104927649A (en) * 2015-06-25 2015-09-23 青岛大学 Anti-fouling super-hydrophobic self-cleaning paint and preparation method thereof
CN105219206A (en) * 2014-07-03 2016-01-06 浙江省海洋开发研究院 The preparation method of silicone modified acrylic hydrogel antifouling paint

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3470336B2 (en) * 1995-02-20 2003-11-25 ダイキン工業株式会社 Antifouling agent and composition for non-aqueous paint containing the same
CN102344747A (en) * 2010-07-30 2012-02-08 雍飞 Low surface energy organosilicon coating material composition, preparation method, updating method and application thereof
US20150223450A1 (en) * 2012-08-09 2015-08-13 Rohm And Haas Company Coating composition with biocide
CN105219206A (en) * 2014-07-03 2016-01-06 浙江省海洋开发研究院 The preparation method of silicone modified acrylic hydrogel antifouling paint
CN104927649A (en) * 2015-06-25 2015-09-23 青岛大学 Anti-fouling super-hydrophobic self-cleaning paint and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109021629A (en) * 2018-07-12 2018-12-18 中国科学院海洋研究所 A kind of environmentally friendly selfreparing hydrogel anticorrosive paint and its synthetic method
CN109401228A (en) * 2018-11-07 2019-03-01 长沙浩然医疗科技有限公司 A kind of plastic additive and production technology
CN109988445A (en) * 2019-04-09 2019-07-09 浙江国能科技有限公司 A kind of super water paint for going water decontamination to go stain
CN111268959A (en) * 2019-12-02 2020-06-12 哈尔滨工程大学 Concrete for inducing adhesion of marine periphyton and promoting growth and preparation method thereof
CN111718486A (en) * 2020-06-22 2020-09-29 湖北回天新材料股份有限公司 Thixotropic agent and two-component silicone sealant containing same
CN112940610A (en) * 2021-01-17 2021-06-11 浙江大学 Bromo-pyrrole-nitrile grafted silicone hydrogel super-lubricating non-adhesion antifouling coating
CN114716913A (en) * 2022-03-17 2022-07-08 中国船舶重工集团公司第七二五研究所 Amphiphilic antifouling active agent and preparation method thereof
CN114716913B (en) * 2022-03-17 2023-03-03 中国船舶重工集团公司第七二五研究所 Amphiphilic antifouling active agent and preparation method thereof

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