CN104830190A - Sustained-release anti-fouling paint and preparation method thereof - Google Patents

Sustained-release anti-fouling paint and preparation method thereof Download PDF

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Publication number
CN104830190A
CN104830190A CN201510267685.0A CN201510267685A CN104830190A CN 104830190 A CN104830190 A CN 104830190A CN 201510267685 A CN201510267685 A CN 201510267685A CN 104830190 A CN104830190 A CN 104830190A
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CN
China
Prior art keywords
preparation
composite material
antifouling
hydrotalcite composite
antifouling paint
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Pending
Application number
CN201510267685.0A
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Chinese (zh)
Inventor
孙智勇
蔺存国
郑纪勇
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725th Research Institute of CSIC
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725th Research Institute of CSIC
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Priority to CN201510267685.0A priority Critical patent/CN104830190A/en
Publication of CN104830190A publication Critical patent/CN104830190A/en
Pending legal-status Critical Current

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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
    • C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
    • C09D193/04—Rosin
    • 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
    • C09D115/00—Coating compositions based on rubber derivatives
    • C09D115/02—Rubber derivatives containing halogen
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention belongs to the technical field of ocean engineering anti-fouling paint preparation, and particularly relates to sustained-release anti-fouling paint and a preparation method thereof. The preparation method comprises the following steps of: firstly preparing an anti-fouling molecule intercalated hydrotalcite composite material by adopting an anti-fouling molecule intercalated hydrotalcite composite material and a preparation method thereof which are disclosed by the Chinese patent 201410360490.6; then selecting and adding dimethylbenzene and methylbenzene to a reaction kettle with a stirrer, a condensate return device and a thermometer for reaction according to a set weight ratio; then adding chlorinated rubber, polymethyl methacrylate and rosin, and stirring the mixture so as to be sufficiently dissolved; then adding dioctyl phthalate, the anti-fouling molecule intercalated hydrotalcite composite material, iron oxide red, talcum powder and zinc oxide, and stirring the mixture so that the components are uniformly dispersed; and finally filtering the mixture by using a 100-mesh filter so as to obtain the anti-fouling paint. The preparation method is simple, environment-friendly and efficient, and can be widely applied to the anti-fouling treatment of ocean engineering and facilitates of ships, harbors, wharfs and the like.

Description

A kind of control release type antifouling paint and preparation method thereof
Technical field:
The invention belongs to oceanographic engineering antifouling paint preparing technical field, be specifically related to a kind of control release type antifouling paint and preparation method thereof, for the antifouling process of the oceanographic engineerings such as boats and ships, harbour, harbour and facility.
Background technology:
The oceanographic engineerings such as boats and ships, harbour, harbour be positioned at gauging line with lower part long-term and contact with sea water, be subject to that the corrosion of seawater and halobiontic attachment cause boats and ships to be advanced being obstructed, the speed of a ship or plane declines, increase fuel oil consumption, quickenings of shell corrosion speed, the breaking-up of Wharf Platform facility, power plant cooling water pipeline obstruction, destruction material or works surface anticorrosion coating, affect the security of oceanographic engineering, the appearance of above problem can be prevented at the surface-coated marine antifouling coating of the oceanographic engineerings such as boats and ships, harbour, harbour; Marine antifouling coating is a kind of speciality coating, its Main Function is progressively oozing out by stain control agent in paint film, have an effect with marine organisms, kill or drive away marine organisms, thus stop marine organisms to be attached to material surface, prevent stained to oceanographic engineerings such as boats and ships, harbour, harbours of marine organisms; At present, Marine Paints mixes wherein to have and suppresses the stain control agent such as organic tin, cupric class, organic zinc class of marine organisms attachment to kill or drive away halobiontic effect to reach, but, violent release phenomenon is there is in stain control agent at the release initial stage, discharge fast with the amount far exceeding effective concentration, cause the release of stain control agent uncontrolled, lost efficacy at short notice, cause the waste of antifouling paint.
Paeonol (Paeonolum) is white or the glossiness needle crystal of micro-yellow, colorless needle crystals (ethanol), fusing point 49 DEG C-51 DEG C, smell is special, taste is micro-peppery, be soluble in ethanol and methyl alcohol, be dissolved in ether, acetone, benzene, in chloroform and dithiocarbonic anhydride, slightly water-soluble, dissolve in the hot water, be insoluble to cold water, can volatilize with water vapor, Paeonol is a kind of Chinese medicinal materials extracted from the dry root skin from ranunculaceae peony, there is analgesia, anti-inflammatory, antipyretic and suppress allergic effect, research shows: Paeonol has the performance of significant anti-biofouling, it is a kind of environment amenable anti-fouling material, hydrotalcite intercalation material (LDHs) is a series of supramolecular materials assembled by hydrotalcite and houghite compound intercalation, it is the novel inorganic functional materials that a class has laminate structure, belong to anion type laminated compound, LDHs laminate species of metal ion and ratio can modulations, interlayer anion has interchangeability, its chemical stability is good, there is superpower heat resistanceheat resistant performance, when being heated to 200 DEG C, LDHs only loses interlayer moisture, when being heated to 250 ~ 450 DEG C, LDHs loses more moisture, when being heated to 450 ~ 500 DEG C, LDHs generates bimetal composite oxide, when Heating temperature is more than 600 DEG C, the metal oxide formed after LDHs decomposes starts sintering, therefore, research and development one can control stain control agent rate of release, improves stain control agent utilization ratio, and extend effect of antifouling phase, control release type antifouling paint of environmental protection and preparation method thereof, has vast potential for future development and using value.
Summary of the invention:
The object of the invention is to the shortcoming overcoming prior art existence, research and development one can control stain control agent rate of release, improves stain control agent utilization ratio, extends effect of antifouling phase, control release type antifouling paint of environmental protection and preparation method thereof.
To achieve these goals, the control release type antifouling paint weight ratio proportioning component that the present invention relates to is: dimethylbenzene 13-17 part, toluene 7-13 part, chlorinated rubber 3-7 part, polymethylmethacrylate 4-6 part, rosin 4-7 part, dioctyl phthalate (DOP) 3-5 part, antifouling molecule intercalation hydrotalcite composite material 32-50 part, red iron oxide 4-6 part, talcum powder 0-2 part and zinc oxide 4-6 part.
The control release type antifouling paint preparation method that the present invention relates to comprises the preparation of antifouling molecule intercalation hydrotalcite composite material and two steps prepared by antifouling paint:
(1), antifouling molecule intercalation hydrotalcite composite material preparation
A kind of antifouling molecule intercalation hydrotalcite composite material and preparation method thereof disclosed in Chinese patent 201410360490.6 is adopted to prepare antifouling molecule intercalation hydrotalcite composite material;
(2), antifouling paint preparation
Dimethylbenzene 13-17 part is chosen and toluene 7-13 part joins with agitator according to weight ratio proportioning, in the reactor of condensation reflux device and thermometer, setting agitator speed is 200-10000r/min, react 1 hour at normal temperatures, add chlorinated rubber 3-7 part again, polymethylmethacrylate 4-6 part and rosin 4-7 part, stir the mixture and make it fully dissolve, add dioctyl phthalate (DOP) 3-5 part again, antifouling molecule intercalation hydrotalcite composite material 32-50 part, red iron oxide 4-6 part, talcum powder 0-2 part and zinc oxide 4-6 part, stir the mixture and make each component dispersed, then 100 object metre filter mixtures are used, obtain antifouling paint.
The antifouling molecule intercalation hydrotalcite composite material particle diameter that the present invention relates to is less than 20 μm.
The present invention compared with prior art, adopt and prepare controllable type antifouling paint based on the controlled release composite material of Paeonol and derivative intercalated houghite thereof, make the release rate of stain control agent in antifouling paint controlled, antifouling phase effect extends, utilization ratio improves, and its preparation method is simple, environment-friendly high-efficiency, cheap, there is good application and development prospect and potential economic benefit.
Embodiment:
Below by embodiment, the invention will be further described.
Embodiment 1:
The control release type antifouling paint preparation method that the present embodiment relates to comprises the preparation of antifouling molecule intercalation hydrotalcite composite material and two steps prepared by antifouling paint:
(1), antifouling molecule intercalation hydrotalcite composite material preparation
A kind of antifouling molecule intercalation hydrotalcite composite material and preparation method thereof disclosed in Chinese patent 201410360490.6 is adopted to prepare antifouling molecule intercalation hydrotalcite composite material;
(2), antifouling paint preparation
Choosing dimethylbenzene 9g and toluene 9g joins in the reactor with agitator, condensation reflux device and thermometer, setting agitator speed is 5000r/min, react 1 hour at normal temperatures, add chlorinated rubber 6g, polymethylmethacrylate 5g and rosin 7g again, stir the mixture and make it fully dissolve, add dioctyl phthalate (DOP) 5g, antifouling molecule intercalation hydrotalcite composite material 45g, red iron oxide 6g, talcum powder 2g and zinc oxide 6g again, stir the mixture and make each component dispersed, then use 100 object metre filter mixtures, obtain antifouling paint.
The antifouling molecule intercalation hydrotalcite composite material particle diameter that the present embodiment relates to is less than 20 μm.
Embodiment 2:
The control release type antifouling paint preparation method that the present embodiment relates to is identical with embodiment 1 with obtained control release type antifouling paint main component; Step (2) joins in the reactor with agitator, condensation reflux device and thermometer for choosing dimethylbenzene 13g and toluene 13g, setting agitator speed is 200r/min, react 1 hour at normal temperatures, add chlorinated rubber 3g, polymethylmethacrylate 6g and rosin 4g again, stir the mixture and make it fully dissolve, add dioctyl phthalate (DOP) 3g, antifouling molecule intercalation hydrotalcite composite material 32g, red iron oxide 4g and zinc oxide 5g again, stir the mixture and make each component dispersed, then use 100 object metre filter mixtures, obtain antifouling paint.
Embodiment 3:
The control release type antifouling paint preparation method that the present embodiment relates to is identical with embodiment 1 with obtained control release type antifouling paint main component, step (2) is for choosing dimethylbenzene 17g and toluene 7g joins with agitator, in the reactor of condensation reflux device and thermometer, setting agitator speed is 10000r/min, react 1 hour at normal temperatures, add chlorinated rubber 7g again, polymethylmethacrylate 4g and rosin 6g, stir the mixture and make it fully dissolve, add dioctyl phthalate (DOP) 4g again, antifouling molecule intercalation hydrotalcite composite material 50g, red iron oxide 5g, talcum powder 1g and zinc oxide 4g, stir the mixture and make each component dispersed, then 100 object metre filter mixtures are used, obtain antifouling paint.
Embodiment 4:
The control release type antifouling paint preparation method that the present embodiment relates to is identical with embodiment 1 with obtained control release type antifouling paint main component; Step (2) is for choosing methacrylate-acrylic acid phenyl ester (1:1) multipolymer 65g, colloid silica 2.5g, antifouling molecule intercalation hydrotalcite composite material 18g, talcum powder 1g, dimethylbenzene 9.5g and ferric oxide 3g, put into dispersion machine after mixing to shake 2-3 hour and make it grind evenly, then use 100 object metre filter mixtures, obtain antifouling paint.

Claims (4)

1. a control release type antifouling paint, is characterized in that this control release type antifouling paint weight ratio proportioning component is: dimethylbenzene 13-17 part, toluene 7-13 part, chlorinated rubber 3-7 part, polymethylmethacrylate 4-6 part, rosin 4-7 part, dioctyl phthalate (DOP) 3-5 part, antifouling molecule intercalation hydrotalcite composite material 32-50 part, red iron oxide 4-6 part, talcum powder 0-2 part and zinc oxide 4-6 part.
2. a preparation method for control release type antifouling paint, is characterized in that specifically comprising the preparation of antifouling molecule intercalation hydrotalcite composite material and two steps prepared by antifouling paint:
(1), antifouling molecule intercalation hydrotalcite composite material preparation
A kind of antifouling molecule intercalation hydrotalcite composite material and preparation method thereof disclosed in Chinese patent 201410360490.6 is adopted to prepare antifouling molecule intercalation hydrotalcite composite material;
(2), antifouling paint preparation
Dimethylbenzene 13-17 part is chosen and toluene 7-13 part joins with agitator according to weight ratio proportioning, in the reactor of condensation reflux device and thermometer, setting agitator speed is 200-10000r/min, react 1 hour at normal temperatures, add chlorinated rubber 3-7 part again, polymethylmethacrylate 4-6 part and rosin 4-7 part, stir the mixture and make it fully dissolve, add dioctyl phthalate (DOP) 3-5 part again, antifouling molecule intercalation hydrotalcite composite material 32-50 part, red iron oxide 4-6 part, talcum powder 0-2 part and zinc oxide 4-6 part, stir the mixture and make each component dispersed, then 100 object metre filter mixtures are used, obtain antifouling paint.
3. control release type antifouling paint according to claim 1, is characterized in that described antifouling molecule intercalation hydrotalcite composite material particle diameter is less than 20 μm.
4. the preparation method of control release type antifouling paint according to claim 2, is characterized in that described antifouling molecule intercalation hydrotalcite composite material particle diameter is less than 20 μm.
CN201510267685.0A 2015-05-22 2015-05-22 Sustained-release anti-fouling paint and preparation method thereof Pending CN104830190A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0084782A1 (en) * 1982-01-12 1983-08-03 Mitsubishi Rayon Co., Ltd. Antifouling coating composition
CN102391782A (en) * 2011-10-26 2012-03-28 陈瑜 Antifouling paint for ship bottoms
CN102558989A (en) * 2010-12-09 2012-07-11 海洋化工研究院 Anti-fouling coating material with excellent compatibility and use thereof
CN104140704A (en) * 2014-07-28 2014-11-12 中国船舶重工集团公司第七二五研究所 Anti-fouling molecule intercalation hydrotalcite composite material and preparing method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0084782A1 (en) * 1982-01-12 1983-08-03 Mitsubishi Rayon Co., Ltd. Antifouling coating composition
CN102558989A (en) * 2010-12-09 2012-07-11 海洋化工研究院 Anti-fouling coating material with excellent compatibility and use thereof
CN102391782A (en) * 2011-10-26 2012-03-28 陈瑜 Antifouling paint for ship bottoms
CN104140704A (en) * 2014-07-28 2014-11-12 中国船舶重工集团公司第七二五研究所 Anti-fouling molecule intercalation hydrotalcite composite material and preparing method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
朱洪法编著: "《精细化工产品配方与制造（第三册）》", 31 August 2002, 金盾出版社 *

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