CN109504275A - A kind of environment-friendly type Marine Antifouling Paint suitable for large ship - Google Patents
A kind of environment-friendly type Marine Antifouling Paint suitable for large ship Download PDFInfo
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- CN109504275A CN109504275A CN201811360507.2A CN201811360507A CN109504275A CN 109504275 A CN109504275 A CN 109504275A CN 201811360507 A CN201811360507 A CN 201811360507A CN 109504275 A CN109504275 A CN 109504275A
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- CN
- China
- Prior art keywords
- environment
- friendly type
- large ship
- antifouling paint
- marine antifouling
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Classifications
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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
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C09D179/085—Unsaturated polyimide precursors
-
- 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
- C09D5/08—Anti-corrosive 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
- 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
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of environment-friendly type Marine Antifouling Paints suitable for large ship, consist of the following components in percentage by weight: epoxy resin 15%-25%, ultra-fine barium sulfate 5%-8%, precipitated calcium carbonate 8%-12%, thixotropic agent 1%-3%, curing agent 5%-10%, film forming catalyst 0.1%-0.2%, algicide 1%-3%, dispersing agent 1%-2%, amine resins 25%-35%, nano silica 0.05%-0.1%, toner 5%-8% and silicon powder surplus.A small amount of film forming catalyst lanthana is added in coating in the present invention, under its catalytic action, intensity and anti-permeability after film forming significantly improve, enhance the surface strength and anti-chloride permeability performance of coating, and nano silica height is incorporated in film surface, facilitate the nano size voids of filled film, enhances film-strength.
Description
Technical field
The present invention relates to anticorrosive paint technology field more particularly to a kind of environment-friendly type marine anticorrosions suitable for large ship
Coating.
Background technique
Marine Antifouling Paint is to be applied to the substance for guaranteeing longer corrosion protection service life in the infrastructure of ocean, energy and steel construction
Surface iron atoms fast reaction, generating has physics, chemical double protection, can long-term resistance to firmly chloride ion corrosion.
Data show that ocean plays the role of the economy and society development in Deposits in Eastern Coastal China area huge.Coastal 12
The land area of province, district and city accounts for national territorial area, and only 14%, GDP but accounts for the 60% of the whole nation.It is within the national marine economy output value 1980
8000000000 yuan, nineteen ninety is 43,800,000,000 yuan, and 2000 are 413,300,000,000 yuan, reaches within 2004 1.3 trillion yuans, reaches 3.8 trillion within 2010
Member, speedup are up to 20% or more.
With the fast development of China's marine economy, ship and ocean engineering facility anti-corrosion have become and are badly in need of solving in development
Important topic, the development prospect of Marine Paints also increasingly had an optimistic view of by people.2010, China's shipbuilding amount was more than Korea Spro for the first time
State leaps to the first in the world.Container makes case amount then from late 1990s, has just been sure to occupy the first in the world, volume of production and marketing accounts at present
The 95% of world's total amount.Since marine paint accounts for 90% or more of whole Marine Paints demands, as shipbuilding amount leaps to head
Position, China has become the country of world ocean weight of coated paint first.China's Marine Paints market scale has surpassed 35,000,000,000 within 2010
Member.
With a large amount of exploitations of offshore oil field, the pipeline for conveying oil gas also occurs in succession.It is reported that China had been on active service
There are about 160 for offshore platform, while a large amount of ships and submarine transport oil pipeline are offshore oil exploitation service.It has visited at present
Bright, China's offshore petroleum resources amount accounts for the 1/4 of national petroleum total output, and the gross reserves that only Bohai Bay Oil is verified at present is just more than
45000000000 tons, and China will invest more than 500 hundred million yuan and build 50 production platforms, 1100 mouthfuls of productions in the Bohai Sea in recent years
Well.
Marine Antifouling Paint currently on the market ignores influence of the use to marine environment of coating, in order to promote coating
Environmental-protecting performance, the present invention provides a kind of environment-friendly type Marine Antifouling Paints suitable for large ship.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of environment-friendly type oceans suitable for large ship
Anticorrosive paint.
Technical scheme is as follows:
A kind of environment-friendly type Marine Antifouling Paint suitable for large ship, consists of the following components in percentage by weight:
Epoxy resin 15%-25%
Ultra-fine barium sulfate 5%-8%
Precipitated calcium carbonate 8%-12%
Thixotropic agent 1%-3%
Curing agent 5%-10%
Film forming catalyst 0.1%-0.2%
Algicide 1%-3%
Dispersing agent 1%-2%
Amine resins 25%-35%
Nano silica 0.05%-0.1%
Toner 5%-8%
Silicon powder surplus.
Preferably, the silicon powder partial size is 800 mesh, and the partial size of ultra-fine barium sulfate is 500 mesh, nano silica.
Preferably, the thixotropic agent is organobentonite.
Preferably, the curing agent is organic acid as curing agent.
Preferably, the film forming catalyst is lanthana.
Preferably, the epoxy resin epoxy equivalent is 3000-4500g/eq.
Preferably, the amine resins are bimaleimide resin.
Bismaleimide (abbreviation BMI) is the another kind of resin system derived from by polyimide resin system, is with horse
Come acid imide (MI) be active end group bifunctional compound, have with mobility similar in epoxy resin and mouldability, can
Machine-shaping is carried out with the similar conventional method of epoxy resin, overcomes the relatively low disadvantage of epoxy resin heat resistance, because
This, is rapidly developed in the latest 20 years and is widely applied.
Bimaleimide resin (BMI) with its excellent heat resistance, electrical insulating property, wave, radiation hardness, anti-flammability,
The features such as good mechanical property and dimensional stability, moulding process is similar to epoxy resin, is widely used in aviation, boat
It, in the industrial circles such as machinery, electronics, resin matrix, high-temperature insulation material and adhesive of advanced composite material etc..
Main performance
(1) heat resistance
BMI due to containing phenyl ring, acid imide heterocycle and crosslink density it is higher and make its solidfied material have excellent heat resistance,
Its Tg is generally higher than 250 DEG C, and use temperature range is 177 DEG C~232 DEG C or so.Ethylenediamine is most stable of in aliphatic BMI,
As starting thermal decomposition temperature (Td) that increases of methylene number will decline.The Td of aromatic series BMI is generally higher than aliphatic
BMI, wherein the Td of 2,4. diaminobenzene classes is higher than other types.In addition, Td and crosslink density have close relationship, certain
Td is increased with the increase of crosslink density in range.
(2) dissolubility
Common BMI monomer cannot be dissolved in common organic as that can only be dissolved in dimethylformamide in acetone, ethyl alcohol, chloroform
(DMF), in the solvent that N-Methyl pyrrolidone (NMP) etc. is highly polar, toxicity is big, price is high.This is because the molecular polarity of BMI
And the symmetry of structure is determined, therefore how to improve dissolubility is modified important content of BMI.
(3) mechanical property
The curing reaction of BMI resin belongs to add-on type polymerization reaction, releases in forming process without low molecule by-product, and hold
It is easy to control.Solidfied material compact structure, defect is few, thus BMI intensity and modulus with higher.But due to the crosslinking of solidfied material
Density is high, molecule chain rigidity is strong and BMl is made to show great brittleness, it shows, and impact strength is poor, elongation at break is small,
Fracture toughness Gic low (< 5J/m2).And poor toughness is exactly to hinder BMI to adapt to high-tech to require, expand the great of new opplication field
Obstacle determines one of BMI application and key problem in technology of development so how to improve toughness just and become.In addition, BMI also have it is excellent
The performances such as electrical property, chemical-resistance and radiation hardness.
The invention has the beneficial effects that:
Bismaleimide is added in coating in the present invention, traditional bismaleimide has heat resistance, electrical isolation
Property, wave, radiation hardness, anti-flammability, good mechanical property and dimensional stability, but film strength has no advantage；This hair
It is bright it is middle a small amount of film forming catalyst lanthana is added, it is strong after bismaleimide and epoxy resin film forming under its catalytic action
Degree and anti-permeability significantly improve, and enhance the surface strength and anti-chloride permeability performance of coating, and nano silica
Height is incorporated in film surface, facilitates the nano size voids of filled film, enhances film-strength.
Specific embodiment
Embodiment 1:
A kind of environment-friendly type Marine Antifouling Paint suitable for large ship, consists of the following components in percentage by weight:
Epoxy resin 18%
Ultra-fine barium sulfate 6%
Precipitated calcium carbonate 10%
Thixotropic agent 2%
Curing agent 7%
Film forming catalyst 0.15%
Algicide 1.5%
Dispersing agent 1.5%
Amine resins 28%
Nano silica 0.07%
Toner 6%
Silicon powder surplus.
The silicon powder partial size is 800 mesh, and the partial size of ultra-fine barium sulfate is 500 mesh, nano silica.
The thixotropic agent is organobentonite.
The curing agent is organic acid as curing agent.
The film forming catalyst is lanthana.
The epoxy resin epoxy equivalent is 3000-4500g/eq.
The amine resins are bimaleimide resin.
Embodiment 2:
A kind of environment-friendly type Marine Antifouling Paint suitable for large ship, consists of the following components in percentage by weight:
Epoxy resin 25%
Ultra-fine barium sulfate 5%
Precipitated calcium carbonate 12%
Thixotropic agent 1%
Curing agent 10%
Film forming catalyst 0.1%
Algicide 3%
Dispersing agent 1%
Amine resins 35%
Nano silica 0.05%
Toner 8%
Silicon powder surplus.
The silicon powder partial size is 800 mesh, and the partial size of ultra-fine barium sulfate is 500 mesh, nano silica.
The thixotropic agent is organobentonite.
The curing agent is organic acid as curing agent.
The film forming catalyst is lanthana.
The epoxy resin epoxy equivalent is 3000-4500g/eq.
The amine resins are bimaleimide resin.
Embodiment 3:
A kind of environment-friendly type Marine Antifouling Paint suitable for large ship, consists of the following components in percentage by weight:
Epoxy resin 15%
Ultra-fine barium sulfate 8%
Precipitated calcium carbonate 8%
Thixotropic agent 3%
Curing agent 5%
Film forming catalyst 0.2%
Algicide 1%
Dispersing agent 2%
Amine resins 25
Nano silica 0.1%
Toner 5%
Silicon powder surplus.
The silicon powder partial size is 800 mesh, and the partial size of ultra-fine barium sulfate is 500 mesh, nano silica.
The thixotropic agent is organobentonite.
The curing agent is organic acid as curing agent.
The film forming catalyst is lanthana.
The epoxy resin epoxy equivalent is 3000-4500g/eq.
The amine resins are bimaleimide resin.
Comparative example 1
By the lanthana removal in embodiment 1, remaining proportion and preparation method are constant.
Comparative example 2
By the bimaleimide resin removal in embodiment 1, remaining proportion and preparation method are constant.
The performance of the sample of embodiment 1-3 and comparative example 1-2 is tested below, specific test result is shown in Table 1.
Table 1: the performance test results of coating sample；
| Adhesive force | Surface drying/min | Film formation compactness | |
| Embodiment 1 | 100 | <30min | Fenestra < 1nm |
| Embodiment 2 | 100 | <30min | Fenestra < 1nm |
| Embodiment 3 | 100 | <30min | Fenestra < 1nm |
| Comparative example 1 | 100 | <30min | Fenestra > 30nm |
| Comparative example 2 | 100 | <30min | Fenestra > 10nm |
The coating sample of each embodiment and comparative example: being sprayed on the iron sheet surrounded surface of 200mm × 200mm by test 2, is applied
The dry thickness of layer is 5mm；Test block is put into the testing cassete of 200mm × 200mm, is poured into seawater (real sea water is derived from Shanghai), often
The fresh seawater of replacement in 1 month, takes out after 24 months.Water soluble chloride ion average mass fraction in coating is investigated,
Test result such as table 2.
Table 2: the sea water resistance test data of coating sample；
| Chloride ion average mass fraction % | |
| Before test | It is not detected |
| Embodiment 1 | It is not detected |
| Embodiment 2 | It is not detected |
| Embodiment 3 | It is not detected |
| Comparative example 1 | 0.327 |
| Comparative example 2 | 0.187 |
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of environment-friendly type Marine Antifouling Paint suitable for large ship, which is characterized in that by the group of following weight percent
Part composition:
Epoxy resin 15%-25%
Ultra-fine barium sulfate 5%-8%
Precipitated calcium carbonate 8%-12%
Thixotropic agent 1%-3%
Curing agent 5%-10%
Film forming catalyst 0.1%-0.2%
Algicide 1%-3%
Dispersing agent 1%-2%
Amine resins 25%-35%
Nano silica 0.05%-0.1%
Toner 5%-8%
Silicon powder surplus.
2. being suitable for the environment-friendly type Marine Antifouling Paint of large ship as described in claim 1, which is characterized in that the silicon is micro-
Powder diameter is 800 mesh, and the partial size of ultra-fine barium sulfate is 500 mesh, nano silica.
3. being suitable for the environment-friendly type Marine Antifouling Paint of large ship as described in claim 1, which is characterized in that the touching
Change agent is organobentonite.
4. being suitable for the environment-friendly type Marine Antifouling Paint of large ship as described in claim 1, which is characterized in that described consolidates
Agent is organic acid as curing agent.
5. as described in claim 1 be suitable for large ship environment-friendly type Marine Antifouling Paint, which is characterized in that it is described at
Film catalyst is lanthana.
6. being suitable for the environment-friendly type Marine Antifouling Paint of large ship as described in claim 1, which is characterized in that the ring
Oxygen resin epoxy equivalent weight is 3000-4500g/eq.
7. being suitable for the environment-friendly type Marine Antifouling Paint of large ship as described in claim 1, which is characterized in that the amine
Resinoid is bimaleimide resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811360507.2A CN109504275A (en) | 2018-11-15 | 2018-11-15 | A kind of environment-friendly type Marine Antifouling Paint suitable for large ship |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811360507.2A CN109504275A (en) | 2018-11-15 | 2018-11-15 | A kind of environment-friendly type Marine Antifouling Paint suitable for large ship |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109504275A true CN109504275A (en) | 2019-03-22 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811360507.2A Pending CN109504275A (en) | 2018-11-15 | 2018-11-15 | A kind of environment-friendly type Marine Antifouling Paint suitable for large ship |
Country Status (1)
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| CN (1) | CN109504275A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112251086A (en) * | 2020-10-23 | 2021-01-22 | 湖州汇邦环保科技有限公司 | Environment-friendly marine anticorrosive paint suitable for underwater construction |
| CN112251126A (en) * | 2020-10-29 | 2021-01-22 | 浩力森化学科技（江苏）有限公司 | Water-based environment-friendly high-performance low-temperature coating and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530921A (en) * | 2014-12-30 | 2015-04-22 | 厦门双瑞船舶涂料有限公司 | Method for preparing epoxy heavy corrosion-resistant paint with toughness |
-
2018
- 2018-11-15 CN CN201811360507.2A patent/CN109504275A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530921A (en) * | 2014-12-30 | 2015-04-22 | 厦门双瑞船舶涂料有限公司 | Method for preparing epoxy heavy corrosion-resistant paint with toughness |
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| 中国科学技术协会: "《2016-2017稀土科学技术学科发展报告》", 30 June 2018, 科学普及出版社 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112251086A (en) * | 2020-10-23 | 2021-01-22 | 湖州汇邦环保科技有限公司 | Environment-friendly marine anticorrosive paint suitable for underwater construction |
| CN112251126A (en) * | 2020-10-29 | 2021-01-22 | 浩力森化学科技（江苏）有限公司 | Water-based environment-friendly high-performance low-temperature coating and preparation method thereof |
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Application publication date: 20190322 |
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