CN102702422B - Preparation method of bipolar ionic type antifouling additive - Google Patents
Preparation method of bipolar ionic type antifouling additive Download PDFInfo
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- CN102702422B CN102702422B CN201210200584.8A CN201210200584A CN102702422B CN 102702422 B CN102702422 B CN 102702422B CN 201210200584 A CN201210200584 A CN 201210200584A CN 102702422 B CN102702422 B CN 102702422B
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- butyl acrylate
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Abstract
The invention relates to a preparation method of a bipolar ionic type antifouling additive and belongs to the technical field of ocean antifouling materials. The additive is prepared by reactants through free radical copolymerization reaction, wherein the reactants consist of butyl acrylate, polymerizable-double-bond containing silane coupling agents and methylacryloyl ethyl sulphobetaine, acetone accounts for 10 to 40 mass percent of mixed solvents in the copolymerization reaction, the temperature of the copolymerization reaction is 65 to 80 DEG C, and the reaction time is 1.5 to 3.5 hours, in the reactants, the mol ratio of the butyl acrylate to the methylacryloyl ethyl sulphobetaine is 1:1-2:1, the mol ratio of the polymerizable-double-bond containing silane coupling agents to the methylacryloyl ethyl sulphobetaine is 1:10-4:10, the additive is stored in a sealed way, and the additive is mainly added into antifouling paint prepared by using condensation organic silicon elastic body as film formers. The preparation method has the advantages that the process is simple, the operation is safe and reliable, the product quality is good, the environment-friendly effect is realized, nontoxicity is realized, and good antifouling performance is realized.
Description
Technical field:
The present invention relates to the preparation method of a kind of pair of property ionic antifoulant additive, particularly a kind of synthetic process that can form two antifouling microcell antifoulant additives of property ionic based on trimethyl-glycine on antifouling coating surface, belongs to marine anti-pollution material technology field.
Background technology:
Marime fouling has huge harm to marine ship and facility, can increase the running resistance of boats and ships, have a strong impact on the route speed of boats and ships, increase fuel oil consumption, also can destroy the corrosion protection coating on boats and ships and works surface simultaneously, thereby cause the corrosion breakage on hull and works surface, have a strong impact on its security; Can cause maritime facilities seawaterline by fouling organism, to be stopped up and works surface corrosion and structure deteriorate simultaneously, therefore find suitable approach and prevent that marine biofouling from having very important significance.Be used at present preventing that the main path of sea marine organism pollution from being the external coating antifouling paint at boats and ships housing and marine structure, traditional organotin self polishing copolymer antifouling paint is because meeting causes accumulation in vivo with in ocean environment, cause the gender variation of oyster, blood clam and mussel and housing distortion, the serious harm marine eco-environment and human health and disabled.In recent years, research institution and antifouling paint manufacturer have developed a series of nontoxic or low-toxicity anti-fouling coating both at home and abroad, mainly comprise low surface energy class antifouling paint and tin-free self-polishing class antifouling paint etc., low surface energy anti-fouling paint is by utilizing the low surface energy feature of anti-fouling material, suppress biological attachment, reach antifouling object, but this class material still has fouling organism in actual applications, adhere to generation, also need to remove by external force; Tin-free Spc Anti-fouling Paint, by adding nontoxic or low toxicity high-efficiency pollution-proof agent, reaches good antifouling object, but antifouling phase effect is shorter, expends highlyer, therefore by research, finds new nontoxic, long-acting and anti-fouling agent and is very important.
At present, international numerous scientific research institution is by the unremitting research to anti-soil technology, build consensus gradually: because sea marine organism pollution occurs at material surface, the behavior of adhering to of fouling organism in the character remarkably influenced of material surface, as the microscopic appearance of material surface, surface energy and chemical property etc.By building aqueous gel surface, microcell gel area and double ion water-wetted surface at coating surface, carrying out antifouling research, is forward position and the hot fields of current marine anti-pollution technical study, has produced a series of new technology, novel method.The anti-fouling material prepared due to the method is nontoxic, antifouling property well has broad application prospects.The organosilicon pollution release type antifouling paint of new generation of international coatings company exploitation is by add fluorine-containing polyglycol ether in coating, can form hydrophilic microcell, special surface that hydrophobic microcell is alternate at coating surface, reaches the object that improves pollution release performance.The people such as the Paul T.Charles of United States Naval Research Laboratory biology/molecular science and engineering center reach the object that reduces protein adsorption by poly ethyldiol modified carbopol gel; The people such as the John A.Finlay of University of Birmingham reach by polyoxyethylene glycol being assembled in to material surface formation wetting ability unimolecular layer the object that inhibition fouling organism ulva spores adheres to.Trimethyl-glycine has better antifouling property owing to can forming double ion hydrophilic surface, and external pertinent literature has been inferred its antifouling mechanism by theory, but concrete action principle is still very not clear and definite, relevant antifouling patent rare report at home and abroad.
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, seek a kind of two property ionic antifoulant additives of preparation, disabled for current organotin stain control agent, Red copper oxide and organic biocide exist comparatively serious to environmental destruction, simple bioantifouling agent is in use subject to the impact of environment for use condition larger, simple low surface energy anti-fouling material need to can be realized the shortcomings such as the final removing to some settled organismes by external force again, a kind of additive that can form two antifouling microcells of property ionic on antifouling coating surface based on material self-characteristic is provided, can in seawater, migrate to gradually antifouling coating surface, form two property ion antifouling surfaces and reach antifouling object, environmentally friendly, nontoxic, there is good antifouling property, can be applied to and prepare marine antifouling coating.
To achieve these goals, the additive the present invention relates to is by butyl acrylate, be prepared from by free radicals copolymerization reaction containing silane coupling agent and the methacryloyl ethyl sultaine anabolic reaction thing of polymerizable double bond; The silane coupling agent containing polymerizable double bond of copolyreaction comprises γ-methacryloxypropyl trimethoxy silane and vinyltriethoxysilane; Copolyreaction solvent for use is the mixed solvent of acetone and ethylene glycol composition, and wherein acetone accounts for the 10-40% of mixed solvent mass percent; The temperature of described copolyreaction is 65～80 ℃, and the reaction times is 1.5～3.5 hours; Described by butyl acrylate, containing in the silane coupling agent of polymerizable double bond and reactant that methacryloyl ethyl sultaine forms, the mol ratio of butyl acrylate and methacryloyl ethyl sultaine is 1:1～2:1; Containing the silane coupling agent of polymerizable double bond and the mol ratio of methacryloyl ethyl sultaine, be 1:10～4:10; The preserving type of prepared additive is airtight preservation; It is in the antifouling paint prepared of film forming matter that additive mainly adds to by condensed type organic silicon elastomerics.
The present invention compared with prior art, by migrate to gradually antifouling coating surface in seawater, form two property ion antifouling surfaces and reach antifouling object, its preparation technology is simple, principle of operation is safe and reliable, good product quality, and effect is good, environmentally friendly and nontoxic, there is good antifouling property.
Embodiment:
Below by embodiment, the invention will be further described.
Embodiment 1: the preparation of the two property ionic antifoulant additives of trimethyl-glycine
In the 23.6g mixed solvent that the acetone that it is 40% that the present embodiment is first dissolved into by mass percent by 0.082g Diisopropyl azodicarboxylate, the positive Dodecyl Mercaptan of 40 μ l, 60% ethylene glycol form, make A solution; Getting 3.54g A solution joins in tri-mouthfuls of round-bottomed flasks of 250ml that whipping appts, condenser, thermometer are housed, be warming up to 80 ℃, in 10 minutes backward there-necked flasks, drip the mixing solutions by 0.01 mol propylene acid butyl ester, 0.002 molar ethylene ethyl triethoxy silicane alkane, 0.005 mole of methacryloyl ethyl sultaine and 17.7gA solution composition; After dripping half an hour, drip again remaining A solution; Then continue at 80 ℃ of temperature insulation reaction and after 3.5 hours, obtain homogeneous transparent polymers soln and be antifoulant additive, by airtight this additive preservation, for the preparation of marine antifouling coating.
Embodiment 2: the preparation of the two property ionic antifoulant additives of trimethyl-glycine
In the 20.24g mixed solvent that the acetone that it is 10% that the present embodiment is first dissolved into by mass percent by 0.041g Diisopropyl azodicarboxylate, the positive Dodecyl Mercaptan of 20 μ l, 90% ethylene glycol form, make A solution.Getting 3.04g A solution joins in tri-mouthfuls of round-bottomed flasks of 250ml that whipping appts, condenser and thermometer are housed, be warming up to 65 ℃, in 10 minutes backward there-necked flasks, drip the mixing solutions by 0.005 mol propylene acid butyl ester, 0.0005 mole of γ-methacryloxypropyl trimethoxy silane, 0.005 mole of methacryloyl ethyl sultaine and 15.18gA solution composition.After dripping half an hour, drip remaining A solution; Then continue at 65 ℃ of temperature insulation reaction and after 1.5 hours, obtain homogeneous transparent polymers soln and be the two property ionic antifoulant additives of trimethyl-glycine, by airtight this additive preservation, for the preparation of marine antifouling coating.
Embodiment 3: the preparation of the antifouling coating that contains the two property ionic additives of trimethyl-glycine and antifouling property test.
The present embodiment is first placed in slide glass the clean beaker that proper amount of acetone is housed, and cleans 3 minutes with ultrasonic washing instrument, then rinses dry for standby with deionized water well; Choose additive prepared by embodiment 2 and join in organo-silicone rubber, add-on is 6% of silicon rubber quality; After both are mixed, be coated on slide glass, after silicon rubber solidifies completely, again the antifouling coating after solidifying be soaked in water to 48 hours, standby; By diatom, with the dilution of sterilizing seawater, be 1.0 × 10
6the concentration of individual/ml, so that the organic silicon coating containing this additive is not blank as contrasting, the antifouling surface coating test piece contrast of preparing with this embodiment is carried out diatom and is adhered to test, and after 24 hours, diatom is 23.6/cm in the organic silicon coating surface attachment amount containing antifoulant additive not
2, diatom is 15.4/cm in the organic silicon coating surface attachment amount containing antifoulant additive
2, inhibiting rate improves 34.7%; Illustrate that this organic silicon coating surface that contains antifoulant additive has better antifouling property with respect to simple low surface energy organic silicon coating.
Claims (1)
1. a preparation method for two property ionic antifoulant additives, is characterized in that additive is by butyl acrylate, be prepared from by free radicals copolymerization reaction containing silane coupling agent and the methacryloyl ethyl sultaine anabolic reaction thing of polymerizable double bond; The silane coupling agent containing polymerizable double bond of copolyreaction comprises γ-methacryloxypropyl trimethoxy silane and vinyltriethoxysilane; Copolyreaction solvent for use is the mixed solvent of acetone and ethylene glycol composition, and wherein acetone accounts for the 10-40% of mixed solvent mass percent; The temperature of copolyreaction is 65～80 ℃, and the reaction times is 1.5～3.5 hours; By butyl acrylate, containing in the silane coupling agent of polymerizable double bond and reactant that methacryloyl ethyl sultaine forms, the mol ratio of butyl acrylate and methacryloyl ethyl sultaine is 1:1～2:1; Containing the silane coupling agent of polymerizable double bond and the mol ratio of methacryloyl ethyl sultaine, be 1:10～4:10; The airtight preservation of additive, adding to by condensed type organic silicon elastomerics is in the antifouling paint prepared of film forming matter.
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| CN105037781A (en) * | 2015-07-09 | 2015-11-11 | 江苏华晖环保科技有限公司 | Method for preparing novel ion exchange membrane |
| CN107033278B (en) | 2017-04-14 | 2019-05-14 | 华南理工大学 | A kind of polishing amphoteric ion antifouling resin and its preparation and application certainly with main chain degradability |
| CN111363099A (en) * | 2020-03-17 | 2020-07-03 | 中国船舶重工集团公司第七二五研究所 | Novel bionic antifouling material and preparation method thereof |
| CN112341628B (en) * | 2020-11-27 | 2021-11-30 | 中国科学院兰州化学物理研究所 | Self-lubricating acrylic resin, preparation method and application thereof, and self-lubricating marine antifouling transparent coating |
| CN112961277A (en) * | 2021-02-05 | 2021-06-15 | 浙江本立科技股份有限公司 | Preparation method of high-selectivity sevelamer carbonate |
| CN115595029B (en) * | 2022-10-19 | 2023-10-27 | 复旦大学 | Zwitterionic environment-friendly marine antifouling paint and preparation method thereof |
| CN115594851B (en) * | 2022-10-31 | 2024-02-13 | 华南理工大学 | Reactive amphiphilic additive and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1858080A (en) * | 2005-04-29 | 2006-11-08 | 广州宏昌胶粘带厂 | Single component room temperature crosslinked water fluoric resin emulsion and its preparing method and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1858080A (en) * | 2005-04-29 | 2006-11-08 | 广州宏昌胶粘带厂 | Single component room temperature crosslinked water fluoric resin emulsion and its preparing method and use |
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