CN103030733A - Polyacrylate antifouling copolymerization resin with side chain comprising benzisothiazolinone and preparation method thereof - Google Patents
Polyacrylate antifouling copolymerization resin with side chain comprising benzisothiazolinone and preparation method thereof Download PDFInfo
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- CN103030733A CN103030733A CN2012105520802A CN201210552080A CN103030733A CN 103030733 A CN103030733 A CN 103030733A CN 2012105520802 A CN2012105520802 A CN 2012105520802A CN 201210552080 A CN201210552080 A CN 201210552080A CN 103030733 A CN103030733 A CN 103030733A
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Abstract
The invention relates to polyacrylate antifouling copolymerization resin with a side chain comprising benzisothiazolinone and a preparation method thereof. The clear and transparent polyacrylate antifouling copolymerization resin with the side chain comprising the benzisothiazolinone can be obtained by performing solution copolymerization reaction on a N-substituted propenyl acyloxy methyl benzisothiazolinone functional monomer and other one or two or three alkenyl-containing monomers in an organic solvent. The sterilizing copolymerization resin is used as a film forming agent of antifouling paint and has excellent antifouling performance and self-polishing performance; and the resin preparation process is simple and easy to operate.
Description
Technical field
The present invention relates to the antifouling copolymer resins of a kind of polyacrylic ester, particularly relate to a kind of side chain and contain antifouling copolymer resins of polyacrylic ester of BIT and preparation method thereof.
Background technology
Adhering to boats and ships and maritime facilities harm of marine fouling organism brings huge financial loss to the mankind, and the most direct approach that addresses this problem is the brushing antifouling paint.Isothiazolinone biocide agent fungicidal activity is strong, under the concentration of about 0.5～1ppm, just can suppress widely all kinds of microbial growths, and the energy fast degraded biologically, environmentally safe, therefore be widely used in the fields such as industrial circulating cooling water, weaving, coating, agricultural environmental protection.The nineties in 20th century, U.S. Rohrnhaas company develop goes out 4,5-, two chloro-Kathons (Seanine 911), and is applied to the United States Naval ship antifouling paint as the high-efficiency pollution-proof agent with addition manner.Because Seanine 911 adds in the middle of the coating with small molecules, therefore according to Fick's law, the application initial stage, stain control agent release rate in the coating is too fast, after ship's navigation for some time, the anti-fouling effect of coating will descend, and antifouling coating is difficult to reach the even control release of stain control agent as stanniferous self polishing copolymer antifouling paint, thereby causes the antifouling time limit relatively short.The invention provides a kind of side chain and contain antifouling copolymer resins of polyacrylic ester of BIT and preparation method thereof, this antifouling copolymer resins molecular weight of polyacrylic ester with sterilizing function is larger, therefore being difficult for diffusion in application process runs off, simultaneously again can be by the hydrolysis of ester group bactericide-release equably, thereby sterilant is efficiently utilized, can overcome the deficiency of above-mentioned antifouling paint.
Summary of the invention
The invention provides a kind of side chain and contain antifouling copolymer resins of polyacrylic ester of BIT and preparation method thereof, preparation is simple for antifouling copolymer resins, and antifouling paint has good antifouling property and from polishing performance.
A kind of side chain contains the antifouling copolymer resins of polyacrylic ester of BIT, it is characterized in that its structure can represent with following general formula:
R in the formula
1, R
2Be alkoxyl group, or hydroxyl, or amino; R
3Be alkyl acyloxy, or phenyl, or cyano group; R
4, R
5, R
6, R
7Be hydrogen, or methyl; A is 0～12000; B is 2～4000; C is 0～12000; D is 0～5000.
A kind of side chain contains the preparation method of the antifouling copolymer resins of polyacrylic ester of BIT, it is characterized in that implementing in the steps below: in an amount of organic solvent, add an amount of N-replace acryloxy methyl BIT function monomer and other one or both or three kinds contain alkenyl monomer, add again an amount of initiator, under nitrogen protection, be warming up to 80～100 ℃, insulation reaction 3～8 hours, the side chain that can obtain faint yellow clear contains the antifouling copolymer resins of polyacrylic ester of BIT; It can be N-acryloxy methyl BIT that N-described above replaces acryloxy methyl BIT, or N-methacryloxy methyl BIT; Organic solvent described above can be dioxane, or ethylene dichloride, or DMF, or toluene, or a kind of in the dimethylbenzene, or two kinds, or three kinds, or multiple mixture; Initiator described above can be Diisopropyl azodicarboxylate, or 2,2'-Azobis(2,4-dimethylvaleronitrile), or dibenzoyl peroxide.As the base resin of antifouling paint configuration antifouling paint, antifouling paint has good film forming properties and physical and mechanical properties with this resin, has excellent in polishing performance and antifouling property.
Be further described below by example.
Embodiment 1
In being housed, the 500ml four-hole boiling flask of reflux exchanger and thermometer adds 150gN, dinethylformamide, add 15g N-acryloxy methyl BIT, 65g methyl methacrylate, the 20g butyl acrylate, the 1g Diisopropyl azodicarboxylate, logical nitrogen limit, limit was stirred and is warming up to 80 ℃, 82 ± 2 ℃ of insulation reaction 5 hours, cooling, the side chain that namely gets faint yellow clear contains the antifouling copolymer resins 1 of BIT polyacrylic ester.
Embodiment 2
In being housed, the 500ml four-hole boiling flask of reflux exchanger and thermometer adds 150g N, dinethylformamide, add 15g N-methacryloxy methyl BIT, 61g methyl methacrylate, the 24g butyl acrylate, 1 gram Diisopropyl azodicarboxylate, logical nitrogen limit, limit was stirred and is warming up to 80 ℃, 82 ± 2 ℃ of insulation reaction 5 hours, cooling, the side chain that namely gets faint yellow clear contains the antifouling copolymer resins 2 of BIT polyacrylic ester.
Embodiment 3
In being housed, the 500ml four-hole boiling flask of reflux exchanger and thermometer adds 150g N, dinethylformamide, add 15g N-methacryloxy methyl BIT, 55g methyl methacrylate, the 20g butyl acrylate, 10g vinyl acetate between to for plastic, 1.5g Diisopropyl azodicarboxylate, logical nitrogen limit, limit is stirred and is warming up to 80 ℃, 82 ± 2 ℃ of insulation reaction 5 hours, cooling, the side chain that namely gets faint yellow clear contains the antifouling copolymer resins 3 of BIT polyacrylic ester.
Embodiment 4
The 120g side chain is contained the antifouling copolymer resins of BIT polyacrylic ester, 10g red iron oxide, 10g titanium dioxide, 20g talcum powder, 50g toluene, 10g o-phthalic acid dibutyl ester, put into basket dispersing grinder, rotating speed with 2000r/min grinds, make the grain diameter of coating less than 20 μ m, get final product to such an extent that side chain contains the antifouling copolymer resins coating of BIT polyacrylic ester.Polyacrylate resin marketed coating and side chain are contained the antifouling copolymer resins coating of BIT polyacrylic ester to be brushed respectively on the mild steel plate of 250 * 150 * 1.5mm, requirement with reference to GB5370-2007 " antifouling varnish model shallow sea soak test method " fixedly is placed on 1m place under water, Mai Dao marine site, Qingdao, then respectively at 1 month, 3 months and 6 months are observed it, the result shows that the model that scribbles polyacrylic ester resin marketed coating soaked 1 month in seawater, after 3 months and 6 months, stained thing bond area rate reaches respectively 20%, 42% and 95%; Be respectively 0 (0) and scribble model stained thing bond area rate within the corresponding time that side chain contains antifouling copolymer resins 1 coating of BIT polyacrylic ester (antifouling copolymer resins 3 coating), 3% (2.6%) and 12% (8.9%), illustrate that antifouling resin has good anti-fouling effect.
Certainly, above-mentioned explanation is not to be limitation of the present invention, and the present invention also is not limited to above-mentioned giving an example, those skilled in the art, and in essential scope of the present invention, the variation of making, interpolation or replacement all should belong to protection scope of the present invention.
Claims (2)
1. antifouling copolymer resins of polyacrylic ester that side chain contains BIT is characterized in that its structure can represent with following general formula:
R in the formula
1, R
2Be alkoxyl group, or hydroxyl, or amino; R
3Be alkyl acyloxy, or phenyl, or cyano group; R
4, R
5, R
6, R
7Be hydrogen, or methyl; A is 0～12000; B is 2～4000; C is 0～12000; D is 0～5000.
2. side chain claimed in claim 1 contains the preparation method of the antifouling copolymer resins of polyacrylate of BIT, it is characterized in that implementing in the steps below: in an amount of organic solvent, add an amount of N-replace acryloxy methyl BIT function monomer and other one or both or three kinds contain alkenyl monomer, add again an amount of initiator, under nitrogen protection, be warming up to 80～100 ℃, insulation reaction 3～8 hours, the side chain that can obtain faint yellow clear contains the antifouling copolymer resins of polyacrylic ester of BIT; It can be N-acryloxy methyl BIT that N-described above replaces acryloxy methyl BIT, or N-methacryloxy methyl BIT; Organic solvent described above can be dioxane, or ethylene dichloride, or DMF, or toluene, or a kind of in the dimethylbenzene, or two kinds, or three kinds, or multiple mixture; Initiator described above can be Diisopropyl azodicarboxylate, or 2,2'-Azobis(2,4-dimethylvaleronitrile), or dibenzoyl peroxide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210552080.2A CN103030733B (en) | 2012-12-06 | 2012-12-06 | Polyacrylate antifouling copolymerization resin with side chain comprising benzisothiazolinone and preparation method thereof |
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| CN201210552080.2A CN103030733B (en) | 2012-12-06 | 2012-12-06 | Polyacrylate antifouling copolymerization resin with side chain comprising benzisothiazolinone and preparation method thereof |
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| CN103030733A true CN103030733A (en) | 2013-04-10 |
| CN103030733B CN103030733B (en) | 2014-12-10 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761667A (en) * | 2015-02-16 | 2015-07-08 | 中国船舶重工集团公司第七二五研究所 | Method for preparation of zinc acrylate resin by grafting modified benzisothiazolinone |
| CN111574658A (en) * | 2020-01-17 | 2020-08-25 | 海南大学 | Structure of acrylic ester antifouling resin grafted with benzisothiazolinone formate monomer and preparation method thereof |
| CN111574654A (en) * | 2019-10-21 | 2020-08-25 | 海南大学 | Structure and preparation method of acrylate antifouling resin containing benzo [ d ] isothiazoline-3-ketone-triazine-based monomer |
| CN111635374A (en) * | 2019-09-28 | 2020-09-08 | 海南大学 | Structure and preparation method of acrylic resin containing benzisothiazolinone formamide functional monomer |
| CN112279957A (en) * | 2019-07-22 | 2021-01-29 | 广东迪美生物技术有限公司 | Water-based polyacrylate antibacterial emulsion, preparation method thereof and application thereof in coating |
| CN114573762A (en) * | 2022-03-02 | 2022-06-03 | 北京化工大学 | Polyurethane acrylate polymer containing benzisothiazolinone derivative with antibacterial property and preparation method thereof |
| CN115340626A (en) * | 2022-10-07 | 2022-11-15 | 石家庄学院 | Bactericidal antifouling resin grafted with phenol isothiazolinone acrylate monomer and preparation method thereof |
| CN116355476A (en) * | 2023-05-12 | 2023-06-30 | 江苏晨光涂料有限公司 | Heat-insulating paint for building and preparation method thereof |
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| CN1671674A (en) * | 2002-05-29 | 2005-09-21 | Sk化学株式会社 | Isothiazolone composition and method for stabilizing isothiazolone |
| CN102234251A (en) * | 2010-04-20 | 2011-11-09 | 中国科学院烟台海岸带研究所 | Benzisothiazolinone compound and application thereof |
| CN101967316A (en) * | 2010-09-08 | 2011-02-09 | 中国乐凯胶片集团公司 | Nontoxic antifouling paint for oceanographic ship and facilities and method for preparing paint |
| CN102675992A (en) * | 2011-03-07 | 2012-09-19 | 嘉宝莉化工集团股份有限公司 | Expanded type aqueous facing fireproof coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104761667B (en) * | 2015-02-16 | 2017-01-04 | 中国船舶重工集团公司第七二五研究所 | A kind of by the method for modified BIT grafting preparation zinc acrylate resin |
| CN104761667A (en) * | 2015-02-16 | 2015-07-08 | 中国船舶重工集团公司第七二五研究所 | Method for preparation of zinc acrylate resin by grafting modified benzisothiazolinone |
| CN112279957A (en) * | 2019-07-22 | 2021-01-29 | 广东迪美生物技术有限公司 | Water-based polyacrylate antibacterial emulsion, preparation method thereof and application thereof in coating |
| CN111635374A (en) * | 2019-09-28 | 2020-09-08 | 海南大学 | Structure and preparation method of acrylic resin containing benzisothiazolinone formamide functional monomer |
| CN111574654B (en) * | 2019-10-21 | 2021-09-17 | 海南大学 | Structure and preparation method of acrylate antifouling resin containing benzo [ d ] isothiazoline-3-ketone-triazine-based monomer |
| CN111574654A (en) * | 2019-10-21 | 2020-08-25 | 海南大学 | Structure and preparation method of acrylate antifouling resin containing benzo [ d ] isothiazoline-3-ketone-triazine-based monomer |
| CN111574658A (en) * | 2020-01-17 | 2020-08-25 | 海南大学 | Structure of acrylic ester antifouling resin grafted with benzisothiazolinone formate monomer and preparation method thereof |
| CN111574658B (en) * | 2020-01-17 | 2021-10-22 | 海南大学 | Structure of acrylic ester antifouling resin grafted with benzisothiazolinone formate monomer and preparation method thereof |
| CN114573762A (en) * | 2022-03-02 | 2022-06-03 | 北京化工大学 | Polyurethane acrylate polymer containing benzisothiazolinone derivative with antibacterial property and preparation method thereof |
| CN114573762B (en) * | 2022-03-02 | 2023-12-15 | 北京化工大学 | Antibacterial benzisothiazolinone derivative-containing polyurethane acrylate polymer and preparation method thereof |
| CN115340626A (en) * | 2022-10-07 | 2022-11-15 | 石家庄学院 | Bactericidal antifouling resin grafted with phenol isothiazolinone acrylate monomer and preparation method thereof |
| CN115340626B (en) * | 2022-10-07 | 2024-05-24 | 广东省漆色彩新型材料有限公司 | Sterilization and antifouling resin grafted with phenolic isothiazolinone acrylate monomer and preparation method thereof |
| CN116355476A (en) * | 2023-05-12 | 2023-06-30 | 江苏晨光涂料有限公司 | Heat-insulating paint for building and preparation method thereof |
| CN116355476B (en) * | 2023-05-12 | 2024-01-16 | 江苏晨光涂料有限公司 | Heat-insulating paint for building and preparation method thereof |
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