CN103113528A - Acrylic ester grafted epoxy resin containing benzisothiazolinone structure and preparation method thereof - Google Patents
Acrylic ester grafted epoxy resin containing benzisothiazolinone structure and preparation method thereof Download PDFInfo
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- CN103113528A CN103113528A CN2013100216143A CN201310021614A CN103113528A CN 103113528 A CN103113528 A CN 103113528A CN 2013100216143 A CN2013100216143 A CN 2013100216143A CN 201310021614 A CN201310021614 A CN 201310021614A CN 103113528 A CN103113528 A CN 103113528A
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Abstract
The invention relates to an acrylic ester grafted epoxy resin containing a benzisothiazolinone structure and a preparation method thereof. In an organic solvent, a mixed monomer composed of N-substituted acryloxymethyl benzisothiazolinone functional monomer and other one or two or three alkenyl-containing monomers is applied to graft copolymerization reaction of the epoxy resin to obtain the clear and transparent acrylic ester grafted epoxy resin containing the benzisothiazolinone structure. The anti-fouling resin serves as the film-forming agent of the anti-fouling coating, and has excellent anti-fouling performance and self-polishing performance; and the resin preparation process is simple and feasible.
Description
Technical field
The present invention relates to a kind of acrylic ester grafted epoxy resin, particularly relate to a kind of acrylic ester grafted epoxy resin that contains the BIT structure 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, just can suppress widely all kinds of microbial growths under the concentration of about 0.5～1ppm, 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 (Seanine911), and is applied to the United States Naval ship antifouling paint as the high-efficiency pollution-proof agent with addition manner.Because Seanine911 adds in the middle of coating with small molecules, therefore according to Fick's law, the application initial stage, stain control agent release rate in 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 acrylic ester grafted epoxy resin that contains the BIT structure and preparation method thereof, this acrylic ester grafted molecular weight of epoxy resin 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 acrylic ester grafted epoxy resin that contains benzene isothiazolinone structure and preparation method thereof, adopt the standby antifouling paint of this resin to have good antifouling property and from polishing performance.
A kind of acrylic ester grafted epoxy resin that contains benzene isothiazolinone structure is characterized in that being prepared by following a kind of preparation method who contains the acrylic ester grafted epoxy resin of benzene isothiazolinone structure.
a kind of structure contains acrylic ester grafted epoxy resin of benzene isothiazolinone and preparation method thereof, it is characterized in that implementing in the steps below: add epoxy resin in appropriate organic solvent, add again appropriate by N-replace acryloxy methyl BIT function monomer and other one or both or three kinds contain the mix monomer that alkenyl monomer forms, stir, add again appropriate initiator, under nitrogen protection, 80～100 ℃ of lower insulation reaction 3～8 hours, can obtain the acrylic ester grafted epoxy resin that contains the BIT structure of faint yellow clear, epoxy resin described above is bisphenol A type epoxy resin, it can be N-acryloxy methyl BIT that N-described above replaces acryloxy methyl BIT, or N-methacryloxy methyl BIT, the weight percent that its consumption accounts for the mix monomer total amount can be 5%～100%, mix monomer consumption described above and the weight ratio of content of epoxy resin can be 0.05～20: 1, the alkenyl monomer that contains described above can be methyl acrylate, or ethyl propenoate, or butyl acrylate, or Propylene glycol monoacrylate, or Hydroxyethyl acrylate, or methyl methacrylate, or β-dimethyl-aminoethylmethacrylate, or butyl methacrylate, or Rocryl 410, or hydroxyethyl methylacrylate, or vinyl cyanide, or vinylbenzene, or vinyl acetate between to for plastic, organic solvent described above can be dioxane, or ethylene dichloride, or DMF, or toluene, or a kind of in 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.By the base resin configuration antifouling paint of the prepared resin of aforesaid method as antifouling paint, antifouling paint has good film forming properties and physical and mechanical properties, 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 100g epoxy resin E-51,15gN-acryloxy methyl BIT, 65g methyl methacrylate, 20g butyl acrylate, 2g Diisopropyl azodicarboxylate, logical nitrogen limit, limit is stirred and is warming up to 90 ℃, 92 ± 2 ℃ of insulation reaction 5 hours, cooling namely got the acrylic ester grafted epoxy resin 1 that contains the BIT structure of faint yellow clear.
Embodiment 2
In being housed, the 500ml four-hole boiling flask of reflux exchanger and thermometer adds 150g N, dinethylformamide, add the 100g epoxy resin E-44,15g N-methacryloxy methyl BIT, 61g methyl methacrylate, 24g butyl acrylate, 2 gram Diisopropyl azodicarboxylates, logical nitrogen limit, limit is stirred and is warming up to 90 ℃, 92 ± 2 ℃ of insulation reaction 5 hours, cooling namely got the acrylic ester grafted epoxy resin 2 that contains the BIT structure of faint yellow clear.
Embodiment 3
In being housed, the 500ml four-hole boiling flask of reflux exchanger and thermometer adds 150g N, dinethylformamide, add 100g epoxy resin E-51,15g N-methacryloxy methyl BIT, 55g methyl methacrylate, the 20g butyl acrylate, the 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, lower the temperature, namely get the acrylic ester grafted epoxy resin 3 that contains the BIT structure of faint yellow clear.
Embodiment 4
In being housed, the 500ml four-hole boiling flask of reflux exchanger and thermometer adds 150g N, dinethylformamide, add 100g epoxy resin E-51,15g N-acryloxy methyl BIT, 50g methyl methacrylate, 20g butyl acrylate, 15g vinylbenzene, the 2g Diisopropyl azodicarboxylate, logical nitrogen limit, limit was stirred and is warming up to 90 ℃, 92 ± 2 ℃ of insulation reaction 5 hours, lower the temperature, namely get the acrylic ester grafted epoxy resin 4 that contains the BIT structure of faint yellow clear.
Embodiment 5
The acrylic ester grafted epoxy resin 1 (resin 3), 10g red iron oxide, the 10g titanium dioxide that 120g are contained the BIT structure, 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 contain the acrylic ester grafted epoxy resin antifouling paint 1 (antifouling paint 3) of BIT structure.polyacrylate resin marketed coating and the acrylic ester grafted epoxy resin antifouling paint that contains the BIT structure are brushed respectively on the mild steel plate of 250 * 150 * 1.5mm, fixedly be placed on 1m place under water, Mai Dao marine site, Qingdao with reference to the requirement of GB5370-2007 " antifouling varnish model shallow sea soak test method ", then respectively at 1 month, it was observed in 3 months and 6 months, 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%, and the model stained thing bond area rate within the corresponding time that scribbles the antifouling paint 1 (antifouling paint 3) of the acrylic ester grafted epoxy resin that contains the BIT structure is respectively 0 (0), 2.7% (2.1%) and 7.2% (6.9%), illustrate that this 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. preparation method who contains the acrylic ester grafted epoxy resin of benzene isothiazolinone structure, it is characterized in that implementing in the steps below: add epoxy resin in appropriate organic solvent, add again appropriate by N-replace acryloxy methyl BIT function monomer and other one or both or three kinds contain the mix monomer that alkenyl monomer forms, stir, add again appropriate initiator, under nitrogen protection, 80～100 ℃ of lower insulation reaction 3～8 hours, can obtain the acrylic ester grafted epoxy resin that contains the BIT structure of faint yellow clear, epoxy resin described above is bisphenol A type epoxy resin, it can be N-acryloxy methyl BIT that N-described above replaces acryloxy methyl BIT, or N-methacryloxy methyl BIT, the weight percent that its consumption accounts for the mix monomer total amount can be 5%～100%, mix monomer consumption described above and the weight ratio of content of epoxy resin can be 0.05～20: 1, the alkenyl monomer that contains described above can be methyl acrylate, or ethyl propenoate, or butyl acrylate, or Propylene glycol monoacrylate, or Hydroxyethyl acrylate, or methyl methacrylate, or β-dimethyl-aminoethylmethacrylate, or butyl methacrylate, or Rocryl 410, or hydroxyethyl methylacrylate, or vinyl cyanide, or vinylbenzene, or vinyl acetate between to for plastic, organic solvent described above can be dioxane, or ethylene dichloride, or DMF, or toluene, or a kind of in 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.
2. an acrylic ester grafted epoxy resin that contains benzene isothiazolinone structure, is characterized in that and can be prepared by the described method of claim 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310021614.3A CN103113528B (en) | 2013-01-05 | 2013-01-05 | Acrylic ester grafted epoxy resin containing benzisothiazolinone structure and preparation method thereof |
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| CN201310021614.3A CN103113528B (en) | 2013-01-05 | 2013-01-05 | Acrylic ester grafted epoxy resin containing benzisothiazolinone structure and preparation method thereof |
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| CN103113528B CN103113528B (en) | 2015-01-28 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109677681A (en) * | 2018-12-28 | 2019-04-26 | 康熹智能科技（东莞）有限公司 | Fully-automatic packaging tableware recrater |
| 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 |
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| WO2008121308A1 (en) * | 2007-03-28 | 2008-10-09 | The Sherwin-Williams Company | Self-polishing anti-fouling compositions |
| 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 |
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- 2013-01-05 CN CN201310021614.3A patent/CN103113528B/en not_active Expired - Fee Related
Patent Citations (2)
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|---|---|---|---|---|
| WO2008121308A1 (en) * | 2007-03-28 | 2008-10-09 | The Sherwin-Williams Company | Self-polishing anti-fouling compositions |
| 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 |
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| 于良民等: "异噻唑啉酮类化合物及其在海洋防污涂料中的应用", 《涂料工业》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109677681A (en) * | 2018-12-28 | 2019-04-26 | 康熹智能科技（东莞）有限公司 | Fully-automatic packaging tableware recrater |
| CN111635374A (en) * | 2019-09-28 | 2020-09-08 | 海南大学 | Structure and preparation method of acrylic resin containing benzisothiazolinone formamide functional 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 |
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| CN103113528B (en) | 2015-01-28 |
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