CN103113528B - 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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- CN103113528B CN103113528B CN201310021614.3A CN201310021614A CN103113528B CN 103113528 B CN103113528 B CN 103113528B CN 201310021614 A CN201310021614 A CN 201310021614A CN 103113528 B CN103113528 B CN 103113528B
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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 containing BIT structure and preparation method thereof.
Background technology
The attachment of marine fouling organism causes serious harm to boats and ships and maritime facilities, brings huge financial loss to the mankind, and the most direct approach addressed this problem is brushing antifouling paint.Isothiazolinone biocide agent fungicidal activity is strong, just all kinds of microbial growth can be suppressed widely under the concentration of about 0.5 ~ 1ppm, and energy fast degraded biologically, environmentally safe, be therefore widely used in the fields such as industrial circulating cooling water, weaving, coating, agricultural environmental protection.The nineties in 20th century, Rohrnhaas company of the U.S. successfully develops the chloro-Kathon of 4,5-bis-(Seanine 911), and is applied to United States Naval ship antifouling paint as high-efficiency pollution-proof agent with addition manner.Because Seanine 911 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, when after ship's navigation for some time, the anti-fouling effect of coating will decline, and antifouling coating is difficult to the equal control release reaching stain control agent as stanniferous self polishing copolymer antifouling paint, thus causes the antifouling time limit relatively short.The invention provides a kind of acrylic ester grafted epoxy resin containing BIT structure and preparation method thereof, this acrylic ester grafted molecular weight of epoxy resin with sterilizing function is larger, therefore in application process, not easily loss is spread, simultaneously again can by the hydrolysis of ester group bactericide-release equably, thus make sterilant obtain efficiency utilization, the deficiency of above-mentioned antifouling paint can be overcome.
Summary of the invention
The invention provides a kind of acrylic ester grafted epoxy resin containing benzene isothiazolinone structure and preparation method thereof, adopt the standby antifouling paint of this resin-made to have good antifouling property and from polishing performance.
Containing an acrylic ester grafted epoxy resin for benzene isothiazolinone structure, it is characterized in that being prepared by the preparation method of following a kind of acrylic ester grafted epoxy resin containing 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: in appropriate organic solvent, add epoxy resin, add again and appropriate replace propylene acyloxy methyl benzisothiazolinone functional monomer and other one or both or three kinds of mix monomers formed containing alkenyl monomer by N-, stir, add appropriate initiator again, under nitrogen protection, insulation reaction 3 ~ 8 hours at 80 ~ 100 DEG C, namely the acrylic ester grafted epoxy resin containing BIT structure of faint yellow clear is obtained, epoxy resin described above is bisphenol A type epoxy resin, it is N-acryloyloxymethyl BIT that N-described above replaces acryloyloxymethyl BIT, or N-methacryloxymethyl BIT, the weight percent that its consumption accounts for mix monomer total amount is 5% ~ 100%, mix monomer consumption described above and the weight ratio of content of epoxy resin are 0.05 ~ 20: 1, described above is methyl acrylate containing alkenyl monomer, 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 is dioxane, or ethylene dichloride, or DMF, or toluene, or the one in dimethylbenzene, or two kinds, or three kinds, or multiple mixture, initiator described above is Diisopropyl azodicarboxylate, or 2,2'-Azobis(2,4-dimethylvaleronitrile), or dibenzoyl peroxide.Resin prepared by aforesaid method is as the base resin configuration antifouling paint of antifouling paint, and 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
150gN is added in the 500ml four-hole boiling flask that reflux exchanger and thermometer are housed, dinethylformamide, add 100g epoxy resin E-51,15g N-acryloyloxymethyl BIT, 65g methyl methacrylate, 20g butyl acrylate, 2g Diisopropyl azodicarboxylate, while lead to the stirring of nitrogen limit to be warming up to 90 DEG C, 92 ± 2 DEG C of insulation reaction 5 hours, cooling, obtained the acrylic ester grafted epoxy resin 1 containing BIT structure of faint yellow clear.
Embodiment 2
150gN is added in the 500ml four-hole boiling flask that reflux exchanger and thermometer are housed, dinethylformamide, add 100g epoxy resin E-44,15g N-methacryloxymethyl BIT, 61g methyl methacrylate, 24g butyl acrylate, 2 grams of Diisopropyl azodicarboxylates, while lead to the stirring of nitrogen limit to be warming up to 90 DEG C, 92 ± 2 DEG C of insulation reaction 5 hours, cooling, obtained the acrylic ester grafted epoxy resin 2 containing BIT structure of faint yellow clear.
Embodiment 3
150g N is added in the 500ml four-hole boiling flask that reflux exchanger and thermometer are housed, dinethylformamide, add 100g epoxy resin E-51,15g N-methacryloxymethyl BIT, 55g methyl methacrylate, 20g butyl acrylate, 10g vinyl acetate between to for plastic, 1.5g Diisopropyl azodicarboxylate, while lead to the stirring of nitrogen limit to be warming up to 80 DEG C, 82 ± 2 DEG C of insulation reaction 5 hours, cooling, obtains the acrylic ester grafted epoxy resin 3 containing BIT structure of faint yellow clear.
Embodiment 4
150gN is added in the 500ml four-hole boiling flask that reflux exchanger and thermometer are housed, dinethylformamide, add 100g epoxy resin E-51,15g N-acryloyloxymethyl BIT, 50g methyl methacrylate, 20g butyl acrylate, 15g vinylbenzene, 2g Diisopropyl azodicarboxylate, stirs be warming up to 90 DEG C, 92 ± 2 DEG C of insulation reaction 5 hours while leads to nitrogen limit, cooling, obtains the acrylic ester grafted epoxy resin 4 containing BIT structure of faint yellow clear.
Embodiment 5
By acrylic ester grafted epoxy resin 1 (resin 3), 10g red iron oxide, the 10g titanium dioxide of 120g containing BIT structure, 20g talcum powder, 50g toluene, 10g o-phthalic acid dibutyl ester, put into basket dispersing grinder, grind with the rotating speed of 2000r/min, make the grain diameter of coating be less than 20 μm, containing the acrylic ester grafted epoxy resin antifouling paint 1 (antifouling paint 3) of BIT structure.By polyacrylate resin marketed coating with brush respectively on the mild steel plate of 250 × 150 × 1.5mm containing the acrylic ester grafted epoxy resin antifouling paint of BIT structure, requirement with reference to GB5370-2007 " antifouling varnish model shallow sea soak test method " is fixedly placed on 1m place under water, Mai Dao marine site, Qingdao, then respectively at 1 month, it was observed in 3 months and 6 months, result shows that the model scribbling polyacrylic ester resin marketed coating soaks 1 month in the seawater, after 3 months and 6 months, stained thing bond area rate reaches 20% respectively, 42% and 95%, and the model stained thing bond area rate within the corresponding time scribbled containing the antifouling paint 1 (antifouling paint 3) of the acrylic ester grafted epoxy resin of 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 limitation of the present invention, and the present invention is also not limited to above-mentioned citing, those skilled in the art, and in essential scope of the present invention, the change made, interpolation or replacement, all should belong to protection scope of the present invention.
Claims (2)
1. the preparation method containing the acrylic ester grafted epoxy resin of benzene isothiazolinone structure, it is characterized in that implementing in the steps below: in appropriate organic solvent, add epoxy resin, add again and appropriate replace propylene acyloxy methyl benzisothiazolinone functional monomer and other one or both or three kinds of mix monomers formed containing alkenyl monomer by N-, stir, add appropriate initiator again, under nitrogen protection, insulation reaction 3 ~ 8 hours at 80 ~ 100 DEG C, namely the acrylic ester grafted epoxy resin containing BIT structure of faint yellow clear is obtained, epoxy resin described above is bisphenol A type epoxy resin, it is N-acryloyloxymethyl BIT that N-described above replaces acryloyloxymethyl BIT, or N-methacryloxymethyl BIT, the weight percent that its consumption accounts for mix monomer total amount is 5% ~ 100%, mix monomer consumption described above and the weight ratio of content of epoxy resin are 0.05 ~ 20: 1, described above is methyl acrylate containing alkenyl monomer, 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 is dioxane, or ethylene dichloride, or DMF, or toluene, or the one in dimethylbenzene, or two kinds, or three kinds, or multiple mixture, initiator described above is Diisopropyl azodicarboxylate, or 2,2'-Azobis(2,4-dimethylvaleronitrile), or dibenzoyl peroxide.
2., containing an acrylic ester grafted epoxy resin for benzene isothiazolinone structure, it is characterized in that being prepared by method described in 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 true CN103113528B (en) | 2015-01-28 |
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| CN109677681B (en) * | 2018-12-28 | 2021-06-29 | 康熹智能科技（东莞）有限公司 | Full-automatic tableware packaging and boxing machine |
| 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 |
| 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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| US20080293848A1 (en) * | 2007-03-28 | 2008-11-27 | The Sherwin-Williams Company | Self-polishing anti-fouling compositions |
| CN102234251B (en) * | 2010-04-20 | 2013-04-24 | 中国科学院烟台海岸带研究所 | Benzisothiazolinone compound and application thereof |
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