CN102718919A - Hydrolyzing-speed-controllable anti-pollution estersil material as well as preparation method and application thereof - Google Patents
Hydrolyzing-speed-controllable anti-pollution estersil material as well as preparation method and application thereof Download PDFInfo
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- CN102718919A CN102718919A CN2012102187121A CN201210218712A CN102718919A CN 102718919 A CN102718919 A CN 102718919A CN 2012102187121 A CN2012102187121 A CN 2012102187121A CN 201210218712 A CN201210218712 A CN 201210218712A CN 102718919 A CN102718919 A CN 102718919A
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Abstract
The invention discloses a hydrolyzing-speed-controllable anti-pollution estersil material as well as a preparation method and application thereof. The preparation method comprises the following steps of: proportionally mixing an unsaturated vinyl ester monomer, unsaturated vinyl estersil and an unsaturated hydrolyzed regulated and controlled vinyl monomer, adding the mixture into a solvent under inert-gas protection, and then carrying out polymerization reaction with a free-radical initiator to generate the hydrolyzing-speed-controllable anti-pollution estersil material. In the preparation method, the hydrolyzing performance of the prepared estersil material has an adjustable characteristic to a greater degree by introducing the hydrolyzed regulated and controlled monomer, so that the dependency problem of traditional self-polishing materials on navigational speeds is solved, new surfaces can also be continuously refreshed through a hydrolytic action even though ships are stopped, and the anti-pollution requirements of low-navigational-speed ships, submarines and offshore oil-producing platform facilities can be well met; and the process is simple, the cost is lower, the hydrolyzing-speed-controllable anti-pollution estersil material is suitable for industrialized production, and the prepared estersil material has good application prospects in the field of ocean anti-pollution coatings.
Description
Technical field
The invention belongs to the materials chemistry field, relate to marine anti-pollution material and preparation method thereof technology, be specifically related to controlled antifouling estersil material of a kind of hydrolysis rate and preparation method thereof and application.
Background technology
Cause huge harm for the exploration, exploitation, utilization etc. of sea transport and oceanic resources attached to the biodeterioration on hull and maritime facilities surface in the ocean.The stained meeting of this type significantly increases the hull quality, increases running resistance, and then increases fuel consumption and greenhouse gas emission; Can change the condition of surface of hull and other maritime facilities, thereby accelerate its corrosion speed; In the sea farming industry, marine biofouling also makes the mesh of cage culture stop up, and causes the fishes and shrimps big area dead.
At present, the application marine antifouling coating is to reduce the most effective, the convenient and economic method of marine biofouling.
Increasingly stringent along with the sea environment-friendly rules; Antifouling paint develops towards the direction that does not contain organotin, the cuprous content of suboxide, do not contain the heavy metal sterilant and do not have a sterilant, and antifouling paint substrate resin plays critical effect to the performance and the feature of environmental protection of antifouling paint.Self polishing copolymer antifouling paint is the practical antifouling varnish product of present main flow, mainly is base-material with the vinyl resin, and Red copper oxide is stain control agent, and coating makes polymer dissolution through ion exchange in seawater, discharges stain control agent and plays anti-fouling effect.But this type material has certain dependency to the speed of a ship or plane, because the souring of seawater is less, upgrades weak effect when static, causes anti-fouling effect undesirable, can not finely satisfy boats and ships, submarine and offshore production platform facility antifouling of the low speed of a ship or plane.
Summary of the invention
The objective of the invention is provides controlled antifouling estersil material of a kind of hydrolysis rate and preparation method thereof and application to the deficiency of current material with technology.The antifouling estersil material property of the present invention's preparation is controlled, and the hydrolysis rate of coating has controllability, thereby satisfies different application needs.
In order to achieve the above object, the present invention has adopted following technical scheme:
The controlled antifouling estersil material of a kind of hydrolysis rate has following structural formula:
Wherein, R
1Be H or CH
3R
2Be CH
3, CH
2CH
3, CH
2CH
2CH
3, CH
2CH
2CH
2CH
3, C
6H
13, C
8H
17, C
12H
25, C
14H
29, C
16H
33Or C
18H
37R
3Be CH
3, CH
2CH
3, CH
2CH
2CH
3, CH (CH3)
2, CH
2CH
2CH
2CH
3, CH
2CH
2CH
2CH
2CH
3, C
6H
13, C
8H
17Or C
6H
5R
4Be hydrolysis regulation and control group; Wherein m is 10 ~ 200, and n is 5 ~ 100, and x is 0 ~ 20.
Said hydrolysis regulation and control group is dimethylaminoethyl, lignocaine ethyl ester, dimethyl benzyl ammonium chloride, trimethyl ammonium chloride, hydroxyl ethyl ester, hydroxypropyl acrylate, Trimethoxy silane, triethoxyl silane, glycidyl ether, 2; 4, one or more in 6-bromophenisic acid, pyridine, hydroxyl, amino, T 46155, pyrrolidone, quaternary ammonium salt, sulphonic acid betaine or the carboxylic acid trimethyl-glycine.
The molecular weight of the controlled antifouling estersil material of said hydrolysis rate is 1 * 10
3~ 5 * 10
4
The present invention also provides a kind of hydrolysis rate controlled antifouling estersil preparation methods; May further comprise the steps: unsaturated hydrolysis regulation and control monomer of the unsaturated esters monomer of vinyl, the unsaturated estersil of vinyl and vinyl and radical initiator is mixed by proportioning; Under protection of inert gas, mixture slowly is added drop-wise in the solvent continuously, generates the controlled antifouling estersil material of hydrolysis rate in 60 ~ 120 ℃ of polyreaction 4 ~ 24h;
The weight percent of said each material is: the unsaturated esters monomer 10 ~ 90% of vinyl; The unsaturated estersil 10 ~ 85% of vinyl; The unsaturated controlled hydrolysis monomer 0 ~ 20% of vinyl, the quality of radical initiator are 0.1 ~ 3% of the unsaturated hydrolysis regulation and control of the unsaturated esters monomer of vinyl, the unsaturated estersil of vinyl and vinyl monomer three quality sum.
The unsaturated esters monomer of said vinyl is TEB 3K or Jia Jibingxisuanyizhi; The unsaturated estersil of said vinyl is methylacrylic acid three normal-butyl estersil, methylacrylic acid tri-phenyl-silane ester, vinylformic acid triisopropyl estersil or methylacrylic acid tributyl silicon ester; The unsaturated hydrolysis regulation and control of said vinyl monomer is methacryloxypropyl trimethoxy silane, vinylformic acid, the low macrogol ester of methylacrylic acid, methylacrylic acid-2; 4,6-tribromo phenolic ester, dimethylaminoethyl methacrylate or Rocryl 400.
Said radical initiator is Diisopropyl azodicarboxylate or Lucidol.
Said solvent is one or more in THF, N, N,N-DIMETHYLACETAMIDE, butylacetate, toluene, YLENE, acetone or the propyl carbinol; The ratio of the unsaturated hydrolysis regulation and control of the unsaturated esters monomer of the quality of said solvent and vinyl, the unsaturated estersil of vinyl and vinyl monomer three quality sum is 100: (50 ~ 200).
Said rare gas element is argon gas or nitrogen.
The present invention also provides the application of the controlled antifouling estersil material of a kind of hydrolysis rate in the preparation marine antifouling coating.
The present invention compared with prior art has the following advantages and beneficial effect:
(1) introduced hydrolysis regulation and control monomer in the estersil material of the present invention's preparation; Its hydrolysis property has tunable characteristic largely; Solved tradition from the dependency of polishing material to the speed of a ship or plane; Even boats and ships also can constantly refresh the surface that makes new advances through hydrolytic action when stopping, can satisfy the boats and ships of the low speed of a ship or plane well, the antifouling requirement of submarine and offshore production platform facility;
(2) the continuable all even thorough hydrolysis polishing in seawater of estersil material of the present invention makes boats and ships smooth at the term of voyage coatingsurface, thereby reduces surfaceness, reduces running resistance, gives material and has from polishing and the dual performance of drag reduction;
(3) preparing method's technology of the present invention is simple, and cost is lower, is fit to suitability for industrialized production, and the estersil material of preparation has good application prospects in the marine anti-pollution coatings art.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but the scope that the present invention requires to protect is not limited in this.
Embodiment 1
100g YLENE is joined in the four-hole boiling flask that prolong, whisking appliance and TM are housed, behind the logical nitrogen 30min, be heated to 90 ℃; Under nitrogen protection, in 4h, at the uniform velocity splash into the mixture of 50g TEB 3K, 48g vinylformic acid triisopropyl estersil, 2g methyl propenoic acid glycidyl ether and 1g Diisopropyl azodicarboxylate; Dropwise back insulation reaction 4h, obtain the estersil material.
The estersil material of embodiment 1 preparation is passed through the composite stain control agent of formulating of recipe, brush or the spraying film forming, room temperature is placed 3d.Should antifouling mould material link plate through detecting, does not have large-scale pollution biological attachment after December in shallow sea, Xiamen, Fujian, show that this material has good anti-fouling effect.
Embodiment 2
The 120g THF is joined in the four-hole boiling flask that prolong, whisking appliance and TM are housed, behind the logical nitrogen 30min, be heated to 60 ℃; Under argon shield, in 4h, at the uniform velocity splash into the mixture of 50g TEB 3K, 30g methylacrylic acid three normal-butyl estersil, 10g methacryloxypropyl trimethoxy silane and 0.9g Diisopropyl azodicarboxylate; Dropwise back insulation reaction 4h, obtain the estersil material.
The estersil material of embodiment 2 preparations is passed through the composite stain control agent of formulating of recipe, brush or the spraying film forming, room temperature is placed 3d.Should antifouling mould material link plate through detecting, does not have large-scale pollution biological attachment after December in shallow sea, Xiamen, Fujian, show that this material has good anti-fouling effect.
Embodiment 3
180g YLENE and the mixing of 20g butylacetate are put into the four-hole boiling flask that prolong, whisking appliance and TM are housed, behind the logical nitrogen 30min, be heated to 120 ℃; Under nitrogen protection, in 4h, at the uniform velocity splash into the mixture of 108.0g Jia Jibingxisuanyizhi, 88.4g methylacrylic acid tri-phenyl-silane ester, 3.6g vinylformic acid and 1.5g Diisopropyl azodicarboxylate; Dropwise back insulation reaction 4h, obtain the estersil material.
The estersil material of embodiment 3 preparations is passed through the composite stain control agent of formulating of recipe, brush or the spraying film forming, room temperature is placed 3d.Should antifouling mould material link plate through detecting, does not have large-scale pollution biological attachment after December in shallow sea, Xiamen, Fujian, show that this material has good anti-fouling effect.
Embodiment 4
100g YLENE is joined in the four-hole boiling flask that prolong, whisking appliance and TM are housed, behind the logical nitrogen 30min, be heated to 90 ℃; Under nitrogen protection, in 4h, splash into the mixture of 100g TEB 3K, 48g vinylformic acid triisopropyl estersil, the low macrogol ester of 2g methylacrylic acid and 0.15g Diisopropyl azodicarboxylate; Dropwise back insulation reaction 4h, obtain the estersil material.
The estersil material of embodiment 4 preparations is passed through the composite stain control agent of formulating of recipe, brush or the spraying film forming, room temperature is placed 3d.Should antifouling mould material link plate through detecting, does not have large-scale pollution biological attachment after December in shallow sea, Xiamen, Fujian, show that this material has good anti-fouling effect.
Embodiment 5
The 150g N is joined in the four-hole boiling flask that prolong, whisking appliance and TM are housed, behind the logical nitrogen 30min, be heated to 100 ℃; Under nitrogen protection, in 4h, splash into the mixture of 40g TEB 3K, 40g methylacrylic acid three normal-butyl estersil, 20g methylacrylic acid-bromol ester and 3g Lucidol; Dropwise back insulation reaction 4h, obtain the estersil material.
The estersil material of embodiment 5 preparations is passed through the composite stain control agent of formulating of recipe, brush or the spraying film forming, room temperature is placed 3d.Should antifouling mould material link plate through detecting, does not have large-scale pollution biological attachment after December in shallow sea, Xiamen, Fujian, show that this material has good anti-fouling effect.
Embodiment 6
90g YLENE, 10g propyl carbinol, 90g TEB 3K, 10g methylacrylic acid tributyl silicon ester, 0.5g Diisopropyl azodicarboxylate are joined in the four-hole boiling flask that prolong, whisking appliance and TM are housed, behind the logical nitrogen 0.5h, be heated to 80 ℃; Reaction 24h obtains the estersil material under nitrogen protection.
The estersil material of embodiment 6 preparations is passed through the composite stain control agent of formulating of recipe, brush or the spraying film forming, room temperature is placed 3d.Should antifouling mould material link plate through detecting, does not have large-scale pollution biological attachment after December in shallow sea, Xiamen, Fujian, show that this material has good anti-fouling effect.
Embodiment 7
100g YLENE, 10g TEB 3K, 85g methylacrylic acid tributyl silicon ester, 5g Rocryl 400 and 1g Diisopropyl azodicarboxylate are joined in the four-hole boiling flask that prolong, whisking appliance and TM are housed; Behind the logical nitrogen 0.5h, be heated to 90 ℃; Reaction 24h obtains the estersil material under nitrogen protection.
The estersil material of embodiment 7 preparations is passed through the composite stain control agent of formulating of recipe, brush or the spraying film forming, room temperature is placed 3d.Should antifouling mould material link plate through detecting, does not have large-scale pollution biological attachment after December in shallow sea, Xiamen, Fujian, show that this material has good anti-fouling effect.
Claims (9)
1. controlled antifouling estersil material of hydrolysis rate is characterized in that having following structural formula:
Wherein, R
1Be H or CH
3R
2Be CH
3, CH
2CH
3, CH
2CH
2CH
3, CH
2CH
2CH
2CH
3, C
6H
13, C
8H
17, C
12H
25, C
14H
29, C
16H
33Or C
18H
37R
3Be CH
3, CH
2CH
3, CH
2CH
2CH
3, CH (CH3)
2, CH
2CH
2CH
2CH
3, CH
2CH
2CH
2CH
2CH
3, C
6H
13, C
8H
17Or C
6H
5R
4Be hydrolysis regulation and control group; Wherein m is 10 ~ 200, and n is 5 ~ 100, and x is 0 ~ 20.
2. the controlled antifouling estersil material of hydrolysis rate according to claim 1; It is characterized in that; Said hydrolysis regulation and control group is dimethylaminoethyl, lignocaine ethyl ester, dimethyl benzyl ammonium chloride, trimethyl ammonium chloride, hydroxyl ethyl ester, hydroxypropyl acrylate, Trimethoxy silane, triethoxyl silane, glycidyl ether, 2; 4, one or more in 6-bromophenisic acid, pyridine, hydroxyl, amino, T 46155, pyrrolidone, quaternary ammonium salt, sulphonic acid betaine or the carboxylic acid trimethyl-glycine.
3. the controlled antifouling estersil material of hydrolysis rate according to claim 1 and 2 is characterized in that the molecular weight of the controlled antifouling estersil material of said hydrolysis rate is 1 * 10
3~ 5 * 10
4
4. the controlled antifouling estersil preparation methods of the described hydrolysis rate of one of claim 1 ~ 3; It is characterized in that; May further comprise the steps: the unsaturated esters monomer of vinyl, the unsaturated estersil of vinyl, the unsaturated hydrolysis regulation and control monomer of vinyl and radical initiator are mixed; Under protection of inert gas, mixture slowly is added drop-wise in the solvent continuously, generates the controlled antifouling estersil material of hydrolysis rate in 60 ~ 120 ℃ of polyreaction 4 ~ 24h;
The weight percent of said each material is: the unsaturated esters monomer 10 ~ 90% of vinyl; The unsaturated estersil 10 ~ 85% of vinyl; The unsaturated controlled hydrolysis monomer 0 ~ 20% of vinyl, the quality of radical initiator are 0.1 ~ 3% of the unsaturated hydrolysis regulation and control of the unsaturated esters monomer of vinyl, the unsaturated estersil of vinyl and vinyl monomer three quality sum.
5. preparation method according to claim 4 is characterized in that, the unsaturated esters monomer of said vinyl is TEB 3K or Jia Jibingxisuanyizhi; The unsaturated estersil of said vinyl is methylacrylic acid three normal-butyl estersil, methylacrylic acid tri-phenyl-silane ester, vinylformic acid triisopropyl estersil or methylacrylic acid tributyl silicon ester; The unsaturated hydrolysis regulation and control of said vinyl monomer is methacryloxypropyl trimethoxy silane, vinylformic acid, the low macrogol ester of methylacrylic acid, methylacrylic acid-2; 4,6-tribromo phenolic ester, dimethylaminoethyl methacrylate or Rocryl 400.
6. preparation method according to claim 5 is characterized in that, said radical initiator is Diisopropyl azodicarboxylate or Lucidol.
7. preparation method according to claim 6 is characterized in that, said solvent is one or more in THF, N, N,N-DIMETHYLACETAMIDE, butylacetate, toluene, YLENE, acetone or the propyl carbinol; The ratio of the unsaturated hydrolysis regulation and control of the unsaturated esters monomer of the quality of said solvent and vinyl, the unsaturated estersil of vinyl and vinyl monomer three quality sum is 100: (50 ~ 200).
8. preparation method according to claim 7 is characterized in that, said rare gas element is argon gas or nitrogen.
9. the application of the controlled antifouling estersil material of the described hydrolysis rate of one of claim 1 ~ 3 in the preparation marine antifouling coating.
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| CN201210218712.1A CN102718919B (en) | 2012-06-29 | 2012-06-29 | Hydrolyzing-speed-controllable anti-pollution estersil material as well as preparation method and application thereof |
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| CN201210218712.1A CN102718919B (en) | 2012-06-29 | 2012-06-29 | Hydrolyzing-speed-controllable anti-pollution estersil material as well as preparation method and application thereof |
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Cited By (7)
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| CN103131289A (en) * | 2013-02-28 | 2013-06-05 | 海洋化工研究院有限公司 | Preparation and application of self-polishing antifouling coating matrix resin |
| CN103396513A (en) * | 2013-07-24 | 2013-11-20 | 华南理工大学 | Preparation method and application of main chain fracture type polyacrylic acid silane ester resin |
| CN105209561A (en) * | 2013-04-24 | 2015-12-30 | 日东化成株式会社 | Antifouling paint composition, copolymer for antifouling paint composition and method for manufacturing same, and painted object having on surface antifouling paint film formed using said composition |
| CN111533854A (en) * | 2020-06-02 | 2020-08-14 | 上海亿祺化工技术有限公司 | Silicon modified acrylic resin and application thereof |
| CN112210108A (en) * | 2020-10-29 | 2021-01-12 | 银金达(上海)新材料有限公司 | Preparation method and application of stain-resistant scratch-resistant PET (polyethylene terephthalate) film |
| CN113939565A (en) * | 2019-05-22 | 2022-01-14 | 日东化成株式会社 | Multilayer antifouling coating film and coated article having the same on surface |
| CN114958131A (en) * | 2022-06-20 | 2022-08-30 | 中国船舶重工集团公司第七二五研究所 | Antifouling paint with seawater temperature and pH response and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131289A (en) * | 2013-02-28 | 2013-06-05 | 海洋化工研究院有限公司 | Preparation and application of self-polishing antifouling coating matrix resin |
| CN103131289B (en) * | 2013-02-28 | 2015-05-27 | 海洋化工研究院有限公司 | Preparation and application of self-polishing antifouling coating matrix resin |
| CN105209561A (en) * | 2013-04-24 | 2015-12-30 | 日东化成株式会社 | Antifouling paint composition, copolymer for antifouling paint composition and method for manufacturing same, and painted object having on surface antifouling paint film formed using said composition |
| CN105209561B (en) * | 2013-04-24 | 2019-02-12 | 日东化成株式会社 | Antifouling paint compositions, antifouling paint compositions copolymer and its manufacturing method, surface have the painting object of the antifouling coat formed using the composition |
| CN103396513A (en) * | 2013-07-24 | 2013-11-20 | 华南理工大学 | Preparation method and application of main chain fracture type polyacrylic acid silane ester resin |
| WO2015010390A1 (en) * | 2013-07-24 | 2015-01-29 | 华南理工大学 | Preparation method and application of main chain scission-type polyacrylic silane ester resin |
| CN103396513B (en) * | 2013-07-24 | 2016-03-02 | 华南理工大学 | A kind of preparation method of main chain fracture type polyacrylic acid silane ester resin and application |
| US9701794B2 (en) | 2013-07-24 | 2017-07-11 | South China University Of Technology | Method for preparing main chain scission-type polysilyl (meth)acrylate resin and application thereof |
| CN113939565A (en) * | 2019-05-22 | 2022-01-14 | 日东化成株式会社 | Multilayer antifouling coating film and coated article having the same on surface |
| CN111533854A (en) * | 2020-06-02 | 2020-08-14 | 上海亿祺化工技术有限公司 | Silicon modified acrylic resin and application thereof |
| CN112210108A (en) * | 2020-10-29 | 2021-01-12 | 银金达(上海)新材料有限公司 | Preparation method and application of stain-resistant scratch-resistant PET (polyethylene terephthalate) film |
| CN114958131A (en) * | 2022-06-20 | 2022-08-30 | 中国船舶重工集团公司第七二五研究所 | Antifouling paint with seawater temperature and pH response and preparation method thereof |
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|---|---|
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