CN102372817A - Preparation method of amide derivative copolymer and application thereof - Google Patents
Preparation method of amide derivative copolymer and application thereof Download PDFInfo
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- CN102372817A CN102372817A CN2010102507915A CN201010250791A CN102372817A CN 102372817 A CN102372817 A CN 102372817A CN 2010102507915 A CN2010102507915 A CN 2010102507915A CN 201010250791 A CN201010250791 A CN 201010250791A CN 102372817 A CN102372817 A CN 102372817A
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- phenmethyl
- hydroxyl
- usaf
- methoxyl group
- acrylic amide
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Abstract
The invention relates to a preparation method of an amide derivative copolymer. Anti-fouling paint prepared from the copolymer of the invention can prevent marine organisms from adhering to the surfaces of nets, ships and coastal facilities, etc., and has the advantages of good antifouling performance, no occurrence of checking and exfoliation and other problems.
Description
Technical field
The present invention relates to a kind of preparation method of amide derivatives multipolymer and the application in antifouling paint thereof.
Technical background
When fishing net, hull bottom, underwater facility etc. are exposed in the seawater for a long time; Its outward appearance and function very easily stick to surface growth because of various marine fouling organisms and breeding suffers damage, and these marine fouling organisms comprise algae and mushrooms such as bacterium, fungi such as animals such as barnacle, hydra, Ascidian, diatom, green alga.When marine fouling organism sticks on the fishing net surface growth and breeding, stop up mesh, make the resistance of Fixed nets device increase, catch descends; And the inside and outside water body exchange of aquaculture net cage minimizing, the dissolved oxygen content in the case reduces, and the speed of growth of culturing sea-food descends even death; Make the weight of fishing net and the resistance of current increase, shorten the work-ing life of netting gear.At present, the people is arranged the multipolymer of methylacrylic acid tributyl tin ester and TEB 3K and Red copper oxide (Cu
2O) compsn is coated on surfaces such as hull bottom as a kind of antifouling paint, can prevent the harm of marine fouling organism effectively.Multipolymer in this antifouling paint is the meeting hydrolysis in seawater, discharges tributyl tin (TBT), brings into play antifouling effect.But the TBT harm marine eco-environment and sea farming industry cause gender variation and the housing distortion of oyster, blood clam and mussel like TBT.For example; The silyl ester class antifouling paint of in Japanese publication flat 4 (1992)-264170, flat 4 (1992)-264169 peaceful 4 (1992)-264168, describing can be used as not stanniferous antifouling paint; Yet as what in flat 6 (1994)-157941 peace 6 (1994)-157940 of Japanese publication, point out; This type antifouling paint not only antifouling property is poor, and very easily generation of cracks with problem such as peel off.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method and application of amide derivatives multipolymer, it can remedy the above-mentioned deficiency of prior art.
A kind of preparation method of amide derivatives multipolymer is characterized in that under action of free radical initiator, makes acrylamide deriv and unsaturated vinyl monomer copolymerization.
A kind of amide derivatives multipolymer is characterized in that preparing antifouling paint with it.
Multipolymer of the present invention can be used for preparing antifouling paint, and this coating can prevent that sea life from adhering on surfaces such as netting gear, naval vessel and coastal facility, and antifouling property is good, can generation of cracks with problem such as peel off.
Embodiment
Further specify the present invention with reference to embodiment below.
In the present embodiment; During the preparation multipolymer; In a reactor drum that whisking appliance, condensing surface, TM, Dropping feeder, nitrogen ingress pipe and heating jacket be housed, add 10kg toluene (solvent), 0.2kg Diisopropyl azodicarboxylate (radical initiator); In nitrogen gas stream 80 ℃ of following heated and stirred; Insulation; In 2 hours, in reactor drum, drip the mixture of 130kg Bing Xisuandingzhi (reactant), 110kg TEB 3K (reactant), 32.5kgN-(4-hydroxyl-3-methoxyl group-phenmethyl)-acrylic amide (reactant), 42.5kg ethyl propenoate (reactant) and 154kg N (solvent), drip the mixture of 6.5kg Diisopropyl azodicarboxylate and 200kg toluene simultaneously.Drip the back after under the identical temperature reaction solution being stirred 3 hours, add the 0.5kg Diisopropyl azodicarboxylate, under same temperature,, obtain the multipolymer of water white N-(4-hydroxyl-3-methoxyl group-phenmethyl)-acrylic amide reaction solution restir 3 hours.
Used reactant (methyl) acrylamide deriv of the present invention is N-(4-hydroxyl-3-methoxyl group-phenmethyl)-acrylic amide or N-(3-hydroxyl-4-methoxyl group-phenmethyl)-acrylic amide or N-(3; 4-dimethoxy-phenmethyl)-acrylic amide or N-(3; 4-dihydroxyl-phenmethyl)-acrylic amide or N-(4-hydroxyl-3-methoxyl group-phenmethyl)-USAF RH-1 or N-(3-hydroxyl-4-methoxyl group-phenmethyl)-USAF RH-1 or N-(3; 4-dimethoxy-phenmethyl)-one or more of USAF RH-1 or N-(3,4-dihydroxyl-phenmethyl)-USAF RH-1.
Used unsaturated vinyl monomer is methyl acrylate, ethyl propenoate, n-butyl acrylate, NSC 20949, tert-butyl acrylate, Isooctyl acrylate monomer, TEB 3K, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, vinylbenzene, vinyl acetate between to for plastic, butyric acid ethene, vinylchlorid among the present invention.When preparing multipolymer of the present invention, be preferably in the organic solvent and carry out, described organic solvent is toluene, YLENE, vinyl acetic monomer, N-BUTYL ACETATE, N, pimelinketone or mibk.Used radical initiator is a normal starter, for example the azo cpd or the superoxide of two butyronitrile of azo and so on.
Multipolymer of the present invention contains N-(4-hydroxyl-3-methoxyl group-phenmethyl)-acrylic amide, N-(3-hydroxyl-4-methoxyl group-phenmethyl)-acrylic amide, N-(3; 4-dimethoxy-phenmethyl)-acrylic amide, N-(3; 4-dihydroxyl-phenmethyl)-acrylic amide, N-(4-hydroxyl-3-methoxyl group-phenmethyl)-USAF RH-1, N-(3-hydroxyl-4-methoxyl group-phenmethyl)-USAF RH-1, N-(3; 4-dimethoxy-phenmethyl)-USAF RH-1 or N-(3; 4-dihydroxyl-phenmethyl)-and in the USAF RH-1 one or more, the weight content in multipolymer is 2～50%.
But multipolymer film forming of the present invention is water insoluble, but seawater erodable.Its structural formula is expressed as
Wherein X be H or-CH
3R is a kind of bioactive group that has, and R can select from following composition :-CH
2C
6H
3R
1R
2, R wherein
1And R
2Be independently hydroxyl, methoxy or ethoxy.B is the remaining part of unsaturated vinyl monomer.
Multipolymer of the present invention can be used for preparing antifouling paint, and this antifouling paint contains this multipolymer, softening agent, weighting agent and stain control agent, and their part by weight scope is respectively 150-250,5-20,1-35,5-60.Wherein multipolymer has filming function.Described softening agent is Vaseline or chlorinated paraffin etc.; Described weighting agent is red iron oxide, talcum powder or zinc oxide etc.; Described stain control agent is alpha-bromo-cinnamaldehyde, N-phenylmaleimide, tetramethyl-thiuram disulfide, 4,5-two chloro-2-n-octyls-4-isothiazoline-3-ketone (SeaNine
TM211) one or more in.During preparation, N-(4-hydroxyl-3-methoxyl group-phenmethyl)-multipolymer of acrylic amide, 15g Vaseline, 2gSeaNine that 200g is made
TM211,20g tetramethyl-thiuram disulfide, 5g alpha-bromo-cinnamaldehyde and 5g red iron oxide (Bayferrox
TM4130) vibration 2 hours in a paint shaker that contains granulated glass sphere of mixture is filtered with 100 purpose strainers then.The antifouling property of the antifouling paint that obtains for test; After the fishing net of two 40 * 40cm soaked in the multipolymer of the N-that makes (4-hydroxyl-3-methoxyl group-phenmethyl)-acrylic amide and antifouling paint respectively; Take out and dry, the net sheet increases weight 26% and 38% respectively, will net sheet and manage after frame fixes with the UPVC of 40 * 40 * 1.6cm; This experimental network sheet is hung over Deep sea net cage culture zone, Xun Shan town, Rongcheng City (5～December) obtained goodish experimental result, like following table.
Annotate: 0 adheres to for no any sea life; 100 is that sea life adhere to the net sheet full.
Claims (10)
1. the preparation method of an amide derivatives multipolymer is characterized in that under action of free radical initiator, makes acrylamide deriv and unsaturated vinyl monomer copolymerization.
2. an amide derivatives multipolymer is characterized in that preparing antifouling paint with it.
3. an antifouling paint is characterized in that containing amide derivatives multipolymer, softening agent, weighting agent and stain control agent, and their part by weight scope is respectively 150-250,5-20,1-35,5-60.
4. preparation method as claimed in claim 1; It is characterized in that described acrylamide deriv is N-(4-hydroxyl-3-methoxyl group-phenmethyl)-acrylic amide or N-(3-hydroxyl-4-methoxyl group-phenmethyl)-acrylic amide or N-(3; 4-dimethoxy-phenmethyl)-acrylic amide or N-(3; 4-dihydroxyl-phenmethyl)-acrylic amide or N-(4-hydroxyl-3-methoxyl group-phenmethyl)-USAF RH-1 or N-(3-hydroxyl-4-methoxyl group-phenmethyl)-USAF RH-1 or N-(3; 4-dimethoxy-phenmethyl)-in USAF RH-1 or N-(3,4-dihydroxyl-phenmethyl)-USAF RH-1 one or more.
5. preparation method as claimed in claim 1; It is characterized in that described copolyreaction carries out in organic solvent, described organic solvent is one or more in toluene, YLENE, vinyl acetic monomer, N-BUTYL ACETATE, N, pimelinketone or the mibk.
6. preparation method as claimed in claim 1 is characterized in that described unsaturated vinyl monomer is methyl acrylate, ethyl propenoate, n-butyl acrylate, NSC 20949, tert-butyl acrylate, Isooctyl acrylate monomer, TEB 3K, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, vinylbenzene, vinyl acetate between to for plastic, butyric acid ethene or vinylchlorid.
7. preparation method as claimed in claim 1; It is characterized in that described multipolymer contains N-(4-hydroxyl-3-methoxyl group-phenmethyl)-acrylic amide, N-(3-hydroxyl-4-methoxyl group-phenmethyl)-acrylic amide, N-(3; 4-dimethoxy-phenmethyl)-acrylic amide, N-(3; 4-dihydroxyl-phenmethyl)-acrylic amide, N-(4-hydroxyl-3-methoxyl group-phenmethyl)-USAF RH-1, N-(3-hydroxyl-4-methoxyl group-phenmethyl)-USAF RH-1, N-(3; 4-dimethoxy-phenmethyl)-and in USAF RH-1 or N-(3,4-dihydroxyl-phenmethyl)-USAF RH-1 one or more, the weight content in multipolymer is 2～50%.
8. antifouling paint as claimed in claim 3 is characterized in that described softening agent is Vaseline or chlorinated paraffin.
9. the antifouling material that freezes as claimed in claim 3 is characterized in that described weighting agent is red iron oxide, talcum powder or zinc oxide.
10. antifouling paint as claimed in claim 3 is characterized in that described stain control agent is alpha-bromo-cinnamaldehyde, N-phenyl horse water imide, tetramethyl-thiuram disulfide, 4, one or more in 5-two chloro-2-n-octyls-4-isothiazoline-3-ketone.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102507915A CN102372817A (en) | 2010-08-11 | 2010-08-11 | Preparation method of amide derivative copolymer and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102507915A CN102372817A (en) | 2010-08-11 | 2010-08-11 | Preparation method of amide derivative copolymer and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014087817A1 (en) * | 2012-12-05 | 2014-06-12 | 独立行政法人科学技術振興機構 | Resin for nanoimprinting, laminate containing resin for nanoimprinting, printed board containing resin for nanoimprinting, and method for producing nanoimprint substrate |
| WO2015152176A1 (en) * | 2014-03-31 | 2015-10-08 | 独立行政法人物質・材料研究機構 | Nano-coating material, method for manufacturing same, coating agent, functional material, and method for manufacturing same |
| CN114591468A (en) * | 2020-12-03 | 2022-06-07 | 中国石油化工股份有限公司 | Oil-water interface activation drag reducer for cold production of thickened oil and preparation method thereof |
-
2010
- 2010-08-11 CN CN2010102507915A patent/CN102372817A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014087817A1 (en) * | 2012-12-05 | 2014-06-12 | 独立行政法人科学技術振興機構 | Resin for nanoimprinting, laminate containing resin for nanoimprinting, printed board containing resin for nanoimprinting, and method for producing nanoimprint substrate |
| JP5689207B2 (en) * | 2012-12-05 | 2015-03-25 | 独立行政法人科学技術振興機構 | Nanoimprint resin composition, nanoimprint substrate, and method for producing nanoimprint substrate |
| US11492432B2 (en) | 2012-12-05 | 2022-11-08 | Japan Science And Technology Agency | Resin for nanoimprinting, laminate containing resin for nanoimprinting, printed board containing resin for nanoimprinting, and method for producing nanoimprint substrate |
| WO2015152176A1 (en) * | 2014-03-31 | 2015-10-08 | 独立行政法人物質・材料研究機構 | Nano-coating material, method for manufacturing same, coating agent, functional material, and method for manufacturing same |
| US10177383B2 (en) | 2014-03-31 | 2019-01-08 | National Institute For Materials Science | Nano-coating material, method for manufacturing same, coating agent, functional material, and method for manufacturing same |
| CN114591468A (en) * | 2020-12-03 | 2022-06-07 | 中国石油化工股份有限公司 | Oil-water interface activation drag reducer for cold production of thickened oil and preparation method thereof |
| CN114591468B (en) * | 2020-12-03 | 2024-01-26 | 中国石油化工股份有限公司 | Oil-water interface activation drag reducer for thickened oil cold recovery and preparation method |
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Application publication date: 20120314 |