CN1425700A - Process for preparing copolymer of amide derivative and use - Google Patents
Process for preparing copolymer of amide derivative and use Download PDFInfo
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- CN1425700A CN1425700A CN 03111823 CN03111823A CN1425700A CN 1425700 A CN1425700 A CN 1425700A CN 03111823 CN03111823 CN 03111823 CN 03111823 A CN03111823 A CN 03111823A CN 1425700 A CN1425700 A CN 1425700A
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- phenmethyl
- acrylamide
- hydroxyl
- methoxyl group
- methacrylamide
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Abstract
The present invention features that under the action of free radical initiator, propenyl amide derivative and unsaturated vinyl monomer are made to copolymerize to produce amide derivative copolymer for preparing antifouling paint. The antifouling paint consists of the polymer plasticizer, stuffing and antifouling agent in the weight ratio of 150-250 to 5-20 to 1-35 to 5-60. The antifouling paint can prevent marine organisms from attaching to the surface of net, ship and coast facilities, and has high antifouling performance, no chap and falling.
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 methacrylic acid tributyl tin ester and methyl methacrylate and Red copper oxide (Cu
2O) composition 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 as TBT.For example, the silyl ester class antifouling paint of describing in, flat 4 (1992)-264169 peace 4 (1992)-264168 flat 4 (1992)-264170 in Japanese publication 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, not only antifouling property is poor for this class antifouling paint, and be full of cracks very easily takes place and 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 derivative 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 marine organisms from adhering on surfaces such as netting gear, naval vessel and coastal facility, and antifouling property is good, be full of cracks can not take place and problem such as peel off.
Embodiment
Further specify the present invention below with reference to embodiment.
In the present embodiment, during the preparation multipolymer, to one agitator is housed, condenser, thermometer, Dropping feeder, add 10kg toluene (solvent) in the reactor of nitrogen ingress pipe and heating jacket, 0.2kg Diisopropyl azodicarboxylate (radical initiator), in nitrogen gas stream 80 ℃ of following heated and stirred, insulation, in 2 hours, in reactor, drip 130kg butyl acrylate (reactant), 110kg methyl methacrylate (reactant), (32.5kgN-4-hydroxyl-3-methoxyl group-phenmethyl)-acrylamide (reactant), 42.5kg the mixture of ethyl propenoate (reactant) and 154kg dimethyl formamide (solvent) drips 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)-acrylamide reaction solution restir 3 hours.
Used reactant (methyl) acrylamide derivative of the present invention is N-(4-hydroxyl-3-methoxyl group-phenmethyl)-acrylamide or N-(3-hydroxyl-4-methoxyl group-phenmethyl)-acrylamide or N-(3,4-dimethoxy-phenmethyl)-acrylamide or N-(3,4-dihydroxyl-phenmethyl)-acrylamide or N-(4-hydroxyl-3-methoxyl group-phenmethyl)-Methacrylamide or N-(3-hydroxyl-4-methoxyl group-phenmethyl)-Methacrylamide or N-(3,4-dimethoxy-phenmethyl)-one or more of Methacrylamide or N-(3,4-dihydroxyl-phenmethyl)-Methacrylamide.
Used unsaturated vinyl monomer is methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, 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, dimethylbenzene, vinyl acetic monomer, N-BUTYL ACETATE, dimethyl formamide, pimelinketone or mibk.Used radical initiator is a normal starter, for example azo-compound of Diisopropyl azodicarboxylate and so on or superoxide.
Multipolymer of the present invention contains N-(4-hydroxyl-3-methoxyl group-phenmethyl)-acrylamide, N-(3-hydroxyl-4-methoxyl group-phenmethyl)-acrylamide, N-(3,4-dimethoxy-phenmethyl)-acrylamide, N-(3,4-dihydroxyl-phenmethyl)-acrylamide, N-(4-hydroxyl-3-methoxyl group-phenmethyl)-Methacrylamide, N-(3-hydroxyl-4-methoxyl group-phenmethyl)-Methacrylamide, N-(3,4-dimethoxy-phenmethyl)-Methacrylamide or N-(3,4-dihydroxyl-phenmethyl)-and in the Methacrylamide 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 that a profit has bioactive group, 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 part of unsaturated vinyl monomer remainder.
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 acrylamide, 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)-acrylamide and antifouling paint respectively, take out and dry, the net sheet increases weight 26% and 38% respectively, with the net sheet with the UPVC of 40 * 40 * 1.6cm pipe frame fixing after, this experimental network sheet is hung over Deep sea net cage culture zone, Xun Shan town, Rongcheng City (5～December) obtained goodish experimental result, as following table.
| 1 month | 2 months | 6 months | |
| Blank net sheet | 20 | ?40 | ?100 |
| Soaked the net sheet of N-(4-hydroxyl-3-methoxyl group-phenmethyl)-acrylamide copolymer | 0 | ?5 | ?30 |
| Soaked the net sheet of antifouling paint | 0 | ?0 | ?5 |
Annotate: 0 adheres to for no any marine organisms; 100 is that marine organisms adhere to the net sheet completely.
Claims (10)
1, a kind of preparation method of amide derivatives multipolymer is characterized in that under action of free radical initiator, makes acrylamide derivative and unsaturated vinyl monomer copolymerization.
2, a kind of amide derivatives multipolymer is characterized in that preparing antifouling paint with it.
3, a kind of 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 derivative is N-(4-hydroxyl-3-methoxyl group-phenmethyl)-acrylamide or N-(3-hydroxyl-4-methoxyl group-phenmethyl)-acrylamide or N-(3,4-dimethoxy-phenmethyl)-acrylamide or N-(3,4-dihydroxyl-phenmethyl)-acrylamide or N-(4-hydroxyl-3-methoxyl group-phenmethyl)-Methacrylamide or N-(3-hydroxyl-4-methoxyl group-phenmethyl)-Methacrylamide or N-(3,4-dimethoxy-phenmethyl)-in Methacrylamide or N-(3,4-dihydroxyl-phenmethyl)-Methacrylamide 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, dimethylbenzene, vinyl acetic monomer, N-BUTYL ACETATE, dimethyl formamide, 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, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, 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)-acrylamide, N-(3-hydroxyl-4-methoxyl group-phenmethyl)-acrylamide, N-(3,4-dimethoxy-phenmethyl)-acrylamide, N-(3,4-dihydroxyl-phenmethyl)-acrylamide, N-(4-hydroxyl-3-methoxyl group-phenmethyl)-Methacrylamide, N-(3-hydroxyl-4-methoxyl group-phenmethyl)-Methacrylamide, N-(3,4-dimethoxy-phenmethyl)-Methacrylamide or N-(3,4-dihydroxyl-phenmethyl)-and in the Methacrylamide 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, antifouling paint 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-phenylmaleimide, tetramethyl-thiuram disulfide, 4, one or more in 5-two chloro-2-n-octyls-4-isothiazoline-3-ketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03111823 CN1188439C (en) | 2003-01-10 | 2003-01-10 | Process for preparing copolymer of amide derivative and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03111823 CN1188439C (en) | 2003-01-10 | 2003-01-10 | Process for preparing copolymer of amide derivative and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1425700A true CN1425700A (en) | 2003-06-25 |
| CN1188439C CN1188439C (en) | 2005-02-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03111823 Expired - Fee Related CN1188439C (en) | 2003-01-10 | 2003-01-10 | Process for preparing copolymer of amide derivative and use |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531865B (en) * | 2009-04-03 | 2011-02-16 | 中国船舶重工集团公司第七二五研究所 | Method for preparing pollution-proof surface material suitably applied in marine environment |
| CN107513123A (en) * | 2017-08-11 | 2017-12-26 | 浙江海洋大学 | One kind is based on catechol structure functionalization silicone-contained acrylic resin solution and its preparation method and application |
| CN107603396A (en) * | 2017-09-01 | 2018-01-19 | 浙江海洋大学 | A kind of aquiculture net cage etting antifouling paint |
-
2003
- 2003-01-10 CN CN 03111823 patent/CN1188439C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531865B (en) * | 2009-04-03 | 2011-02-16 | 中国船舶重工集团公司第七二五研究所 | Method for preparing pollution-proof surface material suitably applied in marine environment |
| CN107513123A (en) * | 2017-08-11 | 2017-12-26 | 浙江海洋大学 | One kind is based on catechol structure functionalization silicone-contained acrylic resin solution and its preparation method and application |
| CN107603396A (en) * | 2017-09-01 | 2018-01-19 | 浙江海洋大学 | A kind of aquiculture net cage etting antifouling paint |
| CN107603396B (en) * | 2017-09-01 | 2020-06-09 | 浙江海洋大学 | Antifouling paint for aquaculture net cage net clothes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1188439C (en) | 2005-02-09 |
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