CN1273457C - Alkoxy propyl isothiazolinone and its preparation process and use - Google Patents
Alkoxy propyl isothiazolinone and its preparation process and use Download PDFInfo
- Publication number
- CN1273457C CN1273457C CN 200410035989 CN200410035989A CN1273457C CN 1273457 C CN1273457 C CN 1273457C CN 200410035989 CN200410035989 CN 200410035989 CN 200410035989 A CN200410035989 A CN 200410035989A CN 1273457 C CN1273457 C CN 1273457C
- Authority
- CN
- China
- Prior art keywords
- isothiazolinone
- propyl
- ammonia
- propyl group
- alkoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to alkoxy propyl isothiazolinone which is characterized in that the molecular formula of the present invention is C6H6Cl2NO2SR; in the molecular formula, R stands for CH3, CH2CH3, CH(CH3)2 or CH2CH2CH2CH3. A preparation method of the present invention comprises the following steps: sodium polysulfide reacts with methyl acrylate, which generates dithiodipropionic acid dimethyl ester; the dithiodipropionic acid dimethyl ester and alkoxy propylamine have an aminolysis reaction, which generates N, N'-dialkoxy propyl dithio dipropionamide; the N, N'-dialkoxy propyl dithio dipropionamide reacts with sulfuryl chloride. The alkoxy propyl isothiazolinone can be used as antifouling agents used for preparing pollution prevention marine coating. The pollution prevention marine coating can be rapidly degraded and isolated in the marine environment, and the pollution prevention marine coating has the limited bioavailability for marine lives. Little alkoxy propyl isothiazolinone can be accumulated in organisms, the toxicity is low, the effect on pollution prevention is good, and the service life is long. When the alkoxy propyl isothiazolinone is prepared, the raw material is easily obtained, the cost is low, and the yield is high.
Description
Technical field
The present invention relates to a kind of isothiazolinone derivatives, particularly relate to a kind of alkoxyl group propyl group isothiazolinone compound and preparation method thereof and the application in the preparation marine antifouling coating.
Background technology
Surfaces such as the netting gear of long period of soaking in seawater, hull, underwater facility are usually adhering to various marine organisms, and halobiontic adhering to can cause its surface stained, increases surperficial frictional resistance, also quickened corrosion.The most popular method that solves sea marine organism pollution is the coating that brushing contains stain control agent.At present, the stain control agent of widely applying is the stain control agent that contains organotin and Red copper oxide both at home and abroad, promptly 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.Its mechanism of action is sustained release poison material tributyltin oxide (TBT) and Red copper oxide, harmful dirt settling (barnacle, Ascidian, marine alga etc.) that commute is attached to hull, maritime facilities surface has lethal effect, but simultaneously, TBT can cause gender variation and housing distortion, the serious harm marine eco-environment and the sea farming industry of oyster, blood clam and mussel.The most famous self polishing copolymer antifouling paint that contains TBT is that the patent No. is the European patent of EP-A-51930.This patent is the work of the milestone of announcement TBT multipolymer.Since then the TBT antifouling paint has been ruled antifouling paint market and has been reached 20 years.Up to 1987, people recognized that this organo-tin compound has very strong toxicity, pollutes the environment, even has influence on human beings'health by food chain.For this reason, need the not stanniferous marine antifouling coating of exploitation to replace the organotin marine antifouling coating.
Summary of the invention
The purpose of this invention is to provide a kind of alkoxyl group propyl group isothiazolinone and preparation method thereof, and it is applied to prepare marine antifouling coating, to remedy the above-mentioned deficiency of prior art.
A kind of alkoxyl group propyl group isothiazolinone, the molecular formula that it is characterized in that it is C
6H
6Cl
2NO
2SR, structural formula is:
In the formula, R is CH
3, CH
2CH
3, CH (CH
3)
2Or CH
2CH
2CH
2CH
3
The preparation method of above-mentioned alkoxyl group propyl group isothiazolinone, it is characterized in that generating the dithio dipropyl dimethyl phthalate with sodium polysulphide and methyl acrylate reaction, it generates N with alkoxypropan ammonia aminolysis reaction again, and N '-dialkoxy propyl disulfide is for dipropyl acidamide, and the latter and sulfuryl chloride react.
Above-mentioned alkoxyl group propyl group isothiazolinone is used to prepare marine antifouling coating as stain control agent.
Alkoxyl group propyl group isothiazolinone of the present invention can be degraded in environment fast as stain control agent, isolate fast, marine organisms are produced limited bioavailability, have accumulation in the very little organism, low toxicity, good antifouling effect, long service life, and in the preparation, raw material is easy to get, cost is low, the productive rate height.
Embodiment
1, the preparation of dithio dipropyl dimethyl phthalate
In the there-necked flask of the 500ml that whipping appts, condenser, thermometer are housed, add 200ml 10% (concentration expressed in percentage by weight, down together) NaHCO successively
3Solution, 21.7g (0.25mol) methyl acrylate are cooled to-5～10 ℃ and remain under this temperature, drip the good sodium polysulfide solution of above-mentioned cooling in 0.5～2 hour.Dropwise, remove ice-water bath, at room temperature continue reaction 5-6h, reaction finishes.Standing demix, branch vibration layer, the Na of adding 120ml1mol/L in oil reservoir
2SO
3Solution continues reaction 2～5h down at 50 ℃ then, and reaction finishes.Standing demix again, branch vibration layer, oil reservoir washes with water.The gained crude product gets flaxen oily matter 26.8g through underpressure distillation, and productive rate is 89.3%, and boiling point is 182-185 ℃/7mmHg.
2, N, N '-dimethoxy propyl disulfide is for the preparation of dipropyl acidamide
In being housed, the 500ml there-necked flask of whipping appts, condenser, thermometer adds 26.7g (0.3mol) γ-methoxy propyl ammonia, 2.5ml triethylamine successively, the control temperature of reaction system was-5～5 ℃ and remains under this temperature, dripped the β-dithio dipropyl dimethyl phthalate 23.8g (0.1mol) for preparing in 0.5～1.5 hour.Dropwise, remove ice-water bath, at room temperature continue reaction 24 hours, finish reaction, obtain golden yellow solid.Suction filtration obtains the faint yellow solid product.Dry back dehydrated alcohol recrystallization.Obtain white plates crystal 2 4.1g, productive rate is 68.4%.Fusing point: 103.3-105.1 ℃.
γ in the present embodiment-methoxy propyl ammonia is replaced with γ-ethoxy-c ammonia, γ-isopropoxy third ammonia or γ-butoxy third ammonia can obtain N respectively, N '-diethoxy propyl disulfide is for dipropyl acidamide, N, N '-diisopropoxy propyl disulfide is for dipropyl acidamide or N, and N '-dibutoxy propyl disulfide is for dipropyl acidamide
3,4, the preparation of 5-two chloro-2-methoxy-propyls-4-isothiazoline-3-ketone
In being housed, the 250ml there-necked flask of whipping appts, condenser, thermometer adds the ethyl acetate of 175ml and the N of 18.0g (0.05mol) respectively, N '-dimethoxy propyl disulfide is for dipropyl acidamide, the control temperature of reaction system is-10～5 ℃, drip 40.0g (0.3mol) sulfuryl chloride subsequently, drip off in 3 hours, drip this temperature continuation reaction of complete maintenance and slowly be warming up to room temperature after 3 hours, 30～35 ℃ of reactions of water-bath 3 hours, end was reacted again.The vibration of adding 50ml water is 3 minutes in the solution that obtains, and leaves standstill the back separatory, adds the 15.0g anhydrous magnesium sulfate in organic phase wherein, dry 15 minutes after-filtration, and filtrate is used Rotary Evaporators pressure reducing and steaming solvent.Obtain yellow thick liquid 15.4g, thick productive rate is 63.9%.The isolating pure product productive rate of post is 56.6%.
With the N in the present embodiment, N '-dimethoxy propyl disulfide replaces with N for dipropyl acidamide, N '-diethoxy propyl disulfide is for dipropyl acidamide, N, N '-diisopropoxy propyl disulfide is for dipropyl acidamide or N, N '-dibutoxy propyl disulfide can obtain 4 respectively for dipropyl acidamide, 5-dichloro 2-ethoxycarbonyl propyl-4-isothiazoline-3-ketone, 4,5-two chloro-2-isopropoxide propyls-4-isothiazoline-3-ketone or 4,5-dichloro 2-butoxy propyl group-4-isothiazoline-3-ketone.
With products therefrom with nucleus magnetic resonance (
1H NMR) method characterizes, and its characteristic peak ownership is as shown in the table:
Compound of the present invention can be used for preparing marine antifouling coating, this marine antifouling coating is made up of resin solution, softening agent, one or more stopping composition and one or more compounds of the present invention, and their weight percentage scope is 20～60,1～20,1～30 and 1～50.Resin solution concentration range wherein is 20%～60% (concentration expressed in percentage by weight, down together), can adopt acrylic resin soln, chlorinated rubber solution, zinc acrylate resin solution, acrylate resin solution, filming function is arranged, and organic solvent can be ethyl acetate, butylacetate, dimethylbenzene, toluene, butanols; Softening agent is Vaseline, clorafin, dibutyl phthalate or dioctyl phthalate (DOP); Stopping composition is red iron oxide, talcum powder, titanium dioxide, aerosil or zinc oxide.During preparation, with concentration butylacetate solution, 2.5g clorafin, 12g red iron oxide, the aerosil of 2.5g, the 33g 4 of 40% 50g acrylic resin, the vibration 2 hours in a paint shaker that contains granulated glass sphere of the mixture of 5-two chloro-2-butoxy propyl group-4-isothiazoline-3-ketone is filtered with 100 purpose strainers then.The antifouling property of the antifouling paint that obtains for test, with reference to national standard " antifouling varnish model shallow sea soak test method " (GB 5370-85), with the antifouling paint brushing plate long for 250mm, wide be that the experiment model adopts use iron bolt in the rectangular batten of trough of belt two to fix on 150mm, the thick soft steel experiment model for 2mm.Should test model and hang over Deep sea net cage culture zone, Xun Shan town, Rongcheng City (2 years) and obtained goodish experimental result, as shown in the table.
| 6 months | 12 months | 24 months | |
| Blank model | 20 | 40 | 100 |
| Soaked the model of antifouling paint | 0 | 0 | 3 |
Annotate: 0,3,20,40,100 is the bond area percentage ratios of marine organisms on model.
Claims (6)
1, a kind of alkoxyl group propyl group isothiazolinone, the molecular formula that it is characterized in that it is C
6H
6Cl
2NO
2SR, structural formula is:
In the formula, R is CH
3, CH
2CH
3, CH (CH
3)
2Or CH
2CH
2CH
2CH
3
2, the preparation method of the described alkoxyl group propyl group of claim 1 isothiazolinone, it is characterized in that generating the dithio dipropyl dimethyl phthalate with sodium polysulphide and methyl acrylate reaction, it generates N with alkoxypropan ammonia aminolysis reaction again, N '-dialkoxy propyl disulfide is for dipropyl acidamide, and the latter and sulfuryl chloride react.
3, preparation method as claimed in claim 2, it is characterized in that described alkoxyl group propyl group isothiazolinone is 4,5-two chloro-2-methoxy-propyls-4-isothiazoline-3-ketone, 4,5-two chloro-2-ethoxycarbonyl propyls-4-isothiazoline-3-ketone, 4,5-two chloro-2-isopropoxide propyls-4-isothiazoline-3-ketone or 4,5-two chloro-2-butoxy propyl group-4-isothiazoline-3-ketone.
4, preparation method as claimed in claim 2 is characterized in that described alkoxypropan ammonia is γ-methoxy propyl ammonia, γ-ethoxy-c ammonia, γ-isopropoxy third ammonia or γ-butoxy third ammonia.
5, the described alkoxyl group propyl group of claim 1 isothiazolinone is used to prepare marine antifouling coating.
6, marine antifouling coating as claimed in claim 5, it is characterized in that it is made up of described one or more alkoxyl group propyl group isothiazolinone of resin solution, softening agent, one or more stopping composition and claim 1, their weight percentage scope is 20～60,1～20,1～30 and 1～50, resin in the described resin solution is acrylic resin, chlorinated rubber, zinc acrylate resin, acrylate resin, solvent is ethyl acetate, butylacetate, dimethylbenzene, toluene, butanols, and the concentration of resin solution is 20%～60%.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410035989 CN1273457C (en) | 2004-10-16 | 2004-10-16 | Alkoxy propyl isothiazolinone and its preparation process and use |
| PCT/CN2005/001629 WO2006037274A1 (en) | 2004-10-10 | 2005-09-30 | Alkoxypropyl isothiazolinone and preparation method and use thereof |
| AT05795406T ATE555100T1 (en) | 2004-10-10 | 2005-09-30 | ALKOXYPROPYLISOTHIAZOLINONE AND PRODUCTION METHOD AND USE THEREOF |
| JP2007534990A JP4789950B2 (en) | 2004-10-10 | 2005-09-30 | Alkoxypropylisothiazolinone, and its production and use |
| PT05795406T PT1810966E (en) | 2004-10-10 | 2005-09-30 | Alkoxypropyl isothiazolinone and preparation method and use thereof |
| EP05795406A EP1810966B1 (en) | 2004-10-10 | 2005-09-30 | Alkoxypropyl isothiazolinone and preparation method and use thereof |
| DK05795406.7T DK1810966T3 (en) | 2004-10-10 | 2005-09-30 | Alkoxypropylisothiazolinone and method of preparation and use thereof |
| ES05795406T ES2386770T3 (en) | 2004-10-10 | 2005-09-30 | Alkoxypropylisothiazolinone and method of preparation and use thereof |
| US11/664,717 US7442240B2 (en) | 2004-10-10 | 2005-09-30 | Alkoxylpropylisothiazolinone and preparation method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410035989 CN1273457C (en) | 2004-10-16 | 2004-10-16 | Alkoxy propyl isothiazolinone and its preparation process and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1634899A CN1634899A (en) | 2005-07-06 |
| CN1273457C true CN1273457C (en) | 2006-09-06 |
Family
ID=34845753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410035989 Expired - Fee Related CN1273457C (en) | 2004-10-10 | 2004-10-16 | Alkoxy propyl isothiazolinone and its preparation process and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1273457C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7893273B2 (en) | 2006-04-03 | 2011-02-22 | Beijing Tianqing Chemicals Co. Ltd. | Preparation of N-substituted isothiazolinone derivatives |
| CN104230916B (en) * | 2014-09-30 | 2020-04-28 | 上海化学试剂研究所有限公司 | Isothiazolinone compound and preparation method and application thereof |
| 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 |
-
2004
- 2004-10-16 CN CN 200410035989 patent/CN1273457C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1634899A (en) | 2005-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1709925B (en) | Resin of zinc acrylate or copper acrylate containing capsaicin function group, its preparation and use | |
| KR101464898B1 (en) | Antifouling material composition, antifouling film, and method for controlling hydrolysis rate of antifouling film | |
| KR101015932B1 (en) | Antibiotic composition and preparation method thereof | |
| CN102300944A (en) | Marine organism anti-fouling paint and preparing method and use thereof | |
| CN1709921B (en) | Resin of zinc acrylate or copper acrylate containing indole function group, its preparation and use | |
| CN1273457C (en) | Alkoxy propyl isothiazolinone and its preparation process and use | |
| CN1317270C (en) | Alkoxy ethoxy propyl isothiazolinone and its preparation process and use | |
| EP3339387A1 (en) | Compounds based on of adducts with isocyanates for coating compositions | |
| CN1266130C (en) | Ester derivative of indole, its preparation method and application | |
| CN1702084A (en) | Carboxymethyl chitosan copper or zinc salts and their preparation method and use thereof | |
| EP0841380B1 (en) | Method of making polymeric binders and use thereof in antifouling paints | |
| CN104230916B (en) | Isothiazolinone compound and preparation method and application thereof | |
| CN1266132C (en) | Amide derivative of indole, its preparation method and application | |
| CN1192013C (en) | Rosin amine anti-fouling agents | |
| EP0659847A1 (en) | Anti-fouling compositions and fouling control of harmful aquatic organisms | |
| CN1709868A (en) | Dithio dipropyl acidamide, and its preparing method and use | |
| CN102125038B (en) | Anti-fouling agent containing paeonolum and nicotine structure and preparation method thereof | |
| KR20030097815A (en) | Alkylamine derivatives as antifouling agents | |
| EP2285914A1 (en) | Novel environmental friendly anti-microbial adhesion agents for anti-fouling paints and anti-fouling paints containing them | |
| CN116082178A (en) | Preparation method and new application of pyrene-containing acrylamide derivative | |
| JPH05286820A (en) | Agent for preventing adhesion of noxious aquatic organism | |
| JP2008515820A (en) | Alkoxypropylisothiazolinone, and its production and use | |
| JP4920002B2 (en) | Antifouling agent against underwater harmful organisms | |
| KR19990081985A (en) | Triphenylborane-rosin amine addition compound and use thereof | |
| KR101365715B1 (en) | Antifoul agent and antifouling paint composition comprising cyclodextrin complex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060906 Termination date: 20151016 |
|
| EXPY | Termination of patent right or utility model |