CN1260260C - Acrylic amide resin with side chain hanging pepper ring and preparation method and application thereof - Google Patents
Acrylic amide resin with side chain hanging pepper ring and preparation method and application thereof Download PDFInfo
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- CN1260260C CN1260260C CN 200410035999 CN200410035999A CN1260260C CN 1260260 C CN1260260 C CN 1260260C CN 200410035999 CN200410035999 CN 200410035999 CN 200410035999 A CN200410035999 A CN 200410035999A CN 1260260 C CN1260260 C CN 1260260C
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- acrylamide
- side chain
- resin
- preparation
- piperonyl cyclonene
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Abstract
The present invention relates to an acrylamide resin with a peperic ring hung on a side chain and a preparation method thereof. During preparation, firstly, the F-C reaction of peperic ring and N-hydroxymethyl acrylamide or N-methylol-alpha-methacrylamide is performed in the presence of an acidic catalyst to obtain an acrylamide derivative; secondly, the acrylamide derivative reacts with methacrylic ester and acrylic ester through copolymerization to obtain the acrylamide resin with a peperic ring hung on a side chain. The acrylamide resin with a peperic ring hung on a side chain is used for preparing an antifouling marine coating prepared from 25 to 60 wt% of a solution of the acrylamide resin with a peperic ring hung on a side chain, 1 to 20 wt% of plasticizing agent, 1 to 30 wt% of filling material and 1 to 40 wt% of antifouling agent. The acrylamide resin with a peperic ring hung on a side chain not only can be used as a film forming material for the antifouling marine coating, but also has favorable antifouling activity.
Description
Technical field
The present invention relates to a kind of acrylamide resin, acrylamide resin of particularly a kind of suspended side chain piperonyl cyclonene and preparation method thereof and the application in the preparation marine antifouling coating.
Background technology
As everyone knows, marine organisms are attached to hull bottom, increase running resistance, reduce ship's speed, many power consumptions source; Be attached to the sea farming net, the mesh that results in blockage influences the seawater convection current, can cause dysplasia of mariculture fish and shellfish even death; Be attached to the cooled with seawater pipeline inner wall, can cause line clogging, thereby lead to Serious Accident.All these has brought enormous economic loss to the mankind.The optimal path that solves marine biofouling at present is to apply the coating that contains stain control agent, for example a kind of multipolymer and Red copper oxide (Cu that has comprised methacrylic acid tributyl tin ester and methyl methacrylate
2O) composition as a kind of antifouling paint, is coated on surfaces such as hull bottom, can prevent the harm of marine fouling organism effectively.Multipolymer in this antifouling paint is the meeting hydrolysis in seawater, thereby discharges tributyl tin (TBT), brings into play antifouling effect.Yet tributyl tin (TBT) has endangered the marine eco-environment and sea farming industry, causes gender variation and the housing distortion of oyster, blood clam and mussel as TBT.Thereby International Maritime Organizaton (IMO) passes through " international control boats and ships system's pact of harmful antifouling end " October 1 calendar year 2001, proposition was from January 1st, 2003, and various countries' boats and ships all should ban use of has bigger toxic organo-tin compound (TBT) antifouling paint to marine organisms.Therefore, need development not contain the antifouling paint of organotin as surrogate.
Summary of the invention
The object of the present invention is to provide a kind of acrylamide resin and preparation method thereof with antifouling property, suspended side chain piperonyl cyclonene, this resin is as the filmogen of marine antifouling coating, not only have good from polishability, and have the friendly performance of nontoxic ecology, to remedy the demand of prior art.
A kind of acrylamide resin of suspended side chain piperonyl cyclonene is characterized in that its structural formula is
R in the formula
1Be H or CH
3R
2Be CH
3, CH
2CH
3, CH
2CH
2CH
2CH
3, CH
2CH (CH
3)
2Or C (CH
3)
3R
3Be H or CH
3R
4Be H, CH
2CHCONHCH
2Or CH
2C (CH
3) CONHCH
2R
5Be H or CH
3R
6Be CH
3, CH
2CH
3, CH
2CH
2CH
2CH
3, CH
2CH (CH
3)
2Or C (CH
3)
3M is 0～12000; N is 2～4000; O is 0～12000.
The preparation method of the acrylamide resin of above-mentioned suspended side chain piperonyl cyclonene is characterized in that earlier by piperonyl cyclonene and N hydroxymethyl acrylamide or N-methylol-Alpha-Methyl acrylamide F-C taking place in the presence of an acidic catalyst reacts, and makes acrylamide derivative; The latter reacts with methacrylic ester and/or acrylic ester copolymer again.
The application of the acrylamide resin of above-mentioned suspended side chain piperonyl cyclonene in the preparation marine antifouling coating.
The acrylamide resin of suspended side chain piperonyl cyclonene of the present invention not only can be used as the film forming matter of antifouling paint, and has good antifouling property and ecological friendly.
Embodiment
1, the preparation of acrylamide derivative
During preparation, in ice-water bath, under the induction stirring, in there-necked flask, add 735ml dehydrated alcohol, the 115ml vitriol oil, 196g piperonyl cyclonene and 326gN-n-methylolacrylamide successively; Be warming up to 35 ℃, kept under this temperature stirring reaction 7～8 days, then with in the above-mentioned reaction mixture impouring frozen water, leaving standstill is that the adularescent precipitation produces.Filter, and water, saturated sodium carbonate solution and water washing filter cake are to neutral successively, oven dry promptly gets the used acrylamide derivative of the present invention.
The above-mentioned an acidic catalyst vitriol oil can be used phosphoric acid, hydrogenchloride, aluminum chloride, iron trichloride, titanium tetrachloride, tin tetrachloride, H type storng-acid cation exchange resin sulphonated coal, sulfonated phenylethylene copolymer or sulfonated phenol formaldehyde resin instead.
The structural formula of F-C reaction gained acrylamide derivative is:
Or/and
Compound I Compound I I
With products therefrom with nucleus magnetic resonance (
1H NMR) method characterizes, and its characteristic peak ownership is as follows:
Compound I:
1H?NMR：δ4.31(d，4H，J＝5.5，CH
2-10，CH
2-14)，5.61(q，2H，J＝10.2，J＝2.2，H-7，H-11)，5.97(s，2H，CH
2-15)，6.13(q，2H，J＝16.7，J＝2.2，H-7’，H-11’)，6.25(q，2H，J＝16.7，J＝10.2，H-8，H-12)，6.80(s，2H，H-3，H-6)，8.52(t，2H，J＝5.5，N-H)；
13CNMR：δ39.5(C-10，C-14)，101.1(C-15)，108.8(C-3，C-6)，125.5(C-7，C-11)，130.2(C-8，C-12)，131.5(C-4，C-5)，146.2(C-1，C-2)，164(C＝O，C-9，C-13)..
Compound I I:
1H?NMR：δ4.24(d，2H，J＝5.5，CH
2-10)，5.61(q，1H，J＝10.1，J＝2.3，H-7)，5.98(s，2H，CH
2-11)，6.12(q，2H，J＝16.8，J＝2.3，H-7’)，6.24(q，2H，J＝16.8，J＝10.1，H-8)，6.82～6.86(m，3H，H-3，H-4，H-6)，8.53(t，H，J＝5.5，N-H)。
2, the preparation of the acrylamide resin of suspended side chain piperonyl cyclonene
During preparation, earlier 5.4g toluene, 0.2g azo isobutyronitrile (AIBN) are added in the 250ml there-necked flask, after stirring heating is warming up to 80 ℃, with 21.1g butyl acrylate, 9.1g ethyl propenoate, 17.5g methyl methacrylate, the acrylamide derivative of the above-mentioned preparation of 5.0g, 20.9gN, the mixture of the mixture of dinethylformamide and 34.5g toluene, 1.3g azo isobutyronitrile (AIBN) is added drop-wise in the there-necked flask simultaneously, dropwises in about 1 hour.Keep 80 ℃ of temperature of reaction then, continue to stir copolyreaction 10 hours, promptly get the acrylamide resin of suspended side chain piperonyl cyclonene, its structural formula is
R in the formula
1Be H or CH
3R
2Be CH
3, CH
2CH
3, CH
2CH
2CH
2CH
3, CH
2CH
2CH (CH
3)
2Or C (CH
3)
3R
3Be H or CH
3R
4Be H, CH
2CHCONHCH
2Or CH
2C (CH
3) CONHCH
2R
5Be H or CH
3R
6Be CH
3, CH
2CH
3, CH
2CH
2CH
2CH
3, CH
2CH (CH
3)
2Or C (CH
3)
3M is 0～12000; N is 2～4000; O is 0～12000.In order to guarantee that resin of the present invention has good didirtresistance, fixedly n value back is regulated m and o value to make the aforesaid propylene amide derivatives account for weight resin percentage ratio is 2～50%.
3, the preparation of marine antifouling coating:
Described marine antifouling coating is made up of resin solution, softening agent, stopping composition and stain control agent, and their weight percentage scope is respectively 25～60,1～20,1～30 and 1～40.Described resin solution is a concentration range 30-60% (concentration expressed in percentage by weight, the acrylamide resin solution of suspended side chain piperonyl cyclonene down together), described organic solvent is ethyl acetate, butylacetate, dimethylbenzene, toluene, butanols or N, one or more of dinethylformamide; Described softening agent is Vaseline, clorafin, dibutyl phthalate or dioctyl phthalate (DOP); Described stopping composition is one or more in red iron oxide, talcum powder, titanium dioxide, aerosil solid particulate or the zinc oxide; Described stain control agent is alpha-bromo-cinnamaldehyde, N-phenylmaleimide, tetramethyl-thiuram disulfide or SeaNine211
TMIn one or more.During preparation, the acrylamide resin toluene-N of the suspended side chain piperonyl cyclonene that 60g is above-mentioned, dinethylformamide solution, 8g Vaseline, 3gSeaNine
TM211, the mixture of 8g tetramethyl-thiuram disulfide, 4.5g alpha-bromo-cinnamaldehyde, 13g red iron oxide and 3.5g aerosil solid particulate vibration 2.5 hours in a paint shaker that contains granulated glass sphere is filtered with 100 purpose strainers then.Promptly get marine antifouling coating compositions.The evaluation of antifouling property:
With reference to national standard " anti-fouling paint model shallow sea soak test method " (GB 5370-85), It is 250mm that the antifouling paint brushing is grown at plate, and wide is 150mm, and thick is the mild steel reality of 1.5mm Test on the model, the experiment model adopts the rectangular batten of trough of belt two to use iron bolt to fix. Should be real Test model and hang over peaceful angle, Qingdao City Chinese Marine University aquaculture Experimental Base shallow sea net cage The culture zone, respectively at 1,2 and 6 months after measure blank model and be coated with and be brushed with make antifouling The model of coating has been obtained fairly good experimental result, and is as shown in the table.
| 1 month | 2 months | 6 months | |
| Blank model | 20 | 38 | 100 |
| The acrylamide polymer that the suspended side chain piperonyl cyclonene is arranged | 0 | 5 | 32 |
| Marine antifouling coating compositions | 0 | 0 | 5 |
Annotate: 0,5,20,32,38,100 is the bond area percentages of marine organisms on model.
Claims (5)
1, a kind of acrylamide resin of suspended side chain piperonyl cyclonene is characterized in that its structural formula is
R in the formula
1Be H or CH
3R
2Be CH
3, CH
2CH
3, CH
2CH
2CH
2CH
3, CH
2CH (CH
3)
2Or C (CH
3)
3R
3Be H or CH
3R
4Be H, CH
2CHCONHCH
2Or CH
2C (CH
3) CONHCH
2R
5Be H or CH
3R
6Be CH
3, CH
2CH
3, CH
2CH
2CH
2CH
3, CH
2CH (CH
3)
2Or C (CH
3)
3M is 0～12000; N is 2～4000; O is 0～12000.
2, the preparation method of the acrylamide resin of the described suspended side chain piperonyl cyclonene of claim 1, it is characterized in that earlier under an acidic catalyst effect by piperonyl cyclonene and N-hydroxyacrylamide or N-methylol-Alpha-Methyl acrylamide reaction synthesis of acrylamide derivatives, react by acrylamide derivative and methacrylic ester and/or acrylic ester copolymer again.
3, preparation method as claimed in claim 2 is characterized in that described an acidic catalyst is sulfuric acid, phosphoric acid, hydrogenchloride, aluminum chloride, iron trichloride, titanium tetrachloride, tin tetrachloride, H type storng-acid cation exchange resin sulphonated coal, sulfonated phenylethylene copolymer or sulfonated phenol formaldehyde resin.
4, the application of the acrylamide resin of the described suspended side chain piperonyl cyclonene of claim 1 in the preparation marine antifouling coating.
5, application as claimed in claim 4, it is characterized in that described marine antifouling coating by being made up of acrylamide resin solution, softening agent, stopping composition and the stain control agent of suspended side chain piperonyl cyclonene, their weight percentage scope is respectively 25～60,1～20,1～30 and 1～40.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410035999 CN1260260C (en) | 2004-10-17 | 2004-10-17 | Acrylic amide resin with side chain hanging pepper ring and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410035999 CN1260260C (en) | 2004-10-17 | 2004-10-17 | Acrylic amide resin with side chain hanging pepper ring and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1624017A CN1624017A (en) | 2005-06-08 |
| CN1260260C true CN1260260C (en) | 2006-06-21 |
Family
ID=34763506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410035999 Expired - Fee Related CN1260260C (en) | 2004-10-17 | 2004-10-17 | Acrylic amide resin with side chain hanging pepper ring and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1260260C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033281B (en) * | 2007-04-23 | 2011-06-01 | 大连交通大学 | Furan modified acrylic resin and anti-fouling paint prepared by the same |
| CN101412780B (en) * | 2008-11-28 | 2011-01-12 | 东华大学 | Liquid crystal fluoroalkyl acrylic resin with suspended side chain, and preparation and use thereof |
| CN102127185B (en) * | 2010-12-15 | 2013-01-09 | 浙江海洋学院 | Acrylic resin with epoxy cycle on side chain and preparation and use thereof |
| CN102757673B (en) * | 2011-04-27 | 2015-10-14 | 香港科技大学 | Amides is preventing the purposes in marine biofouling |
| WO2019199542A1 (en) * | 2018-04-10 | 2019-10-17 | Basf Se | Acrylic copolymers for wet pressure-sensitive adhesives |
-
2004
- 2004-10-17 CN CN 200410035999 patent/CN1260260C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1624017A (en) | 2005-06-08 |
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