CN101412779B - Acrylic resin containing amphipathic lateral chain, and preparation and use thereof - Google Patents
Acrylic resin containing amphipathic lateral chain, and preparation and use thereof Download PDFInfo
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- CN101412779B CN101412779B CN2008102035885A CN200810203588A CN101412779B CN 101412779 B CN101412779 B CN 101412779B CN 2008102035885 A CN2008102035885 A CN 2008102035885A CN 200810203588 A CN200810203588 A CN 200810203588A CN 101412779 B CN101412779 B CN 101412779B
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- acrylic resin
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- lateral chain
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Abstract
The invention relates to acrylic resin containing amphiphilic lateral chains, a preparation method thereof and application of the acrylic resin containing the amphiphilic lateral chains. The general structural formula of the acrylic resin containing the amphiphilic lateral chains is as shown in a figure 1. The preparation method comprises the following steps: (1) dichloromethane, tetraethylene glycol and triethylamine are added, acryloyl chloride is slowly dripped into the mixture under the protection of nitrogen, and the mixture is subjected to temperature rise and stirring; (2) ester obtained in the step (1) is dissolved in anhydrous dichloromethane, dipped with acyl fluoride containing perfluor polyether chains, and stirred at a temperature of 80 DEG C below zero and 25 DEG C; and (3) 100 to 150 millimeters of tetrahydrofuran and 800 to 900 milligrams of initiator are added, and the mixture is subjected to temperature rise to between 60 and 80 DEG C, added with 15 to 20 grams of methacrylic ester, 12 to 15 grams of glycidyl methacrylate and 15 to 25 grams of acrylic acid derivatives under the protection of the nitrogen, stirred, subjected to temperature rise to between 65 and 80 DEG C, maintained at a constant temperature for 48 to 72 hours to obtain the acrylic resin containing the amphiphilic lateral chains. The resin not only can be taken as a film former of marine antifouling coating but also has nontoxic and eco-friendly performance.
Description
Technical field
The invention belongs to the functional resin field that marine antifouling coating is used, particularly relate to a kind of acrylic resin that contains amphipathic lateral chain and its production and application.
Background technology
As everyone knows, marine organisms are attached to hull bottom, increase running resistance, reduce the speed of a ship or plane, increase the fuel oil loss in the transportation; Be attached to the cooled with seawater inside pipe wall, can cause line clogging, thereby lead to Serious Accident; Be attached to other seabed engineering building, also can cause a lot of adverse influences.All these can bring enormous economic loss to the mankind.Traditional marine anti-pollution method is a large amount of deleterious cupric oxide and organo-tin compounds of using.Fact proved that these deleterious coating or japanning anti-fouling effect clearly can prevent the harm of marine fouling organism effectively.Yet find that in harbour, harbour a large amount of toxic substances exist, serious harm the living environment of marine life, cause biological distortion such as oyster, shellfish and fish, even dead.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 2003, and various countries' boats and ships all should ban use of has bigger toxic organo-tin compound (TBT) antifouling paint to marine organisms.And China is a boats and ships big country, but in antifouling paint or japanning development than later, and abroad compare, have a long way to go, stain control agent especially in the market is mostly by external paint company monopolization.Therefore, need a kind of environmentally friendly antifouling paint of development or antifouling varnish that very important meaning is arranged.
Summary of the invention
Technical problem to be solved by this invention provides a kind of acrylic resin that contains amphipathic lateral chain and its production and application, and this resin not only can be used as the film forming matter of marine antifouling coating, and has the friendly performance of nontoxic ecology.
A kind of acrylic resin that contains amphipathic lateral chain of the present invention, its general structure 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 or CH
3X is 1-45; Y is 2-20.m＝0-2000；n＝0-10000；o＝0-11000。
A kind of preparation method who contains the acrylic resin of amphipathic lateral chain of the present invention comprises:
(1) add 300ml-700ml methylene dichloride, 67.9g-150g TEG and 15.2g-35g triethylamine, under nitrogen protection, slowly drip the 15.6g-38g methacrylic chloride, be warming up to 25 ℃-40 ℃, stirring reaction 1d-2d gets monolateral esterification products;
(2) ester that step (1) is obtained is dissolved in the anhydrous methylene chloride, under nitrogen protection, drip the acyl fluorides of 20g-45g perfluoro-polyether chain, under-80 ℃-25 ℃, stir 20h-36h and make the acrylate derivative of forming by PFPE chain and polyethyleneglycol unit;
(3) add 100ml-150ml tetrahydrofuran (THF) (THF); the 800mg-900mg initiator; 60 ℃-80 ℃ of heat temperature raisings; under nitrogen protection; the acrylic acid derivative that adds 15g-20g methacrylic ester, 12g-15g glycidyl methacrylate and the above-mentioned preparation of 15g-20g stirs, and is warmed up to 65 ℃-80 ℃; constant temperature 48h-72h, promptly.
The mol ratio of described step (1) acrylate chloride and polyoxyethylene glycol is 2:7,2:8,2:9,3:7,3:8 or 3:9.
The initiator of described step (3) is Diisopropyl azodicarboxylate (ABIN) or 2,2'-Azobis(2,4-dimethylvaleronitrile) (AVBN).
The acrylic resin that contains amphipathic lateral chain is applied to the marine anti-pollution coating.
The acrylic resin that contains amphipathic lateral chain is in cationic initiator and lamp and high pressure mercury effect, becomes a kind of highly stablely, and with ground (as glass, metal) film forming matter of good adhesion arranged.
This functional resin that contains amphipathic lateral chain has good antifouling activity also can be effectively medium-term and long-term at seawater, and this base polymer of antifouling property test proof has good marine anti-pollution activity.In suppressing the ocean absorption of diatom and settle down aspect, compare commercialization both at home and abroad, most popular polydimethyl silane (PDMS) resin, the novel acrylic resin that contains amphipathic lateral chain of the present invention has better antifouling property, has very big potential value.
The acrylic resin that contains amphipathic lateral chain 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.
Description of drawings
Fig. 1 contains the general structure of the acrylic resin of amphipathic lateral chain;
Frustule adhesion condition on Fig. 2 model.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) preparation of acrylate derivative
During preparation; in oil bath under the induction stirring; in an absolute anhydrous there-necked flask, add 300mL methylene dichloride, 67.9g TEG and 15.2g triethylamine successively; under protection of nitrogen gas, slowly drip the 15.6g methacrylic chloride, be warming up to 25 ℃-40 ℃; stirring reaction 24 hours; until light yellow liquid occurring, then above-mentioned reaction mixture is transferred in the single port bottle, just obtain monolateral esterification products after being spin-dried for.Then this esterification products is dissolved in the anhydrous methylene chloride; squeeze in the there-necked flask that fills triethylamine that drying crosses with syringe; under protection of nitrogen gas; slowly drip the acyl fluorides of perfluoro-polyether chain; be warming up to-80 ℃ to 25 ℃; stirring reaction several hours, just obtain the used acrylate derivative of the present invention.
With products therefrom nuclear magnetic resonance analyser (NMR), Fourier infrared spectrograph, gas-matter coupling mass spectrograph, elemental analyser carries out data analysis and characterizes as follows:
1HNMR(300MHz，CDCl
3，δ)：6.06(q，1H)，5.60(q，1H)，4.65(m，2H)，3.83(t，2H)，3.71(m，2H)，2.02(d，3H)
19FNMR(284.2MHz，CF
3COOH，δ)：-80.00，-80.74，-80.81，-82.11，-82.23，-83.06，-84.91，-130.26，-131.95，-145.54
IR(neat)3101.02cm
-1，2876.48cm
-1，1784.10cm
-1，1772.17cm
-1，1638.9cm
-1，1237.58cm
-1，1036.40cm
-1
EI(m/z)：113(100)，522(41.05)
Anal.Calcd.for?C
21H
21F
17O
9：C，34.07；H，2.86.Found：C，34.11；H，2.86.
(2) contain the preparation of the acrylic resin of amphipathic lateral chain
During preparation; in oil bath under the induction stirring; in an absolute anhydrous there-necked flask, add 100mL tetrahydrofuran (THF) (THF) successively, the 800mg initiator, heat to 60 ℃ after; will be under protection of nitrogen gas; add the acrylate derivative of 15g methacrylic ester, 12g glycidyl methacrylate and the above-mentioned preparation of 15g, stir after 2 minutes, be warming up to 65 ℃ of constant temperature 48 hours; promptly obtain containing the acrylic resin of amphipathic lateral chain, its structure is
R in the formula
1Be CH
3R
2Be CH
3R
3Be CH
3R
4Be CH
3X is 4; Y is 3.Products therefrom is carried out data analysis and characterizes as follows with nuclear magnetic resonance analyser (NMR), GPC determinator:
1HNMR(300MHz，CDCl
3，δ)：4.52-4.56，4.31，3.60-3.78，3.22，2.85，2.64，1.85-1.93，1.69，0.89-1.48
19FNMR(282.4MHz，CF
3COOH，δ)：-79.93，-81.24，-81.57，-82.13，-82.19，-82.22，-129.49，-131.46，-131.51，-145.06，-145.11，-145.18
GPC：Mn＝19000g/mol；Mw＝32000g/mol，D＝1.64
(4) preparation of antifouling coating
Above-described acrylic resin and a spot of cationic initiator that contains amphipathic lateral chain is dissolved among a small amount of butanone and the F113 together, directly be tiled on sheet glass or the metal substrate, under the illumination of high voltage mercury lamp, crosslinked film forming, after this continue under 120 ℃, to be heated several hours, strengthen sticking power.
(5) test of antifouling property
At there being a large amount of stained these facts of property diatom in the ocean, the experiment model that is covered with above antifouling coating is immersed in the seawater that contains a large amount of diatoms, after placement for some time, the frustule adhesion condition on the model, as shown in Figure 2.
From above-mentioned test result, can illustrate that the acrylic resin antifouling property that contains amphipathic lateral chain of the present invention has better anti-fouling effect than commercial polydimethyl silane resin, has very big using value.
Claims (6)
1. acrylic resin that contains amphipathic lateral chain, its general structure 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 or CH
3X is 1-45; Y is 2-20; 0＜m≤2000,0＜n≤10000,0＜o≤11000.
2. preparation method who contains the acrylic resin of amphipathic lateral chain comprises:
(1) add 300ml-700ml methylene dichloride, 67.9g-150g TEG and 15.2g-35g triethylamine, under nitrogen protection, slowly drip the 15.6g-38g acrylate chloride, be warming up to 25 ℃-40 ℃, stirring reaction 1d-2d gets monolateral esterification products;
(2) ester that step (1) is obtained is dissolved in the anhydrous methylene chloride, under nitrogen protection, drip the acyl fluorides of 25g-40g perfluoro-polyether chain, under-80 ℃-25 ℃, stir 20h-36h and make the acrylate derivative of forming by PFPE chain and polyethyleneglycol unit;
(3) add the 100ml-150ml tetrahydrofuran THF; the 800mg-900mg initiator; 60 ℃-80 ℃ of heat temperature raisings; under nitrogen protection; the acrylic acid derivative that adds 15g-20g methacrylic ester, 12g-15g glycidyl methacrylate and the above-mentioned preparation of 15g-20g stirs, and is warmed up to 65 ℃-80 ℃; constant temperature 48h-72h, promptly.
3. a kind of preparation method who contains the acrylic resin of amphipathic lateral chain according to claim 2 is characterized in that: the mol ratio of described step (1) acrylate chloride and polyoxyethylene glycol is 2: 7,2: 8, and 2: 9,3: 7,3: 8 or 3: 9.
4. a kind of preparation method who contains the acrylic resin of amphipathic lateral chain according to claim 2 is characterized in that: the initiator of described step (3) is Diisopropyl azodicarboxylate ABIN or 2,2'-Azobis(2,4-dimethylvaleronitrile) AVBN.
5. the acrylic resin that contains amphipathic lateral chain according to claim 1 is characterized in that: this acrylic resin that contains amphipathic lateral chain is applied to the marine anti-pollution coating.
6. a kind of acrylic resin that contains amphipathic lateral chain according to claim 1, it is characterized in that: the described acrylic resin of amphipathic lateral chain that contains is under cationic initiator and lamp and high pressure mercury effect, become a kind of highly stable, and and glass, metal has the film forming matter of good adhesion.
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| CN101412779B true CN101412779B (en) | 2011-06-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102051101B (en) * | 2010-11-18 | 2012-07-04 | 浙江大学 | Method for preparing normal temperature-cured anti-fouling anti-drag hydrogel soft coating |
| CN102181018B (en) * | 2011-03-16 | 2012-08-08 | 天津大学 | Fluorine-containing amphiphilic modified material for preparing anti-pollution film and preparation method thereof |
| CN102532559A (en) * | 2011-12-30 | 2012-07-04 | 中国船舶重工集团公司第七二五研究所 | Comb type acrylic resin of lateral chain grafting polyester resin and preparation method and application thereof |
| JP6410460B2 (en) * | 2014-04-23 | 2018-10-24 | キヤノン株式会社 | Composition, method for producing film using the composition, and method for producing liquid ejection head |
| CN115073660B (en) * | 2022-07-25 | 2022-12-30 | 中海油天津化工研究设计院有限公司 | Integrated thickening agent for fracturing and preparation method thereof |
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