CN1709921B - Resin of zinc acrylate or copper acrylate containing indole function group, its preparation and use - Google Patents
Resin of zinc acrylate or copper acrylate containing indole function group, its preparation and use Download PDFInfo
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- CN1709921B CN1709921B CN 200510081682 CN200510081682A CN1709921B CN 1709921 B CN1709921 B CN 1709921B CN 200510081682 CN200510081682 CN 200510081682 CN 200510081682 A CN200510081682 A CN 200510081682A CN 1709921 B CN1709921 B CN 1709921B
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- indoles
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Abstract
This is a kind of acrylic zinc or cuprum resin containing indole functional group and its preparation method. Its characteristics are: firstly prepare monomer containing indole functional group, then synthesize acrylic resin containing functional group and carboxyl, finally make the acrylic resin and zinc hydroxide or cuprum hydroxide react to obtain acrylic zinc or cuprum resin containing indole functional group; the reaction temperature of the said synthesizing monomer containing indole functional group is -10 - 10 Deg. C, the reaction time is 1.5 - 5 hours. The resin of the invention can be used for preparing sea antifouling dope. In the seawater, the organic zinc or cuprum acrylic ester on the polymer linear main chain of the coat surface hydrolyzes, and send out organic zinc or cuprum; the hydrolyzed polymer main chain contains indole functional group with highly efficient antifouling activeness, which makes the hydrolyzed polymer main chain still has sterilization activeness. So the dope can effectively prevent halobios from clinging on the surface of fishing tools, ships and seacoast establishments, and has good antifouling performance.
Description
Technical field
The present invention relates to the resin of a kind of zinc acrylate resin or copper, particularly relate to a kind of the contain zinc acrylate resin of indoles functional group or resin of copper and preparation method thereof and the application in the preparation marine antifouling coating.
Technical background:
Exist thousands of kinds fouling organism in the ocean, more than half swimming at seashore and bay place arranged in these fouling organisms, their apposition growths alow, on buoy, water pipe, cooling duct, raft and the netting gear.Adhering to of these fouling organisms can cause the surperficial stained of these facilities, increases surperficial frictional resistance, also quickened corrosion speed simultaneously.What solve the sea marine organism pollution most popular method is the coating that brushing contains stain control agent.At present, the antifouling paint of widely applying contains organotin and Red copper oxide both at home and abroad, for example the multipolymer of methacrylic acid tributyl tin ester and methyl methacrylate and Red copper oxide (Cu
2O) composition is as a kind of antifouling paint, be coated on the surfaces such as hull bottom, can prevent the harm of marine fouling organism effectively, its role is to 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 that discloses the TBT multipolymer, and since then the TBT antifouling paint has been ruled market and reached 20 years.Up to 1987, people recognized that just 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 and a kind ofly contain the zinc acrylate resin of indoles functional group or resin of copper and preparation method thereof, and it is applied to prepare marine antifouling coating, to remedy the demand of prior art.
A kind of zinc acrylate resin of indoles functional group or resin of copper of containing is characterized in that structural formula is:
R is the organic acid acid group in the formula, and this organic acid is phenylformic acid, m-methyl benzoic acid, p-methylbenzoic acid or naphthenic acid, R
1Be H or CH
2N (CH
3)
2, X is H or CH
3, X
1Be H, Cl or Br, X
2Be H, Cl or Br, B is the part of unsaturated vinyl monomer remainder.
The above-mentioned preparation method who contains the zinc acrylate resin or the resin of copper of indoles functional group, it is characterized in that preparation earlier contains the monomer of indoles functional group, resynthesis contains the acrylic resin of indoles functional group and carboxyl simultaneously, makes the reaction of this acrylic resin and zinc hydroxide or copper hydroxide obtain containing the zinc acrylate resin of indoles functional group or the resin of copper at last; The described synthetic temperature of reaction that contains the indoles monomer is-10～10 ℃, reaction times is 1.5～5 hours, the described synthetic temperature of reaction that contains the acrylic resin of indoles functional group and carboxyl simultaneously is 75～150 ℃, reaction times is 0.5～4 hour, the temperature of reaction of the resin of described synthetic zinc acrylate resin that contains indoles functional group or copper is 80～150 ℃, and the reaction times is 3～12 hours.
The above-mentioned application of resin in the preparation marine antifouling coating that contains the zinc acrylate resin or the copper of indoles functional group.
Resin of the present invention can be used for preparing marine antifouling coating, in seawater, the acrylate generation hydrolysis of organic zinc on the coatingsurface polymeric linear main chain or copper, discharge organic zinc or copper, and also contain indoles functional group on the main polymer chain after the hydrolysis with efficient antifouling activity, make the polymer chain after the hydrolysis still have fungicidal activity, so this coating can prevent effectively that marine organisms from adhering on surfaces such as netting gear, naval vessel and coastal facility, antifouling property is good.
Embodiment
1, the monomeric preparation of 1-acryloyl indoles
Put into tetrahydrofuran (THF), 3.5g1-hydrogen indoles, 3.9g sodium cyanide that 50mL newly steamed in there-necked flask successively, room temperature reaction 30 minutes obtains the indoles sodium salt.The 3.3g acrylate chloride is dissolved in the 10mL tetrahydrofuran (THF), and in the above-mentioned indoles sodium salt that makes, control reaction temperature is 0 ℃ with it, reacts 2.5 hours, obtains 1-acryloyl indoles monomer.
Above-mentioned 1-hydrogen indoles is replaced with halogeno indole, 1-hydrogen gramine or halo gramine,, can obtain 1-acryloyl halogeno indole, 1-acryloyl gramine or 1-acryloyl halide equally for the gramine monomer by above-mentioned preparation method.
2, contain the preparation of the acrylic resin of indoles functional group and carboxyl
Whipping appts is being housed, condenser, adding toluene and their weight ratio of propyl carbinol are 4: 1 mixed solvent 262g in the there-necked flask of thermometer, be warming up to about 105 ℃, in 2.5 hours, drip then and contain 30g1-acryloyl indoles, 30g vinylformic acid, the 47g methyl methacrylate, the 64g ethyl propenoate, the 29g butyl acrylate, the mixing solutions of 4g Diisopropyl azodicarboxylate (AIBN), react in half an hour, to have added again after two hours and contain 2g initiator A IBN, weight ratio is 4: 1 the toluene and the mixed solvent 30g of propyl carbinol, is incubated 1.5 hours afterreactions and finishes.
If above-mentioned 1-acryloyl indoles is replaced with 1-acryloyl halogeno indole, 1-acryloyl gramine or 1-acryloyl halide for gramine, can obtain having on the molecular chain polymkeric substance of corresponding acryloyl derivative equally, the weight percentage of the group of corresponding acryloyl derivative is 2～50% in this polymkeric substance.
Unsaturated vinyl monomer of the present invention 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; Described organic solvent is toluene, propyl carbinol, dimethylbenzene, vinyl acetic monomer, N-BUTYL ACETATE, dimethyl formamide, pimelinketone or mibk; Described radical initiator is Diisopropyl azodicarboxylate or Benzoyl Peroxide; The weight percentage of described vinylformic acid in multipolymer is 2～26%.
3, the preparation of indole acrylic acid zinc resin
With phenylformic acid 30.6g, Zn (OH)
224g, above-mentioned acrylic resin 300g, the butylacetate 114g that contains indoles functional group and carboxyl, toluene that weight ratio is 4: 1 and the mixed solvent 60g of propyl carbinol join in the there-necked flask that whipping appts, condenser, water-and-oil separator, thermometer are housed simultaneously.Keep 80 ℃ of temperature of reaction, 7 hours afterreaction mixture trend vitreous staties are warming up to 125 ℃ of dehydrations, be sure of that exclusion distillates the back and finishes reaction, obtain containing the zinc acrylate resin of indoles functional group or the resin of copper.
Above-mentioned phenylformic acid is replaced with m-methyl benzoic acid, p-methylbenzoic acid or naphthenic acid can obtain containing the zinc acrylate resin of indoles functional group or the resin of copper equally.
Resin of the present invention can be used for preparing marine antifouling coating, this marine antifouling coating is made up of resin solution of the present invention, softening agent, one or more stopping composition and one or more stain control agents, and their weight percentage scope is respectively 20～60,1～20,1～30 and 1～50.During preparation, with concentration expressed in percentage by weight ethyl acetate solution, 2.5g clorafin, 12g red iron oxide, the aerosil of 2.5g, the 33g 4 of 40% 50g indole acrylic acid zinc of the present invention 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 " (GB5370-85), with this antifouling paint brushing plate long for 250mm, wide be that the experiment model adopts rectangular batten two use iron bolt of trough of belt 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.
During the preparation marine antifouling coating, can also use above-mentioned indole acrylic acid zinc resin instead halogeno indole zinc acrylate resin of the present invention or resin of copper, gramine zinc acrylate resin or resin of copper or halo gramine zinc acrylate resin or resin of copper; Used organic solvent ethyl acetate can be used butylacetate, dimethylbenzene, toluene or butanols instead; Used softening agent Vaseline can be used clorafin, dibutyl phthalate or dioctyl phthalate (DOP) instead; Used stopping composition red iron oxide can be used talcum powder, titanium dioxide, aerosil or zinc oxide instead, all can obtain obvious effects.
The concentration expressed in percentage by weight of the resin solution described in the present invention is 20-60%.
Claims (7)
1. Development of Zinc Acrylate Resin method that contains indoles functional group is characterized in that the step of this method is:
(1) the monomeric preparation of acryloyl indoles
In there-necked flask, put into 50ml tetrahydrofuran (THF), 3.5g1-hydrogen indoles, 3.9g sodium cyanide successively, at room temperature reacted 30 minutes, obtain the indoles sodium salt, the 3.3g acrylate chloride is dissolved in the 10ml tetrahydrofuran (THF), again with it in the above-mentioned indoles sodium salt that makes, control reaction temperature is 0 ℃, reacts 2.5 hours, obtains 1-acryloyl indoles monomer;
(2) contain the preparation of the acrylic resin of indoles functional group and carboxyl
In there-necked flask, add by weight 4: 1 blended toluene and n-butanol mixed solvent 262g, be warming up to 105 ℃, in 2.5 hours, drip the mixing solutions that contains 30g 1-acryloyl indoles monomer, 30g vinylformic acid, 47g methyl methacrylate, 64g ethyl propenoate, 29g butyl acrylate, 4g Diisopropyl azodicarboxylate then, react in half an hour, added again after two hours contain 2g initiator Diisopropyl azodicarboxylate, with 4: 1 blended toluene of weight ratio and n-butanol mixed solvent 30g, be incubated 1.5 hours afterreactions and finish;
(3) preparation of indole acrylic acid zinc resin
With phenylformic acid 30.6g, Zn (OH)
224g, above-mentioned acrylic resin 300g, the butylacetate 114g that contains indoles functional group and carboxyl, join in the there-necked flask simultaneously with 4: 1 blended toluene of weight ratio and n-butanol mixed solvent 60g, keeping 7 hours afterreaction mixture trends of 80 ℃ of reactions of temperature of reaction vitreous state, be warming up to 125 ℃ of dehydrations again, be sure of that exclusion distillates the back and finishes reaction, obtain containing the zinc acrylate resin of indoles functional group.
2. preparation method according to claim 1, it is characterized in that the monomeric preparation of described acryloyl indoles is to allow acrylate chloride and 1-hydrogen halogeno indole, 1-hydrogen gramine or 1-hydrogen halo gramine react, and obtains acryloyl indoles monomer 1-acryloyl halogeno indole, 1-acryloyl gramine or 1-acryloyl halide respectively for gramine.
3. preparation method according to claim 1, it is characterized in that the 1-acryloyl indoles monomer that uses when the described acrylic resin that contains indoles functional group and carboxyl prepares replaces for gramine with 1-acryloyl halogeno indole, 1-acryloyl gramine or 1-acryloyl halide, the content of these monomeric monomeric units in described acrylic resin is to count 2-50% with described total resin weight.
4. preparation method according to claim 1 is characterized in that described initiator Diisopropyl azodicarboxylate replaces with Benzoyl Peroxide.
5. according to the zinc acrylate resin that contains indoles functional group of the described method of each claim among claim 1-4 preparation.
6. the application of zinc acrylate resin in the preparation marine antifouling coating that contains indoles functional group according to claim 5.
7. application according to claim 6, it is characterized in that what described marine antifouling coating was made up of described zinc acrylate resin solution, softening agent, one or more stopping composition and one or more stain control agents that contains indoles functional group of claim 5, in described marine antifouling coating gross weight, their weight percentage is respectively 20-60%, 1-20%, 1-30% and 1-50%; The described solvent that contains the zinc acrylate resin solution of indoles functional group is ethyl acetate, butylacetate, dimethylbenzene, toluene or butanols, and the concentration of this resin is the zinc acrylate resin total solution weight 20-60% that contains indoles functional group in described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510081682 CN1709921B (en) | 2005-04-18 | 2005-07-04 | Resin of zinc acrylate or copper acrylate containing indole function group, its preparation and use |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510043362.X | 2005-04-18 | ||
| CN200510043362 | 2005-04-18 | ||
| CN 200510081682 CN1709921B (en) | 2005-04-18 | 2005-07-04 | Resin of zinc acrylate or copper acrylate containing indole function group, its preparation and use |
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| Publication Number | Publication Date |
|---|---|
| CN1709921A CN1709921A (en) | 2005-12-21 |
| CN1709921B true CN1709921B (en) | 2011-09-28 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167775A (en) * | 2011-03-02 | 2011-08-31 | 上海大学 | Synthesis technology of zinc acrylate or copper acrylate self-polishing anti-fouling resin |
| CN103012243B (en) * | 2012-12-06 | 2015-09-09 | 青岛大学 | A kind of acrylate functional monomer containing gramine structure and preparation method thereof |
| CN103030732B (en) * | 2012-12-06 | 2015-01-14 | 青岛大学 | Polyacrylate antifouling copolymerization resin with side chain with donaxine structure and preparation method thereof |
| CN103113529B (en) * | 2013-01-05 | 2014-12-10 | 青岛大学 | Acrylic ester grafted epoxy resin containing donaxine structure and preparation method thereof |
| CN104946065A (en) * | 2015-06-01 | 2015-09-30 | 芜湖县双宝建材有限公司 | Marine low-surface-energy anti-fouling coating |
| CN105199041A (en) * | 2015-10-29 | 2015-12-30 | 中国船舶重工集团公司第七二五研究所 | Method for preparing antifouling resin from hexadecanoic acid grafted acrylic prepolymer |
| CN114806312A (en) * | 2022-04-15 | 2022-07-29 | 哈尔滨工程大学 | Preparation method of polybenzazole modified graphene oxide/fluoroboric acrylate composite antifouling coating |
| CN114702618A (en) * | 2022-04-15 | 2022-07-05 | 哈尔滨工程大学 | Preparation method of indoleacetic acid modified acrylic acid fluorine polymer and coating thereof |
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