CN102911309A - Waterborne acrylic macromolecular compound as well as preparation method and application thereof - Google Patents
Waterborne acrylic macromolecular compound as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN102911309A CN102911309A CN2012104339576A CN201210433957A CN102911309A CN 102911309 A CN102911309 A CN 102911309A CN 2012104339576 A CN2012104339576 A CN 2012104339576A CN 201210433957 A CN201210433957 A CN 201210433957A CN 102911309 A CN102911309 A CN 102911309A
- Authority
- CN
- China
- Prior art keywords
- acid
- water soluble
- macromolecular compound
- salt
- soluble acrylic
- 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.)
- Granted
Links
- 0 CCC(*)(C(C)(C)C(C)CC(C(C(C)(C)C(C(C(C)(C)C(C)(C)CC(C)(*)C(**[N+](*)(*)**)=O)C(N*)=O)=C)=C)C(O*(C)O)=O)C(O*)=O Chemical compound CCC(*)(C(C)(C)C(C)CC(C(C(C)(C)C(C(C(C)(C)C(C)(C)CC(C)(*)C(**[N+](*)(*)**)=O)C(N*)=O)=C)=C)C(O*(C)O)=O)C(O*)=O 0.000 description 1
Images
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to a waterborne acrylic macromolecular compound and salts thereof, as well as preparation methods and applications thereof. The method comprises the following steps of: dissolving hydrophilic acrylic monomers containing amino, acrylic monomers containing hydroxyl, acrylic monomers containing quaternary ammonium salts and acrylic monomers containing carboxyl in water, then adding a water-soluble azo compound as an initiator, and dropwise adding the monomer hybrid solution containing the initiator to water or alcohol-water solution for copolymerization reaction. Stain-proof paints prepared by using metal salts of the waterborne acrylic macromolecular compound can effectively prevent adhesion of fouling organism in seawater, and have the advantage of being environment-friendly.
Description
[technical field]
The invention belongs to technical field of polymer materials.More specifically, the present invention relates to a kind of water soluble acrylic acid macromolecular compound, also relate to the preparation method of described compound, also relate to the purposes of described compound.
[background technology]
Be immersed in the maritime facilities in the seawater, its surface can form because of biological action the biological attachment layer of one deck complexity.This biological attachment is on the maritime facilities surface and make its phenomenon that affects adversely be called marine biofouling.Marine biofouling is very harmful, and with regard to boats and ships, it can accelerate the corrosion of hull on the one hand, shortens Ship Life; Can increase the hull own wt on the other hand, ship resistance is increased, thereby reduce ship's speed and increase fuel consumption.According to statistics, when the marine biofouling rate was 5%, the resistance of boats and ships just was equivalent to 2 times of clean hull surface, and simultaneously fuel consumption increases by 10%, with the increase fuel consumption of fouling organism amount even can increase by 40%.Biodeterioration also can result in blockage maritime facilities pipeline (such as coastal fuel-burning power plant, offshore platform and deep-sea heat-exchanger pipeline), damage oceanographic instrumentation, reduce the harm such as mariculture output.
From economic angle and anti-fouling effect two aspects, but the anti-fouling method of unique widespread use of generally acknowledging at present is the brushing antifouling paint.Antifouling paint mainly is to kill settled organism by the release toxic component to play a role, such as organotin self-polishing coating and the present prevailing Tin-free Spc Anti-fouling Paint take Red copper oxide as main stain control agent of 80～nineties of 20th century.Although these antifouling paints can prevent effectively adhering to of fouling organism that the toxic substance that discharges has caused serious harm to the marine eco-environment.Given this, low toxicity, nontoxic environmentally friendly antifouling paint become the direction of antifouling paint development.
One of gordian technique of environmentally friendly antifouling paint is the exploitation of low toxicity or nontoxic stain control agent.The macromolecule metal that makes as main raw material take nontoxic, the cm-chitosan of easy degraded, Lalgine, carboxymethyl cellulose is exactly a kind of stain control agent better anti-fouling effect and that satisfy the environmental friendliness characteristic that has.Although such macromolecule metal salt has eco-friendly characteristic, raw materials used cost height has limited its practical application.
The inventor is according to the constructional feature of cm-chitosan, carboxymethyl cellulose, Lalgine, synthesize the water soluble acrylic acid macromolecular compound with above-mentioned polymer characteristic group (carboxyl, hydroxyl, amido), and made macromolecule metal salt to solve the before this shortcoming of invention take it as raw material.
[summary of the invention]
[technical problem that will solve]
The purpose of this invention is to provide a kind of water soluble acrylic acid macromolecular compound.
Another object of the present invention provides the preparation method of described water soluble acrylic acid macromolecular compound.
Another object of the present invention provides the purposes of described water soluble acrylic acid macromolecular compound.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of water soluble acrylic acid macromolecular compound.
Described water soluble acrylic acid macromolecular compound has following chemical structural formula:
In the formula:
R
1, R
4Represent hydrogen atom or methyl, R
2The carbochain that representative is comprised of 1～4 methylene radical, R
3Represent hydrogen atom or contain the hydroxyalkyl of 1～4 carbon atom, R
5, R
6With R
7Represent methylidene or ethyl, R
8Represent oxygen or nitrogen-atoms, a, b, c and d represent respectively an integer that is selected from 1～10.
The invention still further relates to the preparation method of described water soluble acrylic acid macromolecular compound.
This preparation method's step is as follows:
A, according to the weight ratio 1～10 of described monomer total amount and water, the hydrophilic amino-contained acrylic monomer of 10～40 weight parts, 10～40 weight part hydroxy acryl acid class monomers, 30～70 weight parts are contained quaternary ammonium salt group acrylic monomer and 5～35 weight parts, and to contain carboxy acrylic class monomer soluble in water, obtains a kind of monomer mixture solution;
Described wetting ability amino-contained acrylic monomer is acrylamide, n-methylolacrylamide or hydroxyethyl acrylamide; The described quaternary ammonium salt group acrylic monomer that contains is acryloyloxyethyl trimethyl ammonium chloride, the 2-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryloxyethyldimethyl benzyl ammonium chloride, methylacryoyloxyethyl dimethylbutyl brometo de amonio, methylacryoyloxyethyl dimethyl dodecyl bromination ammonium, methylacryoyloxyethyl dimethyl hexadecyl brometo de amonio, 3-acrylamido oxypropyl trimethyl ammonium chloride, methacryloyl amido ethyl-trimethyl salmiac or methacryloyl amido oxypropyl trimethyl ammonium chloride; The described carboxy acrylic class monomer that contains is acrylic or methacrylic acid; Described hydroxy acryl acid class monomer is Hydroxyethyl acrylate, Propylene glycol monoacrylate or vinylformic acid hydroxy butyl ester; Then,
B, will join in the monomer mixture solution that steps A obtains in above-mentioned total monomer weight 0.005～5% water-soluble azo compounds initiator, obtain a kind of monomer mixture solution that contains initiator;
Described initiator is azo-bis-isobutyrate hydrochloride, azo two isobutyl imidazoline salt hydrochlorates, azo dicyano valeric acid or azo di-isopropyl tetrahydroglyoxaline; Then,
C, under the condition that stirs, under 50～95 ℃ of temperature, in 0.5～24 hour, the monomer mixture solution that contains initiator that obtains at step B is added drop-wise to and carries out copolyreaction in 110～1100 weight parts waters or the alcohol solution, obtain the solution that solids content is 5～60 % by weight; Separate its solid, be described water soluble acrylic acid macromolecular compound, its weight-average molecular weight is 1.000x10
5～5.000x10
6KDa.
A preferred embodiment of the invention, contains the quaternary ammonium salt group acrylic monomer and contains the total amount of carboxy acrylic class monomer and the weight ratio of water is 1:2～6 described amino-contained acrylic monomer, hydroxy acryl acid class monomer.
According to another kind of preferred implementation of the present invention, the concentration of described alcohol solution is by weight 3～20%.
According to another kind of preferred implementation of the present invention, described alcohol is one or more alcohol that are selected from ethanol, propyl alcohol, ethylene glycol or glycerol.
The invention still further relates to the metal-salt of described water soluble acrylic acid macromolecular compound.This compound metal salt has following chemical structural formula:
In the formula:
R
1～R
8Limit such as the front with a, b, c and d;
R
9Represent a kind of phenylformic acid that is selected from, Chlorodracylic acid, 2, the 4-dichlorobenzoic acid, m-methyl benzoic acid, p-methylbenzoic acid, para-amino benzoic acid, 2, the 3-mesitylenic acid, p-tert-butyl benzoic acid, to Phenylbenzoic acid, p-nitrobenzoic acid, 2-chloro-4-thiamphenicol benzoic acid, o-ethoxybenzoic acid, 3,5-dihydroxyl-4-tolyl acid, 3, the 5-resorcylic acid, anisic acid, naphthenic acid, 2,5-two chloro-4-nitrobenzoic acids, 3, the 5-dinitrobenzoic acid, 3-(1-indyl) propionic acid, 3-(5,6-two chloro-1-indyls) propionic acid, 3-(5-bromo-1-indyl) propionic acid, 3-(5,6-two chloro-1-indyls) propionic acid, 3-(3-dimethylamine methyl-5,6-two chloro-1-indyls) propionic acid, 3-(3-dimethylamine methyl-5-bromo-1-indyl) propionic acid, 3-(3-dimethylamine methyl isophthalic acid-indyl) propionic acid, 3-indolyl acetic acid, rosin, proline(Pro), leucine, phenylalanine, the carboxylate radical of arginine or Serine;
M is Ca
2+, Mg
2+, Cu
2+Or Zn
2+
The invention still further relates to the preparation method of described water soluble acrylic acid macromolecular compound metal-salt.
This preparation method's step is as follows:
A, foregoing water soluble acrylic acid macromolecular compound, alkali metal hydroxide and organic acid alkali metal salt is soluble in water obtains aqueous solution I;
Described basic metal is one or more basic metal that are selected from sodium, potassium or lithium;
B, soluble in water the hydrochloride of calcium, magnesium, copper or zinc, nitrate, vitriol or acetate obtains aqueous solution II;
The mol ratio of described water soluble acrylic acid macromolecular compound and alkali metal hydroxide is 1:1.0～1.1;
The concentration of described water soluble acrylic acid macromolecular compound, described organic acid alkali metal salt and described calcium, magnesium, copper or zinc salt solution is 0.01～3mol/L; Their mol ratio is 1:0.9～1.1:1.0～1.4;
C, will be added drop-wise at the aqueous solution I that steps A obtains in the solution II that step B obtains, under the condition of 10～80 ℃ of stirring and temperature of reaction, reacted 0.5～18 hour, then carry out solid-liquid separation, washing and dry, so obtain described water soluble acrylic acid macromolecular compound metal-salt.
According to another kind of preferred implementation of the present invention, in described organic acid alkali metal salt, described organic acid is selected from phenylformic acid, Chlorodracylic acid, 2, the 4-dichlorobenzoic acid, m-methyl benzoic acid, p-methylbenzoic acid, para-amino benzoic acid, 2, the 3-mesitylenic acid, p-tert-butyl benzoic acid, to Phenylbenzoic acid, p-nitrobenzoic acid, 2-chloro-4-thiamphenicol benzoic acid, o-ethoxybenzoic acid, 3,5-dihydroxyl-4-tolyl acid, 3, the 5-resorcylic acid, anisic acid, naphthenic acid, 2,5-two chloro-4-nitrobenzoic acids, 3, the 5-dinitrobenzoic acid, 3-(1-indyl) propionic acid, 3-(5,6-two chloro-1-indyls) propionic acid, 3-(5-bromo-1-indyl) propionic acid, 3-(5,6-two chloro-1-indyls) propionic acid, 3-(3-dimethylamine methyl-5,6-two chloro-1-indyls) propionic acid, 3-(3-dimethylamine methyl-5-bromo-1-indyl) propionic acid, 3-(3-dimethylamine methyl isophthalic acid-indyl) propionic acid, 3-indolyl acetic acid, rosin, proline(Pro), leucine, phenylalanine, arginine or Serine.
The invention still further relates to the purposes of described water soluble acrylic acid macromolecular compound metal-salt in the preparation marine antifouling coating.
Described marine antifouling coating composed as follows, in weight part:
Vinylformic acid is from polishing resin ... 20～60 parts
Softening agent ... 1～20 part
Red copper oxide ... 1～20 part
Stopping composition ... 1～30 part
1～50 part of described water soluble acrylic acid macromolecular compound metal-salt.
Described vinylformic acid is one or more resins that are selected from zinc acrylate resin, acrylate resin, silicone resin from polishing resin;
Described softening agent is one or more softening agent that are selected from clorafin, Vaseline, dibutyl phthalate or dioctyl phthalate (DOP);
Described stopping composition is one or more stopping composition that are selected from red iron oxide, aerosil, talcum powder, titanium dioxide or zinc oxide.
The below will describe the present invention in more detail.
The present invention relates to a kind of water soluble acrylic acid macromolecular compound.
Described water soluble acrylic acid macromolecular compound has following chemical structural formula:
In the formula:
R
1, R
4Represent hydrogen atom or methyl, R
2The carbochain that representative is comprised of 1～4 methylene radical, R
3Represent hydrogen atom or contain the hydroxyalkyl of 1～4 carbon atom, R
5, R
6With R
7Represent methylidene or ethyl, R
8Represent oxygen or nitrogen-atoms, a, b, c and d represent respectively an integer that is selected from 1～10.
The present invention relates to the preparation method of described water soluble acrylic acid macromolecular compound.
This preparation method's step is as follows:
A, according to the weight ratio 1～10 of described monomer total amount and water, the hydrophilic amino-contained acrylic monomer of 10～40 weight parts, 10～40 weight part hydroxy acryl acid class monomers, 30～70 weight parts are contained quaternary ammonium salt group acrylic monomer and 5～35 weight parts, and to contain carboxy acrylic class monomer soluble in water, obtains a kind of monomer mixture solution;
Described amino-contained acrylic monomer is acrylamide, n-methylolacrylamide or hydroxyethyl acrylamide;
The described quaternary ammonium salt group acrylic monomer that contains is acryloyloxyethyl trimethyl ammonium chloride, the 2-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryloxyethyldimethyl benzyl ammonium chloride, methylacryoyloxyethyl dimethylbutyl brometo de amonio, methylacryoyloxyethyl dimethyl dodecyl bromination ammonium, methylacryoyloxyethyl dimethyl hexadecyl brometo de amonio, 3-acrylamido oxypropyl trimethyl ammonium chloride, methacryloyl amido ethyl-trimethyl salmiac or methacryloyl amido oxypropyl trimethyl ammonium chloride;
The described carboxy acrylic class monomer that contains is acrylic or methacrylic acid;
Described hydroxy acryl acid class monomer is Hydroxyethyl acrylate, Propylene glycol monoacrylate or vinylformic acid hydroxy butyl ester.
All monomeric compounds that the present invention uses all are product solds in the market.
Preferably, described amino-contained acrylic monomer, contain the quaternary ammonium salt group acrylic monomer, the weight ratio that contains carboxy acrylic class monomer and hydroxy acryl acid class monomer is 15～35:15～38:42～58:10～28.
More preferably, described amino-contained acrylic monomer, contain the quaternary ammonium salt group acrylic monomer, the weight ratio that contains carboxy acrylic class monomer and hydroxy acryl acid class monomer is 20～28:22～30:48～52:16～20.
Described amino-contained acrylic monomer, hydroxy acryl acid class monomer, contain the quaternary ammonium salt group acrylic monomer and contain the total amount of carboxy acrylic class monomer and the weight ratio of water is 1:2～6.
Preferably, described amino-contained acrylic monomer, hydroxy acryl acid class monomer, contain the quaternary ammonium salt group acrylic monomer and contain the total amount of carboxy acrylic class monomer and the weight ratio of water is 1:2.5～4.0.
B, will join in the monomer mixture solution that steps A obtains in above-mentioned total monomer weight 0.005～5% water-soluble azo compounds initiator, obtain a kind of monomer mixture solution that contains initiator;
Described initiator is azo-bis-isobutyrate hydrochloride, azo two isobutyl imidazoline salt hydrochlorates, azo dicyano valeric acid or azo di-isopropyl tetrahydroglyoxaline.
All water-soluble azo compounds initiators that the present invention uses all are product solds in the market.
Preferably, described initiator is azo-bis-isobutyrate hydrochloride, azo two isobutyl imidazoline salt hydrochlorates or azo di-isopropyl tetrahydroglyoxaline.
More preferably, described initiator is azo-bis-isobutyrate hydrochloride or azo di-isopropyl tetrahydroglyoxaline.
In the present invention, the amount of described initiator less than in above-mentioned total monomer weight 0.005% time, then can be because of the impact of stopper smooth initiated polymerization; The amount of described initiator the too low phenomenon of water soluble acrylic acid molecular weight polymeric then can occur greater than in above-mentioned total monomer weight 5% time; Therefore, the amount of described initiator is in above-mentioned total monomer weight 0.005～5%, and is suitable.
C, under the condition that stirs, under 50～95 ℃ of temperature, in 0.5～24 hour, the monomer mixture solution that contains initiator that obtains at step B is added drop-wise to and carries out copolyreaction in 110～1100 weight parts waters or the alcohol solution, obtain the solution that solids content is 5～60 % by weight; Separate its solid, be described water soluble acrylic acid macromolecular compound, its weight-average molecular weight is 1.000x10
5～5.000x10
6KDa.
Adopt conventional infrared spectroscopy that described water soluble acrylic acid macromolecular compound has been carried out Infrared spectroscopy, its analytical results is listed in the accompanying drawing 1.Can be found out by accompanying drawing 1, at 3647～3131cm
-1Wider absorption peak be-O-H ,-the stretching vibration absorption peak of N-H because-the stretching vibration absorption peak of O-H is in 3650～3100cm
-1, and-the stretching vibration absorption peak of N-H is in 3500～3400cm
-1, both exist interval overlapped and do not go out respectively; At 2598cm
-1Place's absorption peak is that the stretching vibration that is in the carboxyl-O-H of association state absorbs; 2362.37cm
-1And 2337.39cm
-1The place is the absorption peak of carbonic acid gas; At 1660.14cm
-1And 1637.93cm
-1Absorption peak be that stretching vibration by-C=O absorbs and forms; At 1526cm
-1, 1496cm
-1And 1413cm
-1The flexural vibration absorption peak that is in different chemical environment-C-H that occurs; At 769cm
-1, 680cm
-1Near occur that COO-and ammonium ion form-the O-N absorption peak.Can find out, in polymer, the monomer that copolymerization occurred participating in the infrared absorption peak of the functional groups such as hydroxyl, carboxyl, amino and quaternary ammonium salt, can determine thus to have synthesized target product water soluble acrylic acid macromolecular compound.
Described solid content measuring carries out according to GB/T2793-1995, and its concrete operations are the method mensuration of the water soluble acrylic acid macromolecular solution being dried at a certain temperature resulting non-volatile component and the front mass percent ratio of its solution heating.Described weight-average molecular weight is to adopt Wyatt DAWN HELEOS II laser light scattering instrument to measure, and its measuring method is the method for describing according to its product description, measures take water as solvent.
The concentration of described alcohol solution is 3～20 % by weight, preferably 5～15 % by weight, more preferably 5～9 % by weight.
Described alcohol is one or more alcohol that are selected from ethanol, propyl alcohol, ethylene glycol or glycerol.
In the present invention, if when described copolymerization temperature is lower than 50 ℃, then can not cause this polyreaction smoothly because of decomposition of initiator; When if described copolymerization temperature is higher than 95 ℃, then should reaction produce too soon sudden and violent gathering because of polymerization rate; Therefore, to be 50～95 ℃ be suitable to described copolymerization temperature.
The present invention relates to a kind of water soluble acrylic acid macromolecular compound metal-salt.
Described water soluble acrylic acid macromolecular compound metal-salt has following chemical structural formula:
In the formula:
R
1～R
8Defined in a, b, c and d such as front water soluble acrylic acid macromolecular compound.
R
9Represent a kind of phenylformic acid that is selected from, Chlorodracylic acid, 2, the 4-dichlorobenzoic acid, m-methyl benzoic acid, p-methylbenzoic acid, para-amino benzoic acid, 2, the 3-mesitylenic acid, p-tert-butyl benzoic acid, to Phenylbenzoic acid, p-nitrobenzoic acid, 2-chloro-4-thiamphenicol benzoic acid, o-ethoxybenzoic acid, 3,5-dihydroxyl-4-tolyl acid, 3, the 5-resorcylic acid, anisic acid, naphthenic acid, 2,5-two chloro-4-nitrobenzoic acids, 3, the 5-dinitrobenzoic acid, 3-(1-indyl) propionic acid, 3-(5,6-two chloro-1-indyls) propionic acid, 3-(5-bromo-1-indyl) propionic acid, 3-(5,6-two chloro-1-indyls) propionic acid, 3-(3-dimethylamine methyl-5,6-two chloro-1-indyls) propionic acid, 3-(3-dimethylamine methyl-5-bromo-1-indyl) propionic acid, 3-(3-dimethylamine methyl isophthalic acid-indyl) propionic acid, 3-indolyl acetic acid, rosin, proline(Pro), leucine, phenylalanine, the carboxylate radical of arginine or Serine;
M represents Ca
2+, Mg
2+, Cu
2+Or Zn
2+
The invention still further relates to the preparation method of described water soluble acrylic acid macromolecular compound metal-salt.
This preparation method's step is as follows:
A, water soluble acrylic acid macromolecular compound of the present invention, alkali metal hydroxide and organic acid alkali metal salt is soluble in water obtains aqueous solution I.
The mol ratio of described water soluble acrylic acid macromolecular compound and alkali metal hydroxide is 1:1.0～1.1.
In aqueous solution I, the concentration of described water soluble acrylic acid macromolecular compound is 0.01～3mol/L.
In aqueous solution I, the concentration of described alkali metal hydroxide is 0.01～3mol/L.
In described alkali metal hydroxide, described basic metal is one or more basic metal that are selected from sodium, potassium or lithium.
In aqueous solution I, the concentration of described organic acid alkali metal salt is 0.01～3mol/L.
In described organic acid alkali metal salt, described basic metal is one or more basic metal that are selected from sodium, potassium or lithium.
In described organic acid alkali metal salt, described organic acid is selected from phenylformic acid, Chlorodracylic acid, 2, the 4-dichlorobenzoic acid, m-methyl benzoic acid, p-methylbenzoic acid, para-amino benzoic acid, 2, the 3-mesitylenic acid, p-tert-butyl benzoic acid, to Phenylbenzoic acid, p-nitrobenzoic acid, 2-chloro-4-thiamphenicol benzoic acid, o-ethoxybenzoic acid, 3,5-dihydroxyl-4-tolyl acid, 3, the 5-resorcylic acid, anisic acid, naphthenic acid, 2,5-two chloro-4-nitrobenzoic acids, 3, the 5-dinitrobenzoic acid, 3-(1-indyl) propionic acid, 3-(5,6-two chloro-1-indyls) propionic acid, 3-(5-bromo-1-indyl) propionic acid, 3-(5,6-two chloro-1-indyls) propionic acid, 3-(3-dimethylamine methyl-5,6-two chloro-1-indyls) propionic acid, 3-(3-dimethylamine methyl-5-bromo-1-indyl) propionic acid, 3-(3-dimethylamine methyl isophthalic acid-indyl) propionic acid, 3-indolyl acetic acid, rosin, proline(Pro), leucine, phenylalanine, arginine or Serine.
B, soluble in water the hydrochloride of calcium, magnesium, copper or zinc, nitrate, vitriol or acetate obtains aqueous solution II;
The weight ratio of described water soluble acrylic acid macromolecular compound, described organic acid alkali metal salt and described calcium, magnesium, copper or zinc salt solution is 1:0.9～1.1:1.0～1.4.
Preferably, the weight ratio of described water soluble acrylic acid macromolecular compound, described organic acid alkali metal salt and described calcium, magnesium, copper or zinc salt solution is 1:1.0:1.0～1.3.
More preferably, the weight ratio of described water soluble acrylic acid macromolecular compound, described organic acid alkali metal salt and described calcium, magnesium, copper or zinc salt solution is 1: 1.0:1.1～1.2.
Particularly, the hydrochloride of the present invention's use for example is magnesium chloride, calcium chloride, cupric chloride or zinc chloride.
The nitrate that the present invention uses for example is magnesium nitrate, nitrocalcite, cupric nitrate or zinc nitrate.
The vitriol that the present invention uses for example is sal epsom, zinc sulfate or copper sulfate.
The acetate that the present invention uses for example is magnesium acetate, calcium acetate, zinc acetate or neutralized verdigris.
C, will be added drop-wise in the solution I that steps A obtains in the solution II that step B obtains, under the condition of 10～80 ℃ of stirring and temperature of reaction, reacted 0.5～18 hour, then carry out solid-liquid separation, its solid washs and drying, so obtain described water soluble acrylic acid macromolecular compound metal-salt.
In this reaction, if when described temperature of reaction is lower than 10 ℃, too large and the carrying out smoothly of being unfavorable for reacting of water soluble acrylic acid Viscosity of Polymer Solutions then; When if described temperature of reaction is higher than 80 ℃, then the solvability of formed water soluble acrylic acid macromolecule metal salt in water increases and is unfavorable for improving productive rate; Therefore, it is suitable that described copolymerization temperature is 10～80 ℃, preferably 35～65 ℃.
Described solid-liquid separation, washing and drying are a kind of routine operations in the chemical technology field.
The water soluble acrylic acid macromolecular compound metal-salt that adopts the inventive method to prepare also contains calcium salt, magnesium salts, mantoquita or the zinc salt of a small amount of small molecular by product organic acid calcium salt, magnesium salts, mantoquita or zinc salt and water soluble acrylic acid macromolecular compound.Because these by products do not affect its water soluble acrylic acid macromolecular compound metal-salt effect in actual applications, so need not carry out separating-purifying to its water soluble acrylic acid macromolecular compound metal-salt.
The water soluble acrylic acid macromolecular compound metal-salt that the present invention obtains for example is phenylformic acid water soluble acrylic acid polymer mantoquita, 2,4-dichlorobenzoic acid water soluble acrylic acid polymer mantoquita, p-methylbenzoic acid water soluble acrylic acid polymer mantoquita, para-amino benzoic acid water soluble acrylic acid polymer mantoquita, p-nitrobenzoic acid water soluble acrylic acid polymer mantoquita, 3,5-resorcylic acid water soluble acrylic acid polymer mantoquita, anisic acid water soluble acrylic acid polymer mantoquita, 3-(3-dimethylamine methyl-5,6-two chloro-1-indyls) water-based propionic acid acroleic acid macromolecular mantoquita, 3-(3-dimethylamine methyl-5-bromo-1-indyl) water-based propionic acid acroleic acid macromolecular mantoquita, phenylformic acid water soluble acrylic acid polymer zinc salt, 2,4-dichlorobenzoic acid water soluble acrylic acid polymer zinc salt, p-methylbenzoic acid water soluble acrylic acid polymer zinc salt, para-amino benzoic acid water soluble acrylic acid polymer zinc salt, p-nitrobenzoic acid water soluble acrylic acid polymer zinc salt, 3,5-resorcylic acid water soluble acrylic acid polymer zinc salt, anisic acid water soluble acrylic acid polymer zinc salt, 3-(3-dimethylamine methyl-5,6-two chloro-1-indyls) propionic acid water soluble acrylic acid polymer zinc salt, 3-(3-dimethylamine methyl-5-bromo-1-indyl) propionic acid water soluble acrylic acid polymer zinc salt, phenylformic acid water soluble acrylic acid polymer magnesium salts, 2,4-dichlorobenzoic acid water soluble acrylic acid polymer magnesium salts, p-methylbenzoic acid water soluble acrylic acid polymer magnesium salts, para-amino benzoic acid water soluble acrylic acid polymer magnesium salts, p-nitrobenzoic acid water soluble acrylic acid polymer magnesium salts, 3,5-resorcylic acid water soluble acrylic acid polymer magnesium salts, anisic acid water soluble acrylic acid polymer magnesium salts, 3-(3-dimethylamine methyl-5,6-two chloro-1-indyls) propionic acid water soluble acrylic acid polymer magnesium salts, 3-(3-dimethylamine methyl-5-bromo-1-indyl) propionic acid water soluble acrylic acid polymer magnesium salts, phenylformic acid water soluble acrylic acid polymer calcium salt, 2,4-dichlorobenzoic acid water soluble acrylic acid polymer calcium salt, p-methylbenzoic acid water soluble acrylic acid polymer calcium salt, para-amino benzoic acid water soluble acrylic acid polymer calcium salt, p-nitrobenzoic acid water soluble acrylic acid polymer calcium salt, 3,5-resorcylic acid water soluble acrylic acid polymer calcium salt, anisic acid water soluble acrylic acid polymer calcium salt, 3-(3-dimethylamine methyl-5,6-two chloro-1-indyls) propionic acid water soluble acrylic acid polymer calcium salt, 3-(3-dimethylamine methyl-5-bromo-1-indyl) propionic acid water soluble acrylic acid polymer calcium salt.
Adopt conventional infrared spectroscopy that described water soluble acrylic acid macromolecular compound metal-salt has been carried out Infrared spectroscopy, its analytical results is listed in the accompanying drawing 2.Can be found out by accompanying drawing 2, at 3447.65～3009.1cm
-1Near wider hydroxyl and the amido stretching vibration absorption peak of appearance; COO
-The O-Zn key that forms with metal ion is at 846.88～674.79cm
-1Infrared absorption in the scope; At 1643.48cm
-1The place is for the stretching vibration absorption peak of carbonyl-C=O, at 1400.23cm
-1The absorption peak at place is the absorption of carboxyl functional group, and containing part in this explanation macromolecule metal salt does not have and Zn
2+Carboxyl, and owing to also be-absorption peak of C-H flexural vibration, cause 1400.23cm herein
-1Absorption peak produces stack and is highest peak; At 1607.40cm
-1, 1582.42cm
-1And 1507.48cm
-1The place is the stretching vibration absorption peak of phenyl ring skeleton-C=C-; 1163.3cm
-1, 1071.7cm
-1Place's absorption peak be by-C-H ,-flexural vibration of C-C-form.Have hydroxyl, amino, carboxyl, carboxylate salt and phenyl ring in hence one can see that the macromolecule metal salt, this explanation has obtained target product SBM-1 metal-salt.
The invention still further relates to the purposes of described water soluble acrylic acid macromolecular compound metal-salt in the preparation marine antifouling coating.
Water soluble acrylic acid macromolecule metal salt of the present invention has preferably hydrolysis property in seawater, can discharge toxicity lower or nontoxic the small molecular organic acid root with anti-pollution function, polymer residue and metal ion, can effectively stop adhering to of fouling organism, can be used for preparing environmentally friendly marine antifouling coating.
In the present invention, described marine antifouling coating is comprised of from polishing resin, softening agent, Red copper oxide, stopping composition and described water soluble acrylic acid macromolecular compound metal-salt vinylformic acid, and their weight ratio is respectively 20～60,1～20,1～20,1～30 and 1～50.
Described vinylformic acid is that one or more are selected from zinc acrylate resin, acrylate resin or vinylformic acid silicone resin from polishing resin.These vinylformic acid are resins known by the technical staff in the art from polishing resin, and they all are product solds in the market.
Described softening agent is one or more softening agent that are selected from clorafin, Vaseline, dibutyl phthalate or dioctyl phthalate (DOP).These softening agent fat all are normally used softening agent in the art, and they all are product solds in the market.
Described stopping composition is one or more stopping composition that are selected from red iron oxide, aerosil, talcum powder, titanium dioxide or zinc oxide.
Preferably, vinylformic acid is respectively 28～50,5～14,5～14,8～24 and 10～45 from the weight ratio of polishing resin, softening agent, Red copper oxide, stopping composition and water soluble acrylic acid macromolecular compound metal-salt.
More preferably, vinylformic acid is respectively 32～40,8～10,8～10,12～18 and 18～35 from the weight ratio of polishing resin, softening agent, Red copper oxide, stopping composition and water soluble acrylic acid macromolecular compound metal-salt.
When the preparation antifouling paint, described vinylformic acid is from polishing resin, softening agent, Red copper oxide, stopping composition and described water soluble acrylic acid macromolecular compound metal-salt, according to weight ratio 20～60,1～20,1～20,1～30 and 1～50, fully grind from polishing in the resin solvent dimethylbenzene at described vinylformic acid, then filter with 100 order strainers, its filtrate being is contained the antifouling paint of water soluble acrylic acid macromolecular compound metal-salt.
Described antifouling paint can adopt conventional coating process to be coated with.
In sea area, wheat island, Qingdao City, tested the antifouling property that the present invention contains the antifouling paint of water soluble acrylic acid macromolecular compound metal-salt with reference to national standard " antifouling varnish model shallow sea soak test method " (GB/T 5370-2007).
Hydrolysis reaction occurs in water soluble acrylic acid macromolecular compound metal-salt of the present invention in seawater, discharge toxicity lower or nontoxic the small molecular organic acid root with anti-pollution function, polymer residue and metal ion, can effectively stop adhering to of fouling organism.Residual macromolecular chain after the hydrolysis of this water soluble acrylic acid macromolecular compound metal-salt contains the active group of a large amount of character, such as amido, hydroxyl, carboxyl, is easy to degraded in physical environment and very little to environmental influence.Therefore, acrylic acid aqueous macromolecule metal salt of the present invention is applied in the antifouling paint, when preventing that more effectively marine fouling organism from adhering to, also has eco-friendly advantage.
Compare with the polymer of the cm-chitosan of using in the prior art, Lalgine, carboxymethyl cellulose, water soluble acrylic acid macromolecular compound of the present invention does not have the easy crystallization of above-mentioned polymer (because having regular spirane structure and intramolecular hydrogen bond), characteristics that molecular weight is large, thus water soluble acrylic acid macromolecular compound metal-salt of the present invention can be relatively easily hydrolysis and can better bring into play antifouling property in seawater; Also with the stronger quaternary ammonium salt group of antifouling property and more amido, so it also has better antifouling property than cm-chitosan, Lalgine and carboxymethyl cellulose on the macromolecular chain of water soluble acrylic acid macromolecular compound of the present invention.It is cheap to prepare the used cost of material of acrylic acid aqueous polymer, makes acrylic acid aqueous macromolecule metal salt have in actual applications significant cost advantage.
[beneficial effect]
The invention has the beneficial effects as follows: water soluble acrylic acid macromolecular compound metal-salt of the present invention passes through hydrolysis reaction in seawater, discharge lower or avirulent small molecular organic acid root, polymer residue and the metal ion with anti-pollution function of toxicity, the antifouling activity material is played certain slow releasing function, can effectively stop adhering to of fouling organism, have eco-friendly advantage.The cost of material that the present invention uses is cheap, and production cost is low, therefore has very good application prospect.
[description of drawings]
Fig. 1 is the infrared spectra spectrogram of water soluble acrylic acid macromolecular compound of the present invention.
Fig. 2 is the infrared spectra spectrogram of water soluble acrylic acid macromolecular compound metal-salt of the present invention.
[embodiment]
Can understand better the present invention by following embodiment.
Embodiment 1: the preparation of water soluble acrylic acid macromolecular compound
The implementation step of this embodiment is as follows:
A, according to the weight ratio 1 of described monomer total amount and water, 10 weight part acrylamides, 10 parts by weight of acrylic acid hydroxyl ethyl esters, 30 weight part acryloyloxyethyl trimethyl ammonium chlorides and 5 parts by weight of acrylic acid are soluble in water, obtain a kind of monomer mixture solution; Then,
B, will join in the monomer mixture solution that steps A obtains in above-mentioned total monomer weight 0.005% azo-bis-isobutyrate hydrochloride initiator, obtain a kind of monomer mixture solution that contains initiator; Then,
C, under the condition that stirs, carry out copolyreaction in 110 weight parts waters in 0.5 hour, the monomer mixture solution that contains initiator that obtains at step B being added drop-wise under the condition of temperature 50 C, obtain described water soluble acrylic acid macromolecular compound SBM-1 solution;
The solids content that adopts the method for describing in the present specification to measure described water soluble acrylic acid macromolecular compound solution is in its total solution weight 60%, and weight-average molecular weight is 1.0520x10
6～1.2651 * 10
6KDa.
Resulting water soluble acrylic acid macromolecular compound solution has been carried out Infrared spectroscopy, and it the results are shown in accompanying drawing 1.Can be found out by accompanying drawing 1, in prepared water soluble acrylic acid macromolecular compound, the infrared absorption peak of the entrained functional groups such as hydroxyl, carboxyl, amino and quaternary ammonium salt of the monomer of copolymerization occurs participating in, can determine thus the synthetic title product water soluble acrylic acid macromolecular compound SBM-1 that obtains.
Embodiment 2: the preparation of water soluble acrylic acid macromolecular compound
The implementation step of this embodiment is as follows:
A, according to the weight ratio 10 of described monomer total amount and water, 40 weight part n-methylolacrylamide, 30 parts by weight of acrylic acid hydroxypropyl acrylates, 70 weight part methylacryloxyethyldimethyl benzyl ammonium chlorides and 35 weight part methacrylic acids are soluble in water, obtain a kind of monomer mixture solution; Then,
B, will join in the monomer mixture solution that steps A obtains in above-mentioned total monomer weight 1% azo two isobutyl imidazoline salt hydrochlorate initiators, obtain a kind of monomer mixture solution that contains initiator; Then,
C, under the condition that stirs, under temperature 70 C, in 4 hours, the monomer mixture solution that contains initiator that obtains at step B is added drop-wise to and carries out copolyreaction in 1100 weight parts waters, obtain described water soluble acrylic acid macromolecular compound solution;
The solids content that adopts the method for describing in the present specification to measure described water soluble acrylic acid macromolecular compound solution is in its total solution weight 5%, and weight-average molecular weight is 3.0125～3.2174x10
5KDa.
Embodiment 3: the preparation of water soluble acrylic acid macromolecular compound
The implementation step of this embodiment is as follows:
A, according to the weight ratio 4 of described monomer total amount and water, 20 weight part hydroxyethyl acrylamides, 40 parts by weight of acrylic acid hydroxy butyl esters, 45 weight part 3-acrylamido oxypropyl trimethyl ammonium chlorides and 15 weight part methacrylic acids are soluble in water, obtain a kind of monomer mixture solution; Then,
B, will join in the monomer mixture solution that steps A obtains in above-mentioned total monomer weight 1% azo dicyano valeric acid initiator, obtain a kind of monomer mixture solution that contains initiator; Then,
C, under the condition that stirs, under 65 ℃ of temperature, in 1.5 hours, the monomer mixture solution that contains initiator that obtains at step B is added drop-wise to 520 weight parts and carries out copolyreaction in 15% aqueous ethanolic solution by weight, obtain described water soluble acrylic acid macromolecular compound solution;
The solids content that adopts the method for describing in the present specification to measure described water soluble acrylic acid macromolecular compound solution is in its total solution weight 24%, and weight-average molecular weight is 0.9210～1.2011 * 10
5KDa.
Embodiment 4: the preparation of water soluble acrylic acid macromolecular compound
The implementation step of this embodiment is as follows:
A, according to the weight ratio 6 of described monomer total amount and water, 30 weight part n-methylolacrylamide, 20 parts by weight of acrylic acid hydroxyl ethyl esters, 55 weight part 2-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 24 parts by weight of acrylic acid are soluble in water, obtain a kind of monomer mixture solution; Then,
B, will join in the monomer mixture solution that steps A obtains in above-mentioned total monomer weight 0.5% azo di-isopropyl tetrahydroglyoxaline initiator, obtain a kind of monomer mixture solution that contains initiator; Then,
C, under the condition that stirs, under temperature 70 C, in 1.5 hours, the monomer mixture solution that contains initiator that obtains at step B is added drop-wise to 880 weight parts and carries out copolyreaction in 20% aqueous solution of propylene glycol by weight, obtain described water soluble acrylic acid macromolecular compound solution;
The solids content that adopts the method for describing in the present specification to measure described water soluble acrylic acid macromolecular compound solution is in its total solution weight 48%, and weight-average molecular weight is 1.8131～1.9625 * 10
6KDa.
Embodiment 5: the preparation of water soluble acrylic acid macromolecular compound metal-salt
The implementation step of this embodiment is as follows:
A, water soluble acrylic acid macromolecular compound, sodium hydroxide and the o-ethoxybenzoic acid potassium of above-described embodiment 1 preparation is soluble in water, contained simultaneously embodiment 1 gained water soluble acrylic acid macromolecular compound sodium salt, o-ethoxybenzoic acid aqueous solutions of potassium I, the carboxylate radical concentration that water soluble acrylic acid macromolecular compound sodium salt and o-ethoxybenzoic acid potassium provide in this solution is 0.15mol/L; The contained carboxyl of described water soluble acrylic acid macromolecular compound is 1:1 with the mol ratio that adds sodium hydroxide;
B, soluble in water zinc nitrate obtains concentration and is 0.15mol/L aqueous solution II;
C, will be added drop-wise at the aqueous solution I that steps A obtains in the solution II that step B obtains, reaction is 2.5 hours under the condition of 50 ℃ of stirring and temperature of reaction, then carry out the solid particulate precipitate and separate, use washing with acetone with dry, so obtain described water soluble acrylic acid macromolecular compound zinc salt.The mol ratio of described aquosity acroleic acid macromolecular compound sodium salt, o-ethoxybenzoic acid potassium and zinc nitrate is 1:1:1;
Resulting water soluble acrylic acid high molecular metal salts solution has been carried out Infrared spectroscopy, and it the results are shown in the accompanying drawing 2.Can be found out by accompanying drawing 2, exist hydroxyl, amino, carboxyl, carboxylate salt and phenyl ring in described water soluble acrylic acid high molecular metal salt, this illustrates the synthetic synthetic metal-salt that obtains water soluble acrylic acid macromolecular compound SBM-1 that obtained.
Embodiment 6: the preparation of water soluble acrylic acid macromolecular compound metal-salt
The implementation step of this embodiment is as follows:
A, water soluble acrylic acid macromolecular compound, sodium hydroxide and the Sodium Benzoate of above-described embodiment 2 preparations is soluble in water, contained simultaneously the water soluble acrylic acid macromolecular compound sodium salt of embodiment 2 preparations, the aqueous solution I of Sodium Benzoate, the carboxylate radical concentration that water soluble acrylic acid macromolecular compound sodium salt and Sodium Benzoate provide in this solution is 0.1mol/L; The contained carboxyl of described water soluble acrylic acid macromolecular compound is 1: 1 with the mol ratio that adds sodium hydroxide;
B, soluble in water calcium chloride obtains concentration and is 0.1mol/L aqueous solution II;
C, will be added drop-wise at the aqueous solution I that steps A obtains in the solution II that step B obtains, reaction is 3 hours under the condition of 40 ℃ of stirring and temperature of reaction, then carry out the solid particulate precipitate and separate, wash with water and drying, so obtain described water soluble acrylic acid macromolecular compound calcium salt.The mol ratio of described water soluble acrylic acid macromolecular compound sodium salt, Sodium Benzoate and calcium chloride water is 1:1:1.2.
Embodiment 7: the preparation of water soluble acrylic acid macromolecular compound metal-salt
The implementation step of this embodiment is as follows:
A, with water soluble acrylic acid macromolecular compound, potassium hydroxide and the 3-(5 of above-described embodiment 3 preparation, 6-two chloro-1-indyls) propionic acid sylvite is soluble in water, contained simultaneously water soluble acrylic acid macromolecular compound sylvite and 3-(5,6-, two chloro-1-indyls) potassium propionate salt concn and be 0.1mol/L aqueous solution I; The mol ratio of the contained carboxyl of described water soluble acrylic acid macromolecular compound and potassium hydroxide is 1:1;
B, soluble in water the sulfuric acid mantoquita, obtaining concentration is 0.1mol/L aqueous solution II;
C, will be added drop-wise at the aqueous solution I that steps A obtains in the solution II that step B obtains, reaction is 2 hours under the condition of 50 ℃ of stirring and temperature of reaction, then carry out the solid particulate precipitate and separate, wash with water and dry sediment, so obtain described water soluble acrylic acid macromolecular compound metal-salt.The mol ratio of described water soluble acrylic acid macromolecular compound sylvite, 3-(5,6-, two chloro-1-indyls) propionic acid sylvite and copper sulfate is 1:1:1.4.
Embodiment 8: the preparation of water soluble acrylic acid macromolecular compound metal-salt
The implementation step of this embodiment is as follows:
A, water soluble acrylic acid macromolecular compound, sodium hydroxide and the proline(Pro) sodium salt of above-described embodiment 4 preparations is soluble in water, the aqueous solution that is contained simultaneously water soluble acrylic acid macromolecular compound sodium salt and Sodium proline, the contained carboxylate radical of water soluble acrylic acid macromolecular compound sodium salt, Sodium proline concentration are 0.1mol/L aqueous solution I; The mol ratio of described water soluble acrylic acid macromolecular compound and sodium hydroxide is 1:1.1;
B, soluble in water the acetic acid zinc salt, obtaining concentration is 1mol/L aqueous solution II;
C, will be added drop-wise at the aqueous solution I that steps A obtains in the solution II that step B obtains, reaction is 4 hours under the condition of 55 ℃ of stirring and temperature of reaction, then separate, wash and drying, so obtain described water soluble acrylic acid macromolecular compound metal-salt.The mol ratio of described water soluble acrylic acid macromolecular compound sodium salt, proline(Pro) sodium salt and acetic acid zinc salt is 1:1:1.1.
Application Example 1: preparation marine antifouling coating
After the water soluble acrylic acid macromolecular compound metal-salt of zinc acrylate resin, clorafin softening agent, Red copper oxide, red iron oxide stopping composition and above-described embodiment 5 preparations fully ground in the solvent xylene of described resin according to weight ratio 32,5,5,5 and 15, filter with 100 order strainers, its filtrate being is contained the antifouling paint of water soluble acrylic acid macromolecular compound metal-salt.This antifouling paint adopts conventional coating process to be coated with." antifouling varnish model shallow sea soak test method " (GB/T 5370-2007) tests the antifouling property of this antifouling paint according to national standard, and the real extra large panel experiment test-results of antifouling paint of the present invention the results are shown in Fig. 3.
Application Example 2: preparation marine antifouling coating
After the water soluble acrylic acid macromolecular compound metal-salt of zinc acrylate resin, Vaseline softening agent, Red copper oxide, aerosil stopping composition and above-described embodiment 6 preparations fully ground in the solvent xylene of described resin according to weight ratio 20,2,5,5 and 15, filter with 100 purpose strainers, its filtrate being is contained the antifouling paint of water soluble acrylic acid macromolecular compound metal-salt.This antifouling paint adopts conventional coating process to be coated with." antifouling varnish model shallow sea soak test method " (GB/T 5370-2007) tests the antifouling property of this antifouling paint according to national standard, and the real extra large panel experiment test-results of antifouling paint of the present invention is listed in Fig. 3.
These test pieces are plunged into the commercial sea mid-November, and this moment, marine increment of organism totally began to reduce, but the growth of marine marine alga and multiple epizoite is still vigorous.Soaked as seen from Figure 3 the sea 38 days to 97 days, blank model length has a thick-layer biological mucosa, and have many kelps to adhere to, and Application Example of the present invention 1 only is attached with very thin one deck biological mucosa with Application Example 2 preparation marine antifouling coating model surfaces; From soaking the sea 160 days to 222 days, ocean epizoite just, such as the season of the amount reproductions such as happy shellfish, barnacle growth, the a large amount of happy shellfish of contrast model surface attachment, and Application Example 1 of the present invention a small amount of mud and biological mucosa only occur with Application Example 2 preparation marine antifouling coating model surfaces, and this illustrates that adhering to of water soluble acrylic acid macromolecule metal salt pair marine animal of the present invention has certain restraining effect.Compare and now widely used stain control agent, it has eco-friendly characteristics.
Claims (10)
1. water soluble acrylic acid macromolecular compound is characterized in that it has following chemical structural formula:
In the formula:
R
1, R
4Represent hydrogen atom or methyl, R
2The carbochain that representative is comprised of 1～4 methylene radical, R
3Represent hydrogen atom or contain the hydroxyalkyl of 1～4 carbon atom, R
5, R
6With R
7Represent methylidene or ethyl, R
8Represent oxygen or nitrogen-atoms, a, b, c and d represent respectively an integer that is selected from 1～10.
2. the preparation method of water soluble acrylic acid macromolecular compound according to claim 1 is characterized in that the step of the method is as follows:
A, according to the weight ratio 1～10 of described monomer total amount and water, the hydrophilic amino-contained acrylic monomer of 10～40 weight parts, 10～40 weight part hydroxy acryl acid class monomers, 30～70 weight parts are contained quaternary ammonium salt group acrylic monomer and 5～35 weight parts, and to contain carboxy acrylic class monomer soluble in water, obtains a kind of monomer mixture solution;
Described wetting ability amino-contained acrylic monomer is acrylamide, n-methylolacrylamide or hydroxyethyl acrylamide; The described quaternary ammonium salt group acrylic monomer that contains is acryloyloxyethyl trimethyl ammonium chloride, the 2-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryloxyethyldimethyl benzyl ammonium chloride, methylacryoyloxyethyl dimethylbutyl brometo de amonio, methylacryoyloxyethyl dimethyl dodecyl bromination ammonium, methylacryoyloxyethyl dimethyl hexadecyl brometo de amonio, 3-acrylamido oxypropyl trimethyl ammonium chloride, methacryloyl amido ethyl-trimethyl salmiac or methacryloyl amido oxypropyl trimethyl ammonium chloride; The described carboxy acrylic class monomer that contains is acrylic or methacrylic acid; Described hydroxy acryl acid class monomer is Hydroxyethyl acrylate, Propylene glycol monoacrylate or vinylformic acid hydroxy butyl ester; Then,
B, will join in the monomer mixture solution that steps A obtains in above-mentioned total monomer weight 0.005～5% water-soluble azo compounds initiator, obtain a kind of monomer mixture solution that contains initiator;
Described water-soluble azo compounds initiator is azo-bis-isobutyrate hydrochloride, azo two isobutyl imidazoline salt hydrochlorates, azo dicyano valeric acid or azo di-isopropyl tetrahydroglyoxaline; Then,
C, under the condition that stirs, under 50～95 ℃ of temperature, in 0.5～24 hour, the monomer mixture solution that contains initiator that obtains at step B is added drop-wise to and carries out copolyreaction in 110～1100 weight parts waters or the alcohol solution, obtain the solution that solids content is 5～60 % by weight; Separate its solid, be described water soluble acrylic acid macromolecular compound, its weight-average molecular weight is 1.000x10
5～5.000x10
6KDa.
3. preparation method according to claim 2 is characterized in that described amino-contained acrylic monomer, hydroxy acryl acid class monomer, contains the quaternary ammonium salt group acrylic monomer and contains the total amount of carboxy acrylic class monomer and the weight ratio of water is 1:2～6.
4. preparation method according to claim 2, the concentration that it is characterized in that described alcohol solution is 3～20 % by weight.
5. according to claim 2 or 4 described preparation methods, it is characterized in that described alcohol is one or more alcohol that are selected from ethanol, propyl alcohol, ethylene glycol or glycerol.
6. the metal-salt of described water soluble acrylic acid macromolecular compound according to claim 1 is characterized in that it has following chemical structural formula:
In the formula:
R
1～R
8With a, b, c and d be as defined in claim 1;
R
9Represent a kind of phenylformic acid that is selected from, Chlorodracylic acid, 2, the 4-dichlorobenzoic acid, m-methyl benzoic acid, p-methylbenzoic acid, para-amino benzoic acid, 2, the 3-mesitylenic acid, p-tert-butyl benzoic acid, to Phenylbenzoic acid, p-nitrobenzoic acid, 2-chloro-4-thiamphenicol benzoic acid, o-ethoxybenzoic acid, 3,5-dihydroxyl-4-tolyl acid, 3, the 5-resorcylic acid, anisic acid, naphthenic acid, 2,5-two chloro-4-nitrobenzoic acids, 3, the 5-dinitrobenzoic acid, 3-(1-indyl) propionic acid, 3-(5,6-two chloro-1-indyls) propionic acid, 3-(5-bromo-1-indyl) propionic acid, 3-(5,6-two chloro-1-indyls) propionic acid, 3-(3-dimethylamine methyl-5,6-two chloro-1-indyls) propionic acid, 3-(3-dimethylamine methyl-5-bromo-1-indyl) propionic acid, 3-(3-dimethylamine methyl isophthalic acid-indyl) propionic acid, 3-indolyl acetic acid, rosin, proline(Pro), leucine, phenylalanine, the carboxylate radical of arginine or Serine;
M is Ca
2+, Mg
2+, Cu
2+Or Zn
2+
7. the preparation method of water soluble acrylic acid macromolecular compound metal-salt according to claim 6 is characterized in that the step of the method is as follows:
A, water soluble acrylic acid macromolecular compound claimed in claim 1, alkali metal hydroxide and organic acid alkali metal salt is soluble in water obtains aqueous solution I;
Described basic metal is one or more basic metal that are selected from sodium, potassium or lithium;
B, soluble in water the hydrochloride of calcium, magnesium, copper or zinc, nitrate, vitriol or acetate obtains aqueous solution II;
The mol ratio of described water soluble acrylic acid macromolecular compound and alkali metal hydroxide is 1:1.0～1.1;
The concentration of described water soluble acrylic acid macromolecular compound, described organic acid alkali metal salt and described calcium, magnesium, copper or zinc salt solution is 0.01～3mol/L; Their mol ratio is 1:0.9～1.1:1.0～1.4;
C, will be added drop-wise at the aqueous solution I that steps A obtains in the solution II that step B obtains, under the condition of 10～80 ℃ of stirring and temperature of reaction, reacted 0.5～18 hour, then carry out solid-liquid separation, its solid washs and drying, so obtain described water soluble acrylic acid macromolecular compound metal-salt.
8. preparation method according to claim 7, it is characterized in that in described organic acid alkali metal salt, described organic acid is selected from phenylformic acid, Chlorodracylic acid, 2, the 4-dichlorobenzoic acid, m-methyl benzoic acid, p-methylbenzoic acid, para-amino benzoic acid, 2, the 3-mesitylenic acid, p-tert-butyl benzoic acid, to Phenylbenzoic acid, p-nitrobenzoic acid, 2-chloro-4-thiamphenicol benzoic acid, o-ethoxybenzoic acid, 3,5-dihydroxyl-4-tolyl acid, 3, the 5-resorcylic acid, anisic acid, naphthenic acid, 2,5-two chloro-4-nitrobenzoic acids, 3, the 5-dinitrobenzoic acid, 3-(1-indyl) propionic acid, 3-(5,6-two chloro-1-indyls) propionic acid, 3-(5-bromo-1-indyl) propionic acid, 3-(5,6-two chloro-1-indyls) propionic acid, 3-(3-dimethylamine methyl-5,6-two chloro-1-indyls) propionic acid, 3-(3-dimethylamine methyl-5-bromo-1-indyl) propionic acid, 3-(3-dimethylamine methyl isophthalic acid-indyl) propionic acid, 3-indolyl acetic acid, rosin, proline(Pro), leucine, phenylalanine, arginine or Serine.
9. water soluble acrylic acid macromolecular compound metal-salt according to claim 6 is in the purposes of preparation in the marine antifouling coating.
10. purposes according to claim 9 is characterized in that the composed as follows of described marine antifouling coating, in weight part:
Vinylformic acid is from polishing resin ... 20～60 parts
Softening agent ... 1～20 part
Red copper oxide ... 1～20 part
Stopping composition ... 1～30 part
1～50 part of described water soluble acrylic acid macromolecular compound metal-salt;
Described vinylformic acid is one or more resins that are selected from zinc acrylate resin, acrylate resin or vinylformic acid silicone resin from polishing resin;
Described softening agent is one or more softening agent that are selected from clorafin, Vaseline, dibutyl phthalate or dioctyl phthalate (DOP);
Described stopping composition is one or more stopping composition that are selected from red iron oxide, aerosil, talcum powder, titanium dioxide or zinc oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210433957.6A CN102911309B (en) | 2012-11-02 | 2012-11-02 | Waterborne acrylic macromolecular compound as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210433957.6A CN102911309B (en) | 2012-11-02 | 2012-11-02 | Waterborne acrylic macromolecular compound as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102911309A true CN102911309A (en) | 2013-02-06 |
| CN102911309B CN102911309B (en) | 2015-07-08 |
Family
ID=47609904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210433957.6A Expired - Fee Related CN102911309B (en) | 2012-11-02 | 2012-11-02 | Waterborne acrylic macromolecular compound as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102911309B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467281A (en) * | 2013-07-25 | 2013-12-25 | 武汉英纳氏药业有限公司 | Phenol derivative and application thereof |
| CN103709319A (en) * | 2013-12-25 | 2014-04-09 | 浙江海洋学院 | Preparation method and application of copper/zinc-containing metal polyacrylate resin |
| CN104479086A (en) * | 2014-09-01 | 2015-04-01 | 英德市雅家涂料有限公司 | Self-polishing copper acrylate resin and synthetic method thereof |
| EP2998374A4 (en) * | 2013-05-13 | 2016-06-15 | Panasonic Ip Man Co Ltd | Coating-agent composition and antimicrobial/antiviral member |
| CN107759730A (en) * | 2017-08-17 | 2018-03-06 | 孟庆桓 | A kind of preparation method of biomass modified drive oil recovery polyacrylamide |
| CN108203484A (en) * | 2016-12-20 | 2018-06-26 | 罗门哈斯公司 | With the functionalized latex of arginine functionalized monomer's structural unit |
| CN108385417A (en) * | 2018-02-26 | 2018-08-10 | 杭州小橙工业设计有限公司 | A kind of resist printing preparation process thereof implementation system |
| JP2018203900A (en) * | 2017-06-06 | 2018-12-27 | 三菱ケミカル株式会社 | Insoluble antifouling coating polymer, resin composition, antifouling coating, coating, underwater friction reducing method, and method for producing insoluble antifouling coating polymer |
| CN110437727A (en) * | 2019-07-23 | 2019-11-12 | 天津大学 | A kind of antibacterial/anti-fog coating and preparation method thereof based on N- hydroxyethyl acrylamide |
| CN114014971A (en) * | 2021-11-25 | 2022-02-08 | 中国海洋大学 | Preparation method and application of acrylic-based hydrogel antifouling material without volatile organic compounds |
| CN115521683A (en) * | 2022-10-21 | 2022-12-27 | 常熟理工学院 | Double-network structure modified organic silicon marine antifouling coating and preparation method thereof |
-
2012
- 2012-11-02 CN CN201210433957.6A patent/CN102911309B/en not_active Expired - Fee Related
Non-Patent Citations (6)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库，工程科技I辑》 20120715 李如 "仿壳聚糖官能结构聚合物的合成及应用" 第2.3.1.3节 1-10 , 第7期 * |
| 《中国博士学位论文全文数据库，工程科技I辑》 20050315 于良民 "环境友好型丙烯酸树脂的合成及其在海洋防污涂料中的应用研究" 第3.2.2.1节 10 , 第1期 * |
| 《中国博士学位论文全文数据库，工程科技I辑》 20080315 董磊 "羧甲基壳聚糖金属盐/壳聚糖包覆氧化亚铜的制备及其海洋防污性能研究" 第3.1节，第3.3.2.3节 6-10 , 第3期 * |
| 于良民: ""环境友好型丙烯酸树脂的合成及其在海洋防污涂料中的应用研究"", 《中国博士学位论文全文数据库，工程科技I辑》 * |
| 李如: ""仿壳聚糖官能结构聚合物的合成及应用"", 《中国优秀硕士学位论文全文数据库，工程科技I辑》 * |
| 董磊: ""羧甲基壳聚糖金属盐/壳聚糖包覆氧化亚铜的制备及其海洋防污性能研究"", 《中国博士学位论文全文数据库，工程科技I辑》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2998374A4 (en) * | 2013-05-13 | 2016-06-15 | Panasonic Ip Man Co Ltd | Coating-agent composition and antimicrobial/antiviral member |
| US10131797B2 (en) | 2013-05-13 | 2018-11-20 | Panasonic Intellectual Property Management Co., Ltd. | Coating agent composition and antibacterial/antiviral member |
| CN103467281B (en) * | 2013-07-25 | 2016-03-23 | 武汉英纳氏药业有限公司 | A kind of phenol derivatives and application thereof |
| CN103467281A (en) * | 2013-07-25 | 2013-12-25 | 武汉英纳氏药业有限公司 | Phenol derivative and application thereof |
| CN103709319A (en) * | 2013-12-25 | 2014-04-09 | 浙江海洋学院 | Preparation method and application of copper/zinc-containing metal polyacrylate resin |
| CN103709319B (en) * | 2013-12-25 | 2016-02-03 | 浙江海洋学院 | The preparation method and application of the polyacrylic acid metal salt resin of a kind of cupric or zinc |
| CN104479086A (en) * | 2014-09-01 | 2015-04-01 | 英德市雅家涂料有限公司 | Self-polishing copper acrylate resin and synthetic method thereof |
| CN108203484A (en) * | 2016-12-20 | 2018-06-26 | 罗门哈斯公司 | With the functionalized latex of arginine functionalized monomer's structural unit |
| CN108203484B (en) * | 2016-12-20 | 2022-03-01 | 罗门哈斯公司 | Latex functionalized with arginine-functionalized monomer building blocks |
| JP7019972B2 (en) | 2017-06-06 | 2022-02-16 | 三菱ケミカル株式会社 | Resin composition, antifouling paint, coating film, underwater friction reduction method, and method for manufacturing resin composition |
| JP2018203900A (en) * | 2017-06-06 | 2018-12-27 | 三菱ケミカル株式会社 | Insoluble antifouling coating polymer, resin composition, antifouling coating, coating, underwater friction reducing method, and method for producing insoluble antifouling coating polymer |
| CN107759730A (en) * | 2017-08-17 | 2018-03-06 | 孟庆桓 | A kind of preparation method of biomass modified drive oil recovery polyacrylamide |
| CN108385417A (en) * | 2018-02-26 | 2018-08-10 | 杭州小橙工业设计有限公司 | A kind of resist printing preparation process thereof implementation system |
| CN110437727B (en) * | 2019-07-23 | 2021-05-14 | 天津大学 | N-hydroxyethyl acrylamide-based antibacterial/antifogging coating and preparation method thereof |
| CN110437727A (en) * | 2019-07-23 | 2019-11-12 | 天津大学 | A kind of antibacterial/anti-fog coating and preparation method thereof based on N- hydroxyethyl acrylamide |
| CN114014971A (en) * | 2021-11-25 | 2022-02-08 | 中国海洋大学 | Preparation method and application of acrylic-based hydrogel antifouling material without volatile organic compounds |
| CN115521683A (en) * | 2022-10-21 | 2022-12-27 | 常熟理工学院 | Double-network structure modified organic silicon marine antifouling coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102911309B (en) | 2015-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102911309B (en) | Waterborne acrylic macromolecular compound as well as preparation method and application thereof | |
| AU646754B2 (en) | Antifouling coatings | |
| CN101287805B (en) | Marine antifouling coating compositions | |
| RU2415168C2 (en) | Composition for obtaining antifouling coating and use thereof on artificial structures | |
| KR101045922B1 (en) | Acid-Capped Quaternary Polymers and Compositions Comprising the Polymers | |
| CN102119192B (en) | Polymer with salt groups and antifouling coating composition comprising the polymer | |
| CN103122187B (en) | ionic liquid modified marine antifouling paint | |
| CN1709925B (en) | Resin of zinc acrylate or copper acrylate containing capsaicin function group, its preparation and use | |
| CN103289007A (en) | Improved preparation method for zinc/copper acrylate resin | |
| WO1991009915A1 (en) | Anti-fouling coating compositions | |
| JP2017538802A (en) | Adhesion inhibiting composition comprising a polymer comprising a silyl ester functional group and a quaternary ammonium group / phosphonium group | |
| CN1709921B (en) | Resin of zinc acrylate or copper acrylate containing indole function group, its preparation and use | |
| CN102167774A (en) | Method for preparing fluorine modified zinc acrylate antifouling resin | |
| CN104031236A (en) | Polyurethane with zwitterion precursor brush-like side chain, and preparation method and application thereof | |
| CN104761991A (en) | Environmental-protection type multi-element collaborative marine anti-fouling coating | |
| JP6387187B2 (en) | Adhesion inhibiting coating composition comprising a polymer containing silyl ester groups and a polymer containing quaternary ammonium / phosphonium sulfonate groups | |
| CN102532396B (en) | Lateral-chain stem grafting glyphosate derivative acrylic resin and preparation method and application thereof | |
| CN1702084A (en) | Carboxymethyl chitosan copper or zinc salts and their preparation method and use thereof | |
| KR101668909B1 (en) | Metal-containing copolymer, manufacturing method therefor, antifouling-paint composition, antifouling paint, and article having coating thereof | |
| CN102051101B (en) | Method for preparing normal temperature-cured anti-fouling anti-drag hydrogel soft coating | |
| CN105255291B (en) | A kind of environment-friendly marine antifouling coating containing polyion liquid broad spectrum type anti-fouling agent and preparation technology thereof | |
| JP2006232808A (en) | Pyrithione metal salt having specific particle size distribution, and, coating composition | |
| JP3824925B2 (en) | Antifouling paint composition, coating film comprising the composition, ship or underwater structure coated with the coating film, and antifouling method | |
| JP6596802B2 (en) | COATING COMPOSITION FOR COATING FORM WITH REDUCED FRICTION RESISTANCE, COATING AND SUBSTRATE WITH COATING | |
| CN102408807B (en) | High performance bionic antifouling composite paint and synthetic method thereof |
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: 20150708 Termination date: 20151102 |
|
| EXPY | Termination of patent right or utility model |