CN102676015B - Humidity-sensitive intelligent betaine fluorinated antifouling paint and preparation method thereof - Google Patents
Humidity-sensitive intelligent betaine fluorinated antifouling paint and preparation method thereof Download PDFInfo
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- CN102676015B CN102676015B CN201210166101.7A CN201210166101A CN102676015B CN 102676015 B CN102676015 B CN 102676015B CN 201210166101 A CN201210166101 A CN 201210166101A CN 102676015 B CN102676015 B CN 102676015B
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Abstract
The invention relates to humidity-sensitive intelligent betaine fluorinated antifouling paint and a preparation method thereof. The paint is mainly made of, by weight, 10%-60% of betaine fluorinated copolymer, 60%-10% of inorganic salt filler, 0.1%-0.5% of water-based paint antifoaming agent, 0.1%-5.0% of dispersing agent and 20%-50% of water. The preparation method includes: firstly, uniformly mixing the betaine fluorinated copolymer solution, the antifoaming agent, the dispersing agent and the water, and secondly, adding the inorganic salt filler while stirring to obtain the humidity-sensitive intelligent betaine fluorinated antifouling paint. The characteristic of foul resistance of fluorinated groups in air and the characteristic of foul resistance of betaine groups in water are integrated to prepare the humidity-sensitive intelligent antifouling paint, and distribution of the fluorinated groups and the betaine groups in coatings can be adjusted according to variation of external media, so that better antifouling function can be kept constantly.
Description
Technical field
The present invention relates to technical field of coatings, be specifically related to fluorine-containing intelligent antifouling paint of a class humidity inductive betaines and preparation method thereof.
Background technology
Marine attaching organism is the common name of animal, plant and the microorganism on long term growth all facility surfaces in boats and ships and ocean, and the biodeterioration that it causes is safeguarded and brought huge financial loss to boats and ships.In the time that marine organisms are attached to hull bottom, can there is along with the growth of these fouling organisms the physicochemical change of series of complex, greatly accelerate the corrosion of hull bottom steel plate, reduce the work-ing life of equipment.Meanwhile, fouling organism can make the deadweight on naval vessel and running resistance increase, thereby increases fuel oil consumption, has a strong impact on instrumented tracking and telemetry ship and finishes the work.The loss that biodeterioration causes is difficult to accurate calculation, and according to incompletely statistics, the whole world loss that only biodeterioration causes to various underwater engineering facilities and ship's fitting can reach more than tens billion of dollars every year.
In numerous anti-fouling methods, most economical, effective means at boats and ships and underwater facility surface-coated antifouling paint, the research of antifouling paint has been experienced high poison to low toxicity, nontoxic transformation, surging along with the development in epoch and environmental protection cry, has proposed new requirement to antifouling paint: nontoxic, efficient, economical.Therefore, carry out the research and development to novel, efficient, the economic pollution-free antifouling paint in ocean, not only there is the military strategy meaning of gaining the initiative, and also have very large economic benefit and social benefit.
Traditional toxicity antifouling paint is general only has restraining effect to some marine organisms, and along with the continuous release of toxicant, its anti-fouling effect also progressively declines.Low surface energy anti-fouling paint by thereon adhere to interface very a little less than, utilize the impact of current or the cleaning of utility appliance in deadweight, navigation to remove easily.And low surface energy anti-fouling paint is the physical action on coating based surface, there is not the release loss problem of toxicant, can play long-term antifouling effect.The low-surface-energy material using is at present mainly organosilicon series and organic fluorine series material.This class coating not containing toxicity, says it is a kind of desirable selection from the angle of environmental protection completely.
Wherein organic fluorine series material is because the electronegativity of fluorine is very large; C-F key is very stable; and fluorine-containing side chain has tendency outwardly; can form " shielding protection " to main chain and interior molecules; thereby make acrylate containing fluorine polymkeric substance there are many good performances, as advantages such as good unreactiveness, weathering resistance, pollution resistance, water-oil resistances.
Just highlighting the many special performance of this base polymer due to fluorine-containing ester paint, as excellent chemical stability, weathering resistance, heat-resisting winter hardiness, erosion resistance, electrical property, radiation resistance etc., in addition surface can be low, hydrophobic oleophobic etc., this base polymer has a wide range of applications at civilian and military industry field.Large-size chemical both domestic and external company is as good in 3M, Du Pont, Asahi Glass, Osaka organic chemistry company, Harbin snow etc., and the research of fluorine cpd is dropped into a large amount of financial resources and material resources, remains on the leading position in this field, embodies the strength of company.But fluorochemicals cost is higher, in Industrial processes, generally fluorochemicals is followed to other acrylic ester compound copolymerization, during as marine finish, due to the strong hydrophobic interaction of fluoro-containing group, the fluoro-containing group of underwater portion can rotate and then other non-fluorin radicals are pushed into surface, thereby greatly reduces the anti-pollution function of film underwater portion.Therefore, although fluorine-containing ester cpds has good anti-pollution function as coating in air, not, ideal as underwater coating compound effect.
And with the amphoteric ion polymer material of equivalent positive and negative charge surface functional group, by solvation of ion, there is extremely strong hydratability.Research shows, these surfaces (zwitter-ion functional group or positively charged ion and anionic functional group's mixture) are interaction based on electric charge and impedance protein adsorption, due to solvation and the hydrogen bond action of charged terminal functionality, form a border in conjunction with water on surface.Research shows that carboxybetaine and sultaine amphoteric ion polymer surface all show extremely low protein adsorption performance, further ulva spores and barnacle cyprid larva are sticked test proves, this amphoteric ion polymer coating good stability, and sticking of impedance marine microorganism effectively.
Summary of the invention
The object of the invention is to overcome prior art above shortcomings, fluorine-containing intelligent antifouling paint of humidity inductive betaines and preparation method thereof is provided.In coating of the present invention, contain two kinds of main functional groups, fluoro-containing group and trimethyl-glycine group.This two classes group all has antifouling function, and this two classes group can regulate fluoro-containing group and the distribution of trimethyl-glycine group in film according to the variation of external agency (mainly referring to humidity), thereby remains good antifouling property.The present invention is achieved by the following technical solutions.
The fluorine-containing intelligent antifouling paint of humidity inductive betaines, the main ingredient of this coating comprises betaines fluorinated copolymer, inorganic salt filler, water-borne coatings defoamer, dispersion agent and water.
In the fluorine-containing intelligent antifouling paint of above-mentioned humidity inductive betaines, further preferred, the consumption of described component is respectively: betaines fluorinated copolymer, and its consumption accounts for the 10%-60% of coating total mass; Inorganic salt filler, its consumption is the 60%-10% of coating total mass; Water-borne coatings defoamer, its consumption accounts for the 0.1%-0.5% of coating total mass; Dispersion agent, its consumption accounts for the 0.1%-5.0% of coating total mass; Water, its consumption accounts for the 20%-50% of coating total mass.
In the fluorine-containing intelligent antifouling paint of above-mentioned humidity inductive betaines, the betaines fluorinated copolymer in described betaines fluorinated copolymer is that more than three kinds monomer copolymerization is synthetic, and wherein the content of fluorinated acrylate accounts for the 10%-90% of described multipolymer total mass; The content of trimethyl-glycine monomer accounts for the 10%-90% of described multipolymer total mass, and other monomers account for described total polymer mass 10%-90%; Betaines fluorinated copolymer number-average molecular weight is at 10000-500000g/mol; Described other monomers comprise methacrylic acid, methacrylic ester, more than one in vinylformic acid, acrylate, vinyl cyanide, Hydroxyethyl acrylate, Propylene glycol monoacrylate.
In the fluorine-containing intelligent antifouling paint of above-mentioned humidity inductive betaines, stating betaines fluorinated copolymer range of molecular weight distributions is 1.05-4.5.
In the fluorine-containing intelligent antifouling paint of above-mentioned humidity inductive betaines, described inorganic salt filler comprises more than one in titanium dioxide, talcum powder, light calcium carbonate, water-ground limestone, and its consumption is the 10%-60% of coating total mass; Described dispersion agent is for containing surface-active amphipathic molecule monomer or telomer.
The preparation method of the fluorine-containing intelligent antifouling paint of above-mentioned humidity inductive betaines, it is characterized in that first betaines fluorinated copolymer solution, defoamer, dispersion agent, water being mixed, under agitation add again inorganic salt filler, obtain the fluorine-containing intelligent antifouling paint of humidity inductive betaines.
Prepare the method for above-mentioned betaines fluorinated copolymer: in reactor, add fluorinated acrylate monomer, trimethyl-glycine monomer, described other monomers and aqueous solvent; after mixing under magnetic agitation; add initiator; be warming up to 75 to 90 DEG C; under nitrogen protection, react 4-6 hour, obtain betaines fluorinated copolymer emulsion.
Prepare in the method for above-mentioned betaines fluorinated copolymer, described initiator comprises ammonium persulphate, Sodium Persulfate, Potassium Persulphate, 4, more than one in 4'-azo two (4-cyanopentanoic acid); Its consumption accounts for the 0.2%-2% of monomer total mass.
Prepare in the method for above-mentioned betaines fluorinated copolymer, described fluorinated acrylate monomer comprises more than one in Hexafluorobutyl mathacrylate, trifluoroethyl methacrylate, dodecafluoroheptyl methacrylate, and this fluorinated acrylate monomer accounts for the 10-90% of whole monomer total mass; Described other monomers comprise methacrylic acid, methacrylic ester, more than one in vinylformic acid, acrylate, vinyl cyanide, Hydroxyethyl acrylate, Propylene glycol monoacrylate, and such monomer accounts for the 10-90% of whole monomer total mass.
Prepare in the method for above-mentioned betaines fluorinated copolymer, described trimethyl-glycine monomer comprises carboxybetaine and sultaine, and structural formula is respectively:
Wherein n is positive integer; M is positive integer, and n, m are 1 ~ 10
5; R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl or the tertiary butyl.This betaines fluorinated copolymer can, separately as coating, also can set it as a kind of modified paint agent mixed with polymethacrylate coating.
Compared with prior art, tool of the present invention has the following advantages and technique effect:
In the coating of the present invention's invention, contain two kinds of main functional groups, fluoro-containing group and trimethyl-glycine group.This two classes group all has antifouling function, and this two classes group can regulate fluoro-containing group and the distribution of trimethyl-glycine group in film according to the variation of external agency, thereby remains good anti-pollution function.Electronegativity due to fluorine in fluoro-containing group is very large, has very strong hydrophobic nature, and in air, fluorine-containing block can gather the surface of film automatically, and fluoro-containing group has fine pollution resistance, and therefore in air, the present invention has anti-pollution function; In trimethyl-glycine group, contain zwitter-ion, its wetting ability is very strong, therefore in the time that the residing air of film changes water into mutually, betaines compound can gather again the surface of film, and trimethyl-glycine group has the effect such as impedance protein and marine organisms absorption, has antifouling property.
Brief description of the drawings
Fig. 1 a and Fig. 1 b are respectively coating desiccated surface contact angle and soaked rear surface contact angle image prepared by embodiment 1.
Fig. 2 a and Fig. 2 b be respectively in air and water in film coated surface contact angle schematic diagram.
Embodiment
Further illustrate the present invention below with reference to embodiment, but described embodiment does not limit the scope of the invention.
The betaines fluorinated copolymer emulsion the present invention relates to can be prepared by following method, but claim of the present invention is not limited.
In 200mL beaker, add 360 parts of (weight parts of water, lower with), 100 parts of Propenoic acid, 2-methyl, isobutyl esters, 33 parts of Hexafluorobutyl mathacrylates, 20 parts of propanesulfonic acid trimethyl-glycines of 3-(2-methylacryoyloxyethyl dimethylin), 1 part of OP-10 emulsifying agent, under normal temperature, be stirred to into stable emulsion.Add 1 part of Potassium Persulphate, continue to be stirred to Potassium Persulphate and complete dissolving.
Emulsion is transferred to 150mL there-necked flask, under magnetic agitation and nitrogen protection, in 80 DEG C of oil bath reaction 4h, obtains betaines fluorinated copolymer emulsion.
This betaines fluorinated copolymer emulsion is coated on to slide surface, is dried afterwards and surveys its performance.
Film coated surface water contact angle test: adopt contact angle measurement to measure the contact angle of distilled water in film coated surface, all measurements are all carried out under room temperature (25 DEG C), and result is as table 1.
table 1
| ? | Water contact angle (desiccated surface) | Water contact angle (containing water surface) |
| Embodiment | 117.4° | 46.7° |
Embodiment explanation, the hydrophilic hydrophobicity performance of film coated surface can change along with the variation of humidity.In air, fluoro-containing group can cover the surface of film, and trimethyl-glycine group is wrapped, and due to the low surface energy of C-F key, film shows hydrophobic nature, water contact angle large (as Fig. 1 a and Fig. 2 a).And in soaked process, pass through molecular chain movement, trimethyl-glycine group can replace fluoro-containing group and cover and film coated surface, fluoro-containing group is wrapped, due to the function of ion polarization of zwitter-ion group, film shows wetting ability, uses JC-2000C1 contact angle instrument to measure, water contact angle greatly reduce (as Fig. 1 b and Fig. 2 b).
The betaines fluorinated copolymer smart coatings the present invention relates to can be prepared by following method, but the scope of the present invention is not limited.
example 1in 500mL beaker, add 0.7 part of 44 parts, water (weight part, lower same), defoamer tributyl phosphate, be stirred to abundant mixing.Add gradually 100 parts of above-mentioned betaines fluorinated copolymer emulsions, offset paper mixes again.Finally, add 3 parts of sodium hexametaphosphate dispersants, 15 parts of filler talcum powder, high-speed stirring 20min is to 30min, to homogeneous.
This betaines fluoro-containing coating is coated on to slide surface, is dried afterwards and surveys its performance.
Through the test in 3 week, in the environment with same fouling organism, the fouling organism that scribbles the glass sheet surface of betaines fluoro-containing coating adheres to quantity obviously than few (area minimizing 95% and fouling organism layer are thinner) on blank glass sheet.This absolutely proves that the prepared betaines fluoro-containing coating of the present invention has excellent fouling resistance performance.
Example 2 adds 0.9 part of 60 parts, water (weight part, lower same), defoamer tributyl phosphate in 500mL beaker, is stirred to abundant mixing.Add gradually 100 parts of betaines fluorinated copolymer emulsions, offset paper mixes again.Finally, add 6 parts of sodium hexametaphosphate dispersants, 20 parts of filler talcum powder, high-speed stirring 20min is to 30min, to homogeneous.
This betaines fluoro-containing coating is coated on to slide surface, is dried afterwards and surveys its performance.
Through the test in 3 week, in the environment with same fouling organism, scribble betaines fluoro-containing coating glass sheet surface fouling organism adhere to quantity obviously than on blank glass sheet few (fouling organism area lack more than 95% and fouling organism layer thinner).This absolutely proves that the prepared betaines fluoro-containing coating of the present invention has excellent fouling resistance performance.
Claims (5)
1. the fluorine-containing intelligent antifouling paint of humidity inductive betaines, is characterized in that the amounts of components of this coating is respectively: betaines fluorinated copolymer emulsion, and its consumption accounts for the 10%-60% of coating total mass; Inorganic salt filler, its consumption is the 60%-10% of coating total mass; Water-borne coatings defoamer, its consumption accounts for the 0.1%-0.5% of coating total mass; Dispersion agent, its consumption accounts for the 0.1%-5.0% of coating total mass; Water, its consumption accounts for the 20%-50% of coating total mass; Betaines fluorinated copolymer in described betaines fluorinated copolymer emulsion is that three kinds of monomer copolymerizations form, and wherein the content of fluorinated acrylate monomer accounts for the 10%-90% of described multipolymer total mass; The content of trimethyl-glycine monomer accounts for the 10%-90% of described multipolymer total mass, and other monomers account for described total polymer mass 10%-90%, and the mass percent sum of described three kinds of monomers is 100%; The number-average molecular weight of betaines fluorinated copolymer is 10000-500000g/mol; Described other monomers comprise methacrylic acid, methacrylic ester, more than one in vinylformic acid, acrylate, vinyl cyanide, Hydroxyethyl acrylate, Propylene glycol monoacrylate; Described fluorinated acrylate monomer comprises more than one in Hexafluorobutyl mathacrylate, trifluoroethyl methacrylate, dodecafluoroheptyl methacrylate; Described trimethyl-glycine monomer comprises carboxybetaine and sultaine, and structural formula is respectively:
Wherein n is positive integer; M is positive integer, and n, m are 1～10
5; R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl or the tertiary butyl;
Described inorganic salt filler comprises more than one in titanium dioxide, talcum powder, light calcium carbonate, water-ground limestone; Described dispersion agent is for containing surface-active amphipathic molecule monomer or telomer.
2. the fluorine-containing intelligent antifouling paint of humidity inductive betaines according to claim 1, the range of molecular weight distributions that it is characterized in that described betaines fluorinated copolymer is 1.05-4.5.
3. the fluorine-containing intelligent antifouling paint of humidity inductive betaines according to claim 1; the preparation method who it is characterized in that described betaines fluorinated copolymer emulsion is as follows: in reactor, add described fluorinated acrylate monomer, trimethyl-glycine monomer, other monomers and aqueous solvent; after mixing under magnetic agitation; add initiator; be warming up to 75 to 90 DEG C; under nitrogen protection, react 4-6 hour, obtain betaines fluorinated copolymer emulsion.
4. the fluorine-containing intelligent antifouling paint of humidity inductive betaines according to claim 3, is characterized in that described initiator comprises ammonium persulphate, Sodium Persulfate, Potassium Persulphate, 4, more than one in 4'-azo two (4-cyanopentanoic acid); Its consumption accounts for the 0.2%-2% of monomer total mass.
5. the preparation method of the fluorine-containing intelligent antifouling paint of humidity inductive betaines claimed in claim 1, it is characterized in that first betaines fluorinated copolymer emulsion, water-borne coatings defoamer, dispersion agent, water being mixed, under agitation add again inorganic salt filler, obtain the fluorine-containing intelligent antifouling paint of humidity inductive betaines.
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| CN201210166101.7A CN102676015B (en) | 2012-05-25 | 2012-05-25 | Humidity-sensitive intelligent betaine fluorinated antifouling paint and preparation method thereof |
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| CN201210166101.7A CN102676015B (en) | 2012-05-25 | 2012-05-25 | Humidity-sensitive intelligent betaine fluorinated antifouling paint and preparation method thereof |
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| CN109821031A (en) * | 2019-02-01 | 2019-05-31 | 中国医学科学院生物医学工程研究所 | The synthesis and application of fluoro- 19 magnetic resonance imaging contrast of carboxylic acid glycine betaine amphoteric ion polymer |
| CN115895322A (en) * | 2022-09-21 | 2023-04-04 | 浙江悦茂科技发展有限公司 | Anti-fouling coating and anti-fouling self-cleaning drainage pipeline system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5116611A (en) * | 1987-06-28 | 1992-05-26 | Nippon Oil And Fats Company Limited | Antifouling paint |
| CN1388196A (en) * | 2002-07-01 | 2003-01-01 | 湖北大学 | Low-surface energy antifouling seagoing ship paint and its prepn |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5116611A (en) * | 1987-06-28 | 1992-05-26 | Nippon Oil And Fats Company Limited | Antifouling paint |
| CN1388196A (en) * | 2002-07-01 | 2003-01-01 | 湖北大学 | Low-surface energy antifouling seagoing ship paint and its prepn |
Non-Patent Citations (2)
| Title |
|---|
| "含氟表面活性剂的特性与用途";蔡继权;《杭州化工》;20100331(第1期);第10-14页 * |
| 蔡继权."含氟表面活性剂的特性与用途".《杭州化工》.2010,(第1期), |
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