CN102676015A - 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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- CN102676015A CN102676015A CN2012101661017A CN201210166101A CN102676015A CN 102676015 A CN102676015 A CN 102676015A CN 2012101661017 A CN2012101661017 A CN 2012101661017A CN 201210166101 A CN201210166101 A CN 201210166101A CN 102676015 A CN102676015 A CN 102676015A
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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 one type of fluorine-containing intelligent antifouling paint of humidity inductive betaines and preparation method thereof.
Background technology
Marine attaching organism is the common name of long term growth animal, plant and mikrobe on all facility surfaces in boats and ships and ocean, and the biodeterioration that it causes is safeguarded to boats and ships and brought enormous economic loss.When sea life during attached to hull bottom, the physicochemical change of a series of complicacies can take place along with the growth of these fouling organisms, quickened the corrosion of hull bottom steel plate greatly, reduced the work-ing life of equipment.Simultaneously, 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 only biodeterioration loss of causing for various underwater engineering facilities and ship's fitting can reach more than tens billion of dollars every year.
In numerous anti-fouling methods; At boats and ships and underwater facility surface-coated antifouling paint is most economical, effective means; The research of antifouling paint has been experienced high poison to low toxicity, nontoxic transformation; Surging along with development of times and environmental protection cry proposed new requirement to antifouling paint: nontoxic, efficient, economical.Therefore, carry out research and development, not only have the military strategy meaning of gaining the initiative, and also have very big economic benefit and social benefit novel, efficient, the economic pollution-free antifouling paint in ocean.
Traditional toxicity antifouling paint is general only to have restraining effect to some sea life, and along with the continuous release of toxicant, its anti-fouling effect also progressively descends.Low surface energy anti-fouling paint by on it adhere to the interface very a little less than, utilize the impact of current in deadweight, the navigation or the cleaning of utility appliance to remove easily.And low surface energy anti-fouling paint is based on the physical action of coating surface, does not have the release loss problem of toxicant, can play long-term antifouling effect.The low-surface-energy material that uses at present mainly is organosilicon series and organic fluorine series material.This type coating does not contain toxicity fully, says it is that a kind of ideal is selected from the angle of environmental protection.
Wherein the organic fluorine series material is because the electronegativity of fluorine is very big; The 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 the acrylate containing fluorine polymkeric substance have many good performances, like advantages such as good unreactiveness, weathering resistance, pollution resistance, water-oil resistances.
Just because the fluorine-containing ester paint highlights the many special performance of this base polymer; Like the chemicalstability of excellence, weathering resistance, heat-resisting winter hardiness, erosion resistance, electrical property, radiation resistance etc.; Surface energy is low in addition, hydrophobic oleophobic etc., and this base polymer has a wide range of applications with military industry field civilian.Large-size chemical company both domestic and external such as 3M, Du Pont, Asahi Glass, Osaka organic chemistry company, Harbin snow are good etc., and the research of fluorine cpd is dropped into a large amount of financial resources and material resources, remain on the leading position in this field, embody the strength of company.But the fluorochemicals cost is higher; In Industrial processes, generally fluorochemicals is followed other acrylic ester compound copolymerization; During as marine finish; Because 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 the surface, thereby greatly reduces the anti-pollution function of the underwater portion of filming.Therefore, though the fluorine-containing ester cpds has the good antifouling function as coating in the air, not very desirable as the underwater coating compound effect.
And have the amphoteric ion polymer material of equivalent positive and negative charge surface functional group, through solvation of ion, have extremely strong hydratability.Research shows; These surfaces (zwitter-ion functional group or positively charged ion and anionic functional group's mixtinite) are based on interaction and the impedance protein adsorption of electric charge; Since the solvation and the hydrogen bond action of charged terminal functionality, the border of a combination water of formation on the 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 the test proof; This amphoteric ion polymer coating good stability, and sticking of impedance marine microorganism effectively.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency that prior art exists, fluorine-containing intelligent antifouling paint of humidity inductive betaines and preparation method thereof is provided.Contain two kinds of main functional groups in the coating of the present invention, fluoro-containing group and trimethyl-glycine group.These two types of groups all have anti-fouling functions, and these two types of groups can regulate fluoro-containing group and the distribution of trimethyl-glycine group in filming according to the variation of external agency (mainly referring to humidity), thereby remain antifouling property preferably.The present invention realizes through following technical scheme.
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 skimmer, dispersion agent and water.
In the fluorine-containing intelligent antifouling paint of above-mentioned humidity inductive betaines, further preferred, the consumption of said component is respectively: the betaines fluorinated copolymer, and its consumption accounts for the 10%-60% of coating total mass; Inorganic salt filler, its consumption are the 60%-10% of coating total mass; The water-borne coatings skimmer, 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 the said betaines fluorinated copolymer is that monomer copolymerization is synthetic more than three kinds, and wherein the content of fluorinated acrylate accounts for the 10%-90% of said multipolymer total mass; The monomeric content of trimethyl-glycine accounts for the 10%-90% of said multipolymer total mass, and other monomers account for said total polymer mass 10%-90%; Betaines fluorinated copolymer number-average molecular weight is at 10000-500000g/mol; Said other monomers comprise methylacrylic acid, methacrylic ester, more than one in vinylformic acid, propenoate, vinyl cyanide, Hydroxyethyl acrylate, the 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, said inorganic salt filler comprises more than one in white titanium pigment, talcum powder, light calcium carbonate, the 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 earlier betaines fluorinated copolymer solution, skimmer, dispersion agent, water being mixed; Under agitation add the inorganic salt filler again, promptly get the fluorine-containing intelligent antifouling paint of humidity inductive betaines.
The method for preparing above-mentioned betaines fluorinated copolymer: in reactor drum, add fluorinated acrylate monomer, trimethyl-glycine monomer, said other monomers and aqueous solvent; After under magnetic agitation, mixing; Add initiator; Be warming up to 75 to 90 ℃, nitrogen protection was reacted 4-6 hour down, got betaines fluorinated copolymer emulsion.
Prepare in the method for above-mentioned betaines fluorinated copolymer, said initiator comprises ammonium persulphate, Sodium Persulfate, Potassium Persulphate, 4, more than one in the 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; Said fluorinated acrylate monomer comprises more than one in methylacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate, the methylacrylic acid ten difluoro heptyl esters, and this fluorinated acrylate monomer accounts for the 10-90% of whole monomer total mass; Said other monomers comprise methylacrylic acid, methacrylic ester, more than one in vinylformic acid, propenoate, vinyl cyanide, Hydroxyethyl acrylate, the 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, said trimethyl-glycine monomer comprises carboxybetaine and sultaine, and structural formula is respectively:
Wherein n is a positive integer; M is a positive integer, and n, m are 1 ~ 10
5R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl or the tertiary butyl.This betaines fluorinated copolymer can also can be used it with separately as coating as a kind of modified paint agent and polymethacrylate coating.
Compared with prior art, the present invention has following advantage and technique effect:
Contain two kinds of main functional groups, fluoro-containing group and trimethyl-glycine group in the coating of the present invention's invention.These two types of groups all have anti-fouling functions, and these two types of groups can regulate fluoro-containing group and the distribution of trimethyl-glycine group in filming according to the variation of external agency, thereby remain anti-pollution function preferably.Because the electronegativity of fluorine is very big, have very strong hydrophobic nature in the fluoro-containing group, fluorine-containing block can gather the surface of filming automatically in air, and fluoro-containing group has fine pollution resistance, and therefore the present invention has anti-pollution function in air; Contain zwitter-ion in the trimethyl-glycine group; Its wetting ability is very strong; Therefore the betaines compound can gather the surface of filming again when the residing air of filming changes water into mutually, and the trimethyl-glycine group has effects such as impedance protein and sea life absorption, has antifouling property.
Description of drawings
Fig. 1 a and Fig. 1 b are respectively the coating desiccated surface contact angle and the soaked back surface contact angle image of embodiment 1 preparation.
Fig. 2 a and Fig. 2 b be respectively in air with water in film coated surface contact angle schematic diagram.
Embodiment
Further specify the present invention with reference to embodiment below, but said embodiment does not limit protection scope of the present invention.
The betaines fluorinated copolymer emulsion that the present invention relates to can prepare by following method, but claim of the present invention is not limited.
In the 200mL beaker, add 360 parts of (weight parts of entry; Down with), 100 parts of Propenoic acid, 2-methyl, isobutyl esters, 33 parts of methylacrylic acid hexafluoro butyl esters, 20 parts of propanesulfonic acid trimethyl-glycines of 3-(2-methylacryoyloxyethyl dimethylin), 1 part of OP-10 emulsifying agent, be stirred to into stable emulsion under the normal temperature.Add 1 part of Potassium Persulphate, continue to be stirred to Potassium Persulphate and accomplish dissolving.
Be transferred to the 150mL there-necked flask to emulsion, under magnetic agitation and nitrogen protection,, get betaines fluorinated copolymer emulsion in 80 ℃ of oil bath reaction 4h.
This betaines fluorinated copolymer emulsion is coated with is attached to slide surface, its performance is also surveyed in dry back.
The test of film coated surface water contact angle: adopt contact angle measurement to measure the contact angle of zero(ppm) water on film coated surface, all measurements are all carried out result such as table 1. under room temperature (25 ℃)
Table 1
| ? | Water contact angle (desiccated surface) | Water contact angle (containing WS) |
| Embodiment | 117.4° | 46.7° |
The 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 filming, and the trimethyl-glycine group is wrapped, because the low surface energy of C-F key, filming shows hydrophobic nature, and water contact angle is big (like Fig. 1 a and Fig. 2 a).And in soaked process; Through molecular chain movement, the trimethyl-glycine group can replace fluoro-containing group and cover and film coated surface, and fluoro-containing group is wrapped; Because the function of ion polarization of zwitter-ion group; Filming shows wetting ability, uses the JC-2000C1 contact angle instrument to measure, and water contact angle reduces (like Fig. 1 b and Fig. 2 b) greatly.
The betaines fluorinated copolymer intelligence coating that the present invention relates to can prepare by following method, but rights protection scope of the present invention is not limited.
Instance 1In the 500mL beaker, add 0.7 part of 44 parts of entry (weight part, down together), skimmer tributyl phosphate, be stirred to thorough mixing.Add 100 parts of above-mentioned betaines fluorinated copolymer emulsions more gradually, offset paper mixes.At last, add 3 parts of sodium hexametaphosphate dispersants, 15 parts of filler talcum powder, high-speed stirring 20min gets final product to sparing matter to 30min.
This betaines fluoro-containing coating is coated with is attached to slide surface, its performance is also surveyed in dry back.
Through the test in 3 week, in having the environment of same fouling organism, the fouling organism that scribbles the glass sheet surface of betaines fluoro-containing coating adheres to quantity obviously than lacking on the blank glass sheet (area minimizing 95% and fouling organism layer are thinner).This proves absolutely that the prepared betaines fluoro-containing coating of the present invention has excellent fouling resistance performance.
Instance 2 adds 0.9 part of 60 parts of entry (weight part, down together), skimmer tributyl phosphate in the 500mL beaker, be stirred to thorough mixing.Add 100 parts of betaines fluorinated copolymer emulsions more gradually, offset paper mixes.At last, add 6 parts of sodium hexametaphosphate dispersants, 20 parts of filler talcum powder, high-speed stirring 20min gets final product to sparing matter to 30min.
This betaines fluoro-containing coating is coated with is attached to slide surface, its performance is also surveyed in dry back.
Test through 3 week; In having the environment of same fouling organism, the fouling organism that scribbles the glass sheet surface of betaines fluoro-containing coating adhere to quantity obviously than lack on the blank glass sheet (the fouling organism area less more than 95% and the fouling organism layer thinner).This proves absolutely that the prepared betaines fluoro-containing coating of the present invention has excellent fouling resistance performance.
Claims (10)
1. the fluorine-containing intelligent antifouling paint of humidity inductive betaines is characterized in that the main ingredient of this coating comprises betaines fluorinated copolymer, inorganic salt filler, water-borne coatings skimmer, dispersion agent and water.
2. the fluorine-containing intelligent antifouling paint of humidity inductive betaines according to claim 1 is characterized in that the consumption of said component is respectively: the betaines fluorinated copolymer, and its consumption accounts for the 10%-60% of coating total mass; Inorganic salt filler, its consumption are the 60%-10% of coating total mass; The water-borne coatings skimmer, 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.
3. the fluorine-containing intelligent antifouling paint of humidity inductive betaines according to claim 1; It is characterized in that the betaines fluorinated copolymer in the said betaines fluorinated copolymer is that monomer copolymerization is synthetic more than three kinds, wherein the content of fluorinated acrylate accounts for the 10%-90% of said multipolymer total mass; The monomeric content of trimethyl-glycine accounts for the 10%-90% of said multipolymer total mass, and other monomers account for said total polymer mass 10%-90%; Betaines fluorinated copolymer number-average molecular weight is at 10000-500000g/mol; Said other monomers comprise methylacrylic acid, methacrylic ester, more than one in vinylformic acid, propenoate, vinyl cyanide, Hydroxyethyl acrylate, the Propylene glycol monoacrylate.
4. the fluorine-containing intelligent antifouling paint of humidity inductive betaines according to claim 2, the said betaines fluorinated copolymer of its characteristic range of molecular weight distributions is 1.05-4.5.
5. the fluorine-containing intelligent antifouling paint of humidity inductive betaines according to claim 1; It is characterized in that said inorganic salt filler comprises more than one in white titanium pigment, talcum powder, light calcium carbonate, the water-ground limestone, its consumption is the 10%-60% of coating total mass; Described dispersion agent is for containing surface-active amphipathic molecule monomer or telomer.
6. the preparation method of the fluorine-containing intelligent antifouling paint of the described humidity inductive betaines of claim 1; It is characterized in that earlier betaines fluorinated copolymer solution, skimmer, dispersion agent, water being mixed; Under agitation add the inorganic salt filler again, promptly get the fluorine-containing intelligent antifouling paint of humidity inductive betaines.
7. the method for preparing each said betaines fluorinated copolymer of claim 1 ~ 6; It is characterized in that in reactor drum, adding fluorinated acrylate monomer, trimethyl-glycine monomer, said other monomers and aqueous solvent; After under magnetic agitation, mixing, add initiator, be warming up to 75 to 90 ℃; Nitrogen protection was reacted 4-6 hour down, got betaines fluorinated copolymer emulsion.
8. the preparation method of betaines fluorinated copolymer according to claim 7 is characterized in that said initiator comprises ammonium persulphate, Sodium Persulfate, Potassium Persulphate, 4, more than one in the 4'-azo two (4-cyanopentanoic acid); Its consumption accounts for the 0.2%-2% of monomer total mass.
9. the preparation method of betaines fluorinated copolymer according to claim 7; It is characterized in that said fluorinated acrylate monomer comprises more than one in methylacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate, the methylacrylic acid ten difluoro heptyl esters, this fluorinated acrylate monomer accounts for the 10-90% of whole monomer total mass; Said other monomers comprise methylacrylic acid, methacrylic ester, more than one in vinylformic acid, propenoate, vinyl cyanide, Hydroxyethyl acrylate, the Propylene glycol monoacrylate, and such monomer accounts for the 10-90% of whole monomer total mass.
10. the preparation method of betaines fluorinated copolymer according to claim 7 is characterized in that said trimethyl-glycine monomer comprises carboxybetaine and sultaine, and structural formula is respectively:
Wherein n is a positive integer; M is a positive integer, and n, m are 1 ~ 10
5R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl or the tertiary butyl.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2012
- 2012-05-25 CN CN201210166101.7A patent/CN102676015B/en active Active
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 |
|---|
| 《杭州化工》 20100331 蔡继权 "含氟表面活性剂的特性与用途" 1,2,4-6 , 第1期 * |
| 蔡继权: ""含氟表面活性剂的特性与用途"", 《杭州化工》, no. 1, 31 March 2010 (2010-03-31) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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