CN104592851B - Biodegradable antifouling marine coating and preparation method thereof - Google Patents

Biodegradable antifouling marine coating and preparation method thereof Download PDF

Info

Publication number
CN104592851B
CN104592851B CN201510002504.1A CN201510002504A CN104592851B CN 104592851 B CN104592851 B CN 104592851B CN 201510002504 A CN201510002504 A CN 201510002504A CN 104592851 B CN104592851 B CN 104592851B
Authority
CN
China
Prior art keywords
lactide
monomer
copolymer
solvent
hydroxyethyl methylacrylate
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.)
Expired - Fee Related
Application number
CN201510002504.1A
Other languages
Chinese (zh)
Other versions
CN104592851A (en
Inventor
郝红
闵江
陈琛
李卓
樊安
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northwest University
Original Assignee
Northwest University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Northwest University filed Critical Northwest University
Priority to CN201510002504.1A priority Critical patent/CN104592851B/en
Publication of CN104592851A publication Critical patent/CN104592851A/en
Application granted granted Critical
Publication of CN104592851B publication Critical patent/CN104592851B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Paints Or Removers (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

The invention relates to a biodegradable antifouling marine coating and a preparation method thereof. The synthetic antifouling marine coating is prepared from the following raw materials in percentage by weight: 65%-85% of copolymer, 10%-30% of a solvent, 1%-2% of nano SiO2, 1%-2% of nano TiO2, 1%-1.5% of KLE-333, 1%-2% of KF-64 and 0.5%-1% of KSL-52. The synthetic biodegradable antifouling marine coating can be hydrolyzed under the action of seawater and the like; the surface layer automatically falls off; the coating has self-polishing property; and the surface energy of a base material is reduced, so that the base material has dual characteristics of self-polishing property and low surface energy. The nano TiO2 is added to the coating as an antifouling agent; growth of planktons in sea and adhesion of the coating can be inhibited under the photo-catalysis action; and the problems that an existing single antifouling marine coating is poor in use effect and large in dosage, and generates secondary pollution to a marine environment are solved.

Description

A kind of biodegradation type marine antifouling coating and preparation method thereof
Technical field
The present invention relates to a kind of biodegradation type marine antifouling coating and preparation method thereof, belong to coating technology application neck Domain.
Technical background
Since the mankind are engaged in Activities of Ocean, the preventing and treating of marine biofouling is always the important topic of research.Ocean is given birth to Thing is stained and not only produces corrosion to the surface of hull, harbour, marine oil pipeline and marine drilling platform, so that is produced from the surface of hull Raw roughness, brings very big frictional resistance, and also resulting in hull weight increases, and reduces ship's speed, needs to consume more fuel, Cause the increase of emissions figure.About the preventing and treating of marime fouling, mankind's history of marine navigation various solutions occurred Method.Wherein most effective, most popular anti-fouling method is that the tributyl tin of last century the seventies research and development applies from polishing antifouling Material（TBT-SPC）, the ship in the whole world 70 percent uses this coating, thus has very huge economic benefit.But TBT-SPC anti-fouling system pollution of marine environment, produces significant impact to halobiontic growth and breeding.
Use what high polymer susceptible to hydrolysis was made from polishing or the skeleton of hydrolysis-type marine antifouling coating or base material Coating, in the skeleton of these high polymers or by adding some insecticides, anti-fouling agent and disinfectant etc., or by Sn, Zn, Cu etc. Some heavy metal ion are incorporated in molecular skeleton, make high polymer（Polyacrylate, poly- amino resins etc. for example）Rise To antifouling effect.Thus prepared film is under the souring of sea water, by carrying out ion friendship with the ion in sea water Change, penetrate institute's metal ion, and then good antifouling property can be played, under the souring of sea water, constantly by table The film polishing in face, constantly exposes new surface, makes surface become smooth, also can make to be already attached to surface while polishing Marine fouling organism on film splits away off, and plays antifouling effect.
Low surface energy antifouling coating for seas has low surface energy, and marine organisms are difficult to adhere in coating surface, even if attached Also insecure, easily come off in the presence of current or other external force.At present, low surface energy anti-fouling paint is mainly Organic fluoride And organosilicon coating.Organic fluoride and organosilicon respectively have pluses and minuses：Fluororesin critical surfaces can be relatively low, and mechanical property is preferable, but Because fluororesin is rigid polymer, top layer fouling organism comes off and needs higher-energy, and expensive；Organic siliconresin Price is less than fluorine resin coating, but its antifouling property and mechanical property are poor.
Content of the invention
One of the object of the invention is to provide a kind of high-performance bio degradation-type from polishing-low surface energy antifouling coating for seas.
Another object of the present invention is to provide the preparation from polishing-low surface energy antifouling coating for seas for the above-mentioned Biodegradable Method.
The present invention to realize process as follows：
A kind of marine antifouling coating, each component weight percentage is：
Copolymer 65%～85%
Solvent 10%～30%
Nano-meter SiO_221%～2%
Nano-TiO21%～2%
KLE-333 1%～1.5%
KF-64 1%～2%
KSL-52 0.5%～1%
Described copolymer is selected from acrylic acid-copolymer of poly lactic acid, acrylic acid-PGA copolymer, acrylic acid-poly- oneself hands over Ester copolymer, acrylic acid-poly (glycolide-lactide) copolymer, acrylic acid-poly- third own lactide copolymers；
Described solvent be esters, alcohols, the mixed solvent of benzene-like compounds, wherein ester type compound be selected from butyl acetate, Ethyl acetate, alcohol compound is selected from butanol, ethanol, and benzene-like compounds are selected from dimethylbenzene, toluene, esters, alcohols, benzene in solvent The mass ratio of class compound is 1:2:3～1:4:6.
Above-mentioned copolymer is obtained as follows：（1）Lactide is mixed with hydroxyethyl methylacrylate, adds catalyst Stannous octoate, first heating and melting, then it is warming up to 100～120 DEG C of reactions, with chloroform dissolving, methanol separates out and precipitates, and is dried to obtain first Base 2-(Acryloyloxy)ethanol-polyactide polymeric monomer, described lactide is selected from Acetic acid, hydroxy-, bimol. cyclic ester, lactide, own lactide；（2）In metering system In sour hydroxyl ethyl ester-polyactide polymeric monomer and solvent add methyl methacrylate, styrene, ethyl acrylate, butyl acrylate, Hydroxyethyl acrylate monomers, are subsequently adding initiator, obtain copolymer in 45～85 DEG C of reactions；Wherein, methyl methacrylate, Styrene is hard monomer, and ethyl acrylate, butyl acrylate are soft monomer, 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate-poly- Lactide polymeric monomer is function monomer.
Above-mentioned steps（1）Described lactide is 15～1 with the mol ratio of hydroxyethyl methylacrylate.
Above-mentioned steps（2）Described initiator is selected from azodiisobutyronitrile, benzoyl peroxide, described soft monomer quality Fraction is 20～70%, and hard monomer mass fraction is 20～70%, and function monomer mass fraction is 10～20%, three kinds of monomers with molten The mass ratio of agent is 0.2～5.
The preparation method of above-mentioned marine antifouling coating, comprises the following steps：
（1）Lactide is mixed with hydroxyethyl methylacrylate, adds octoate catalyst stannous, first heating and melting, then heat up React to 100～120 DEG C, with chloroform dissolving, methanol separates out and precipitates, and is dried to obtain the big list of hydroxyethyl methylacrylate-polyactide Body, described lactide is selected from Acetic acid, hydroxy-, bimol. cyclic ester, lactide, own lactide；
（2）In hydroxyethyl methylacrylate-polyactide polymeric monomer and solvent add methyl methacrylate, styrene, Ethyl acrylate, butyl acrylate, hydroxyethyl acrylate monomers, are subsequently adding initiator, obtain copolymerization in 45～85 DEG C of reactions Thing；Wherein, methyl methacrylate, styrene are hard monomer, and ethyl acrylate, butyl acrylate are soft monomer, acrylic acid hydroxyl Ethyl ester, hydroxyethyl methylacrylate-polyactide polymeric monomer is function monomer；
（3）By copolymer and solvent, Nano-meter SiO_22, nano-TiO2And KLE-333, KF-64, KSL-52 mixed grinding obtains To marine antifouling coating.
Above-mentioned steps（1）Described lactide is 15～1 with the mol ratio of hydroxyethyl methylacrylate；Step（2）Described Soft monomer mass fraction is 20～70%, and hard monomer mass fraction is 20～70%, and function monomer mass fraction is 10～20%, three The mass ratio planting monomer with solvent is 0.2～5, and initiator is selected from azodiisobutyronitrile, benzoyl peroxide.
Advantages of the present invention and good effect：
（1）The marine antifouling coating of present invention synthesis hydrolyzable under the effect such as sea water, top layer meeting Automatic-falling, make coating Have from polishing performance, and so that the surface energy of base material is reduced, therefore base material has from polishing and low-surface-energy double grading；
（2）With nano-TiO2For anti-fouling agent, its can suppress under photocatalysiss in ocean planktonic growth and Attachment to coating；
（3）Instant invention overcomes unitary type marine antifouling coating using effect is poor, consumption is big and produces two to marine environment The deficiency of secondary pollution.
Brief description
Fig. 1 is the infrared spectrum of hydroxyethyl methylacrylate-polylactic acid polymeric monomer；
Fig. 2 is hydroxyethyl methylacrylate-polylactic acid polymeric monomer with CDCl3Do the hydrogen nuclear magnetic resonance spectrogram of solvent（1H- NMR）；
Fig. 3 is hydroxyethyl methylacrylate-polylactic acid polymeric monomer with CDCl3Do the nuclear-magnetism carbon spectrogram of solvent（13C-NMR）；
Fig. 4 is the infrared spectrum of acrylic acid-copolymer of poly lactic acid；
Fig. 5 is the fungistatic effect of different formulations composite ocean antifouling paint；
Fig. 6 soak in the seawater 6 months for film after photo.
Specific embodiment
Embodiment 1
（1）Mol ratio is 15：1 lactide is mixed with hydroxyethyl methylacrylate, adds 0.1% octoate catalyst sub- Stannum, in N2Protection lower elder generation heating and melting, then it is warming up to 100 DEG C, react 4 hours.With chloroform dissolving, methanol separates out precipitation, dry Obtain the solid methyl 2-(Acryloyloxy)ethanol-polylactic acid polymeric monomer of white.Its infrared spectrum is shown in Fig. 1,1759.1cm-1Place occurs Strong absworption peak is ester carbonyl group characteristic absorption peak, 3446.8cm-1Place is the O-H stretching vibration of PLLA chain one end, C-O stretching vibration peak Occur in 1093.6cm-1And 1186.2cm-1Place, this group occurs in HEMA, PLLA, and the company between HEMA and PLLA Connecing is also C-O；In 1653cm-1The absworption peak at place shows that, with the presence of-C=C- key, this double bond is present in the middle of HEMA；? 1384.9cm-1Place and 1458.2cm-1Place is respectively-CH- and-CH3Flexural vibrations peak, in 3022-2900cm-1Locate for- CH-、-CH2- and-CH3Stretching vibration peak；In 935.3cm-1Place does not have ring skeleton peak, and L- lactide drawing in HEMA is described Give and carry out ring-opening polymerization and generate polylactic acid.Fig. 2 and Fig. 3 is hydroxyethyl methylacrylate-polylactic acid polymeric monomer respectively With CDCl3Do the proton nmr spectra of solvent（1H-NMR）Figure and nuclear-magnetism carbon spectrogram（13C-NMR）, in hydrogen spectrogram, chemical shift δ is That occur near 1.57ppm and 5.23ppm is methyl-CH in PLLA repetitives respectively3Proton uptake with methine-CH- Peak, the chemical shift in corresponding carbon spectrogram is respectively 16.9ppm and 69.8ppm.HEMA methylene-CH2The absworption peak of-proton δ is in 4.35ppm, and-OCH2CH2Chemical shift on carbon spectrogram for the O- is about kissed with document substantially in 62.3ppm and 63.4ppm Close, this also illustrates that polylactic acid has been grafted on hydroxyethyl methylacrylate.
（2）Use N2Air in displacement apparatus, by mixed solvent（Mass ratio is 1:2:3 butyl acetate, butanol, diformazan Benzene mixes）It is loaded in four-hole boiling flask with hydroxyethyl methylacrylate-polylactic acid polymeric monomer, Deca methyl methacrylate, benzene second Alkene, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate monomers, are rapidly heated 65 DEG C, then start Deca benzoyl peroxide Formyl, reacts 2 hours, Deca 2/3, is then incubated 2 hours, more remaining benzoyl peroxide is dripped off, reaction 2 hours, It is incubated 1 hour stopped reaction afterwards, obtain faint yellow, uniform viscous liquid and be acrylic acid-copolymer of poly lactic acid（Base material 1）. Wherein, methyl methacrylate, styrene are hard monomer, and ethyl acrylate, butyl acrylate are soft monomer, acrylic acid hydroxyl second Ester, hydroxyethyl methylacrylate-polylactic acid polymeric monomer is function monomer；Soft, hard, function monomer mass ratio is 20:70:10, Monomer is 0.2 with the mass ratio of solvent.
The infrared spectrum of base material 1 is shown in Fig. 4, the 3460cm in spectrogram-1And 3550cm-1The strong absworption peak at place shows polymer In contain-OH absworption peak, in 1750cm-1Strong absworption peak then represent the stretching vibration of carbonyl, show to contain carbonyl in polymer Base；In 2980cm-1And 2890cm-1There are two groups of strong characteristic absorption peaks, respectively-CH2- asymmetric with symmetrical flexible shake Dynamic cause, in 1460cm-1Occur in that corresponding-CH2- bending vibration absworption peak；1660cm-1The absworption peak at place is in polymer The carbon-carbon double bond peak of residual, in 950cm-1With 880cm-1The absworption peak that place occurs, represents also presence-CH=CH in polymer2In C-H, illustrate also to remain the acrylic monomer not participating in reaction.
Embodiment 2
Mol ratio is 10：1 Acetic acid, hydroxy-, bimol. cyclic ester is mixed with hydroxyethyl methylacrylate, adds 0.08% octoate catalyst stannous, In N2Protection lower elder generation heating and melting, then it is warming up to 110 DEG C, react 6 hours.With chloroform dissolving, methanol precipitation precipitation, it is dried to obtain Solid methyl 2-(Acryloyloxy)ethanol-PGA the polymeric monomer of white.Use N2Air in displacement apparatus, by mixed solvent（Matter Amount ratio is 1:4:6 ethyl acetate, ethanol, toluene mixing）It is loaded on four mouthfuls with hydroxyethyl methylacrylate-PGA polymeric monomer In flask, Deca methyl methacrylate, styrene, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate monomers, quickly It is warmed up to 45 DEG C, then start Deca azodiisobutyronitrile and react 2 hours, Deca 2/3, then it is incubated 2 hours, then will be remaining Azodiisobutyronitrile drips off, and reacts 2 hours, is finally incubated 1 hour stopped reaction, obtaining faint yellow, uniform viscous liquid is For acrylic acid-PGA copolymer（Base material 2）.Wherein, methyl methacrylate, styrene are hard monomer, ethyl acrylate, Butyl acrylate is soft monomer, and 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate-PGA polymeric monomer is function monomer；Soft, Firmly, the mass ratio of function monomer is 40:40:20, monomer is 1 with the mass ratio of solvent.
Embodiment 3
Mol ratio is 5:1 own lactide is mixed with hydroxyethyl methylacrylate, adds 0.05% octoate catalyst stannous, In N2Protection lower elder generation heating and melting, then it is warming up to 110 DEG C, react 10 hours.Dissolved with chloroform, methanol separates out and precipitates, dry Solid methyl 2-(Acryloyloxy)ethanol-poly- own lactide polymeric monomer to white.Use N2Air in displacement apparatus, by mixed solvent （Mass ratio is 1:3:5 butyl acetate, ethanol, toluene mixing）It is loaded on hydroxyethyl methylacrylate-poly- own lactide polymeric monomer In four-hole boiling flask, Deca methyl methacrylate, styrene, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate monomers, It is rapidly heated 75 DEG C, then start Deca azodiisobutyronitrile 2 hours, Deca 2/3, then it is incubated 2 hours, then will be remaining Azodiisobutyronitrile drips off, and reacts 2 hours, is finally incubated 1 hour stopped reaction, obtaining faint yellow, uniform viscous liquid is For acrylic acid-poly- own lactide copolymers（Base material 3）.Wherein, methyl methacrylate, styrene are hard monomer, ethyl acrylate, Butyl acrylate is soft monomer, 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate-gather own lactide polymeric monomer for function monomer；Soft, Firmly, the mass ratio of function monomer is 70:20:10, monomer is 4 with the mass ratio of solvent.
Embodiment 4
Mol ratio is 1:1:1 lactide, Acetic acid, hydroxy-, bimol. cyclic ester are mixed with hydroxyethyl methylacrylate, add 0.01% catalyst Stannous octoate, in N2Protection lower elder generation heating and melting, then it is warming up to 120 DEG C, react 4 hours.With chloroform dissolving, methanol separates out heavy Form sediment, be dried to obtain the solid methyl 2-(Acryloyloxy)ethanol-poly (glycolide-lactide) polymeric monomer of white.Use N2Air in displacement apparatus, By mixed solvent（Mass ratio is 1:4:6 ethyl acetate, butanol, dimethylbenzene mixing）With hydroxyethyl methylacrylate-poly- second third Lactide polymeric monomer is loaded in four-hole boiling flask, Deca methyl methacrylate, styrene, ethyl acrylate, butyl acrylate, propylene Sour hydroxyl ethyl ester monomer, is rapidly heated 85 DEG C, then starts Deca benzoyl peroxide 2 hours, Deca 2/3, and then insulation 2 is little When, more remaining benzoyl peroxide is dripped off, react 2 hours, be finally incubated 1 hour stopped reaction, obtain faint yellow, uniform Viscous liquid is acrylic acid-poly (glycolide-lactide) copolymer（Base material 4）.Wherein, methyl methacrylate, styrene are firmly single Body, ethyl acrylate, butyl acrylate are soft monomer, 2-(Acryloyloxy)ethanol, the big list of hydroxyethyl methylacrylate-poly (glycolide-lactide) Body is function monomer；Soft, hard, function monomer mass ratio is 60:25:15, monomer is 5 with the mass ratio of solvent.
Embodiment 5
Mol ratio is 3:1:1 lactide, own lactide are mixed with hydroxyethyl methylacrylate, add 0.1% catalyst pungent Sour stannous, in N2Protection lower elder generation heating and melting, then it is warming up to 120 DEG C, react 4 hours.Dissolved with chloroform, methanol separates out precipitation, Oven drying obtains solid methyl 2-(Acryloyloxy)ethanol-poly- (lactide-own lactide) polymeric monomer of white.Use N2In displacement apparatus Air, by mixed solvent（Mass ratio is 1:2:3 butyl acetate, butanol, dimethylbenzene mixing）With hydroxyethyl methylacrylate- Poly- (lactide-own lactide) polymeric monomer is loaded in four-hole boiling flask, Deca methyl methacrylate, styrene, ethyl acrylate, third Olefin(e) acid butyl ester, hydroxyethyl acrylate monomers, are rapidly heated 85 DEG C, then start Deca benzoyl peroxide 2 hours, Deca 2/ 3, then it is incubated 2 hours, more remaining benzoyl peroxide is dripped off, react 2 hours, be finally incubated 1 hour stopped reaction, obtain Faint yellow, uniform viscous liquid is acrylic acid-poly- (lactide-own lactide) copolymer（Base material 5）.Wherein, methyl-prop E pioic acid methyl ester, styrene are hard monomer, and ethyl acrylate, butyl acrylate are soft monomer, 2-(Acryloyloxy)ethanol, methacrylic acid Hydroxyl ethyl ester-poly- (lactide-own lactide) polymeric monomer is function monomer；Soft, hard, function monomer mass ratio is 70:20:10, single Body is 3 with the mass ratio of solvent.
Embodiment 6
Take 1% polyether-modified polydimethylsiloxane（KLE-333）Acrylic acid-copolymer of poly lactic acid with 78 %（Base material 1）, KLE-333 is added in base material 1 and quickly stirs, mix homogeneously, it is subsequently placed in colloid mill and grind 10～30 minutes.Mixed Bonding solvent（Mass ratio is 1:2:3 butyl acetate, butanol, dimethylbenzene mixing）Take 16 %, nano-TiO2With Nano-meter SiO_22Take simultaneously 1 %, is disperseed with mixed solvent, is then respectively adding in colloid mill, grinds 2～4 hours；It is eventually adding 2% unsaturated many First carboxylate ligand organic siloxane solution（KF-64）With 1% acrylic acid modified brokenly bubble polymer（KSL-52）, grind to go out for 1～3 hour Material, prepared composite ocean antifouling paint (Y1).The key property of analysis film, antibacterial and real sea link plate effect, the results are shown in Table 1st, Fig. 5-6.
Embodiment 7
Take the acrylic acid-copolymer of poly lactic acid of 1.2%KLE-333 and 72 %（Base material 2）, KLE-333 is added to base material 2 In quickly stir, mix homogeneously, be subsequently placed in colloid mill grind 10～30 minutes；Mixed solvent（Mass ratio is 1:2:3 Butyl acetate, butanol, dimethylbenzene mixing）Take 21.8 %, TiO2With SiO2(≤40nm) takes 1.5% simultaneously, with mixed solvent by its Dispersion, is then added in colloid mill, grinds 2～4 hours；It is eventually adding 1%KF-64 and 1%KSL-52, grind 1～3 hour Discharging, prepared composite ocean antifouling paint (Y2).The key property of analysis film, antibacterial and real sea link plate effect, result is shown in Table 1, Fig. 5-6.
Embodiment 8
Take the acrylic acid-copolymer of poly lactic acid of 1.4%KLE-333 and 66 %（Base material 3）, KLE-333 is added to base material 3 In quickly stir, mix homogeneously, then by base material be placed in colloid mill grind 10～30 minutes；Mixed solvent（Mass ratio is 1: 2:3 butyl acetate, butanol, dimethylbenzene mixing）Take 26.6 %, TiO2With SiO2(≤40nm) takes 2% simultaneously, will with mixed solvent Its dispersion, is then added in colloid mill, grinds 2～4 hours；It is eventually adding 1.5%KF-64 and 0.5%KSL-52, grind 1～ Discharging in 3 hours, prepared composite ocean antifouling paint (Y3).The key property of analysis film, antibacterial and real sea link plate effect, Result is shown in Table 1, Fig. 5-6 respectively.
Embodiment 9
Take the acrylic acid-copolymer of poly lactic acid of 1.5%KLE-333 and 65 %（Base material 4）, KLE-333 is added to base material 4 In quickly stir, mix homogeneously, be subsequently placed in colloid mill grind 10～30 minutes；Mixed solvent（Mass ratio is 1:2:3 Butyl acetate, butanol, dimethylbenzene mixing）Take 29 %, TiO2With SiO2(≤40nm) takes 1% simultaneously, is disperseed with mixed solvent, It is then added in colloid mill, grind 2～4 hours；It is eventually adding 1.5%KF-64 and 1%KSL-52, grind to go out for 1～3 hour Material, prepared composite ocean antifouling paint (Y4).The key property of analysis film, antibacterial and real sea link plate effect, result is respectively It is shown in Table 1, Fig. 5-6.
Embodiment 10
Take the acrylic acid-copolymer of poly lactic acid of 1 %KLE-333 and 65 %（Base material 5）, KLE-333 is added to base material 5 In quickly stir, mix homogeneously, be subsequently placed in colloid mill grind 10～30 minutes；Mixed solvent（Mass ratio is 1:2:3 second Acid butyl ester, butanol, dimethylbenzene mixing）Take 30 %, TiO2With SiO2(≤40nm) takes 1% simultaneously, is disperseed with mixed solvent, so After be added in colloid mill, grind 2～4 hours；It is eventually adding 1.2%KF-64 and 0.8%KSL-52, grind to go out for 1～3 hour Material, prepared composite ocean antifouling paint (Y5).The key property of analysis film, antibacterial and real sea link plate effect, result is respectively It is shown in Table 1, Fig. 5-6.
Embodiment 11
Take 1.2%KLE-333 and 71% acrylic acid-copolymer of poly lactic acid（Base material 6）, KLE-333 is added to base material 6 In quickly stir, mix homogeneously, be subsequently placed in colloid mill grind 10～30 minutes；Mixed solvent（Mass ratio is 1:2:3 Butyl acetate, butanol, dimethylbenzene mixing）Take 21.8%, TiO2With SiO2(≤40nm) takes 2% simultaneously, with mixed solvent by its point Dissipate, be then added in colloid mill, grind 2～4 hours；It is eventually adding 1%KF-64 and 1%KSL-52, grind to go out for 1～3 hour Material, prepared composite ocean antifouling paint (Y6).The key property of analysis film, antibacterial and real sea link plate effect, result is respectively It is shown in Table 1, Fig. 5-6.
Embodiment 12
Take the acrylic acid-copolymer of poly lactic acid of 1.5%KLE-333 and 85 %（Base material 7）, KLE-333 is added to base material 7 In quickly stir, mix homogeneously, be subsequently placed in colloid mill grind 10～30 minutes；Mixed solvent（Mass ratio is 1:2:3 Butyl acetate, butanol, dimethylbenzene mixing）Take 10 %, TiO2With SiO2(≤40nm) takes 1% simultaneously, is disperseed with mixed solvent, It is then added in colloid mill, grind 2～4 hours；It is eventually adding 1%KF-64 and 0.5%KSL-52, grind to go out for 1～3 hour Material, prepared composite ocean antifouling paint (Y7).The key property of analysis film, antibacterial and real sea link plate effect, result is respectively It is shown in Table 1, Fig. 5-6.
Embodiment 13
Take the acrylic acid-copolymer of poly lactic acid of 1%KLE-333 and 80 %（Base material 8）, KLE-333 is added in base material 8 Quick stirring, mix homogeneously, it is subsequently placed in colloid mill and grind 10～30 minutes；Mixed solvent（Mass ratio is 1:2:3 acetic acid Butyl ester, butanol, dimethylbenzene mixing）Take 14 %, TiO2With SiO2(≤40nm) takes 1.5% simultaneously, is disperseed with mixed solvent, so After be added in colloid mill, grind 2～4 hours；It is eventually adding appropriate 1%KF-64 and 1%KSL-52, grind 1～3 hour Discharging, prepared composite ocean antifouling paint (Y8).The key property of analysis film, antibacterial and real sea link plate effect, result is divided It is not shown in Table 1, Fig. 5-6.
Prepare a certain amount of artificial seawater, then film has been prepared for ground with steel plate, they have been placed in artificial seawater ring To simulate real sea panel experiment in border, to check their stability finally by measurement hardness.
The key property of the film of table 1 different formulations composite ocean antifouling paint preparation
As seen from Table 1, the film that Y1-Y8 generates smooths, no cracking or trickle cracking；Drying time is substantially little 35～45 When between；Hardness is up to standard；Adhesive force is substantially all identical, is between 0～1 grade.
To different coating（Y1-Y8）The circle footpath antibacterial to escherichia coli is analyzed, and they all have suppression as can be seen from Figure 5 Bacterium effect, effectiveness ranking is：Y5→Y2→Y1→Y4→Y7→Y8→Y6→Y3.
Concrete change when Fig. 6 soaks 6 months in artificial seawater for the film of different formulations.Apply Y1-Y8 to show Effect be preferable, only occur that bubble occurs on a small quantity, lasting adhesive force shown to ground, and top layer is also always maintained at Essentially smooth state.

Claims (8)

1. a kind of marine antifouling coating is it is characterised in that each component weight percentage is：
Copolymer 65%～85%
Solvent 10%～30%
Nano-meter SiO_221%～2%
Nano-TiO21%～2%
KLE-333 1%～1.5%
KF-64 1%～2%
KSL-52 0.5%～1%
Described copolymer is selected from acrylic acid-copolymer of poly lactic acid, acrylic acid-PGA copolymer, acrylic acid-gather own lactide altogether Polymers, acrylic acid-poly (glycolide-lactide) copolymer, acrylic acid-poly- third own lactide copolymers；
Described solvent is esters, alcohols, the mixed solvent of benzene-like compounds, and wherein ester type compound is selected from butyl acetate, acetic acid Ethyl ester, alcohol compound is selected from butanol, ethanol, and benzene-like compounds are selected from dimethylbenzene, toluene；
Described copolymer is obtained as follows,
（1）Lactide is mixed with hydroxyethyl methylacrylate, adds octoate catalyst stannous, first heating and melting, then be warming up to 100 ～120 DEG C of reactions, with chloroform dissolving, methanol separates out and precipitates, and is dried to obtain hydroxyethyl methylacrylate-polyactide polymeric monomer, institute The lactide stated is selected from Acetic acid, hydroxy-, bimol. cyclic ester, lactide, own lactide；
（2）Methyl methacrylate, styrene, propylene is added in hydroxyethyl methylacrylate-polyactide polymeric monomer and solvent Acetoacetic ester, butyl acrylate, hydroxyethyl acrylate monomers, are subsequently adding initiator, obtain copolymer in 45～85 DEG C of reactions；Its In, methyl methacrylate, styrene are hard monomer, and ethyl acrylate, butyl acrylate are soft monomer, 2-(Acryloyloxy)ethanol, Hydroxyethyl methylacrylate-polyactide polymeric monomer is function monomer.
2. according to claim 1 marine antifouling coating it is characterised in that：In described solvent, esters and the mass ratio of alcohols are 1:2～1:4, esters are 1 with the mass ratio of benzene-like compounds:3～1:6.
3. according to claim 1 marine antifouling coating it is characterised in that：Step（1）Described lactide and methacrylic acid The mol ratio of hydroxyl ethyl ester is 15～1.
4. according to claim 1 marine antifouling coating it is characterised in that：Step（2）Described initiator is selected from azo two Isopropyl cyanide, benzoyl peroxide.
5. according to claim 1 marine antifouling coating it is characterised in that：Step（2）Described soft monomer mass fraction is 20～70%, hard monomer mass fraction is 20～70%, and function monomer mass fraction is 10～20%, the matter of three kinds of monomers and solvent Amount ratio is 0.2～5.
6. marine antifouling coating described in claim 1 preparation method it is characterised in that：
（1）Lactide is mixed with hydroxyethyl methylacrylate, adds octoate catalyst stannous, first heating and melting, then be warming up to 100 ～120 DEG C of reactions, with chloroform dissolving, methanol separates out and precipitates, and is dried to obtain hydroxyethyl methylacrylate-polyactide polymeric monomer, institute The lactide stated is selected from Acetic acid, hydroxy-, bimol. cyclic ester, lactide, own lactide；
（2）Methyl methacrylate, styrene, propylene is added in hydroxyethyl methylacrylate-polyactide polymeric monomer and solvent Acetoacetic ester, butyl acrylate, hydroxyethyl acrylate monomers, are subsequently adding initiator, obtain copolymer in 45～85 DEG C of reactions；Its In, methyl methacrylate, styrene are hard monomer, and ethyl acrylate, butyl acrylate are soft monomer, 2-(Acryloyloxy)ethanol, Hydroxyethyl methylacrylate-polyactide polymeric monomer is function monomer；
（3）By copolymer and solvent, Nano-meter SiO_22, anti-fouling agent nano-TiO2And KLE-333, KF-64, KSL-52 mixed grinding Obtain marine antifouling coating.
7. according to claim 6 marine antifouling coating preparation method it is characterised in that：Step（1）Described lactide with The mol ratio of hydroxyethyl methylacrylate is 15～1.
8. according to claim 6 marine antifouling coating preparation method it is characterised in that：Step（2）Described soft monomer Mass fraction is 20～70%, and hard monomer mass fraction is 20～70%, and function monomer mass fraction is 10～20%, three kinds of monomers Mass ratio with solvent is 0.2～5, and initiator is selected from azodiisobutyronitrile, benzoyl peroxide.
CN201510002504.1A 2015-01-06 2015-01-06 Biodegradable antifouling marine coating and preparation method thereof Expired - Fee Related CN104592851B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510002504.1A CN104592851B (en) 2015-01-06 2015-01-06 Biodegradable antifouling marine coating and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510002504.1A CN104592851B (en) 2015-01-06 2015-01-06 Biodegradable antifouling marine coating and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104592851A CN104592851A (en) 2015-05-06
CN104592851B true CN104592851B (en) 2017-02-22

Family

ID=53118927

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510002504.1A Expired - Fee Related CN104592851B (en) 2015-01-06 2015-01-06 Biodegradable antifouling marine coating and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104592851B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106752935A (en) * 2016-12-04 2017-05-31 西北大学 A kind of low surface energy antifouling coating for seas of polishing certainly and preparation method thereof
CN107446402B (en) * 2017-08-30 2021-01-19 深圳先进技术研究院 Charge transfer type automatic redox nano material, preparation method and application thereof, marine antifouling agent and marine antifouling paint
CN109180885B (en) * 2018-08-03 2020-11-24 常州大学 Preparation method of water-based polyacrylate emulsion

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011032301A (en) * 2008-08-08 2011-02-17 Nippon Bee Chemical Co Ltd Lactic acid-based polymer and use thereof
CN102203195A (en) * 2008-10-31 2011-09-28 帝斯曼知识产权资产管理有限公司 Antifouling coating composition comprising functionalized nanoparticules
CN102532559A (en) * 2011-12-30 2012-07-04 中国船舶重工集团公司第七二五研究所 Comb type acrylic resin of lateral chain grafting polyester resin and preparation method and application thereof
CN102731745A (en) * 2012-06-29 2012-10-17 华南理工大学 Degradation type marine anti-fouling material, preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011032301A (en) * 2008-08-08 2011-02-17 Nippon Bee Chemical Co Ltd Lactic acid-based polymer and use thereof
CN102203195A (en) * 2008-10-31 2011-09-28 帝斯曼知识产权资产管理有限公司 Antifouling coating composition comprising functionalized nanoparticules
CN102532559A (en) * 2011-12-30 2012-07-04 中国船舶重工集团公司第七二五研究所 Comb type acrylic resin of lateral chain grafting polyester resin and preparation method and application thereof
CN102731745A (en) * 2012-06-29 2012-10-17 华南理工大学 Degradation type marine anti-fouling material, preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Biobased Polymers: Synthesis of Graft Copolymers and Comb Polymers Using Lactic Acid Macromonomer and Properties of the Product Polymers;Kiyoaki Ishimioto等;《Biomacromolecules》;20121231(第13期);第3757-3768页 *
纳米材料在海洋无毒防污涂料中的应用;沈丽霞;《电镀与精饰》;20110731;第33卷(第7期);参见第4页第4节 *

Also Published As

Publication number Publication date
CN104592851A (en) 2015-05-06

Similar Documents

Publication Publication Date Title
Xie et al. Biodegradable polymer with hydrolysis-induced zwitterions for antibiofouling
Pan et al. Degradable vinyl polymers for combating marine biofouling
Xu et al. Marine biofouling resistance of polyurethane with biodegradation and hydrolyzation
Xie et al. Coatings with a self-generating hydrogel surface for antifouling
Zhou et al. Inhibition of marine biofouling by use of degradable and hydrolyzable silyl acrylate copolymer
Liu et al. Facile preparation of structured zwitterionic polymer substrate via sub-surface initiated atom transfer radical polymerization and its synergistic marine antifouling investigation
Marabotti et al. Fluorinated/siloxane copolymer blends for fouling release: chemical characterisation and biological evaluation with algae and barnacles
JP5989237B2 (en) Antifouling paint composition, antifouling coating film, antifouling substrate and method for producing antifouling substrate
CN102070863B (en) Antifouling material and application thereof
CN104592851B (en) Biodegradable antifouling marine coating and preparation method thereof
WO2011162359A1 (en) Stain-proof coating composition, stain-proof coating film, and method for prevention of staining of base material
Xie et al. Nanodiamond reinforced poly (dimethylsiloxane)-based polyurea with self-healing ability for fouling release coating
TW201022378A (en) Coating composition, method for producing same, coating film and underwater structure
CN107109082B (en) The manufacturing method of two-liquid type antifouling paint compositions, antifouling coat, antifouling substrate and antifouling substrate
Hong et al. Novel hybrid anti-biofouling coatings with a self-peeling and self-generated micro-structured soft and dynamic surface
Ma et al. Degradable polymers for marine antibiofouling: optimizing structure to improve performance
JPWO2010073995A1 (en) Antifouling paint composition and substrate antifouling method
JPWO2017164283A1 (en) Antifouling paint composition, antifouling coating film, antifouling substrate and method for producing the same
Wang et al. Dynamic surface antifouling materials
Lejars et al. Siloxy silylester methacrylate diblock copolymer-based coatings with tunable erosion and marine antifouling properties
Sun et al. Preparation and properties of crosslinked network coatings based on perfluoropolyether/poly (dimethyl siloxane)/acrylic polyols for marine fouling–release applications
Meng et al. Preparation and Characterization of the Cross-Linked Fluoro-Silicon Polyacrylate–Polyurethane Hybrid Emulsions for Superior Performance of Waterborne Coatings
Liu et al. Carp-inspired self-regulating marine antifouling coating: Featuring robust controlled release of eugenol and high-efficiency self-healing performance
Fan Getting glued in the sea
Li et al. Spontaneous directed leaching of slippery lubricant in self-stratified marine antifouling coatings for nonporous surfaces

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: 20170222

CF01 Termination of patent right due to non-payment of annual fee