KR920010049B1 - Erosive ship-bottom paints for control of marine fouling - Google Patents

Abstract

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Description

Corrosive bottom paint for ship antifouling

FIELD OF THE INVENTION The present invention relates to marine antifouling paints which corrode at a predetermined rate, and in particular to polymer binders for antifouling paints, wherein the polymer has a portion which hydrolyzes at a predetermined rate in seawater.

Conventionally, the superiority of antifouling paints has been based on organotin acrylate polymers for a long time, and the conventional leaching type system has been dictated by the ship owner and the ship paint company. This coating system provides excellent antifouling for a long time because the poison, ie alkalinity, is constantly eluted from the surface of the coating film by hydrolysis of the organotin acrylate copolymer in seawater.

In paint varieties of this kind, organotin acrylate copolymers act as film-forming components (bonds).

The organotin portion of the copolymer provides a location for hydrolysis of the polymer by seawater (approximately PH = 8.0-8.3), whereby the polymer surface is free from corrosion by the movement of seawater and new paint surfaces. It slowly changes to an aqueous or absorbent form that can be exposed.

In addition, the hydrolysis of the organotin polymer elutes bis-tributyltin oxide, which is an effective antifouling.

In practice, additional poisons are usually physically mixed into the antifouling paint. These co-toxins elute during gradual hydrolysis or during corrosion of the organotin copolymer media to provide additional contamination protection. An additional advantage of this system is fuel saving, which results from the reduction of the rough surface due to surface conditions or corrosion of the coating. Such a system can be designed to hydrolyze and corrode at high or low rates while incorporating a slow economy characterized by low seawater solubility, as described in Milon and Hailes in US Pat. No. 4,021,392. Milon and Hyles also mention that organotin monomer components in commercially available coatings cannot be made by controlling only the organotin monomer components.

The technique by this organotin copolymer antifouling paint function is described in the coating sheet 53, number 678, pages 46-52. However, these paints are relatively inexpensive and have unnecessary irritants due to the essential presence of hydrolyzable tributyltin moieties.

These paints can be improved with conventional leaching paints in which an oxidizing agent poison is dispersed in a binder of a mixture of a water-sensitive or gentle water-soluble component and a film-forming insoluble resin such as the study team. Such “soluble parent” paint compositions are shown in Table A, for example.

TABLE A

(a) Union Carbide Products

However, these paint systems did not consistently elute the poisons and, moreover, did not corrode well. This was not caused by the leaching of poison (copper oxide) following the selective extraction of the water-soluble components from the inside of the coating film. After the water soluble component of the film (grosene) has been leached out, the mother of the insoluble vinyl resin remains behind. Moreover, since the water penetration required to leach the back to the surface is limited to the residual vinyl resin, the consumed coating can no longer prevent contamination even if the initial level of cuprous oxide contains up to 30-40%. This type of antifouling system does not provide suitable substrates for reapplication because they have poor mechanical properties because of poor adhesion of new coatings resulting in cracking of the membranes.

Attempts have been made to mix poisons with water-soluble polymers in the past and use them as antifouling paints, but did not achieve the desired results.

Although these paints expand in seawater, good mechanical properties and uniform pollution prevention cannot be expected because the entire coating is weakened by immersion in water for a long time. Such paint compositions, such as those described in British Patent No. 1,584,943, do not provide optimal antifouling, which is a physical mixture of water-insoluble and synthetic water-soluble polymer binders in which the synthetic water-soluble polymer binder is replaced with natural gum rosin in conventional paint systems. This is because the paint binder is composed. In the paint system of British Patent No. 1,584,943, the water soluble polymer component can be selectively extracted from the binder system by sea water while representing the same problems caused by conventional gelatin / rosin. Furthermore, long immersion of a portion of the water-soluble resin component in water causes water to be absorbed into the membrane, causing its thickness to expand, resulting in a membrane with poor mechanical properties.

A simple acrylate ester copolymer was proposed in US Pat. No. 4,407,997, published May 26, 1982, as a paint solvent individual that gradually disappears from the surface by moving seawater. However, the main proportion of pigments used in these paints of surface corrosion should be water-sensitive metal-containing pigments. In addition, it is preferable that such a coating contains a high level of 35-50% by volume of the pigment. Therefore, the pigment content should be used according to the required dissolution rate. The pigment content for controlling dissolution can be improved by using polymers of molecular weight as paint binders and by mixing hydrolyzable tributyltin acrylate groups in the polymer chain. These are known water-resistant poly (methyl acrylates) that are only slightly corroded by precipitation of sodium hydroxide or sulfuric acid at room temperature as described in Kierk-Hautmer's Polymer Science and Technology Encyclopedia (Vol. 1, pages 246-328, 1964). ) Consists of a film. Thus, these paints described in British Patent Application No. 2,087,415 do not depend on the properties of the polymer binder more than at high levels of water sensitive pigments. These pigments can be leached by sea water, and even without reinforcing the pigment particles, the resulting blank mother film can be sufficiently weakened and disappear from the surface by the movement of sea water. Such methods of protection against surface growth include self-cleaning antifogging paints. Similar to the method obtained by mixing zinc oxide and hydrophilic anatase titanium dioxide in paints based on acrylic or polyvinyl acetate resin polymers, as described in Paint Technical Publication No. 46, No. 594 (July 1974), page 33. . Such paints are unsuitable for use for a long time due to their poor mechanical properties.

In addition, as can be seen in the specification of European Patent Application No. 0069559 published on January 12, 1983, triorganotin is an effective antifouling agent, but it is inexpensive to use, and it is inexpensive to avoid or reduce the dissolution of triorgano ions. While it is preferable, it is described that it is difficult to obtain the advantage of smoothing the paint by the corrosion medium. This patent application describes the substitution of quinolinyl (or substituted quinolinyl) in place of the organotin group of the acrylate copolymer. This technique can replace one expensive poison with another, but cannot provide a method for controlling the corrosion rate according to the poison concentration.

The present invention is to overcome the conventional problems by the method of properly adjusting the system for the optimum paint binder to achieve the optimum corrosion ratio and the optimum paint composition. According to the present invention there is provided a paint produced from a binder polymer obtained from the copolymerization of one or more copolymerizable ethylenically unsaturated monomers and a monomer having a tubular group which results in a hydrolyzable polymer in seawater.

The antifouling paint according to the present invention contains a poison, a pigment and a polymer binder. The polymeric binder is film-forming, insoluble, seawater corrosive and is represented by the following general formula.

(Wherein X is H or CH ₃ ; R is a non-bioactive alkyl, aryl or arylalkyl moiety and repeater B is a residue of an ethylenically unsaturated monomer)

The polymer has a hydrolysis rate of at least 5 × 10 ⁻⁴ milliequivalents per hour. The resulting paint has a corrosion rate of at least 2 microns per month.

R is selected from the following groups:

또는

a)

or

(Where Z is NO ₂ , halogen or CN)

b)-(CH ₂ ) _n Y

Wherein n is an integer of 1-4; Y is

이고 여기서 R′는 C₁-C₄의 1차, 2차 또는 3차 알킬이고; R″는 H 또는 R′이고; R″′는 알킬 또는 아릴이다)

And wherein R 'is C ₁ -C ₄ primary, secondary or tertiary alkyl; R ″ is H or R ′; R ″ ′ is alkyl or aryl)

c) -SiR "'or -Si (R"') ₃ ; d) halo alkyl groups having at least one trihalomethyl group, wherein the halogen is Br, F, Cl and the alkali has at least two carbons, for example trifluoroethyl acrylate; e) quaternary aminoalkyls represented by the general formula:

(Wherein Y is Br, Cl or I, and R ′, R ″ and R ″ ′ are the same or different alkyl of C ₁ -C ₁₈ )

f)

(Wherein n is 1 or 2; R ″ ″ is a phenyl group or C ₁ -C ₄ primary, secondary or tertiary alkyl)

Other structural formulas are those wherein X is halogen, CN or NO ₂ and R is C ₁ -C ₈ primary, secondary or tertiary alkyl.

The polymer of the present invention is a poison release system, which can be used completely and does not depend on the hydrolysis of the organotin or bioactive component containing the polymer. Thus an effective antifouling agent can be mixed into the paint.

In order to achieve excellent pollution prevention of the bottom, it can be achieved by using a coating material composed mainly of inorganic or organic poisons which are slowly eluted by the hydrolysis of the polymer and organic polymer binder which are slowly hydrolyzed in seawater. The paint is a binder produced by copolymerizing (1) at least one acrylic ester or metaacrylic ester having a functional group capable of producing a polymer that can be hydrolyzed in seawater and (2) one or more copolymerizable ethylenically unsaturated monomers. Prepared from a polymer.

Since general acrylic esters, such as ethyl acrylate, methyl methacrylate and butyl acrylate, are not hydrolyzed in sufficient proportions, antifouling paints can be prepared by using a carboxylate-containing polymer having sufficient susceptibility to corrosion by seawater action.

However, it is possible to improve the ester in order to enhance the hydrolysis sensitivity of the polymer. This can be accomplished by weakening the ester bonds or by supplying functional groups whose corrosion is enhanced by hydroxyl ions.

The monomer is represented by the following general formula.

Where R is

, 메톡시에틸 아크릴레이트와 같은 -OR″′; 메틸티로에틸 아크릴레이트와 같은 -SR″′; P-아미노페닐티오에틸 아크릴레이트; 디페닐 포스핀에틸 아크릴레이트와 같은

여기서 R′는 C₁-C₄의 1차, 2차, 또는 3차 알킬이고, R″는 H 또는 R′이고; R″′는 알킬 또는 아릴 이다.Wherein Z is NO, halogen or CN, for example P-nitrophenyl acrylate, and R can also be represented by the general formula- (CH ₂ ) _n Y where n is an integer from 1-4; Y is the same as dimethylaminoethyl methacrylate

-OR "'such as methoxyethyl acrylate; -SR "'such as methyltyroethyl acrylate; P-aminophenylthioethyl acrylate; Such as diphenyl phosphineethyl acrylate

Wherein R ′ is C ₁ -C ₄ primary, secondary, or tertiary alkyl and R ″ is H or R ′; R ″ ′ is alkyl or aryl.

Alkyl, aryl, and the like also include substituted alkyl, aryl and the like.

And R is -SiR ₃ ″ ″ or -Si (OR ″ ″) ₃ where R ″ is alkyl or aryl. For example triphenylsilyl acrylate, R is quaternary amino alkyl represented by the following general formula:

Wherein Y is Br, Cl or I; R ′, R ″ and R ″ ′ refer to alkyl of the same or different C ₁ -C ₁₈ .

In another structure, R is haloalkyl with at least one trihalomethyl group, where halogen is Br, F or Cl and alkyl has at least two carbons. Trifluoro ethyl acrylate. Representative haloalkyl alcohols are the compounds described in Dupont Zonyl ^R Fluoro Surfactant Guide Publication 8/82.

In addition, R is a tertiary alkyl group having 4 or 5 carbon atoms, and the term "alkyl" as used herein is a general term including, for example, linear, branched, cyclic and substituted alkyl.

(여기서 n는 1 또는 2이고 R″″는 페닐기 또는 C₁-C₄의 1차, 2차 또는 제3차 알킬이다).R is

Where n is 1 or 2 and R ″ ″ is a phenyl group or C ₁ -C ₄ primary, secondary or tertiary alkyl.

Examples are 2-oxopropyl, meth acrylate or 4-phenyl-3-oxobutyl acrylate. The monomers do not have to be synthesized into a polymer by copolymerization of special monomers and comonomers. For example, the polymer may be produced into an acrylic acid or methacrylic acid polymer by adduct ions. The resulting polymer contains a repeating group represented by the following structural formula:

The repeater corresponds to the monomer of the formula:

The coating composition may include water-sensitive pigment components, including polymeric binders, solvents, and poisons, which may be fillers with poisons, inert pigments and economics.

Representative paint components are described in US Pat. No. 4,260,535, UK Pat. No. 2,087,415A and US Pat. No. 4,191,579, which are described herein by reference.

Antifouling toxins include tributyltin fluoride, triphenyltin hydroxide, triphenyltin fluoride, tributyltin oxide, triphenyltin chloride, Cu ₂ O, ZnO, dithiocarbamate derivatives and first thiocyanate.

Sufficient solvent is used in the paint composition to allow the system to be used on the surface to be protected. The pigment volume concentration (PVC) is 10-50 and preferably about 30-45.

The upper limit of hydrolysis of polymers used in paints is not so important because the desired degree of fractionation, even if the polymer is rapidly hydrolyzed in excess of the ratio of functional groups and polymers or copolymers, is described in U.S. Patent Nos. 4,021,392; 4,260,535; This can be achieved by appropriately selecting the use of a slow economy described in British Patent No. 1,589,246, the description of which is described herein by reference.

Corrosion rates of paints depend on the contribution of co-monomers and other ingredients, such as toxins, pigments, mildews, fillers, inert or other nonvolatile components of the paint.

The functionality of the present invention can be replaced by known means for combining with or controlling the corrosion rate.

The amount of hydrolyzable acrylate or methacrylate relative to the non-hydrolyzed ethylene-unsaturated comonomer on the basis of water in the 100 parts copolymer is 10-90 parts. 10-100 parts in the case of acrylic esters or methacrylic esters of amino or quaternary amino alkyl alcohols; 10-80 parts for an acrylic acid ester or a methacrylic acid ester of a haloalkyl alcohol; 10-80 parts for nitrophenyl or nitrobenzyl alcohol esters and 10-80 parts for trialkyl, triaryl or trialkoxy silanol esters.

Ethylenically unsaturated comonomers are known in the art of film formation and are described, for example, in British Patent No. 2,087,415A, line 1, pages 56-59.

Control of the myriad corrosion rates is made of chemically suitable polymers, which are therefore selectively weakened at any point accompanying the polymer chain in the paint / water interior. These weak bonds are slowly corroded by the seawater as the polymer gradually dissolves or expands in seawater. This weakens the polymer film with the hydrolyzed surface to the extent that this movement of seawater removes this layer from washing and exposes new surfaces.

In contrast to conventional systems, the paints in the system of the present invention are relatively impermeable to seawater until hydrolysis of the outer microlayers occurs. Hydrolytic microlayers are removed by “friction” of water. The monomer unit moiety consists of a functional group which provides a weak position, ie a position which hydrolyzes in the presence of seawater. The rate of corrosion is controlled by controlling the ratio of functionalized and non-functionalized monomers. Thus, unlike the system of British Patent Application No. 2,087,415A, where high levels of water-sensitive pigments present corrosion are present, the system of the present invention is characterized by the level and proportion of functional and inert monomers used to make polymers. Adjusted accordingly.

Polymer Manufacturing

Solution polymerization of 70 mole percent dimethylaminoethyl methacrylate (DMAEMA) polymer is carried out as follows:

Incorporation of components (part)

DMAEMA 36.9

Butyl Methacrylate (BMA) 9.5

Methyl Methacrylate (MMA) 3.35

Bajo 64 ¹ 0.25

High Flash Naphtha ² 50.0

100.0

1. Azo bisbutyronitrile polymerization initiator of DuPont.

2. It can be replaced with Amsco solvent-xylene.

fair

1) Put all the flour into a glass 4 resin reactor with a stainless steel stirrer, condenser, nitrogen inlet, thermometer attached to the temperature-sensing head and a glass-col heater.

2) Heat to 80 ° C. for 1 hour under nitrogen gas, stop for 6 hours, cool to 30 ° C. or less, and pack. Improvements needed to make other polymers are by methods known in the art and do not form part of the present invention.

A general method for synthesizing the functional acrylic ester and the meth acrylic ester is as follows.

Method A: P-nitrobenzyl acrylate

153.1 g (1 mole) of P-nitrobenzyl alcohol, 101.2 g (1 mole) of triethylamine and 250 ml of molecular sieve-dry acetone in a 1 liter three-necked flask equipped with a stirrer, condenser, thermostat and dropping funnel Into, cooled to 5 ° C. or less in an ice-water-acetone bath. 905 g (1 mole) acrylic chloride oil in 100 ml of dry acetone is added to the contents of the flask at 0-5 ° C, stirred for an additional hour, then heated to reflux (60 ° C) and left under reflux for 4 hours. Removal is carried out under reduced pressure under trimethylammonium hydrochloride and acetone is removed with a rotary evaporator. The solid product is dissolved in 150 ml of heated methanol and cooled to crystallize. Yield is 45.0 g (53%), white crystals, melting point = 50.0-50.9 ℃, 98% analysis by oxo titration.

Chromatography shows a single component.

52.3 g (0.5 m) of methacryl chloride, 76.6 g (0.5 m) of P-nitrobenzyl alcohol, 50.6 g of triethylamine, and 71.5 g (64.5%) of melting point 87-88 ° C. The meth acrylic acid P-nitrobenzyl is isolated by crystals. In a similar manner, a crude product prepared from 149.4 mg (1 mole) trichloroethanol and 10.0 moles chloride acrylic oil (99.5 g, 1.1 mole) acrylic acid and solvent-washed was distilled under reduced pressure at 41-44 ° C. and 0.7 Hg. You get 69.3% colorless liquid.

The product is 76% pure by NMR. The residue is trichloroethanol. See Table 1 for details.

TABLE 1

Method B: Preparation of Acrylic Acid Monomer for Transesterification

2.5 moles of methyl acrylate, 1 mole of the corresponding alcohol, 2 g of phenothiazine as the polymerization initiator and 3.6 g of dioctyl tin oxide as the catalyst are charged into a tri-neck flask equipped with a stirrer, thermometer and distillation column filled with glass beads. The mixture is heated to a temperature of 75-96 ° C. and the methanol-methyl acrylate azeotropic mixture is distilled at 64-80 ° C. When methyl acrylate is distilled with methol, fresh methyl acrylate is added to replenish the entire distillate. After 10 hours, when the temperature of the reaction liquid reaches 96 ° C., the transesterification reaction ends, and the resulting mixture is distilled off under a pressure of 4-8 mmHg to distill off unreacted methyl acrylate. The product is analyzed by infrared absorption spectral method (IR method), gas chromatography method (GC method) and nuclear magnetic coplanar spectral method (NMR method) to confirm the structure of the product.

Method C: Preparation of Tris (4-methyl-2-pentoxy) -silyl acrylate.

0.23 moles of tris (4-methyl-2-pentoxy) silane, 0.23 moles of triethylamine, 0.02 g of methyl hydroquinone and 82 cc of toluene as a polymerization initiator, 3 with stirrer, funnel, thermometer and condenser Put it in the flask. 0.23 mole of acryl chloride dissolved in 23 cc of toluene is slowly added to the reaction mixture at 3-5 ° C. After the addition is complete the reaction is stirred at 5 ° C. for 1/2 hour. Solid triethylamine hydrochloric acid is filtered and the solvent is distilled off under reduced pressure. Distillation of the crude oil product (boiling point 148-162 ° C./3 mmHg) yields 41 g of product (% gas chromatography purity).

Antifouling paints

Antifouling tests are carried out by preparing paints based on representative hydrolyzable paint polymers containing high and low levels of copper oxide, an acceptable antifouling agent, and exhibiting a suitable hydrolysis ratio. The test coating composition and production method are as follows.

1. The other functional acrylic or methacrylic acid copolymers, manufactured by M & T Chemicals, Laway, NJ, described herein, may be replaced with tributyl tin (TBTM), which is the same volume of solid.

2. A-2989 Toluidine Colorant, Ciba-Geigy, Adsley, New York.

3. M & T Chemicals, Laway, NJ.

4. Johnil FSP, DuPont, Wilmington, Delaware.

Test paint A production

The fumed silica is dispersed in xylene with a suitable speed disperser (coal), methanol is added with stirring, then half of the polymer solution is added slowly. All the pigments are added with moderate stirring and the resulting paste is ground in a cast steel shot mill that is cooled with water. The grinder is washed with the residue of the ketone mixture and the polymer solution and the wash is added to the paste.

Mix the entire paint and pass it through the grinder once more. The paint must be finely pulverized to 4-6 (Hagman gauge) and the paint is adjusted to a final viscosity of 1000-1500 cps with a solvent.

As can be seen from the foregoing description and examples, the poison dissolution system of the present invention can elute the poison at a predetermined rate at a necessary time, and furthermore, the dissolution rate depends on the solubility characteristics of the poison, and in this system the minimum ship room of the poison. Use the wrong amount. Since the use of more than necessary poisons can be avoided, the price is greatly saved because the hydrolysis ratio of the system is optimized with non-uniform poison dissolution rate or suitability compared to the system using excess amount of poisons.

The polymer hydrolysis rate referred to herein means the rate of production of carboxyl ions by 5 g of polymer film powder. The usefulness of the carboxyl ions depends on the functional functionality of the polymer, so the poison dissolution rate depends on the polymer dissolution rate.

Method for measuring hydrolysis rate of pulverized polymer film

The polymer hydrolysis rate is measured by the following method.

Hydrolysis of the polymer film in pH = 9 water at 35 ° C. is determined by reverse titration of the polymer free acid with standard KOH at 24 hour intervals using the method described below: hydrolysis in a 300 ml Florence flask and 3/4 ″. Was stirred with a Teflon-coated magnetic stirrer and immersed in a thermostatically controlled water bath at 35 ° + 1 ° C. under an inert gas obtained by passing nitrogen under the surface of the resin-water mixture for about an hour and a half, and then sealed the flask. Let's do it. 150 ml of distilled water was added to the flask to pH 9.0 with KOH, pulverized with a Waring blender for 20-30 seconds, and a polymer film dried under reduced pressure of 5.0 g was added thereto. PH is measured with an Orion Model 601A Digital Ionlyzer pH meter using a glass KCL electrode combination. Every 24 hours the contents of the flask are back titrated with standard KOH, pH 9.0 and calculated in various milliquivalents. The test is titrated five times for 24 consecutive hours.

The results of the polymer hydrolysis test are shown in the following table. The polymer ^{exhibiting a} hydrolysis ratio of 5 × 10 ^{−4 meg / hr} or more can be used as a binder for water-insoluble and seawater corrosion-resistant antifouling paint. Since the copolymer is hydrolyzed at a rate that shows the suitability as a coating agent for antifouling to 33 mol% level, it can be seen that the effect of the tributyltin copolymer is indirectly confirmed by this experiment.

Hydrolysis of Acrylic Acid Polymers Based on Functional Monomers at 35 ° C with Medium of pH 9

The practicality and novelty of the paint system is confirmed by the fact that the bulk of the paint is insoluble and has a surface of the film that hydrolyzes in contact with sea water, and gradually changes to a water-soluble or water-expandable form.

This layer corrodes and disappears by the movement of seawater, and physically bound poisons elute to prevent contamination and expose new paint surfaces. With this mechanism, the rate at which the hydrolysis and hydrolysis of the polymer proceeds becomes a force to prevent the contamination of the coating film. Such hydrolysis rates can be measured under conditions similar to seawater migration.

Evaluation method-AF film

Panel Making—Fiber glass panels (8 ″ × 10 ＂) are treated with solvent and then sanded to confirm adhesion of the coating.

Paint is used with a tension blade applicator at the center of the panel to a dry film thickness of about 100 microns. The outer edges were not covered and the total contamination inhibition was measured.

Exposed panels were floated on Florina and Biscayne Bay.

Eight panels were caught one foot below the water surface with a two-inch panel spacing on the submerged hanger.

Pollution Rate (FR)-Pollution rate is expressed as follows:

0 = no pollution

+ = Minimum pollution

++ = medium pollution

+++ = Most Contamination

++++ = Complete Contamination

After three months of testing in Biscayne, Florida, and observed with a test paint A composition in which the binder polymer was mixed with a relatively low level of functional monomer, the following results were obtained, which are shown in Tables 2 and 3. Antifouling paints made of relatively low levels of tin glass functional acrylic acid polymers show the effect of the fixed panels on the effect of varying degrees of protection against ship contamination after three months of exposure.

Paint Nos. 2-5 in paints based on functional monomers are not the most effective at completely inhibiting waste streams and seaweeds. Paint systems predominantly DMAEMA (Paint No. 2-1), tBAEMA (No. 2-8) and TFEA (No. 2-9) are effective against waste streams but not suitable for inhibiting seaweed. I don't think it can be accomplished yet. Coating system Nos. 2-4 have some effect on waste and seaweed after three months of exposure.

Most paints are better in antifouling activity after 3 months compared to commercially available tributyltin polymer paints (No. 2-2), but all paints except tributyltin and quaternary polymers were tested for 6 months in Miami. The results indicate a dramatic decrease in activity and indicate that the hydrolysis rate and corrosion rate are insufficient in these systems to achieve a practical goal.

TABLE 2

As a result of the antifouling paints prepared from relatively low levels of tin glass functional acrylic acid polymers, these fixed panels show a wide range of effects in suppressing ship contamination after three months of exposure.

Tables 3 and 4 show the results of testing paints with high levels of functional monomer in the binder polymer.

TABLE 3

TABLE 4

These results show that better performance can be achieved with high levels of functional monomers in the binder polymer. In all cases, this can be done better than the suppression done with paints containing binder polymers that cannot be hydrolyzed by the test paints.

In addition, the failure of paints containing binder polymers that cannot be hydrolyzed by these data is irrelevant to oxidation, etc., and it is confirmed that long-term immersion in seawater does not elute the antifouling poisons from the paint film in such a system.

Functional monomer-abbreviation

Acrylic acid P-nitrophenyl PNPA

Acrylic acid P-nitrobenzyl PNBA

Methacrylic acid N, N-dimethylaminoethyl DMAEMA

Methacrylic acid t-butylaminoethyl t-BAEMA

Acrylic acid hexafluoroisopropyl HFIPA

Acrylic acid 2, 2, 2-trifluoroethyl TFEA

Methyl α-chloroacrylate MαCIA

Methacrylic Acid Hexafluoroisopropyl HFIPMA

Methacrylic acid P-nitrobenzyl PNBMA

Methacrylate Benzyl BzMA

Acrylic acid 2, 2, 2-trichloroethyl TCEA

3-N, N-dimethylaminopropyl DMAPA, acrylic acid

2-methoxyethyl acrylate MEA

2-Methylthioethyl acrylate

Acrylic acid 6-N, N-dimethylaminohexyl DMAHA

4-N, N-dimethylaminobutyl DMABA Acrylic Acid

Acrylic acid tri (4-methyl-2-pentoxy) yl MPSA

DMAEMA / C ₁₄ Br Quat

Methacrylic acid trifluoroethyl TFEMA

Methacrylic Acid Methoxy MEMA

Claims (16)

Antifouling paint for ship surface protection comprising a combination of a) a poison, and b) a water-insoluble, sea-corrosive organotin glass polymer binder having a repeating group represented by the following general formula:

Wherein X is H or CH ₃ ; R is specifically a non-biologically active alkyl, aryl or arylalkyl, B is a residue of an ethylene-unsaturated monomer, and the polymer has at least 5 × 10 ⁻⁴ milliequivalents of valence per hour Has a decomposition rate and the paint has a corrosion rate of at least 2 microns per month in seawater.) The paint as claimed in claim 1, wherein R is represented by the following general formula.

or

(Wherein Z is NO ₂ , halogen or CN) The paint as claimed in claim 2, wherein R is represented by the following general formula. -(CH ₂ ) nY In which n is an integer from 1-4; Y is

Y is The group selected from; Wherein R ′ is C ₁ -C ₄ primary, secondary or tertiary alkyl and R ″ is H or R ′; R ″ ′ is alkyl or aryl.) The paint according to claim 1, wherein R is a quaternary amino alkyl represented by the following general formula.

Wherein Y is Br, Cl or I; R ′, R ″ and R ″ ′ are the same or different alkyl of C ₁ -C ₄ ). The paint as claimed in claim 1, wherein R is haloalkyl having at least one trihalomethyl group, wherein halogen is Br, F or Cl and alkyl has at least two carbons. 2. The chart of claim 1 wherein R is represented by the following general formula

(Wherein n is 1 or 2; R ″ ″ is a phenyl group or C ₁ -C ₄ primary, secondary or tertiary alkyl). The coating according to claim 1, wherein R is -SiR "'or -Si (OR"') ₃ and R "'is alkyl or aryl. 8. The paint as claimed in claim 7, wherein R "'is C ₁ -C ₆ primary, secondary or tertiary alkyl. 8. The paint according to claim 7, wherein R " 'is phenyl. b) a marine surface protection antifouling coating comprising a combination of a) a poison and b) a water-insoluble, anatomically corrosive organotin glass polymer binder having a repeating group represented by the following general formula:

Wherein B is halogen, CN or NO ₂ , R is C ₁ -C ₈ primary, secondary or tertiary alkyl and repeater B, wherein B is a residue of an ethylenically unsaturated copolymerizable intermonomer, the polymer Has a hydrolysis rate of more than 5 × 10 ⁻⁴ milliquivalents per hour and the paint has a corrosion rate of at least 2 microns per month) an antifouling paint for protecting the surface of a ship, comprising a) a poison and b) a repeating group represented by the following general formula:

Wherein B is an ethylene-unsaturated monomer, X is H or CH ₃ and R is selected from the following groups: a)

or

In which Z is NO ₂ halogen or CN; b)-(CH ₂ ) n Y Where n is an integer from 1-4; Y is

R ′ is C ₁ -C ₄ primary, secondary or tertiary alkyl; R ″ is H or R ′; R ″ is alkyl or aryl.) c) quaternary aminoalkyl represented by the following general formula;

(Wherein Y is Br, Cl or I, and R ′, R ″ and R ″ ′ are the same or different alkyl of C ₁ -C ₁₈ ) d) haloalkyl in which the halogen is Br, F or Cl and the alkyl has at least one trihalomethyl group having at least two carbons; e)

(Where n is 1 or 2 and R ″ ″ is a R ′ or phenyl group); f) —Si (R ″ ′) ₃ or —Si (OR ″ ′) ₃ , where R ″ ′ is alkyl or aryl 12. The method of claim 11 wherein, R is -SiR ₃ "'or Si (OR"') ₃ wherein the coating material, characterized in that (wherein R "'is a primary, a secondary or tertiary alkyl of C ₁ -C ₆₎ . 12. The coating as claimed in claim 11, wherein R is -SiR ₃ "'or -Si (OR"') ₃ , wherein R "is phenyl. by coating the surface of the vessel with an antifouling paint comprising a) a poison and a b) a repeating group represented by the general formula: Method of protecting ship surface.

Wherein B is a residue of an ethylene unsaturated monomer, X is H or CH ₃ and R is selected from: a)

or

(Where Z is NO ₂ , halogen or CN) b)-(CH ₂ ) n Y; Wherein n is an integer of 1-4, Y is

(Where R ′ is C ₁ -C ₄ primary, secondary or tertiary alkyl, R ″ is H or R ′ and R ″ ′ is alkyl or aryl) c) quaternary amino alkyl represented by the following general formula;

(Wherein Y is Br, Cl or I, R ', R "and R"' are the same or different is a C ₁ -C ₁₈ alkyl). d) haloalkyl wherein halogen is Br, F or Cl and alkyl has at least two carbons and at least one trihalomethyl group; e)

(Where n is 1 or 2 and R ″ ″ is a R ′ or phenyl group); f) —Si (R ″ ′) ₃ or —Si (OR ″ ′) ₃ , where R ″ ′ is alkyl or aryl. The method of claim 14, wherein R is —SiR ₃ ″ ′ or Si (OR ″ ′) ₃ , wherein R ″ ′ is a primary, secondary or tertiary alkyl of C ₁ -C ₆ . . The method of claim 14, wherein R is —SiR ₃ ″ ′ or —Si (OR ″ ′) ₃ , wherein R ″ is phenyl.