WO2002038627A1

WO2002038627A1 - (meth)acrylic resin compositions in organic solvent medium, method for preparing same and use thereof as binders in antifouling marine paints

Info

Publication number: WO2002038627A1
Application number: PCT/FR2001/003357
Authority: WO
Inventors: Martine Cerf; Holger Senff
Original assignee: Atofina
Priority date: 2000-11-08
Filing date: 2001-10-29
Publication date: 2002-05-16
Also published as: FR2816314A1; AU2002215083A1

Abstract

The invention concerns a resin composition comprising at least a water soluble (meth)acrylic copolymer including at least a unit derived from at least a (meth)acrylic (co)monomer; and at least a unit derived from at least one among an anhydride monomer and a vicinal diacid monomer, the anhydride and/or vicinal diacid functionality having been modified by at least a titanate. One mode for preparing said composition consists, in a first step, in copolymerising, in solvent medium, by free radical polymerisation, at least a (meth)acrylic (co)monomer; and at least an anhydride and/or vicinal diacid monomer; and in a second step, in chemically modifying the anhydride and/or vicinal diacid functionality of the copolymer resulting from the first step with at least a titanate, said titanate(s) being added in the copolymerisation reaction medium of the first step.

Description

COMPOSITIONS OF (METH) ACRYLIC RESINS IN ORGANIC SOLVENT MEDIA, PROCESS FOR THEIR MANUFACTURE, AND THEIR USE AS BINDERS OF ANTI-FOULING MARINE PAINTS.

The present invention relates to new compositions of (eth) acrylic resins in an organic solvent medium, a process for the preparation of these compositions, as well as the application of these compositions as binders in anti-fouling marine paint compositions, having a self-polishing character and not with no negative ecotoxicological impact on the marine environment.

From the 1960s, self-polishing antifouling paints based on organotin derivatives were developed and widely used throughout the world.

The use of these binders has many advantages: increase in the duration of action, reduction in equal performance of the amount of active product to be incorporated, absence of phenomena of intermetallic corrosion. Unlike conventional paints, the use of self-polishing paints allows * to obtain a release of active species constant over time. In addition, the progressive erosion of the polymer makes it possible to obtain an improvement in the surface condition and a reduction in the roughness between two fairings. However, it has been shown, after numerous studies, that high tin concentrations would cause anomalies in the calcification of oysters and a decrease in spat collection. Following these studies, the use of stannic derivatives was prohibited in France for boats of length less than 25 meters and similar restrictions in other countries.

The search for a new resin providing the same anti-fouling paint film with self-polishing properties has been an important area of research since that date. So the preparation of polymers comprising triorganosilyl units has been developed by various companies to obtain polymers having good self-polishing properties, but at a high price. In an attempt to provide a solution to this problem, it has been envisaged to replace silicon with titanium, the stability of which is also known. non-toxicity in oxide form. The use of acrylic monomers bearing titanate groups has been described _. for the preparation of crosslinked polymer particles which can be used as fillers in anti-fouling marine paint compositions: JP 57 565/87 ,. EP 286 243, JP 57 564/87, JP 86-217 781, EP 260 958, JP 86-200 344, EP 259 096. These particles would have the property of disintegrating in slightly basic medium, in particular in water of sea, and lead to self-polishing coatings.

However, these patents do not describe the preparation of organosoluble resins useful as binders in anti-fouling marine paint compositions. Such binders have been presented in European patent application EP-A-0 825.203, which describes an organosoluble composition of methacrylic resin comprising a polymer comprising units derived from methacrylic acid esterified by groups -Ti (OR) 3, in admixture with free Ti (OR) ₄ , which represents the excess of Ti (OR) 4 having been introduced for the preparation of said polymer in an amount sufficient for the resulting composition to be organosoluble and _. not in gel form, R representing one of ethyl, isopropyl, n-butyl, t-butyl, 2-ethylhexyl and t-amyl. This composition can be prepared by modification by Ti (OR) ₄ of a polymer functionalized with methacrylic acid.

The presence of an excess of Ti (OR) 4 however makes these compositions uneconomical. To solve this problem, it ^• has been proposed, according to the French patent application FR-A-2787800, a process wherein the esterification in the presence ^{™ is} carried by at moin ^~ "s"^'~' a monocarboxylic ^" acid" - R 'COOH, R' representing a C 1 -C 4 alkyl radical, linear, branched or cyclic; aryl; alkaryl; or aralkyl, stopping esterification before the formation of a gel, when the -COOH functions of the resin and R 'COOH have been added with a molar ratio Ti (OR) ^ / -COOH functions of the resin between 1 and 3, and a molar ratio R 'COOH / Ti (OR) ^ between 1 and 6.

However, it appeared that these binders and their preparation process could be ^'further improved, as shown below.

The present invention consists in preparing hydrolysable polymers, the hydrolysability being provided by the introduction into the polymer chain of anhydride (or vicinal diacid) functions modified by titanate. The hydrolysable polymers of the invention are prepared in two stages: - the synthesis of copolymers functionalized with anhydrides (or vicinal diacids) obtained by radical polymerization in a solvent medium; and - the chemical modification of the anhydride (or vicinal diacid) function of these copolymers with titanates. , The titanate is added to the reaction medium consisting of the anhydride, or vicinal diacid functional polymer and of the organic solvent. The product obtained is a functionalized titanate polymer resin in an organic solvent medium, said resin then being able to be formulated as a paint for marine application, the polymer playing the role of paint binder. The use of a polymer functionalized with maleic anhydride (or other polymerizable anhydride) (or vicinal diacid) instead of methacrylic acid (or acrylic) which is then modified by a titanate has the following advantages: - the polymer functionalized with maleic anhydride (or vicinal diacid) is soluble in the aromatic solvents conventionally used for anti-fouling paints. ri ^~ n'e ^'st not necessary to use cosolvent such from ethereal solvents or _. 2-methoxy propanol described in the two aforementioned patent applications; .-

- the use of excess. titanate when the polymer is modified is no longer necessary with the anhydride functionalized polymer;

the modification of the functionalized anhydride (or vicinal diacid) copolymer with tetraalkoxytitanes brings the following advantages compared to the same modification carried out on a copolymer functionalized with carboxylic acids (such as acrylic acid or methacrylic acid) ^:

- rapid rate of introduction of tetraalkoxytitanium (from a few minutes to 2-3 hours) while the modification according to French patent application FR-A-2 787 800 requires a process

^• special gels to avoid problems with slow introduction (of several hours may go up to ^'24 hours) of the functionalized polymer mixture and a carboxylic acid ^(C n ^H 2n + l ^{C00H or} other organic acid) on a base stock containing tetraalkoxytitanium;

- the amount of tetraalkoxytitanium is lower than according to the previous patent application

FR-A-2 787 800 ^' in which a strong excess of alkoxytitanium must be used to avoid the problems of freezing. In the present invention, the amount of tetraalkoxytitanium is of the order of stoichiometry in equivalent anhydride functions, which can even be lower, which is impossible according to patent application FR-A-2 787 800.

The present invention therefore firstly relates to a (meth) acrylic resin composition in an organic solvent medium, characterized in that it comprises at least one water-soluble (meth) acrylic copolymer comprising: - at least one unit originating from at least one (co) monomer (eth) acrylic; and

at least one unit originating from at least one of an anhydride monomer and a vicinal diacid monomer, the anhydride and / or vicinal diacid functionality having been modified by at least one titanate.

The (meth) acrylic comonomer (s) are chosen in particular from the hydrocarbyl (meth) acrylates, being for example ethyl methacrylate, ethyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, methacrylate d 2-ethylhexyl, methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate.

The anhydride monomer (s) are chosen in particular from maleic anhydride, itaconic anhydride, citraconic anhydride and dimethylmaleic anhydride, and the vicinal acid monomer (s) are chosen in particular from maleic acid, itaconic acid , fumaric acid, citraconic acid and dimethylmaleic acid. As preferred examples of the invention, mention may be made of resin compositions having a vicinal anhydride and / or diacid functionality derived from maleic anhydride or from a mixture of maleic anhydride and maleic acid. The titanate (s) have been chosen in particular from the tetraalkoxytitanes of formula (I):

Ti (OR ¹ ) (OR ² ) (OR ³ ) (OR ⁴ ) (I)

in which R ¹ , R, R ³ and R ⁴ , identical or different, each represent a hydrocarbon radical, linear or branched or cyclic, saturated or unsaturated, which can be functionalized with _. ether, acid, ine or CH2CF3.

In particular, the radicals R ¹ to R ⁴ can be chosen from linear or branched alkyl radicals ~ ^c n ^H 2n + l ' ^with 1 ≤ n ≤ 22, in particular 2 <n <12, cycloalkyl radicals ^' and radicals aromatics. Examples of ^" particular. ^~ ^" Titanates are: • Ti (OBu) ₄ (Bu = n-butyl);.

• Ti (OEt2Hex) ₄ (Et2Hex = 2-ethylhexyl);

^• Ti (OEt) ₃ (OC ₁₂ H25) (Et ≈ ethyl); and their mixtures. In the resin compositions according to the present invention, the titanate / anhydride and / or vicinal diacid molar ratios are generally 0.2-3 / 1, ^' . being in particular 0.3-1.5 / 1.

The composition according to the invention may also comprise at least one unit originating from at least one

(meth) acrylate containing an ether function and / or at least one vinylaromatic comonomer, these units making it possible to adapt the hydrophilicity / hydrophobicity of the copolymer.

The (meth) acrylate (s) containing an ether function can be chosen from:

• ethoxyethyl (meth) acrylate;

• butyldiglycol (meth) acrylate;

• methoxyethyl (meth) acrylate; and

• polyethylene glycol oxy methyl (meth) acrylate; and the vinyl aromatic monomer (s) can be chosen from styrene and methyl styrene.

Specific compositions of the invention are, for example, those obtained from:

35 to 95 parts by moles of the hydrocarbyl (meth) acrylate (s);

• 5 to 60 parts by moles of the anhydride and / or vicinal acid monomer (s);

• 0 to 60 parts by moles of the (meth) acrylates containing an ether function; and • 0 to 60 parts by moles of the vinyl aromatic monomer (s), for a total of 100 parts by moles.

The anhydride and / or vicinal acid monomer (s) advantageously represent 20 to 40 parts by moles per 100 parts by moles of the total onomeric composition.

The solvent medium is a medium conventionally ^"UTILI ^{^'is"} in ^{^"the'} préparâtiόrï ^~ of ^~ ^vefnl" s ^~ (3u ^'paint for the solubilization of the polymer which is synthesized there; it is advantageously chosen from aromatic solvents, ketones, esters and their mixtures, examples being xylene, toluene, aromatic hydrocarbons, cuts of aromatic hydrocarbons and their mixtures; methyl ethyl ketone, ethyl isobutyl ketone and cyclohexanone; ethyl acetate, acetate, butyl; and their mixtures.

The present invention also relates to a process for the preparation of a (meth) acrylic resin composition as defined above, characterized in that the titanate (s) are introduced with stirring either in batch or gradually during a lapse of time of time ranging from 5 minutes to 3 hours, on an organic solution of said copolymer, brought to a temperature of 5 to 120 ° C., then maintaining the reaction medium for a lapse of time. from 1 minute to 6 hours.

Generally the or 'titanates stirring, either in batch or gradually over a period of time ranging from 5 minutes to 3 ^is introduced hours - preferably

15 minutes to 1 hour - on an organic solution of said copolymer, brought to a temperature of 5 to 120 ° C - preferably from 10 to 100 ° C - then maintaining the reaction medium for a period of time ranging from 1 minute ^' at 6 am - preferably from 15 minutes to 2 hours.

We introduce the. titanates in a titanate / anhydrous or diacid molar ratio of 0.2-3 / 1, in particular 0.3-1.5 / 1.

It is also possible at this stage to introduce at least one coadditive chosen from hydrocarbon alcohols and organic hydrocarbon acids in a coadditive / titanate molar ratio of up to -5.

As examples of hydrocarbon-based alcohols, mention may be made of linear or branched aliphatic alcohols, cyclic alcohols and aromatic alcohols, preferably alcohols _n H2 _{n +} OH, with 1 <n <12. As examples of organic hydrocarbon acids, may include linear or branched aliphatic acids, cyclic acids and aromatic acids, preferably C _n H _{2n + 1} COOH acids, with 1 <n <12.

The organic solution of the copolymer is advantageously constituted by the reaction medium for copolymerization in a solvent medium, by radical route, of the (meth) acrylic (co) monomer (s) and of the vicinal anhydride and / or diacid monomer (s) .

Thus, in this embodiment, in a first step, copoly érise, mid ^• solvent, radical:

- at least one (co) mono (meth) cryl era; and

- at least one anhydride and / or vicinal diacid monomer; and

• in a second step, is carried out the chemical modification of anhydride functionality and / or diacid vicinal of the copolymer obtained in the first step with at least one titanate, said at least ° titanates are added to the reaction medium ^{'copolymerization} of the first step. The reaction medium of the first step comprises in particular, per 100 parts by weight,

- - 30 to 80 parts by weight, in particular 40 to 65 parts by weight, of total monomeric composition;

- from 70 to 20 parts by weight, especially ^'from 60 to 35 parts by weight ,, of a solvent medium.

At the first stage, at least one initiator is generally introduced chosen from azo or peroxidic or hydroperoxidic initiators, in particular at a rate of 0.2 to 5% by moles, in particular from 0.5 to 3% by moles, relative to the total monomer composition.

It is also possible to introduce at this stage at least one mercaptan in an amount which can range up to 2 mol% relative to the total monomeric composition. Mercaptans are conventionally used as agents for limiting the length of chains; alkyl thiols are preferred. According to a particular embodiment of this first step, the mixture of monomers in solution in part of the solvent is introduced at the reaction temperature (40 ° C - 140 ° C, preferably between 50 ° C - 100 ° C) over a period varying from 1 to 10 hours, preferably from 2 to 8 hours, in a reactor containing part of the solvent at the bottom of the tank; the initiator is also introduced diluted in part of the solvent in the reactor over the same period and at the same time as the monomers. As already indicated above, these initiators are those conventionally used in radical polymerization in an organic medium at 50-85 ° C for 10 hours of half-life; the azobisisόbutyronitrilè is preferred, but you can also ^• use ^'of peroxide initiators such as lauryl peroxide or tert. -butyl peroxy 2-ethylhexanoate.

Other methods of synthesis of the copolymer by radical polymerization, well known to those skilled in the art, can also be used; for example there may be mentioned the method in which ^"all the monomers, the initiator and the solvent are introduced into the reactor at room temperature and is gradually increased the temperature to the polymerization temperature. The synthesized modified titanium polymer resins have a solids content generally between 30 and 70%, preferably between 35 and 60%. Their viscosity is generally between 100 and 50,000 mPa.s, preferably between 200 and 5,000 mPa.s to be able to be easily formulated in paint.

The present invention also relates to an anti-fouling marine paint composition, characterized in that it comprises, as a binder, the resin composition as defined above or prepared by the process as defined above.

The binder is generally present in the paint composition at a rate of _. 10 to 60% by weight. Furthermore, the paint composition can also include the other usual ingredients such as:

- adjuvants, such as soy lecithin, modified hydrogenated castor oil, viscosity stabilizers (such as Viocostab ^® CNF 896 manufactured by the company ELF AQUITAINE);

- pigments and fillers, such as non-acicular zinc oxide, cuprous oxide and. ^' rutile titanium; and

- solvents and diluents, such as the solvent naphtha, toluene and xylene.

The following Examples illustrate the present invention without, however, limiting its scope. The mixture of solvents used in these examples was a xylene / Solvesso 150 mixture (ratio 75/25 by weight) ("Solvesso ^®

150 "is a trademark of the company" SHELL "under which aromatic hydrocarbon cuts are marketed. The viscosities of the resins indicated. In the tables of the examples are measured at Brookfield at 23 ° C.

The first value indicates the viscosity of the resin at the end of the synthesis operation, and the second value, the viscosity

Brookfield after stabilization of the change in viscosity after a few days.

The abbreviations used in these examples are:

MAM: methyl methacrylate ABu: butyl acrylate MABu: butyl methacrylate MAN: maleic anhydride AIBN: azobisisobutyronitrile

EXAMPLE 1: PREPARATION OF A MAM / ABu / MAN COPOLYMER

In a 3 liter reactor equipped with a condenser, ^~ a system

and ^" of a temperature, and maintained under a nitrogen atmosphere, 400 g of the solvent mixture are introduced, which is brought to 80 ° C.

The reaction mixture consisting of: 5 - 490 g of MMA; 160 g MAN; 209 g ABu;

- ^'11 g of AIBN; .

- 6.5 g of dodecanethiol; and 10 - 300 g of the mixture of solvents is introduced into the reactor with stirring at 80 ° C over a period of 6 hours.

Once the introduction of the reaction mixture into the reactor is complete, a step of

15 cooking by introducing 2.7 g of AIBN dissolved in 160 g of xylene, in 5 minutes at 80 ° C. The contents of the reactor are then kept stirring for 2 hours at 80 ° C.

The polymer solution obtained is cooled to. be characterized and stored. 20. Its characteristics are reported in the

Table 1 below.

EXAMPLES "2 to 4 ':

The procedure is equivalent to Example 1, adapting the amounts of the monomers, the initiator and the chain transfer agent (mercaptan) as indicated in Table 1.

The characteristics of the polymers obtained are also reported in Table 1. Table 1

EXAMPLE 7: FUNCTIONALIZATION OF THE COPOLYMER WITH A TITANATE ^''

The following are introduced into a reactor fitted with a stirring system and a condenser: - 102 g of. the polymer solution obtained in Example 2; and - 40 g of the mixture of solvents.

Then added to the reactor, - using a dropping funnel, 60 g of Ti (OEt2Hex) ₄ over one hour, at 25 ° C. The contents of the reactor are kept stirring for 4 hours at 25 ° C. to yield the functionalized titanate polymeric resin.

The characteristics of the functionalized titanate polymeric resin are reported in Table 2.

EXAMPLES 8 to 11:

The procedure is as in Example 7, using the polymer solution obtained in Example 1 and adapting the nature of the titanate, its molar ratio to MAN and the modification temperature as indicated in Table 2.

The characteristics of the functionalized titanate polymer resins obtained are reported in Table 2.

Table 2

EXAMPLE 12:

In a reactor fitted with a stirring system and a condenser, the following are introduced:

- 152 g of the polymer solution obtained in Example 1; and

- 70 g of the solvent mixture.

The contents of the reactor are brought to 50 ° C.

90 g of Ti (OEt2 Hex) _{4 are} introduced into the solution of the prepolymer using a dropping funnel over 1 hour 30 minutes, at 50 ° C.

The contents of the reactor are kept stirring for 2 hours. 20 g of ethyl-2hexanol are then introduced.

The reaction medium is thus maintained for 2 hours at 50 ° C to yield the functionalized titanate polymeric resin.

The characteristics of the functionalized titanate polymeric resin are reported in Table 3.

EXAMPLES 13 and 14:

The procedure is as in Example 12, using the polymer solution obtained in Example 3 and adapting the molar ratio Ti (0Et2Hex) ₄ / MAN, the nature of the additive and the molar ratio. additive / MAN as indicated in the

Table 3.

The characteristics of the titanate functionalized polymeric resins obtained are reported in Table 3. Table 3

EXAMPLE 15:

169 g of the polymeric solution obtained in Example 2 are introduced into a reactor fitted with a stirring system and a condenser. The contents of the reactor are brought to 50 ° C. 111 g of Ti (OEt2Hex) are introduced into the solution of the polymer of Example 2 using a dropping funnel over one hour at 50 ° C.

The contents of the reactor are kept stirring for 2 hours ^" . 24.2 g of decanoic acid dissolved in 24.3 g of the solvent mixture are then introduced.

The reaction medium is thus kept under stirring for 2 hours at 50 ° C to yield the functionalized titanate polymeric resin. The characteristics ^of a ^{'functionalized} polymeric titanate resin are reported in Table 4. EXAMPLES 16 to 21

The procedure is as in Example 15, using one of the polymer solutions obtained in Example 2 or 3 or 4 (as indicated in Table 4) and adapting the nature of the titanate, the molar ratio titanate / MAN, the nature of the additive and the additive / MAN molar ratio as indicated in Table 4.

The characteristics of the titanate functionalized polymeric resins obtained are reported in Table 4.

Table 4

EXAMPLE 22:

The following are introduced into a reactor fitted with a stirring system and a condenser: - 130.3 g of the polymer solution obtained in Example 4; and

T- 50 g of the mixture of solvents.

The contents of the reactor are brought to 80 ° C. A mixture is introduced into the prepolymer solution: - 81 g of Ti (0Et2Hex) ₄ ; and 13 g of Ti (OiPr) using a dropping funnel over 1 hour at 80 ° C.

The contents of the reactor are kept stirring for 2 hours. 30 g of decanoic acid dissolved in 15 g of the mixture of solvents are then introduced.

The reaction medium is kept stirring for 1 hour at 80 ° C to yield the functionalized titanium polymer resin.

The characteristics of the functionalized titanate polymeric resin are reported in Table 5.

EXAMPLE 23 and 24

The procedure is as in Example 22, using the polymer solution obtained in Examples 5 and 6 respectively and adapting the nature of the titanate, the molar ratio titanate / MAN, the nature of the additive and the molar ratio additive / MAN as indicated. in Table 5.

The characteristics of the functionalized titanate polymer resin obtained are reported in Table 5. Table 5

Claims

1 - Composition of (meth) acrylic resin in an organic solvent medium, characterized in that it comprises at least one water-soluble (meth) acrylic copolymer comprising:

- at least one unit originating from at least one (meth) acrylic (co) monomer; and

2 - Resin composition according to claim 1, characterized in that the (meth) acrylic comonomer (s) are chosen from (meth) acrylates of hydrocarbyl.

3 - Resin composition according to claim 2, characterized in that the hydrocarbyl (meth) acrylates are chosen from methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, 2-ethyl hexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethyl hexyl acrylate.

4 - Resin composition according to one of claims 1 to 3, characterized in that the anhydride monomer (s) are chosen from maleic anhydride, itaconic anhydride, citraconic anhydride and dimethylmaleic anhydride, and the vicinal acid monomer (s) are chosen from maleic acid, itaconic acid, fumaric acid, citraconic acid and dimethylmaleic acid.

5 - Resin composition according to claim 4, characterized by an anhydride and / or vicinal diacid functionality derived from maleic anhydride or from a mixture of maleic anhydride and maleic acid. 6 - Resin composition according to one of claims 1 to 5, characterized in that the titanate (s) have been chosen from the tetraalkoxytitanes of formula (I):

TKOR ¹ ) (OR ² ) (OR ³ ) (OR ⁴ ) (D

in which R ¹ , R ² , R ³ and R ⁴ , identical or different, each represent a hydrocarbon radical, linear or branched or cyclic, saturated or unsaturated, which can be functionalized with ether, acid, amine or CH2CF3. 7 - Resin composition according to claim 6, characterized in that R ¹ to R ⁴ are chosen from linear or branched alkyl radicals - ^C n ^H 2n + l ' ^with 1 ≤ n ≤ 22, in particular 2 <n ≤ 12, cycloalkyl radicals and aromatic radicals. 8 - Resin composition according to claim 7, characterized in that the titanates have been chosen from:

• Ti (OBu) ₄ (Bu = n-butyl);

• Ti (OEt2Hex) ₄ (Et2Hex = 2-ethylhexyl); ^• Ti (OEt) ^: ₃ (OC ₁₂ H25) (Et = ethylj; and their mixtures.

9 - Composition of. resin according to one of claims 1 to 8, characterized by a titanate / anhydride and / or vicinal diacid molar ratio of 0.2-3 / 1, in particular 0.3-1.5 / 1.

10 - Resin composition according to one of claims 1 to 9, characterized in that it further comprises at least one unit originating from at least one (meth) acrylate containing an ether function and / or from at least a co ^{'vinylaromatic} monomer.

11 - Resin composition according to claim 10, characterized in that the one or more

(meth) acrylates containing an ether function are chosen from: - ethoxyethyl (meth) acrylate ^" • butyldiglycol (meth) acrylate;

• methoxyethyl (meth) acrylate; and

• (meth) acrylate. polyethylene glycol oxy methyl; and the vinyl aromatic monomer (s) are chosen from

5 styrene and methyl styrene.

12 - Resin composition according to one of claims 2 to 11, characterized in that it was obtained from:

35 to 95 mole parts of the hydrocarbyl (meth) acrylate (s);

• 5 to 60 parts by moles of the anhydride and / or vicinal acid monomer (s);

• 0 to 60 parts by moles of the (meth) acrylates containing an ether function; and

0 to 60 parts by moles of the vinyl aromatic monomer (s), for a total of 100 parts by moles.

13 - Composition of _: resin according to claim 12, characterized in that the one or more

20 anhydride and / or vicinal acid monomers represent 20 to 40 parts by moles per 100 parts by moles of the total monomeric composition.

14 • = - Composition. resin according to claim 13, - characterized in that the medium

The solvent is chosen from aromatic solvents, ketones, esters and mixtures thereof.

15 - Resin composition according to claim 15, characterized in that the solvent medium is chosen from xylene, toluene,

30. aromatic hydrocarbons, cuts of aromatic hydrocarbons and mixtures thereof; methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. ; ethyl acetate, butyl acetate; and their mixtures.

16 - Process for the preparation of a (meth) acrylic resin composition as defined in one of claims 1 to 15,. characterized in that the chemical modification is carried out by at least one titanate of the vicinal anhydride and / or diacid functionality α 'a copolymer obtained from at least one (meth) acrylic (co) monomer and from at least one vicinal anhydride and / or diacid monomer.

17 - Process according to claim 16, characterized in that the titanate (s) are introduced with stirring either in batch or gradually over a period of time ranging from 5 minutes to 3 hours, on an organic solution of said copolymer, brought to a temperature from 5 to 120 ° C, then maintaining the reaction medium for a period of time ranging from 1 minute to 6 hours.

18 - Method according to one of claims 16 and

17, characterized in that the titanate (s) are introduced into a titanate / anhydride or diacid molar ratio of 0.2-3 / 1, in particular 0.3-1.5 / 1. 19 - Method ^' according to one of claims 16. to

18, characterized in that at least one coadditive chosen from hydrocarbon alcohols and organic hydrocarbon acids is introduced. in a coadditive / titanate molar ratio of up to 5. 20 - Method according to one of claims 17 to

19, characterized by the fact ^'that the organic solution of the copolymer consists of the reaction medium solvent medium copolymerization par- radical, or of the (co) monomers (meth) acrylic acid (s) and the monomer ° vicinal anhydride and / or diacid.

21 - Process according to claim 20, characterized in that the reaction medium of the copolymerization comprises, per 100 parts by weight,

- 30- to 80 parts by weight of total monomer composition;

- 70 to 20 parts by weight of solvent medium.

22 - Method according to one of claims 20 and 21, characterized in that at the prior polymerization step, introducing at least one initiator selected from azo initiators or peroxide or hydroperoxide at 0.2 to 5 % in moles relative to the total monomeric composition. 23 - Method according to one of claims 20 to 22, characterized in that at the prior polymerization step, at least one mercaptan is introduced in an amount up to 2 mol% relative to the composition total monomeric.

24 - Composition of anti-fouling marine paint, characterized in that it comprises, as binder _/ the resin composition as defined in one of claims 1 to 15 or prepared by the process as defined in one of claims 16 to 23.

25 - paint composition according to claim 24, characterized in that the binder is present in the paint composition in an amount of 10 to 60% by weight. 26 - Paint composition according to one of claims 24 and 25, characterized in that it comprises the other usual ingredients such as:

- adjuvants, such as soy lecithin, modified hydrogenated castor oil, viscosity stabilizers;

- pigments and fillers, such as nonacicular zinc oxide, cuprous oxide and rutile titanium oxide; and

- solvents and diluents, such as the solvent naphtha, toluene and xylene.