BR102014014775A2 - compound, compound synthesis process, composition, composition production process, antifouling composition, antifouling composition production process, biocidal composition, biocide composition production process, antifouling method, biocide method and use of compound - Google Patents

Abstract

compound, compound synthesis process, composition, composition production process, antifouling composition, antifouling composition production process, biocidal composition, biocide composition production process, antifouling method, biocide method and use of compound. The present invention describes compounds derived from the ether glycerophospholipid class and their antifouling properties. Specifically, the present invention comprises a compound represented by the formula (I) and wherein R1 is an alkyl group containing from 1 to 30 carbon atoms, comprising 0 to 5 unsaturations, R2 is h or alkyl group containing from 1 to 30 carbon atoms. carbon, comprising 0 to 5 unsaturation; r3 is oh or o-; and r4 is {n + (ch3) 3} or {n + h (ch3) 2}. The present invention also comprises the compound synthesis process, compositions containing said compound, composition production process, antifouling method, biocidal method and use of the compound. The present invention is in the fields of chemistry and biology.

Description

Inventory Patent Report Compound, Compound Synthesis Process, Composition, Composition Production Process, Antifouling Composition, Antifouling Composition Production Process, Biocidal Composition, Biocidal Composition Production Process, Antifouling Method Field of the Invention The present invention describes ether-glycerophospholipid subclass compounds and their antifouling and / or biocidal activity. It also relates to the process of synthesizing said compounds, compositions comprising said compounds, antifouling method and uses of the compound. The present invention is in the fields of chemistry and biology. Background of the Invention The world market for marine antifouling paints urgently needs a substitute for tributyl tin (ΤΒΤ), the main and most efficient biocidal agent ever used in this industrial segment. Although globally recognized as an effective substance and long used by the shipping industry, TBT was banned in 2008 by international environmental laws as a scientifically proven cause of various damage to the marine environment (CHAMP 2000; IMO 2008; GIPPERTH 2009; SONAK et al (2009; QIAN etal., 2010).

As a perspective of the demand of this industrial segment - which has a market estimate of five billion dollars for the year 2012 and which, despite the global economic recession, continues to grow - there is the statistics concerning the world fleet. of gross tonnage merchant ships above 100 GT (Gross Tonnagef, approximately 400mJ total internal volume (Vi), carried out at the close of 2010, recording a total of 102,000 operating units and about 28,000 new orders in last three years (ANNEX A) (WRIGHT, 2009; PIANOFORTE, 2011).

It should be emphasized in this statistic that the countless group of small merchant and recreational vessels other than the so-called war vessels are excluded, and furthermore that all these vessels, without exception, will require maintenance repainting at intervals ranging from 2 to 5 years.

To address this huge industrial segment - currently surrounded by the ban on the use of TBT and the scarcity of innovative alternative options with broad spectrum characteristics, possible industrialization, low cost and compliance with environmental laws - marine paint industries have had necessarily take up the ancient use of paints with copper oxides (~ 10 U $ / kg) as the main biocide, which, however, have been modernized with organic or organometallic compounds of copper, zinc or manganese - also known as additive biocides, supporting biocides or Boosters - many of which are also expensive and highly toxic (KONSTANTINOU and ALBANIS, 2004; READMAN, 2006; ONDUKA et al, 2010; THOMAS and BROOKS, 2010; BANERJEE et al, 2011; CASTRO et there, 2011).

Marine biofouling and its prevention Notorious and remote is the fact that marine biofouling causes many logistical problems and economic losses, and there are records of its prevention dating back several centuries BC (WHOl, 1952). Problems due to their presence are extensive, ranging from a simple clogging of pipelines, to structural compromise of platforms, pillars and pipelines, to the damaging action of submerged vessels and equipment performance (YEBRA, 2004; EGUIA and TRUEBA, 2007; MARECHAL and HELLIO, 2009; DAFFORN et al, 2011).

Marine biofouling is actually the result of the natural process of colonization and growth of marine micro and macroorganisms on submerged surfaces. Its development involves different stages and starts with the adsorption to that surface of organic molecules available in the water column, such as polysaccharides and proteins, which allows the subsequent adhesion of microorganisms such as bacteria, cyanobacteria, diatoms and protozoa. This stage is characterized by biofilm formation, which is the facilitating agent of the settlement and the development of macroorganisms such as mollusks, bryozoans, polychaetes, balanids, crustaceans and algae (BHADURY and WRIGHT, 2004; FUSETANI, 2004 YEBRA et al, 2004; CALLOW and CALLOW, 2002; 2006; MARECHAL and HELLIO, 2009).

Technically, biofouling develops in a four-stage process, not strictly sequential but interdependent. The first stage begins as early as the first minutes of surface contact with water when organic molecules such as polysaccharides and proteins accumulate. This allows, in the next few hours (24-96 h), the development of early colonization by bacteria and diatoms, which together with cyanobacteria, protozoa and rotifers, secrete different polysaccharides, called exopolysaccharides, which in a complex mixture with acids nucleic acids, proteins, minerals, nutrients, cell residues and microorganisms themselves form the second stage known as biofilm (ARCE et al, 2004; BHASKAR and BHOSLE, 2005; CALLOW and CALLOW, 2006).

The presence of biofilm allows microorganisms to have greater protection against predators, toxins and environmental changes, and allows a good availability of nutrients, seized from the marine environment, which are dispersed in the biofilm itself. This name, biofilm, should not be understood in the strict sense of the word, because in fact it does not present itself as a continuous or homogeneous layer, or as a film (film), its structure being heterogeneous in space and time, changing due to external and internal processes (COSTERTON, et al. 1994; DONLAN, 2002). In fact, its structure most often presents clusters of clustered microorganisms, having channels that allow water to pass through bringing nutrients, oxygen and consequently other possible compounds such as biocides (DAVEY and 0T00LE, 2000; SUTHERLAND, 2001; DONLAN, 2002; DUNNE, 2002).

Thus, ships and platforms remaining in tropical or subtropical areas are understood to be subject to the most severe biofouling attacks, particularly in shallower or coastal waters, where there is a greater availability of light, heat and nutrients. example, the bay of Guanabara-RJ.

The result of a millenary sequence of attempts and progressive transformations, the prevention of marine biofouling has now been effectively controlled mainly by the use of biocides applied in coating paints, TBT being the most efficient biocide. already used; however, due to its definitive ban from September 2008, marine paint industries have specifically resumed the use of copper oxides and other metal compounds as antifouling biocides, which, however, are already being re-evaluated. its use by several countries, having as its first impetus the search for the reduction of the rate of copper release to the environment (WHOI, 1952; YEBRA et al, 2004; DAFFORN et al., 2011).

Another highly valued but still little industrially successful antifouling approach has been the use of "natural appeal" products, which have been intensively prospected in the marine environment and evaluated for their biocidal antifouling action. (BLUNT et al., 2009; RAVEENDRAN and MOL 2009; FUSETANI, 2011, STOWE et al., 2011.) This approach, based on the present invention, has as its main feature the exemption of metallic compounds in antifouling composition and mitigation. of harmful side effects to the environment.

[0014] Ether-glycerophospholipids as antifouling compounds [0015] Glycerophospholipids have been used as an adjuvant to reduce protein and bacterial adhesion in materials employed in certain technological areas such as food, beverage and drug processing equipment ; medical materials, for example prosthetics, ophthalmic lenses and catheters; filtering equipment; etc., as such non-stick properties are supposed to be related to the peculiarities of the zwitterionic and amphiphilic nature of its molecule (SARIRI and TOOSI, 2003; GOREISCH et al, 2004; IWASAKI and ISHIHARA, 2005; XU et al., 2008; WATANABE and ISHIHARA , 2008 :).

Glycerophospholipid ether known as Platelet Activating Factor (PAF) is a potent biological mediator produced by various cell types, which triggers various physiological reactions (PRESCOTT et al., 1990; VENABLE et al., 1993; OWEN et al., 2007).

[0017] This compound was elucidated at the same time by the groups of professors Jacques Benveniste of the Institute of Chemistry of Natural Substances - France; Donald Hanahan of the University of Texas Department of Biochemistry and Fred Snyder of the Oak Ridge, Tennessee Institute of Nuclear Studies Medical Sciences Division, who conducted independent investigations into rabbit anaphylaxis and antihypertensive action in rats (DEMOPOULOS). et al, 1979; BLANK et al, 1979; HANAHAN, 1986). After its structure was unveiled, a new research field was opened, with the main objective of the medical area (VENABLE et al, 1993).

The idea of using ether glycerophospholipids as a biocide is based on what happens in other cell types widely used in the medical and pharmacological field (VENABLE et al, 1993; BOTITSI et al, 1998; KULIKOV and MUZYA, 1998) , based on the possible triggering of an antagonistic reaction or inflammatory process in the cells of the fouling organisms in contact with such products.

Ether-glycerophospholipids have some special properties linked to their molecular structure, being amphiphilic, as they have a hydrophilic and a hydrophobic site, and zwitterionics, that is, have negative and positive charges (bipolar radical) in their structure, besides also have low molecular weights (MW) - 500 Daltons. These properties are important when confronted with diffusion by EPS and possible absorption pathways by microorganisms. Due to its hydrophobic site, a long saturated alkyd chain attached at one end of the molecule, this compound can easily permeate through the lipid bilayers of the cell envelope and plasma membrane of organisms (JONES and OSBORN, 1977a, b). Because it is an amphiphilic molecule and has low PM, they have good potential to diffuse into the biofilm and, because of this feature, pass through the transmembrane proteins present in the cell envelope and plasma membranes, as some of these proteins, called porins, have Low specificity and generally allow the diffusion of hydrophilic molecules with MW less than 600 daltons (NIKAIDO and YAARA, 1985; KOEBNIK et al, 2000).

Another important factor is that these compounds, without acyl radical at sn-2 position, can act as a signaling molecule when in contact with or absorbed by microorganisms without undergoing termination of their agonist action by phospholipase-like enzymes. allowing it to accumulate in the cell envelope, wall or interior, triggering an antagonistic cellular response process that will inhibit development or destroy the microorganism (MARATHE et al, 2001; CROFT and ENGEL, 2006; FRUHWIRTH et al, 2007; WELCH et al, 2009).

In the search for the state of the art in scientific and patent literature, the following documents dealing with the subject were found: [0022] Document US8657943 (B2), entitled “l-Hydroxy-2-O-Acyl-Sn- Glycero-3-Phosphocholine Compounds, Preparation Process, Antifouling Composition, Process For Its Preparation, Method To Prevent Fouling, Method To Turn A Surface Into An Antifouling Surface, And, Reveals 1-Hydroxy-2-0 Compounds -Acil-Sn-Glycer-3-Phosphocholines and / or 1-O-Acyl-2-Hydroxy -Sn-Glycer-3-Phosphocholines and their application as antifouling. These compounds disclosed in the document have the O-acyl group in glycerophospholipid structure. However, the document does not disclose or suggest compounds containing the O-alkyl group in the glycerophospholipid structure.

[0023] US 20140083324 A1, entitled "Anti-fouling Paints and Coatings" discloses coatings comprising molecules such as peptides and / or metal-shielding enzymes through antibiotic and / or antifouling properties. However, the document does not disclose compounds containing the O-alkyl group in the glycerophospholipid structure, nor their application as antifouling actives.

[0024] US5306840 (A) entitled "Process for preparing pure L-alpha-glycerylphosphoryl-D-myoinositol and its salts" discloses a process for the pure preparation of L-alpha-Glycerylphosphoryl-D-myoinositol and its salts. The process consists of soy lectin methanolysis and subsequent purification steps. However, there is no mention in the document regarding alkylation of the compounds obtained in the soybean lectin methanolysis reaction.

US2011040053 (A1) entitled "Polysiloxane, Acrylic Compound And Vinylic Compound" discloses polysiloxane derivative compounds as well as their synthesis processes. One step of the synthesis process involves adding vinyl compound to the polysiloxane compound. . However, the document does not disclose compounds containing the O-alkyl group in the glycerophospholipid structure, nor their application as antifouling actives.

Thus, from what is clear from the researched literature, no documents were found anticipating or suggesting the teachings of the present invention, so that the solution proposed here has novelty and inventive activity in relation to the state of the art.

Thus, there remains a need in the art for the development of antifouling compounds, compositions and methods so that the compounds have high efficiency, are easily synthesized, and do not cause harm to the environment.

SUMMARY OF THE INVENTION Thus, the present invention provides a solution to the prior art problem from compounds of an ether-glycerophospholipid subclass. A new synthesis process of these compounds has been developed, in which the product obtained has an O-alkyl group. Experimental tests have shown that these compounds of the ether glycerophospholipid subcassium (which have an O-alkyl substituent on the glycerol structure) exhibit superior biocidal and antifouling activity than has been reported in the prior art. This property of these compounds enables their application in the technical sector of industrial-scale underwater coatings and paints to protect against the harmful effects of biofouling on submerged and floating structures such as boat hulls, buoys, oil rigs and ducts.

In a first object, the present invention relates to the compounds represented by formula (I) and wherein: R1 is an alkyl group containing from 1 to 30 carbon atoms, comprising from 0 to 5 unsaturation; R2 is H or alkyl group containing from 1 to 30 carbon atoms, comprising from 0 to 5 unsaturation; R3 is OH or O '; and R4 is {N + (CH3) 3} or {N + H (CH3) 2}.

In another object, the present invention relates to a process for the synthesis of the compounds of formula I, which process comprises alkylating the compound of formula (VI): and wherein: R1 is a hydroxyl group or a group O-acyl containing from 1 to 30 carbon atoms, comprising from 0 to 5 unsaturation; R2 is a hydroxyl group or an O-acyl group containing from 1 to 30 carbon atoms, comprising from 0 to 5 unsaturation; R3 is OH or O "; and R4 is [N + (CH3) 3] or [N + H (CH3) 2]; and wherein the alkylation comprises the steps of: a) contacting the compound of formula (VI) with solvent organic, alkyl halide, and alkaline hydroxide, in the presence of surfactant b) removal of organic solvent c) addition of alcohol and hydroxide d) extraction with organic solvent.

In another object, the present invention relates to a composition comprising the compound represented by formula (I).

In another object, the present invention relates to a process for producing said composition comprising the step of adding the compound represented by formula (I) to an acceptable carrier.

In another object, the present invention relates to an antifouling composition comprising the compound represented by formula (I).

In another object, the present invention relates to a process for producing said antifouling composition comprising the step of adding the compound represented by formula (I) to an acceptable carrier.

In another object, the present invention relates to a biocidal composition comprising the compound represented by formula (I).

In another object, the present invention relates to a process for producing said biocidal composition comprising the step of adding the compound represented by formula (I) to an acceptable carrier.

In another object, the present invention provides an antifouling method comprising contacting a compound represented by formula (I) with a surface suitable for water submersion or flotation.

In another object, the present invention provides a biocidal method comprising contacting the compound represented by formula (I) with aquatic microorganisms and / or macroorganisms.

In another object, the present invention relates to the use of the compounds represented by formula (I) for the prevention of biofouling.

Still, the inventive concept common to all claimed protection contexts resides in the ether-glycerophospholipid subclass compounds which have antifouling and biocidal activity, enabling their application for this purpose.

[0041] These and other objects of the invention will be immediately appreciated by those skilled in the art and companies having an interest in the segment, and will be described in sufficient detail for their reproduction in the following description. Brief Description of the Figures In order to further define and clarify the contents of the present patent application, the following figures are presented: Figure 1 shows an illustration of the hypothetical biocide diffusion (LPC). The biocide component of the ink is carried by seawater from pores formed by wear (maximum concentration - C max) and diffuses through the biofilm coming into contact with microorganisms. By overcoming the biofilm layer it becomes diluted by the action of sea water in the hydrodynamic boundary layer. Reaching its total dilution (C - * 0) in the outermost region. (Adapted from Source: YEBRA et al, 2006).

[0044] Figure 2 shows total ion chromatogram (CIT) of methanolysis reaction product - 1a Synthesis (in blue), obtained from liquid chromatograph effluent, compared to CIT of GPC Glycerophosphoipipid Standards (16: 0/16 : 0); GPC (14: 0/14: 0); PAF and Lyso-PAF (in red).

Figure 3 shows mass spectrum of 1st synthesis showing ions eluting between 5 and 11 minutes.

Figure 4 shows mass spectra of the 1st synthesis. Eluted peaks at retention times of 6.3 and 6.8 minutes.

Figure 5a shows the Mass Spectrum (EM abbreviation) of molecular ion m / z 439.7 of the product of the 1st Synthesis [0048] Figure 5b shows proposed fragmentation scheme for molecular ion m / z 439.4 of the product of the 1st Synthesis.

Figure 6a shows Mass Spectrum (MS abbreviation) of molecular ion m / z 328.5. Product of 1st Synthesis;

Figure 6b shows proposed fragmentation scheme for molecular ion m / z 328.4 of the product of the 1st Synthesis.

Figure 7 shows mass spectra related to the major 1st Synthesis ions eluted in the retention time range from 7.0 to 7.7 and 7.8 to 8.5 minutes.

Figure 8 shows MS of molecular ion m / z 714.5 and MS of its product ions m / z 696.4 and m / z 534.4 obtained for the product of the 1st synthesis.

Figure 9 shows MS of the molecular ion m / z 696.5 and MS of its product ions m / z 516.4 and m / z 262.1 obtained for the product of the 1st Synthesis.

Figure 10 shows proposed fragmentation scheme for molecular ion m / z 714.5 of the product of the 1st synthesis. Methanolysis reaction.

Figure 11 shows mass spectrum related to the major ions of the 1st Synthesis product eluted in the retention time range of 8.4 to 10 minutes.

Figure 12 shows mass spectrum of the ions of the 2nd Synthesis step. Sum of times 5 to 20 minutes.

Figure 13 shows mass spectra related to eluted peaks at retention times between 5 and 11 minutes. General aspect.

Figure 14 shows mass spectra related to eluted peaks at retention times greater than 11 minutes. General aspect.

Figure 15 shows mass spectrum of the 2nd Stage of Synthesis for the 9.1 minute eluted peak. Figure 16a shows MS of molecular ion m / z 510.6 and MS of its product ions m / z. 492.6 in m / z 286.4 obtained for the product of the 2nd Synthesis. Alkylation reaction.

Figure 16b shows the proposed fragmentation of the molecular ion m / z 510.4 of the alkylation product.

Figure 17a shows the mass spectrum (EM abbreviation) of the molecular ion m / z 592.6 and MS of its product ions m / z 330.3 and m / z obtained for the product of the 2nd Synthesis. Alkylation reaction.

Figure 17b shows the proposed fragmentation scheme for molecular ion m / z 592.5 of the alkylation product.

[0064] Figure 18 shows specimen (control) painted only with anti-corrosion paint. Inspection after three weeks of immersion (left) and after eight weeks (right).

Figure 19 shows specimens painted with coating A. Inspection after three weeks of immersion (upper) and after eighth week of immersion (lower).

[0066] Figure 20 shows specimens painted with coating B. Inspection after three weeks of immersion (upper) and after eighth week of immersion (lower).

Figure 21 shows specimens painted with the C. coating. Inspection after three weeks of immersion (upper) and after eighth week of immersion (lower).

[0068] Figure 22 shows specimens painted with coating D, Inspection after three weeks of immersion (upper) and after eighth week of immersion (lower).

[0069] Figure 23 shows H-NMR hydrogen resonance spectroscopic analysis of the molecular ion m / z 510.6 of the second synthesis (ie, the alkylation reaction).

Figure 24 shows infrared (IR) spectrophotometric analysis of the molecular ion m / z 510.6 (ie, the alkylation reaction).

Background of the Invention In a first object, the present invention provides compounds represented by formula (I) and wherein: R1 is an alkyl group containing from 1 to 30 carbon atoms, comprising from 0 to 5 unsaturation; R2 is H or alkyl group containing from 1 to 30 carbon atoms, comprising from 0 to 5 unsaturation; R3 is OH or O '; and R4 is {N + (CH3) 3} or {N + H (CH3) 2}.

It has been proven by laboratory and field testing that these compounds are shown to be very effective as biocides and antifouling actives. The O-alkyl group plays an important role in the compound's structure and gives the molecule greater activity, especially with regard to biocidal and antifouling activities.

In one embodiment, R 1 is an alkyl group containing between 5 and 25 carbon atoms, comprising from 0 to 3 unsaturation; and R2 is H or alkyl group containing from 1 to 20 carbon atoms, comprising from 0 to 3 unsaturation.

In one embodiment, R1 is an alkyl group containing between 10 and 20 carbon atoms, comprising from 0 to 3 unsaturation; and R2 is H or alkyl group containing from 1 to 15 carbon atoms, comprising from 0 to 3 unsaturation.

In one embodiment, the compound is represented by formula (I) or formula (III): In one embodiment, the compound is represented by formula (IV) or formula (V): In another object, the present invention relates to a process for synthesizing the compound represented by formula (I), which process comprises alkylating the compound of formula (VI): and wherein: R1 is a hydroxyl group or an O-acyl group containing from 1 to 30 carbon atoms, comprising from 0 to 5 unsaturation; R2 is a hydroxyl group or an O-acyl group containing from 1 to 30 carbon atoms, comprising from 0 to 5 unsaturation; R3 is OH or O-; and R4 is [N + (CH3) 3] or [N + H (CH3) 2]; and wherein the alkylation comprises the steps of: a) contacting the compound of formula (VI) with organic solvent, alkyl halide, and alkaline hydroxide in the presence of surfactant; b) removal of organic solvent; c) addition of alcohol and hydroxide; d) extraction with organic solvent.

The process was developed from the methanolysis of soybean lecithins, whose product - compound of formula (VI), was subjected to the alkylation reaction, and then substances with chemical structures of ether-glycerophospholipids type 1-hydroxy- 2-O-alkyl-sn-glycero-3-phosphocholine and / or 1-O-alkyl-2-hydroxy-sn-glycero-3-phosphocholine.

In one embodiment, the alkylation further comprises the steps of: e) water adsorption; and f) evaporation of the solvent.

In one embodiment, the organic solvent is chosen from the group consisting of: 1,2-dichloroethane, chloroform, dichloromethane, chlorobenzene, ethyl acetate and ethyl ether.

In one embodiment, the alkyl halide is an alkyl bromide, chosen from the group consisting of: bromohexane, bromooctane, bromo-decane, bromo-dodecane, bromo-tetradecane and bromo-octadecane.

In one embodiment, alkaline hydroxide is chosen from the group consisting of: sodium hydroxide, potassium hydroxide and lithium hydroxide.

In one embodiment, the surfactant is chosen from the group consisting of: tetrabutylammonium hydrogen sulfate, tetrabutylammonium bromide, cetyl trimethyl ammonium chloride and trimethylphenylammonium tribromide.

In one embodiment, the alkylation step a) takes place over a period of time ranging from 100 to 140 minutes.

In one embodiment, the alkylation step a) takes place over a period of time ranging from 110 to 130 minutes.

In one embodiment, removal of the organic solvent is accomplished by using evaporation or vacuum distillation systems.

In one embodiment, removal of the organic solvent is performed with a rotary evaporator.

In one embodiment, the alcohol is chosen from the group consisting of: methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol and 3-butanol.

In one embodiment, the hydroxide is chosen from the group consisting of: ammonium hydroxide, AgOH, Zn (OH) 2, Be (OH) 2 and Mg (OH) 2.

In one embodiment, the water adsorption step is performed by the addition of adsorbent chosen from the group consisting of: anhydrous sodium sulfate, anhydrous potassium carbonate and anhydrous magnesium sulfate.

Background of the Composition In another object, the present invention provides a composition comprising the compound represented by formula (I).

In one embodiment, the compound is at a concentration ranging from 1% w / w to 90% w / w.

In one embodiment, the compound is at a concentration ranging from 1% w / w to 60% w / w.

In one embodiment, the compound is at a concentration ranging from 1% w / w to 20% w / w.

In one embodiment, the compound is in a concentration ranging from 2% w / w to 10% w / w.

In one embodiment, the composition further comprises elements chosen from: a) binders selected from polyvinyl chloride, acrylic resins, vinyl chloride-vinyl acetate copolymer, butadiene-styrene-acrylonitrile rubbers, all in solvent systems and / or aqueous dispersions. b) organic pigments, inorganic pigments, insoluble dyes; c) plasticizers; d) viscosity modifiers; e) combinations of items a) through d) above.

Background of the Composition Production Process [0102] In another object, the present invention provides a process for producing said composition comprising the step of adding the compound represented by formula I to an acceptable carrier.

In one embodiment the acceptable carrier comprises elements selected from: a) binders selected from polyvinyl chloride, acrylic resins, vinyl chloride-vinyl acetate copolymer, butadiene-styrene-acrylonitrile rubbers, all in solvent systems and / or aqueous dispersions. b) organic pigments, inorganic pigments, insoluble dyes; c) plasticizers; d) viscosity modifiers; e) combinations of items a) through d) above.

In one embodiment, the addition of the compound as defined above to an acceptable carrier occurs by: direct dispersion, formation of chemical bonds, incorporation by microencapsulation or combinations of these media.

Background of the Antifouling Composition In another object, the present invention provides an antifouling composition comprising the compound represented by formula (I).

In one embodiment, the compound is at a concentration ranging from 1% w / w to 90% w / w.

In one embodiment, the compound is at a concentration ranging from 1% w / w to 60% w / w.

[0109] In one embodiment, the compound is at a concentration ranging from 1% w / w to 20% w / w.

In one embodiment, the compound is in a concentration ranging from 2% w / w to 10% w / w.

[0111] The antifouling composition can be applied to the surface of numerous objects, especially those susceptible to fouling by being in constant, frequent or intermittent contact with salt and / or fresh water. Examples of such surfaces include, without limitation, ships, boats, yachts, sailboats, small boats, submarines, ferries, speedboats, frigates, aircraft carriers, icebreakers, rowing boats, sloops, tugs. Other features include surfing boards, windsurfing, water skiing. The surface can also be of a buoy, a pier, a breakwater, oil rigs, fish fences, fishing nets, underwater cages. Other objects like oxygen tanks and scuba gear, periscopes, rudders, propellers, fins.

[0112] In addition to these surfaces, equipment related to water treatment, desalination, hydropower, and food processing or any other industry using aqueous solutions are also considered suitable surfaces.

Membranes and filters are also considered suitable surfaces for coating in accordance with the present invention. Industrial equipment such as pipes, valves, pumps, condensers, evaporators and heat exchangers are considered suitable coating surfaces in accordance with the present invention.

The antifouling composition of the present invention comprises excipients commonly found for such a composition in the prior art, and may contain other known antifouling actives.

In one embodiment, the antifouling composition further comprises another antifouling active, selected from the group comprising antifungals, pesticides, pesticides and combinations thereof.

In one embodiment, the antifouling composition further comprises elements selected from: a) binders selected from polyvinyl chloride, acrylic resins, vinyl chloride-vinyl acetate copolymer, butadiene-styrene-acrylonitrile rubbers, all in solvent systems and / or aqueous dispersions. b) organic pigments, inorganic pigments, insoluble dyes; c) plasticizers; d) viscosity modifiers; e) combinations of items a) through d) above.

In one embodiment, the addition of the compound as defined above to an acceptable carrier occurs by: direct dispersion, chemical bond formation, microencapsulation incorporation or combinations of these media.

Background of the Process of Making the Antifouling Composition In another object, the present invention provides a process of producing said antifouling composition comprising the step of adding the compound as defined above to an acceptable carrier.

In one embodiment the acceptable carrier comprises elements chosen from: a) binders selected from polyvinyl chloride, acrylic resins, vinyl chloride-vinyl acetate copolymer, butadiene-styrene-acrylonitrile rubbers, all in solvent systems and / or aqueous dispersions. b) organic pigments, inorganic pigments, insoluble dyes; c) plasticizers; d) viscosity modifiers; e) combinations of items a) through d) above.

In one embodiment, the addition of the compound of formula (I) to an acceptable carrier occurs by: direct dispersion, formation of chemical bonds, incorporation by microencapsulation or combinations of these media.

Background of the Biocidal Composition In another object, the present invention provides a biocidal composition comprising a compound as defined above.

In one embodiment, the compound is at a concentration ranging from 1% w / w to 90% w / w.

In one embodiment, the compound is at a concentration ranging from 1% w / w to 60% w / w.

In one embodiment, the compound is at a concentration ranging from 1% w / w to 20% w / w.

In one embodiment, the compound is at a concentration ranging from 2% w / w to 10% w / w.

In one embodiment, the composition further comprises another biocidal active, selected from the group comprising antifungals, algicides, pesticides and combinations thereof.

[0129] In one embodiment, the composition further comprises elements selected from: a) binders selected from polyvinyl chloride, acrylic resins, vinyl chloride-vinyl acetate copolymer, butadiene-styrene-acrylonitrile rubbers, all in solvent systems and / or aqueous dispersions. b) organic pigments, inorganic pigments, insoluble dyes; c) plasticizers; d) viscosity modifiers; e) combinations of items a) through d) above.

Background of the Biocidal Composition Production Process In another object, the present invention provides a process for producing said biocidal composition comprising the step of adding the compound as defined above to an acceptable carrier.

[0132] In one embodiment the acceptable carrier comprises elements chosen from: a) binders selected from polyvinyl chloride, acrylic resins, vinyl chloride-vinyl acetate copolymer, butadiene-styrene-acrylonitrile rubbers, all in solvent systems and / or aqueous dispersions. b) organic pigments, inorganic pigments, insoluble dyes; c) plasticizers; d) viscosity modifiers; e) combinations of items a) through d) above.

In one embodiment, the addition of the compound of formula (I) to an acceptable carrier occurs by: direct dispersion, formation of chemical bonds, incorporation by microencapsulation or combinations of these media.

Background of the Antifouling Method In another object, the present invention provides an antifouling method comprising contacting a compound of formula (I) with a surface suitable for water submersion.

[0136] In one embodiment, the surface suitable for water submersion is chosen from: ship hulls, boats, yachts, sailboats, small boats, submarines, rafts, speedboats, frigates, aircraft carriers, icebreaker, rowing boat, sloop , tugboats, surfboards, windsurfing, water skiing, buoys, wharfs, breakwaters, oil rigs, fish fences, fishing nets, underwater cages, oxygen tanks and scuba equipment, periscopes, rudders, propellers, fins , surfaces of equipment related to water treatment, desalination, hydroelectric plants, and food processing, membranes, filters, piping, valves, pumps, condensers, evaporators, heat exchangers and combinations thereof.

[0137] In one embodiment, water submersion is in the marine environment.

Background of the Biocidal Method In another object, the present invention provides a biocidal method comprising contacting the compound of formula (I) with aquatic microorganisms and / or macroorganisms.

[0140] In one embodiment, microorganisms are chosen from the group consisting of: bacteria, cyanobacteria, diatoms, protozoa or rotifers.

In one embodiment, the macroorganisms are chosen from the group consisting of: molluscs, bryozoans, polychaetes, balanids, crustaceans or algae.

Background to the Use of the Compound In another object, the present invention provides use of the compound of formula (I) for the prevention of biofouling.

In one embodiment, the compound is at a concentration ranging from 1% w / w to 90% w / w.

In one embodiment, the compound is at a concentration ranging from 1% w / w to 60% w / w.

In one embodiment, the compound is at a concentration ranging from 1% w / w to 20% w / w.

In one embodiment, the compound is in a concentration ranging from 2% w / w to 10% w / w.

Example 1. Preferred Embodiment The examples shown herein are intended solely to exemplify one of the numerous ways of carrying out the invention, but without limiting the scope thereof.

Example I - Synthesis of Antifouling Compounds [0149] Methanolysis Reaction (1st Synthesis Step) [0150] The 1st Synthesis Step occurred according to the methanolysis reaction disclosed in US8657943 (B2). Thus, the methanolysis reaction involved the treatment of soy lecithin with a solution of sodium methoxide in methanol, being performed under mechanical stirring, without heating, in a 2000mL (five joints 24x40mm) glass reactor equipped with a condenser. reflux with cold water and a mechanical rod and propeller stirrer. 1000mL of methanol, 3g of metallic sodium and 40g of soy lecithin were used. The reaction mixture was allowed to stir for 72 hours at room temperature (approximately 25 ° C). To remove the final reaction product, the reaction mixture was transferred to a beaker and gravity filtered on filter paper to give a solid product and an oily residue.

The filtered solid was subjected to the removal of volatile substances using a vacuum glass desiccator. The final solid product contained 33.4g having a slightly yellowish appearance, soft consistency and slightly rancid odor, the resulting oily residue, after complete evaporation of methanol, provided 6g of material.

[0152] Alkylation reaction (2nd step of synthesis) [0153] The 2nd step of synthesis was performed in a flask under magnetic stirring, where a fraction of the solid methanolysis reaction product, 1,2-dichloroethane, 1- bromohexadecane and an aqueous sodium hydroxide solution in the presence of tetrabutyl ammonium hydrogen sulfate.

The reaction was kept under strong stirring for 2 hours. After this time, dichloroethane was removed using a rotary evaporator and a mixture of methanol and excess ammonium hydroxide was added to the reaction. The reaction was stirred for a further 2 hours, and then the methanol was evaporated to give a slightly brown yellow pasty product. Then the reaction was extracted with dichloromethane and washed with distilled water. To the obtained organic phase was added anhydrous sodium sulfate, the organic solvent was evaporated, and the alkylated products were obtained in 60% yield.

[0155] Synthesis Products [0156] Methanolysis Reaction (1st Synthesis) [0157] Analysis by mass spectrometry of the stream eluting from the liquid chromatograph produced the CIT (Figure 2) - presented here compared to the CIT obtained for the GPC and PAF standards - from which the molecular ions recorded during the time interval in which the variation in the baseline was observed, ie, from the fifth to the eleventh minute, was performed.

[0158] Figure 3 shows the mass spectrum of ions eluting between the fifth and eleventh minute. It can be observed that the most intense component is the m / z 696.5 ion, which may indicate a deficiency in the conversion of the reaction performed, since the expected hydroxylated compounds of this reaction tended to have lower mass charge ratios, varying between m / z. z 350 to 550.

Figure 4 shows the eluted peak-related spectra at retention times of 6.3 and 6.8 minutes, which showed lipophilicities closer to PAF and Lyso-PAF compounds, and thus those compounds may have structures consistent with PAF-analog compounds.

Between the fifth and seventh minutes, molecular ions were observed and evaluated, ordered by retention time: m / z 439.5 and 328.4. Figures 5a and 6a show the EM2-type mass spectra for these molecular ions and Figures 5b and 6b show the respective proposals for the product ions and their fragmentation pathways.

It should also be noted that the samples under analysis, due to the solvent system used in the mobile phase, were subjected to possible protonation, and thus, in reference to what the Nitrogen Rule dictates, ions of the type (M + H) + having odd mass / charge ratios were under suspicion of possibly not having nitrogen in its structure. Thus, initially, the molecular ion m / z 439.4 was considered to have no nitrogen in its molecule and, in addition to its short retention time, it was envisioned and treated as a possible acid glycerophosphate (GPA), having been proposed as Lyso-GPA (18: 0) (see figure 5b).

For the molecular ion m / z 328.5 the product ion m / z 184 was easily observed, indicating that it was a GPC. After evaluation of its fragmentation sequence it was considered to be Lyso-GPC (4: 0) (see figure 6b). which is believed to be the product of parallel reactions of methanolysis.

In the elution interval between 7.0 and 8.5 minutes, the sum of the molecular ions (Figure 7) provided as main components the m / z 696.5 and 714.5 ions.

It is understood herein that the experimental conditions used in the analysis provided an acceptable distribution and separation of the treated lipids, seven minutes early, from those more branched and / or unreacted, such as glycerophosphocholine m / z 780,6; 816.6 and 844.7 observed in the 10-minute range (Figure 11).

Mass spectrometry has shown that the methanolysis reaction achieved a good conversion of soybean lecithin, essentially diacylated glycerophospholipids, into products with lower lipophilicity, producing a mixture of PAF-analogous compounds and lyso-phosphatidic acids. , having been obtained as the main molecular ions m / z 328,5; 439.5 and 714.5, which were respectively structurally related to 1-OH-2-butyl-sn-glycero-3-phosphocholine compounds; 1-OH-2-octadecyl-sn-glycerophosphoric acid and PAF-analog compound GPC (18: 3 / 0-14: 0), the latter possibly an artifact with an additional double bond, possibly not generated by the methanolysis reaction, GPC (18: 2 / 0-14: 0) compound previously identified in the raw material.

[0166] Alkylation reaction. 2nd Synthesis Stage [0167] Analysis by mass spectrometry of the current eluting from the liquid chromatograph produced the CIT from which the molecular ions recorded during the time period in which the variation in the baseline was observed was performed. that is, from the fifth to the twentieth minute. Figure 12 shows the ion mass spectrum eluting between the fifth and twentieth minute. It can be observed that the main components have a charge to mass ratio ranging between m / z 480 and 620, with the most intense molecular ions, m / z 510.6 and 592.6.

Figure 13 presents, in general aspect, the peak-related mass spectra eluted at retention times between 5 and 11 minutes, which show lipophilicity of the same order as the GPC standards used. Figure 14 also presents, in general aspect, the mass spectra related to the peaks with lipophilicity superior to the standard GPC, being possible to observe after 15 minutes, it is believed due to the high concentration of the injected sample in the HPLC, molecular ions with relation to mass charge. corresponding to those normally related to diacylglycerol and triacylglycerol glycerolipids, in this case, originating from the raw material used.

From the main molecular ions observed, the following most intense ions obtained in the ninth minute range were chosen and analyzed (Figure 15): m / z 510.6 and 592.6, considered the main components of the product obtained by the reaction of alkylation.

[0170] To perform the fragmentation, a sample from the 2nd stage of synthesis was treated with formic acid and introduced by direct infusion into the mass spectrometer, obtaining the positive spectra of the product ions EM2 and EM3 (Figures 16a and 17a). ) for the molecular ions m / z 510.6 and 592.6. The main product ions obtained by EM2 and EM3, the proposed molecular ions m / z 510.6 and 592.6 and their respective fragmentation pathways are presented in figures 16b and 17b.

Example II - Biocidal and / or Antifouling Activity Evaluation [0171] In the field tests, metal plates coated with different paint schemes (specimens) prepared by International Tintas - Akzo Nobel were kept submerged in the Bay of Guanabara - RJ, being taken at different time intervals, varying from days to months, and then evaluated in relation to the different species of adhered marine macroorganisms and their coverage percentages.

[0172] Field tests with copper-free inks [0173] Field tests using the product of the 2nd stage of the synthesis were performed by the company International Tintas - Akzo Nobel, using a comparative procedure between four different antifouling coatings and one control, with two replicates each, applied to carbon steel plates (specimens) measuring (15cm x 30cm). The specimens were kept submerged directly in the bay of Guanabara-RJ, using floating rafts, being evaluated for the presence of slime and barnacles, after a period of three weeks and, afterwards, after eight weeks. immersion.

[0174] All specimens were prepared by International Paints - Akzo Nobel, employing a copper-free base paint and biocidal additives (boosters) from its commercial line, and the following coatings were prepared;

Coating A - Micron premium7 (copper-free) commercial antifouling paint having the product of the 2nd synthesis (5% w / w) plus the commercial line Econea8 biocide (2% w / w) as supporting biocides;

Coating B - Micron Premium commercial antifouling paint having only the 2nd synthesis product (5% w / w) as an adjuvant biocide;

Coating C - Micron Premium commercial antifouling paint having only Econea biocide (2% w / w) as supporting biocide;

Coating D - Micron Premium commercial antifouling paint having the 2nd synthesis product (10% w / w) plus the commercial line Econea biocide (2% w / w) as supporting biocides; and Control without antifouling - Intertuf Vinyl Marine Anticorrosive Paint.

[0175] Product of the 2nd synthesis. Using Copper-Free Base Paint [0176] In all treatments used except those without biocidal product (control), a very good tolerance to slime development and barnacle fixation was observed. Figures 18 to 22 show the conditions observed after a continuous 3-week immersion in the International Paints test field located at Guanabara Bay. In the control panel without biocide, painted only with anticorrosive primer paint, a massive presence of slime and barnacles was observed (Figure 18), showing the extreme condition of the Guanabara Bay marine environment in relation to marine fouling.

[0177] In panels painted with coating A (Micron Premium base paint + 5% biocide 2nd synthesis + 2% commercial biocide ECONEA) there was only a small slime formation and the total absence of barnacles until the 3rd week. There was an intensification of the presence of slime in the eighth week, but still with very good action against the settlement of barnacles (Figure 19).

In panels painted with coating B (Micron Premium base paint + 5% biocide 2nd synthesis), there was also a total absence of barnacles up to the 3rd week and a slight presence of barnacles in the eighth week (Figure 20).

[0179] In the C-coated panels (Micron Premium base paint + 2% commercial biocide ECONEA), there was also only a small slime formation and the absence of barnacles until the third week of immersion, but after the eighth One week there was slime, very little barnacles and unconsolidated material (Figure 21).

[0180] D-coated panels (Micron Premium base paint + 10% biocide 2nd synthesis + 2% commercial biocide ECONEA) showed little slime formation and no barnacles until the third week and very little formation. slime and barnacles after the eighth week (Figure 22).

[0181] It is therefore concluded that: [0182] 1 °) Although the antifouling performance of the methanolysis reaction product (1st synthesis) did not achieve that of the conventional commercial coating containing copper and biocidal additives, a Significant reduction of the succession process and growth of biofouling in relation to the control, indicating that its use replacing the conventional biocidal additives of copper-based paints is very promising, mainly due to the possibility of reducing manufacturing costs, as it is a compound. Producable from low cost raw material and additionally by the possibility of reducing the load of metals in the paint; and [0183] 2 °) The product of the 2nd synthesis proves to be much more efficient as an adjuvant biocide in antifouling paints, and it is important to highlight its antifouling activity against the growth of diatom species, a group representing the main microorganisms. biofilm builders, which cannot be satisfactorily contained by the use of commercially available antifouling products. It is understood here that their use may indeed be relevant when considering a possible replacement of organochlorine biocidal additives (eg ECONEA) today used in marine antifouling paints, mainly for use in new copper-free paints.

Examples of major compounds with antifouling activity obtained in 2a. synthesis (alkylation disclosed in the present patent application) are given below, being compounds (IV) and (V), wherein compound (IV) is a glycerophospholipid with a molecular weight of 592.5 (MW = 592.5). and O-alkyl group containing 16 carbon atoms; and compound (V) is a glycerophospholipid having a molecular weight of 510.4 (MW = 510.4), with the O-alkyl group containing 16 carbon atoms.

Those skilled in the art will enhance the knowledge presented herein and may reproduce the invention in the embodiments disclosed and in other embodiments within the scope of the appended claims.

Compound Claims, Compound Synthesis Process, Composition, Composition Production Process, Antifouling Composition, Antifouling Composition Production Process, Biocidal Composition, Biocidal Composition Production Process, Antifouling Method, Biocidal Method and Use of Compound

Claims (14)

A compound according to formula (1) wherein R 1 is an alkyl group containing from 1 to 30 carbon atoms, comprising from 0 to 5 unsaturation; R2 is H or alkyl group containing from 1 to 30 carbon atoms, comprising from 0 to 5 unsaturation; R3 is OH or O '; and R4 is {N + (CH3) 3} or {N + H (CH3) 2}. Synthesis process of the compound as defined in claim 1, characterized in that it comprises alkylation of the compound of formula (VI) and wherein: R1 is a hydroxyl group or an O-acyl group containing from 1 to 30 carbon atoms, comprising from 0 to 5 unsaturation; R2 is a hydroxyl group or an O-acyl group containing from 1 to 30 carbon atoms, comprising from 0 to 5 unsaturation; R3 is OH or O '; and R4 is [N + (CH3) 3] or [N + H (CH3) 2]; and wherein the alkylation comprises the steps of; a) contacting the compound of formula (VI) with organic solvent, alkyl halide, and hydroxide in the presence of surfactant; b) removal of organic solvent; c) addition of alcohol and hydroxide; d) extraction with organic solvent; Composition characterized in that it comprises the compound as defined in claim 1. Composition according to Claim 3, characterized in that the compound is in a concentration ranging from 1% w / w to 90% w / w. Composition process as defined in claim 3 or 4, characterized in that it comprises the step of adding the compound to an acceptable carrier. Antifouling composition comprising compound as defined in claim 1. Composition according to Claim 6, characterized in that it further comprises another antifouling active agent selected from the group comprising antifungals, algicides, pesticides and combinations thereof. Process for producing an antifouling composition as defined in claim 6 or 7, characterized in that it comprises the step of adding the compound to an acceptable carrier. A biocidal composition comprising the compound as defined in claim 1. Composition according to Claim 8, characterized in that it further comprises another biocidal active agent selected from the group consisting of: antifungals, algicides, pesticides and combinations thereof. Process for producing a biocidal composition as defined in claim 12 or 13, comprising the step of adding the compound as defined in claims 1 to 4 to an acceptable carrier. Antifouling method comprising contacting a compound as defined in claim 1 having a surface suitable for water submersion or flotation. A biocidal method comprising contacting a compound as defined in claim 1 with aquatic microorganisms and / or macroorganisms. Use of the compound as defined in claim 1, characterized in that it is for the prevention of biofouling.