WO2016093719A1 - Procédé de fonctionnalisation pour l'immobilisation de biocides dans des matrices polymères - Google Patents

Procédé de fonctionnalisation pour l'immobilisation de biocides dans des matrices polymères Download PDF

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WO2016093719A1
WO2016093719A1 PCT/PT2015/000050 PT2015000050W WO2016093719A1 WO 2016093719 A1 WO2016093719 A1 WO 2016093719A1 PT 2015000050 W PT2015000050 W PT 2015000050W WO 2016093719 A1 WO2016093719 A1 WO 2016093719A1
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biocide
reaction
biocides
functionalization
solvent
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PCT/PT2015/000050
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Elisabete RIBEIRO SILVA GERALDES
João Carlos MOURA BORDADO
Olga Regina VIEIRA FERREIRA
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Instituto Superior Técnico
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic

Definitions

  • the current invention refers to a process for the immobilization of bioactive or antifouling agents (biocides) in polymeric matrices, through the functionalization of biocides with isocyanate reactive function.
  • this process is able to provide antifouling polymeric systems for the biofouling control, avoiding the releasing of toxic agents (leaching) into the environment.
  • it can cover a broad range of applications in aqueous medium, since it is guaranteed the compatibility between the polymeric systems and the isocyanate functionality of the biocides or bioactive modified agents, as well as, assured that the original structure of the biocides remains intact after its functionalization.
  • Water is the survival key of all living organisms. It is a crucial resource for the growth and sustainability of the civilization, both at a commercial level, and for its own survival. But ironically, what should be a benefit also becomes a major cause of problems.
  • a spontaneous colonization by aquatic organisms occurs on surfaces in contact with water (marine or freshwater environment) or on submerged surfaces. This natural phenomenon, known as biofouling, is a major problem in the management of water systems in various industrial activities ⁇ industrial biofouling) .
  • macrofouling that includes the attachment/growth of organisms such as: mollusks (soft macrofouling), seaweeds, corals, sponges and marine crustaceans such as mussels (hard fouling) .
  • the roughness increase provided by heavily attached biofouling, mainly hard fouling can lead to drag friction increases up to 40% (3), and subsequently generating powering penalties as high as 86% at cruising speed (4) .
  • These data show that more energy is required to maintain the same speed of vessels movement, thus promoting higher power consumption (fuel) .
  • Studies on the roughness effect had showed that an average increase of 10 ⁇ m in hulls 'roughness can lead to a fuel consumption increase between 0.3 - 1.0% (5).
  • biofouling In other industrial activities, the impact of biofouling is also quite significant. For instance, its accumulation in treatment circuits, purification and/or distribution of water, which leads in a short term, to the clogging of pipes and/or other units inherent to the process (membranes, heat exchangers, cooling columns, etc.). This accumulation/obstruction increases the circuits loading, and if not removed will substantially reduce the efficiency of the systems, as well as promote the further contamination of the aqueous fluid through the entraining of microorganisms (bacteria, fungi, etc.).
  • biofouling attach is also associated to the deterioration of the contaminated substrates, as a result of blocorrosion effect.
  • biofouling can be responsible for efficiency losses of about 5%, and substrates deterioration by corrosion of about 20% (1).
  • Non-biocidal coatings a) Non-stick polymeric coatings (e.g.: foul-releasing coatings - FRCs), whose technology was developed and used particularly for the shipping industry through antifouling protective coatings. To date, and as an environmentally friendly technology, this alternative is considered the most promising one. In this classification the most effective coatings are composed by silicone based polymers or fluoropolymers, mainly due to their intrinsic smoothness properties, providing coatings with a low surface energy which lead to minimal adhesive smooth surfaces (non-stick properties) .
  • non-stick polymeric coatings e.g.: foul-releasing coatings - FRCs
  • Dimethylpoiysiloxane (FDMSe) based coatings have been the most explored (10 ⁇ , due to their nonpolar properties and low surface energy (Nm ⁇ 22 m -1 ) .
  • this class of non-stick coatings revealed some disadvantages which limit their further application. They are usually more expensive and mechanically fragile, reducing its lifecycle and/or requiring a frequent maintenance, thus becoming an expensive alternative.
  • their hydrophobic properties make them vulnerable to microfouling, i.e., the adhesion of microorganisms which form the biofilm (e.g.: diatoms), limiting their further application in non-stationary conditions (e.g.: limited to be applied on fast moving vessels, up to 15 knots) .
  • Siocidal coatings are those that act by the action of biocidai agents incorporated in the coating formulations.
  • Two main routes of action, resulting from two distinct strategies, for the inclusion of those agents in the formulations can be considered: a) Bioactivity by leaching or a controlled release of the bioactive agent. In this strategy all the processes able to include harmless bioactive agents to aquatic biota in the formulation of the coatings, allowing its further leaching in a controlled way are included.
  • biodegradable biocides and/or biocides exhibiting a lower ecotoxicity in insoluble or soluble polymeric coatings matrices are applied following this strategy (ablative systems, Controlled Depletion Polymer Coatings - CDPs) and Self- Polishing Coatings - SPC) .
  • ablation systems Controlled Depletion Polymer Coatings - CDPs
  • Self- Polishing Coatings - SPC Self- Polishing Coatings
  • the ablative antifouling paint provided by International Interlux, using the BIOLOX technology, operates through a combined action of a biodegradable recent approved biocide, ECGNEA (PESTANAL) with copper oxides.
  • ECGNEA biodegradable recent approved biocide
  • the replacement of synthetic biocides by natural based antifouling agents has gained prominence.
  • natural antifoulants - NPA's natural antifoulants - NPA's
  • the extracted agents from marine natural sources the most promising have been the furanones (21) and Capsaicin (the active component of pepper) from land-based sources (22).
  • Enzymatic antifoulants have also been an emergent alternative, included in this strategy based on natural sources (21, 22).
  • natural based antifouling agents its implementation at an industrial scale is still in an embrionary stage.
  • Essentially technical limitations need to be overcome, in order to become it an industrial sustainable alternative.
  • the costs associated with synthesis and/or extraction processes of organic compounds are generally complex and expensive.
  • the immobilization in a polymeric matrix is still in a development phase, i.e., at a lab scale.
  • the chemical immobilization i.e., the fixation through chemical bonds of antifouling agents in a polymeric matrix
  • PEG polyethylene glycol
  • the claimed process of the present invention is specifically intended to introduce a new process for the immobilization of ancifouling agents, through their functionalizacion with isocyanate reactive function, which makes them able to be fixed in several polymeric systems ie.g. polyurethane and silicone based), thus become them versatile to different applications.
  • This innovation also allows the immobilization of different biocides in a same polymer matrix, extending its range of action and ability to be adapted to different conditions and promoters of biofouling, therefore, supporting synergistic actions of the applied biocidal agents.
  • the encapsulation of the biocide is accomplished by the polymerization reaction (interfaciai condensation) between polyisocyanates (organic phase), and an aqueous phase consisted of several ingredients, including among them a polyamine based crosslinker.
  • the biocide is added to the organic phase before mixing it with the aqueous phase.
  • the polymerization reaction occurs the formation of capsules retaining simultaneously the biocide in their core.
  • the obtained capsules are then extracted becoming able to be added as an additive in polymeric systems, by using conventional dispersion methods. Even though this technology involves a prior immobilization of the biocide, its performance relies however in a process of leaching and/or releasing of the biocide when applied.
  • the encapsulation is a technology whose primary application aims to control the rate of releasing of active ingredients contained in the capsules ( permeable), thus does not involve an effective immobilization of biocide and/or biocide with isocyanate reactive function in polymeric matrices, by a chemical bind strategy. Therefore, it not only does not act by contact, as well as does not provide a compound with isocyanate functionality with biocidal properties, which is far from what is claimed in the present invention.
  • the process claimed in the present invention aims to provide especially and relatively to the available technologies:
  • the isocyanate function recognized for its high reactivity, ensures the success of its immobilization in the polymeric system, after purification/extraction of the functionalized biocide.
  • these strands can be applied in antifouling products used for the protection of: ships" hulls, marine structures (aquaculture, platforms, etc.), pipelines in contact with water (freshwater or seawater) , filters, packages / hospital materials, etc.
  • the present invention relates to a functioncnalizatior. process of biocides with isocyanate (NCC) reactive function, conferring them the ability of immobilization by covalent bonds within compatible polymeric matrices.
  • NCC isocyanate
  • the process is composed of four basic stages: i. Biocide dissolution in a pure and proper dehumidified solvent; li.
  • Functionalization reaction between a diisocyanate and the solution containing the biocide composed of compatible functional groups iii.
  • the process allows to obtain functional biocides, with conversions as high as 95 ⁇ 5%, depending on the purity of the raw materials. Its ability of immobilization and compatibility for a diversity of polymeric systems, allows for its application as an additive or component in polymeric based formulations, providing them with antifouling properties by contact, i.e., without the releasing of any toxic agent into the surroundings.
  • the present invention aims to overcome those limitations by providing an innovative process for the functional!zation of biocidai agents and/or compounds, possessing antifouling properties, with diisocyanates. Such process will provide the antifouling agents with isocyanate reactive functionality, the ability to be immobilized through covalent bonds in a wide range of polymeric systems (e.g.
  • the reactive isocyanate functional biocides with ability to be chemically immobilized in polymeric systems, avoid their further leaching or releasing into the environment, ng a non-toxic alternative for the biofouling control.
  • biofouling should be understood as the colonization by aquatic organisms, coming from marine environments, freshwater or other aqueous medium, on totally or partially immersed structural surfaces, or in contact with the aqueous medium.
  • the present invention particularly illustrates examples of marine biofouling ( Figure 1), which can involve the attachment or fouling, depending on the stage of development (29), with species of organisms such as: bacteria (single cell), macroalgae spores (multicellular), molluscs, crustaceans, etc.
  • structural surfaces in aquatic environment should be understood as stationary and non-stationary structures in contact with an aqueous medium, for example: aquaculture nets and cages, ships, pipelines in aqueous circuits, pools, filters, surgical materials, etc.
  • aqueous medium for example: aquaculture nets and cages, ships, pipelines in aqueous circuits, pools, filters, surgical materials, etc.
  • the type of material used in those structures is not a critical aspect of the invention, since those structures acts as a support for the polymeric material with ant1fouling properties, provided by the immobilization of a single or multiple biocides in the polymeric matrix.
  • compatible biocides are those which follow the criteria: possess in their molecular structure at least one reactive or compatible function with the isocyanate group, for example amines, hydroxy1, carboxyl, etc.; act preferably by contact for biofouling inhibition; and are chemically stable. Alternatively, it is also possible to perform a prior biocide modification in order to provide the required compatibility. In addition, and as an inventive process, it is not limited to biocides that can act by contact. Immobilization of biocidai agents that act by other mechanisms can also prove to be feasible, since the bioactive group or biocide bioactive function relies free, i.e., does not constitute the molecular structural function used for the covalent immobilization *
  • biocide or bioactive agent must also be in accordance with the list of substances allowed by the international regulations, including the European Directive which regulates the Biocidai Products (BPR - EU Regulation No. 528/2012, 22 May 2012) .
  • biocide should be understood as any chemical bioactive compound or substance, i.e. able to inhibit and/or kill fouling organisms. This can include a wide range of biocidai agents, which can be classified as bactericides, pesticides, fungicides, and algaecides, among others, used in several industrial areas.
  • the biccides used as example and for the claimed functionaligation process in the present invention are commercial biocides with proved efficacy, such as: 4-Bromo-2- M- chlorophenyl)-5 ⁇ (trifluoromethyl)-lH-pyrrole-3-carbonitriie (CAS 122454-29-9) and 2- (tert-Butylamlno) -4- (cyclopropylamino) -6- (methylthio)-s-triazine (CAS N o : 23159-98-0) .
  • biocide with reactive function shall be understood as any bioactive chemical compound or substance possessing a reactive functional group, compatible with the isocyanate function * It can for instance include biocides possessing in their structure amine and/or hydroxy1 functional groups.
  • biocide or “biocide with reactive isocyanate function”, according to the present invention shall be understood as any bioactive chemical compound or substance, possessing at least one isocyanate group in its chemical structure.
  • the functional biocides obtained by the claimed process can be applied in a wide range of applications In aqueous medium, being included in formulations (e.g. paints, varnish) as an ingredient or additive, or a component in the composition of polymeric based material (ropes, nets, or natural based polymeric materials), resulting in environmental friendly products with antifouling properties, potentially competitive and with significant impact on large and technological important market segments, such as: marine paints, protective coatings and/or polymeric materials for submerged structure protection on rivers, ports, water treatment circuits, oceans (offshore culture), offshore platforms and hospital materials and equipment. It can also include other market segments of significant dimension such as packaging.
  • formulations e.g. paints, varnish
  • a component in the composition of polymeric based material ropes, nets, or natural based polymeric materials
  • the compatibility and the high isocyanate function reactivity which characterizes the functionalized biocides, ensures the success of the immobilization by applying conventional dispersion processes and providing formulations/polymer systems optimizations well known among the experts in the field or in the suitable industrial sector.
  • the process claimed in the present invention involves in a first step the dissolution of - the selected biocide with a pure and appropriate dehumidified solvent.
  • the selection of the organic solvent should be carefully performed in order to ensure a high solubility, stability and low moisture in the system (non-hygroscopic) .
  • Monpolar and aprotic solvents which allow achieving mass solute concentrations between 1C ⁇ 5Q %, are preferred.
  • Solvent moisture control can be provided by using Karl Fisher analysis, using for instance aportable Karl Fischer Moisture Meter equipment, Model CA-21 front Mitsubishi.
  • the biocide After the dissolution of the biocide is guaranteed, its functionalization is carried out, through its reaction with a diisocyanate under an inert system (under nitrogen) .
  • the selection of the diisocyanate reactant relies preferably on monomers/isomers with high purity and stable under the reaction of functionalization conditions.
  • the reaction time, the diisocyanate content and the temperature of the reaction should be adjusted depending on the type of biocide, diisocyanate reactant, the stoichiometry of the reaction, and the desired or required degree of functionalization.
  • the reaction should proceed slowly, promoting the slow addition of the biocide solution to the diisocyanate.
  • the reaction product, the functionslized biocide will be obtained by spontaneous precipitation during the reaction. If this does not occur during the reaction, the precipitation can be promoted close to the reaction terminus by a reaction process with an in situ solvent distillation, promoted by a gradually increase of the reaction temperature to the boiling temperature of the solvent. It should be mentioned that the purpose of this distillation step is only to induce the precipitation, and thus, it should be stopped after ensuring the setting of the product precipitation, followed by the further extension of the reaction until complete precipitation. This process is only feasible if the solvent boiling temperature does not promote side reactions and/or modifications of the involved reactants.
  • the obtained biocide with reactive isocyanate function can be applied in its solid state in compatible polymeric formulations. Alternatively, it can be used as dispersion or as a concentrated solution, prepared by using compatible solvents. It is preferable its application as a solution in order to ensure an effective dispersion in any polymeric system, as well as, to promote a long-term stability if longer storage is required.
  • the isocyanate reactive function also offers versatile biccides, that are able to be immobilized as a mixture of biocides, i.e., it allows a joint immobilisation of different biocides in a same polymeric matrix. This ability favors the widening of its range of action and suitability for different conditions, through the achievement of potential synergistic effects.
  • the present invention relates to a biocide functionalization process with reactive isocyanate function, providing on those biocides the ability of immobilization by covending bonds in matrices and/or in compatible polymeric based formulations, such as silicones and polyurethanes.
  • These functionalized biocides provide biocidai properties into the materials where they are immobilized.
  • the process is characterized by the following steps:
  • reaction product mainly functionslized biocide. This step can occur spontaneously during the reaction, or after cooling, or can also be induced at the end of the reaction by in situ solvent distillation; (d) Decantation and drying of the precipitate by solvent evaporation under reduced pressure;
  • step (e) Purification of the precipitate by washing with a suitable solvent, followed by a new drying process, step (d>;
  • non-hygroscopic solvents nonpolar and aprotic whose solubility of the biocide allows obtaining concentrations between 10-50% and preferably between 15-30% are preferably used * Solvents with these properties are, for example, butyl acetate, ethyl acetate, hezane, methyl ⁇ pyrrolidone or cyclohexanone, among others.
  • step (b) The reaction of functionalization (step (b) ) is carried out with a temperature between 40 and 90 °C, and a stirring speed between 350 and 500 rpm.
  • step (b) the reaction occurs with molar ratios of the isocyanate function from the diisocyanate and the compatible functional group from the biocide, between 1:0.5 and 1:1, and preferably between 1:0.8 and 1:1.
  • the reaction of functionalization proceeds for periods of time between 7 to 11 hours.
  • the reaction temperature should be gradually increased in the last hour of the reaction at a heating rate between 1 to 3 °C/min.
  • the maximum reaction temperature Is preferably comprised between 80-90 °C.
  • the amount of distilled solvent should not exceed 1/2 of the volume of solvent used in the reaction.
  • step (d) the time and pressure of the evaporation process should be adjusted in accordance with the type and amount of the used solvent.
  • the claimed functionalization process allows obtaining conversions as high as 95 ⁇ 5%, depending on the purity of the used raw materials. Description of the figures
  • Figure 1 illustrates the marine biofouling on specimens coated with antifouling polyurethane based paints, after 1 month of immersion in Portuguese seawater (Peniche), containing mass contents of the inufccbilized biocides (EM-NCO wt.%/IM-NCO wt.%) of: 5/5 (specimen X); 2.4/2.4 (specimen 2); 3.3/6.7 (specimen 3); 6.7/3.4 (specimen A); 7,6/2.5 (specimen S); 3.5/2.4 (specimen 6); 5,9/3 * 9 (specimen 7); 4,2/6.3 (specimen 8); 2 wt.% Zinc pyrithione in the specimen 9; and a specimen coated with a commercial antifouling paint (Olympic ⁇ ) .
  • EM-NCO wt.%/IM-NCO wt.% mass contents of the inufccbilized biocides
  • FIG 2 illustrates the marine biofouling on specimens coated with antifouling polyurethane based paints, after 3.5 months of immersion in Portuguese seawater (Peniche), containing ratios of immobilized biocides (EM-NCC/NCO-IM) of 0 (reference sample); C.5 (sample 3); and 1.5 (sample 7).
  • EM and IM correspond to the same biocides mentioned in Figure .1.
  • Figure 3 shows in detail the not physical attached biofilm on the surface of antifouling paints containing immobilized biocides with ratios (EM-NCO/NCO-IM) of I (specimen 1) after 3.5 months of immersion in Portuguese seawater (Peniche) .
  • EM and IM correspond to the same biocides mentioned in Figure .1.
  • Figure 4 illustrates the marine biofouling on specimens- coated with antifouling silicone based paints, after 2.5 months of immersion in Portuguese seawater (Peniche), containing immobilized biocides with total contents of: 2.57% EM-NCO in specimen 2; 2.53% of the mixture EM-NCO + IM-NCO in the specimen 6, with contents of each biocide of 1 . 02% and 1 , 51%, respectively; and 0% In the control, this is, coated specimen without any biocide.
  • EM and IM correspond to the same biocides mentioned in Figure 1.
  • This first example intends to illustrate the functionalization of the biocide (4-bromo-2-(4-chlorophenyl> -5- (trifluoromethyi) - 1H-pyrroie-3-carbonitrile (CAS: 122454-29-9)), named in this invention by EM, and which possess a reactive amine function (NK), compatible with the isocyanate (NCO) function.
  • EM reactive amine function
  • NCO isocyanate
  • a first step the dissolution of the biocide in the previously dried ethyl acetate (99.5%, Sigma-Aidrich) is carried out, in order to obtain a solute content of 20% .
  • the solution is then placed in a separatory funnel.
  • a pure methylene diphenyl diisocyanate (MDI) was used pure, in particular the 4 , 4-MDI isomer.
  • MDI methylene diphenyl diisocyanate
  • This diisocyanate is characterized by a molecular weight of 250.25 g/mol, a density of 1.230 g/cm ⁇ and an isocyanate content (NCO) of 33. 4 ⁇ 0. 1% .
  • the flask is then heated and kept at a temperature of 45°C.
  • the system is assembled, by attaching a mechanical stirring system, and a separatory funnel containing the biocidal solution, as well as an in situ distillation system.
  • the entire system is then placed under an inert medium (under nitrogen) .
  • the biocidal solution is added dropwise into the diisocyanate for 9 hours, under a continuous stirring rate of 385 rpm.
  • the step of the solvent distillation begins in order to induce the precipitation of the functionalized biocide. This step is accomplished by a gradual increase of the reaction temperature at a rate of 1 °C/min until reaching a temperature of 83 C C, and guaranteeing that the distilled solvent does not exceed 1/2 of the total volume of the used solvent. Subsequently, the heating is ceased and the reaction mixture is left to cool till room temperature, maintaining the stirring, after which the functionalized biocide is collected by filtration, under inert medium.
  • the obtained precipitate is then subjected to a drying process by solvent evaporation in a rotary evaporator at 55°C, and providing a gradual pressure reduction ranging from 193 mbar to 0 mbar. After the first drying, a washing step is followed with the suitable solvent and a further drying of the washed precipitate by evaporation under reduced pressure.
  • the isocyanate (NCO) mass content of the obtained functionalized biocide was 10 s 1%.
  • the EM-NCO was further analyzed in order to prove its functionalization with the reactive NCO function, as well as, to identify its location in the biocide molecule structure. Two techniques were used:
  • Table 1 shows the main characteristic bands of EM biocide structure, as well as its functionalized counterpart, EM-NCO. It is possible, from the data provided in Table 1, to observe multiple bands at higher frequencies (> 3000 cm -1 ), characteristic of amines stretch (N-H) , and at lower frequencies, the characteristic bands of aromatic amines, ranging from 1110 and 1180 cm -1 , this is, attributed to the C-N bonds stretching. These bands attributed to stretching of the amine attached to the benzene ring of the EM structure, disappears when the biocide functionalization occurs with the reactive NCO function, resulting in the appearance of a new band (maximum at 2254 cm -1 ) , characteristic of the NCO stretch group. This bands replacement suggests that the bind between the NCO groups, from the diisocyanate, with the reactive amine CNH) function from EM, occurred. This functionalization is in fact confirmed through the HMR spectra analysis of the EM and its functionaliied counterpart.
  • the reaction was analyzed in the early stages and after 24 hours by using the Spectroscopy Fourier Transform Infrared (FTIR-ATR) in a frequency ranging from 500 and 4000 cm-*.
  • FTIR-ATR Spectroscopy Fourier Transform Infrared
  • Example 3 illustrates specimens coated with antifouling paints, including * functionalized biocides accordingly with the claimed process, after being tested in a real environment.
  • biocides were tested in different media obtained from three species of microorganisms: Escherichia coll (E. coli), coagulase-positive Staphylococci and Pseudomonas aeruginosa, in accordance with the HPAw18, ISO .9308- 1, NP 4343: 1998 and XSO 6266, respectively.
  • This second example intends to illustrate the functionalization of the commercial biocide 2- (tert-Butyiamino) -4- (cyclopropylamino) -6- (methylthio) -s-triazine (CAS No, 28X59-93- 0), named as IM in the present invention.
  • This biocide is a diamine, thus possessing reactive amine function (NH) , which is compatible with isocyanate function (NCO) .
  • a first step the previously dried biocide dissolution in butyl acetate (99.5%, Sigma-Aldrich5 is carried out, in order to obtain a solute concentration of 15 wt.%.
  • the solution is then placed in a separatory funnel.
  • the diisocyanate In a 3-necked flask the diisocyanate is placed.
  • the neat methylene diphenyl diisocyanate (MDI) was selected, in particular the 4, 4-MDI isomer.
  • MDI methylene diphenyl diisocyanate
  • This diisocyanate is characterized by a molecular weight of 250.25 g/mol, a density of X.230 g/cm 3 and an isocyanate content (NCO) of 33.4 t 0.1 wt.%.
  • NCO isocyanate content
  • a second step the system is assembled, by attaching a mechanical stirring system, and a separatory funnel containing the blocidal solution. The entire system is then placed under an inert medium (under nitrogen). After stabilization (inert medium and stable temperature), the biocidal solution is added dropwise into the diisocyanate for about 10 hours under a continuous stirring rate of 385 rpm.
  • reaction condition After 10 hours of reaction, and completed the addition of the biocide solution, the reaction condition are maintained for a period of not less than 30 minutes, ensuring the necessary reaction time.
  • the obtained precipitate is then subjected to a drying process by solvent evaporation in a rotary evaporator at 60°C, and providing a gradual pressure reduction ranging front 40 mbar to C mbar. After the first drying it is followed a washing step with solvent and a further drying of the washed precipitate by evaporation under reduced pressure.
  • the isocyanate (NCO) mass content of the obtained functlonaiized biocide was 9 ⁇ 1%. It should be referred that depending on the molar ratio of the reaction between the diisocyanate and the biocide IM, it can be promoted or not, the full replacement of the two amine groups present in the IM structure. Under the described conditions/ a mixture of IM-NCO monofunctional and bifunctionai relatively the NCO functionality obtained.
  • Microbiological analyses were also performed in three different mediums obtained from three species of microorganisms: Escherichia coll (E. coli) , coaguiase-positive Staphylococci and Pseudomonas aeruginosa, in accordance with the HPAwlS, ISO 9308- 1, HB 4343: 1998 and ISO 6266, respectively.
  • Escherichia coll E. coli
  • coaguiase-positive Staphylococci coaguiase-positive Staphylococci
  • Pseudomonas aeruginosa in accordance with the HPAwlS, ISO 9308- 1, HB 4343: 1998 and ISO 6266, respectively.
  • its bioactivity will only be fully confirmed after field trials tests, i.e., in a real environment, as will be illustrated in Example 3.
  • the immobilization of the biocide in the polymeric matrix was performed by firstly dissolving the biocide in a suitable pure and dehumidified solvent, followed by its addition and blending to the base component of the paint.
  • a suitable pure and dehumidified solvent for example the methyl pyrrolidone (purity 99.5%, Acros Organics, CAS No. 872-50-4) was the selected solvent.
  • the biocide content in the solvent is determined as a function of the desired final biocide content in the final mixture (base
  • the selection of the organic solvent must rely on its compatibility with the components of the polymeric matrix, and which allows obtaining high biocide solubility, in order to promote a minimum solvent content in the final polymeric mixture.
  • the mixing mode of the biocidal solution, as well as the paint application on specimens surfaces follow conventional methods of preparation well-known and established in the field, and therefore, are easily performed by technicians or experts in the field. In particular their application can be performed by using a spray or brush
  • 10x10 cm grade steel specimens with a thickness of 6 mm were used.
  • This type of steel is a material commonly used in ships' hulls, which was kindly provided by the Shipyard Estaleiros Nijn de Peniche (ENP), Portugal. Alternatively, it can be used any other marine environment resistant material, such as rigid PVC, acrylic or fiberglass.
  • the coated specimens were tested in a fixed structure of fiber glass, further suspended by steel wires and immersed in Portuguese seawater in the ENP pontoon at Peniche with the following coordinates 39°21'06.6' 'N 9'22' 10.5* 1 W.
  • the test site is characterized as a quiet and far from the ships maneuvers zone, thus offering test conditions in a relative static medium, and with a maximum solar radiation exposure comprised between 12 and 18 hours, in the afternoon.
  • the followed procedures allows to get a qualitative analysis, but also a quantitative behavior of the antifouling in the used coatings formulations on the samples immersed in seawater.
  • the biofouling is monitored and recorded via visual and digital means, followed by their analysis, excluding about 1 cm in each side of the total surface area of the affected specimen.
  • table 5 the formulations prepared and used to coat the specimens can be found, including the contents of the immobilized biocides in its polymeric matrix.
  • the immersion of specimens was carried out to a depth of 3 meters, with an average temperature of 16 ⁇ 1°C, salinity ranging from 35.2 to 36.7 (average density 1027 kg/m 3 ) and an average pH of 3 ⁇ 4.3.
  • formulations prepared did not suffer any optimization after the biocides Immobilization, but they can require adjustments in order to readjust the original physical-mechanical properties of a marine antifouling paint. Usually such optimizations, if needed, can be easily performed by experts in the field.
  • Test specimen 6 in which was included 1.7 wt,% 2inc pyrithione (pesticide not immobilized in the raatrix).
  • Microfouling Includes the first stage of marine biofouling formed by the physical adsorption of organic molecules (e.g. proteins, polysaccharides), a primary and reversible colonization of unicellular microorganisms (e.g. bacteria) and a secondary colonization of multicellular species (e.g. macroalgae spores). This microfouling forms the known biofilm/sliroe. It is also included at this stage of fouling, any type of debris/dust. And without any antifouling protection of the exposed surface, this physical microorganisms attack will occur within days or even hours .
  • organic molecules e.g. proteins, polysaccharides
  • a primary and reversible colonization of unicellular microorganisms e.g. bacteria
  • multicellular species e.g. macroalgae spores
  • MacroFouling At this stage occurs the tertiary colonization, which includes fouling of macroorganisms, such as macroalgae, sponges, crustaceans, molluscs, etc. Without any antifouling protection of the exposed surface, this laacrofouling will occur after a few days, between 1 to 2 weeks.
  • macroorganisms such as macroalgae, sponges, crustaceans, molluscs, etc.
  • API 100 - (0.2 x covered area by the biofilm/sludge + 0.5 x covered area by seaweed/animal with a size less than 5 mm + 15 x covered area by seaweed/animal with a size exceeding 5 mm) .
  • this API index can be classified into four distinct groups, in accordance with the following table (algorithm based on numerical evaluation of biofouling using the standard ASTM D699C-05) : Table 6: Algorithm of API Antifouling Performance Index *
  • This last example is intended to illustrate the immobilization of functionaiized biocides in a silicone based matrix, as well as, to assess the effect of the immobilization of more than one biocide in the polymeric matrix, as a function of the total content of biocides.
  • the immobilization was carried out following a procedure similar to the one described in example 3, with the exception of the used components, in this suitable for the preparation of the silicone based paint (HEMPASIL X3 87500, Hempei A/S) : resin or reference base: 87509 and the reference crosslinker 99950.
  • the immobilization of the biocides in the polymeric matrix was carried out by a prior dissolution of the biocide in a pure and dehumidified suitable solvent, followed by their addition and blending into the base component of the paint.
  • methyl pyrrolidone purity 99.5%, Acros Organics, CAS No. 372- 50-4
  • the prepared formulations were then used to coat specimens of PVC (poiyvinylchloride) with dimensions of 10x10 cm, and a thickness of 6 mm.
  • the coated specimens were tested in a fixed structure of fiber glass, further suspended by steel wires and immersed in Portuguese seawater in the ENP pontoon at Peniche with the following coordinates 39°21'06.6' ' ⁇ 9*22 , 10.5 , ' W.
  • the test site is characterized as a quiet and far front the ships maneuvers zone, thus offering test conditions in a relative static medium, and with a maximum solar radiation exposure comprised between 12 and 18 hours, in the afternoon.
  • These tests were performed in accordance with the ASTM D6990 standard, and periodic inspections were performed in accordance with ASTM D3623- ' ?$a.
  • Biocide ratio - EM-KCG/IM-NCQ Biocide ratio - EM-KCG/IM-NCQ. Specimens were inspected weekly and/or monthly, depending on the evolution of biofouling. At each monthly inspection the test specimens were smoothly washed with water. The analysis of the formed biofouling on the tested specimens was performed considering the density and type of fouling, in accordance with the procedure described in example 3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Paints Or Removers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne un procédé de fonctionalisation pour des composés biocides présentant une fonction isocyanate réactive, afin de leur conférer la capacité d'être davantage immobilisés par l'intermédiaire de liaisons covalentes dans des matrices polymères compatibles. Cette capacité d'immobilisation de biocides permet son application ultérieure en tant qu'additif pour la préparation de matériaux polymères (par exemple : vernis, peintures, etc.), leur conférant des propriétés anti-salissures par un mécanisme de contact, évitant ainsi l'utilisation de procédés classiques, qui entraînent la lixiviation d'agents toxiques pour lutter contre le bio-encrassement. Le procédé revendiqué est par conséquent une alternative écologique pour la prévention du bio-encrassement. Ledit procédé consiste à faire réagir un diisocyanate avec des composés biocides, dont la structure moléculaire comprend des groupes fonctionnels compatibles avec l'isocyanate (par exemple : des amines, un groupe hydroxyle). Les biocides modifiés sont ensuite obtenus par précipitation, suivie par l'extraction par l'intermédiaire de l'évaporation du solvant sous pression réduite. En fonction du type de biocide utilisé et de la pureté, les conditions réactionnelles optimisées permettent d'atteindre des conversions aussi élevées que 95 ± 5 %.
PCT/PT2015/000050 2014-12-12 2015-12-11 Procédé de fonctionnalisation pour l'immobilisation de biocides dans des matrices polymères WO2016093719A1 (fr)

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