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    • 专利摘要:
    The invention relates to the use of an aqueous dispersion of TMF core / shell structured particle polymer from 0 to 50 ° C, with the polymer phase P1 being a hard core with Tg1 of 60 to 120 ° C and the phase polymer P2 being a soft bark of Tg2 from -20 to 40 ° C and with P1, comprising a monomer M1 with two polymerizable ethylenic unsaturations and a monomer M2 ethylenically unsaturated and bearing an acid / carboxylic anhydride function and P2, representing 40 at 85% by weight of P1 + P2 and comprising in its structure units derived from at least one monomer M3 carrying a polymerizable ethylenic unsaturation and in addition to a ureido functional group or a functional group having a mobile hydrogen alpha to a ketone carbonyl, said use being for the capture and irreversible trapping of a volatile organic compound carrying a function among aldehyde, ketone or amine. More particularly, said use relates to the polymer resulting from said dispersion in the form of film or coating.
    公开号:FR3030303A1
    申请号:FR1463089
    申请日:2014-12-22
    公开日:2016-06-24
    发明作者:Alain Boone；Chantal Roidot；Patricia Beurdeley；Frederic Fournier
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the use of an aqueous dispersion of specific polymer, in particular said polymer resulting from this dispersion, which dispersion has core / shell structured polymer particles with respective hard / soft polymer phases for the capture and irreversible trapping of volatile organic compounds such as aldehydes, ketones or amines and in particular of said aldehyde compounds and more particularly of formaldehyde. Said polymer of said dispersion, carrying functional groups reactive with said volatile organic compounds, can be used for this capture, in particular in the indoor air of a living room, in the form of a film or coating derived from said dispersion preferably in the form of varnish or paint, more preferably in the form of interior paint. The objective is to reduce the rate of said volatile compounds by irreversible trapping and more particularly the cleaning of the interior air of buildings, in particular houses or workplaces where said products or volatile organic compounds (VOCs) may be present by various origins.
    [0002] In the field of paints, especially decorative paints, the improvement of air quality is an important issue to consider in the development of new products. Measurements of the level of volatile organic compounds in the air are controlled and are associated with specific labels or regulations depending on the country. Through the coating, a capture action or capture and trapping of volatile organic molecules can reduce the levels of certain volatile organic compounds in the indoor air, such as aldehydes, ketones or amines and in particular the capture of aldehyde compounds and more particularly formalin. The polymer used according to the present invention has the role of binder in the coatings and comprises at least one function irreversibly reacting with the functions of said volatile organic compounds, in particular aldehydes. VVO 2008/073212 describes the use of functionalized polymers with acetoacetate groups for coating a filter to trap aldehydes. The polymers described are polycondensation polymers such as polyesters or polymers in aqueous dispersion obtained by emulsion polymerization but with unstructured polymer particles. EP 2 496 649 describes film-forming compositions in aqueous dispersion or in solution in a solvent, comprising an agent capable of trapping formaldehyde, said agent being selected from active methylene compounds. Said additive is not grafted onto a polymer but is soluble or dispersed in said composition.
    [0003] VVO 2014/191573 discloses a coating binder comprising a polymer carrying a formaldehyde-fixing function by reaction with formaldehyde present in the air. Said polymer can be a polyester, alkyd, polyurethane, polyamide, polyacrylate, polyvinyl alcohol or epoxy resin. It also describes a method of cleaning the air using a coating based on said binder. Example 2 of this document describes the preparation of an acrylic polymer binder in emulsion and functionalized in acetoacetoxy groups, but does not describe the performance in any way. This document does not describe or suggest the use of specific polymer dispersion with structured particles.
    [0004] EP 2 808 038 describes paints or varnishes for purifying the air by fixing the formaldehyde with the main characteristic of the presence of a binder carrying a formaldehyde fixing function by reaction with formaldehyde in air. However, there is no more detailed specification of said binder, except that it may be an alkyd or an acrylic polymer. The described paint compositions are insufficient in terms of the nature, composition and structure of said binder used in the examples (no name and no characteristic given). VVO 2012/078886 discloses a method for reducing the level of aldehyde on a substrate or near a substrate by applying to said substrate an aldehyde reduction composition comprising aminated functionalized compounds of different types (primary, secondary, tertiary or amine complex). According to variants of this method, the composition may further comprise a film-forming polymer or another compound with an acetoacetyl group or with said film-forming polymer (in addition to said amino compounds) comprises an acetoacetyl group and according to another variant, said polymer may be in dispersion in water. No aqueous dispersion of core / shell structured particle polymer is described or suggested by this document to improve the performance of said binder. However, the closest aqueous dispersions, described in the state of the art for this use, are unstructured and need improvement in their performance, first in terms of the capture efficiency of said compounds to be captured and especially aldehydes such as formalin. Even more particularly, the clean performance of the coating must be sufficient and good, in particular in terms of homogeneous and reproducible filming and in terms of no blocking after filming, no defect filming, or stickiness on the film obtained. The present invention demonstrates in particular the importance and the interest of the specific morphology of the polymer particle and of the concentration of the functions allowing the capture of formaldehyde by irreversible reaction, in the continuous phase resulting from the film obtained from particles of structured polymer core / bark with respective phases P1 / P2 hard / soft. The function allowing the reaction with the functions of the volatile organic compounds to be recovered irreversibly by reaction, in particular aldehydes, is provided by a functional monomer bearing a functional group from a ureido group or a group having an alpha-mobile hydrogen. a carbonyl ketone also called "active methylene" such as a diacetone group or an acetoacetoxy group and must be present exclusively in the soft phase P2 which must also be the continuous phase during the formation of the film drying with a% by weight of at least 40% and up to 85% and preferably this soft phase P2 being predominant by weight relative to the hard phase Pi, that is to say with the polymer phase P2 representing more than 50% and up to 85% of the total weight P1 + P2. The functions of said polymer allowing the reaction with the functions of said volatile organic compounds, in particular the aldehyde functions, are thus more concentrated and more accessible in the soft phase of bark P2, since it can be much softer (according to Tg Fox) than it is not acceptable in an unstructured particle (unstructured in heart / bark) otherwise it becomes very sticky. Thus, the capture of the organic volatile compound in question and in particular aldehydes and more particularly formalin will be significantly improved and more important, as demonstrated by the present invention in the experimental part, in comparison with the use a polymer dispersion representative of the state of the art cited above (unstructured dispersion). The object of the present invention is the use of an aqueous dispersion of polymer, in particular the polymer resulting from said dispersion, for the capture and irreversible trapping of at least one volatile organic compound carrying a function among aldehyde ketone or amine, preferably volatile organic compound carrying an aldehyde function, with said dispersion having a minimum TMF filming temperature of 0 to 50 ° C, preferably 0 to 40 ° C measured according to ISO 2115 and comprising polymer particles structured in the core / bark P1 / P2 hard / soft, with: P1 being the core hard polymer phase of said particle, with a glass transition temperature Tgl ranging from 60 to 120 ° C, preferably 60 at 100 ° C and said phase P1 comprising in its structure units derived from at least one monomer M1 having at least two ethylenic unsaturations copolymerizable and having a crosslinking agent function and units originating from at least one ethylenically unsaturated monomer M2 bearing at least one carboxylic acid and / or carboxylic acid function, P2 being the soft polymer phase in bark having a glass transition temperature Tg2 ranging from -20 to 40 ° C preferably from -20 to 30 ° C, more preferably from -20 to 20 ° C, with P2 representing from 40 to 85% and preferably more than 50% and up to 85% by weight of the total weight of P1 + P2 and comprising in its structure units derived from at least one monomer M3 carrying a polymerizable ethylenic unsaturation and in addition to a functional group ureido or a functional group having a mobile hydrogen alpha to a ketone carbonyl . The Tg values of the polymers P1 (Tg1) and P2 (Tg2) are calculated according to the law (or relationship) of Fox, according to the following precise relation (1): 1 / Tg = E, x, / Tg,. (1) with Tg being the value to be calculated of the glass transition temperature of the polymer in question, in ° K x, fraction by weight in said polymer of monomer component i with E, x, = 1 Tg, glass transition temperature in ° K of the homopolymer of said monomer i. Said volatile organic compounds according to the present invention have a boiling point (or boiling point) at atmospheric pressure of less than 250 ° C and preferably less than 100 ° C. Said functional group of said monomer M3 is preferably selected from ureido, acetoacetoxy or diacetone groups. More particularly, said monomer M3 is selected from diacetone acrylamide (DAAM), acetoacetoxyethyl (meth) acrylate (AAEM), acetoacetoxy propyl (meth) acrylate (AAPM) or N- (2- (meth) acryloyloxyethyl) )) ethylene urea (or ureido ethyl (meth) acrylate: UMA), in particular acetoacetoxyethyl (meth) acrylate (AAEM) and diacetone acrylamide (DAAM) and more particularly acetoacetoxyethyl (meth) acrylate (AAEM) . According to another preferred option, the level of said monomer M3 carrying said functional group, preferably diacetone, acetoacetoxy or ureido, more preferably acetoacetoxy or diacetone and even more preferably acetoacetoxy, ranges from 50 to 1000 and preferably from 100 to 700 mmol per kg. said polymer (P1 + P2). Said monomer M3 is present in said P2 phase at a level by weight of 1 to 25%, preferably of 2.5 to 25% and more preferably of 5 to 15% relative to the total weight of P1 + P2.
    [0005] According to a particularly preferred option, said P2 phase further comprises at least one transfer agent selected from hydrophilic mercaptans, in particular carrying an ionic group. As an example of such an agent, mention may be made of mercaptopropionic acid.
    [0006] Even more particularly, said P2 phase comprises at least one second transfer agent selected from hydrophobic mercaptans with a weight ratio of hydrophilic agent to hydrophobic agent greater than 1 and preferably greater than 1.5. The overall level of said first and second transfer agents may represent, by weight, from 0.02 to 2% and preferably from 0.05 to 1.5% relative to the total weight of the P1 + P2 phases. An example of a hydrophobic transfer agent is n-dodecyl mercatptan. Regarding the glass transition temperatures Tgl and Tg2, they are calculated according to the Fox relationship. In particular, the difference between said Tg1 and Tg2 ranges from 20 to 140 ° C and preferably from 30 to 115 ° C.
    [0007] Said monomers M1 and M2 of the P1 phase may represent an overall weight ratio ranging from 0.5 to 10% and preferably from 1 to 8% of the total weight of the P1 phase with said monomer M2 representing from 0.1 to 5 % and preferably from 0.2 to 4% by weight of said phase Pi. More particularly, said polymer phase P1 consists of a seed polymer PO and a complementary polymer P1, which is complementary to PO to give Pi , with the composition of said PO phase being free of said monomers M1 and M2 and the remainder of the monomer composition (except M1 and M2), the compositions of PO and P1 may be identical or different. The overall composition of the P1 phase corresponds to the average composition between PO and P'l.
    [0008] The monomer M1 of the P1 phase can be chosen from the monomers: monofunctional or multifunctional allylic esters derived from dc, f3-unsaturated carboxylic or dicarboxylic acids such as allyl (meth) acrylate, monoallyl or diallyl maleate, tetrahydrophthalate monoallyl or diallyl or multifunctional allylic esters of saturated di- or polycarboxylic acids such as diallyl phthalate, triallyl trimesitate or other polyallylated monomers, such as triallyl cyanurate functional multifunctional (meth) acrylic esters of at least 2, such as polyalkylene glycol di (meth) acrylates, such as ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, alkylene di (meth) acrylates diols or polyols, preferably with alkylene ranging from C2 to C8, such as 1,6-hexanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, di (meth) acrylate 1,4-butanediol ate, neopentyl glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, and polyvinylbenzenes, such as divinylbenzene or trivinylbenzene, divinyltoluenes, divinylnaphthalenes. Preferred monomers according to M1 are allyl (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate. The monomer M2 of the P1 phase may be chosen from fumaric, maleic, itaconic, vinylbenzoic, crotonic or isocrotonic (meth) acrylic acids and / or their anhydrides and preferably methacrylic acid (AMA) and / or the acid acrylic (AA). AA and AMA are the most preferred. According to one particular variant, the phase P2 can also comprise at least one monomer M2 as defined above for the phase Pi, with respective levels by weight of M2 in the phases P1 and P2 chosen so that the ratio of the M2 weight in P1 on the M2 ratio in P2 ranges from 1/1 to 1/10 and preferably from 1/2 to 1/8. Said phase P2 can comprise, in addition, at least one monomer M4 bearing, in addition to the polymerizable ethylenic unsaturation, at least one functional group selected from: hydroxy, amine, oxirane, phosphates, phosphonates or phosphinates, amide, sulfate or sulfonate, imide, aziridine, oxazoline or imidazole, provided that the choice of M4 monomers is made so as to avoid a reaction between the different M4 monomer groups or between the M4 monomer groups and the groups of the other monomers. As suitable examples of M4 monomers, the following may be given: - hydroxy, as borne by hydroxyalkyl (meth) acrylates with C2 to C4 alkyl (such as HEMA, HPMA), - amine, as carried by aminoalkyl ( meth) acrylates or aminoalkyl (meth) acrylamides, for example MADAME (dimethylaminoethyl methacrylate) or MATBAE (t-butylaminoethyl methacrylate), oxirane, as borne by glycidyl (meth) acrylate (such as MAGLY), - phosphates, phosphonates or phosphinates, as carried by the phosphates or phosphonates or phosphinates of hydroxyl alkyl (meth) acrylates and hydroxyalkyl ethoxylated and / or propoxylated (meth) acrylate, amide, such as (meth) ) acrylamide, - sulphate and sulphonate, as carried by hydroxyalkylsulfonate (meth) acrylate (such as hydroxy ethylsulfonate methacrylate) or hydroxyalkyl sulphonate (meth) acrylamide (such as acidic propane sulphonic acrylamide) and their salts or - imide, such as maleimide or aziridine, as carried by 1- (2-hydroxyethyl), aziridine or oxazoline or imidazole methacrylate, as carried by 2-ethyl (2-oxo-imidazolidin-1-yl) methacrylate, under condition that the choice of these monomers M4 is carried out so as to avoid a reaction or interaction between groups during the synthesis which would make it impossible between the different groups of monomers M4 or between the groups of monomers M4 and the groups of the other monomers. As regards the structure of the monomers (or composition of the monomers) of the polymer phases P1 and P2, they may be either based on purely acrylic monomers and therefore on pure acrylic structure ("acrylic" meaning here both acrylic and / or methacrylic) or else, based on a mixed structure which may comprise, in P1 and P2 but preferably in P1 (hard phase), aromatic vinyl monomers, more particularly styrene and / or its derivatives, such as vinyl toluene or vinyl benzene, and preferably styrene and / or vinyl toluene. More particularly, P1 may include such vinyl aromatic monomers. According to another variant, the phase P1 alone is purely acrylic and according to another variant, the only P2 phase is purely acrylic and according to a third variant the two phases P1 and P2 are purely acrylic and therefore, accordingly, the said dispersion is (purely acrylic) ) as well.
    [0009] The most preferred variants of the dispersion of the invention correspond to: a phase P1 comprising aromatic vinyl monomers with a phase P2 being purely acrylic, the dispersion being in this case of the styrene-acrylic type or a purely acrylic dispersion for P1 and P2.
    [0010] Said phase P1 may comprise and, preferably, comprises a seed polymer PO, with PO free of monomers M1 and M2 as defined above, with said PO phase representing by weight of 2 to 25% and preferably from 5 to 20% of the weight of said phase P1. More particularly, the phase P1 is obtained before said phase P2, which phase P2 is obtained by polymerization of the monomers corresponding to this polymer phase, at a temperature less than or equal to and preferably less than Tg1 as defined above. Even more preferably, it is at a temperature (P2 polymerization) of at least 5 degrees lower than Tg1. According to a variant in this use, said dispersion may comprise, in dispersion with the polymer particles, at least one compound comprising at least one hydrazine or hydrazide function. According to a preferred option, said dispersion does not comprise such reactive additives for said use.
    [0011] Preferably, said volatile organic compound to be trapped or trapped has a boiling point at atmospheric pressure of less than 250 ° C., more preferably less than 100 ° C. More particularly, said volatile organic compound to be trapped or trapped is an aldehyde among C1 to 8 aldehydes, which may be saturated or unsaturated and in particular among formaldehyde (or formaldehyde), acetaldehyde, propanal and acrolein. (Acrylaldehyde), butanal, pentanal, hexanal, heptanal or octanal, preferably formaldehyde, acetaldehyde, acrolein, hexanal and more preferably formalin. According to a variant of the present invention, said use relates to the polymer resulting from said dispersion as defined above and said polymer is in the form of a film or in the form of a coating and in particular in the form of varnish or paint, more particularly under form of painting. The use according to the invention of said dispersion in the form of a coating relates more particularly to the protection and / or decoration of substrates, preferably selected from wood, cardboard, metal, plastic, plaster, concrete, fiber cement, glass. More particularly, said use is that of the polymer resulting from said dispersion as described above and said polymer is used in the form of a thin layer or coating applied to a substrate, in particular on a porous or fibrous substrate. A suitable porous substrate may be plaster, wall paper (painted or paintable) or filter paper or cardboard or wood or composite board with fibrous reinforcement. A fibrous substrate may be a fiber fabric or a nonwoven, optionally prepreg of a thermoplastic polymer. These two types of substrates (porous or fibrous) are characterized in particular by the large specific surface area of said substrate.
    [0012] According to another variant of use, said polymer resulting from said dispersion is used in the form of a qualitative or quantitative detection probe of said volatile compound, in particular of said aldehydes and more particularly of formaldehyde. The use according to the present invention applies in particular to decorative coatings.
    [0013] It can also be applied to industrial protective coatings. According to one particular preference, the use of said polymer dispersion or said polymer resulting from said dispersion concerns the capture of said aldehydes, in particular formaldehyde, in the atmosphere in direct contact with the surface of said polymer, more particularly in the form of a layer. fine polymer or coating.
    [0014] According to another alternative option, said use relates to the capture of formaldehyde released by coatings applied as underlayer or first layer with respect to the sensor coating, in particular with said sensor coating, resulting from said polymer dispersion, being used as coating of surface, that is to say in contact with the air. According to another option, said use relates to the capture of formaldehyde released by a substrate with the latter being coated with a sensor coating derived from said polymer dispersion. More particularly, said formalin-releasing substrate may be selected from: agglomerated or sandwiched wood or plywood and bonded with urea-formaldehyde or melamine-formaldehyde glues, treated textile or fibers treated with a formalin generating treatment composition. For example, textile or fiber treatment compositions may comprise methylol groups, in particular N-methylol functional groups, which generate formalin emissions. According to another variant of use according to the present invention, said use relates to the capture of formaldehyde released by a first "generator" substrate, meaning "formalin generator" and in this case is applied in contact with said "generator" substrate, a second "sensor" substrate, meaning "formalin sensor", impregnated or coated with said aqueous polymer dispersion or impregnated or coated with the polymer resulting from said dispersion. According to this variant, said second "sensor" substrate in contact with said first "generator" substrate may be chosen from: nonwovens, organic or mineral fiber fabrics, in particular fiberglass fabrics, for insulation or for renovation of interior walls. According to another variant of use according to the present invention, it relates to the impregnation of air filters or smoke filters by said aqueous dispersion of polymer. As a particular example of a smoke filter, a cigarette filter can be considered.
    [0015] The following examples are given by way of experimental illustration of the present invention and its performance, without limitation of its scope by said examples. EXPERIMENTAL PART 1) Reference of the tests carried out: see Table 1 below Two dispersions were carried out, one according to the invention (test 1) and a comparative outside the invention (test 2). The dispersion according to the invention of test 1 is comparable to that of test 2 outside the invention with the difference that the dispersion according to test 1 has particles of polymers structured in core / bark as indicated in table 1 and that of Run 2 is a current dispersion without structured particles with the composition of both runs adjusted to have the same film temperature with a TMF of 5 ° C. The phase P1 in the case of the test 1 comprises as monomer M1 the HDDA (2.5% by weight vs P1) and as monomer M2 the AMA (1.6% by weight vs P1).
    [0016] The core / shell structure is demonstrated by AFM microscopy on the film obtained by coalescence of the dispersion of test 1, with the image of FIG. 1 showing the hard phase of the heart appearing in the clear and the continuous phase coalesced around said hearts. , corresponding to the bark appearing dark. Finger-stick tests on the films obtained show that the film obtained with the structured particle dispersion of test 1 shows no stickiness and that the film obtained with the dispersion of test 2 has a sticky finger. (after at least 24 hours of drying). Table 1: Characteristics of tests carried out Test reference 1 2 Type of test Invention Out of invention (comparative)% by weight AAEM (monomer 10 * 10 M3 vs overall weight of polymer)% by weight P1 40 -% by weight P2 60 - Total 100 100 Tg1 Fox vs P1 (° C) 70 - Fox Tg2 vs P2 (° C) -10 - Overall Fox Tg2 (° C) 17 ** -6 MFT measured ISO 2115 (° C) 5 5 * 16.6% compared at P2 ** Overall Tg calculated under the unstructured particle hypothesis with miscible P1 and P2 phases Table 2: Raw materials used in the synthesis of the dispersions of tests 1 and 2 Constituent Function Chemical nature Technical Provider Aerosole A102 Surfactant Sulfosuccinate d ethoxylated fatty alcohol, Cytec sodium salt (010-012) 30% solution in water Disponil® FES Surfactant fatty alcohol sulphate polyglycol ether, Cognis 32 sodium salt 31% solution in water Tergitol ® 15S9 Tensio-active Dow Secondary Ethoxylated Fatty Alcohol with 9 0E, 100% Emulan® TO Tensio-active Fat Alcohol oxylated BASF 4070 with 40 0E, 70% HDDA Crosslinking Hexanediol diacrylate (HDDA) Sartomer ABu Monomer Butyl Acrylate Arkema MAM Methyl Methacrylate Monomer Arkema AA Monomer Acrylic Acid Arkema AMA Monomer Methacrylic Acid Arkema AAEM Crosslinking AcetoAcetoxyEthyl Methacrylate Eastman nDDM Mercaptan n-dodecylmercaptan Acros MPP Mercaptan 80% mercaptopropionic acid Acros Na25208 Peroxide Sodium persulfate Aldrich Na25205 Reducer Sodium metabisulfite Prolabo TBHP Peroxide ter-butyl hydroperoxide 70% Aldrich SFS Reductant Sodium formaldehyde sulfoxylate Bruggeman NaOH Neutralization Sodium hydroxide Prolabo Acticide MBS Biocide Aqueous solution of methylisothiazoline Thor (MIT) and benzisothiazolinone (BIT) (2.5% MIT / 2.5% BIT) All calculated Tg values are calculated according to Fox's law, as already indicated in the description.
    [0017] The Tg values of the homopolymers corresponding to the monomers used, for the purposes of calculating Tg according to Fox's law, are given in ° C, in Table 2a) below.
    [0018] Table 2a): Tg of the homopolymers of the monomers used, for the relationship of Fox Monomer Abbreviation Tg (° C) Acrylic acid AA 106 Methacrylic acid AMA 228 Butyl acrylate ABu -54 Acetoacetoxyethyl methacrylate AAEM 18 Methyl methacrylate MAM 105 La TMF (minimum film temperature) is measured according to ISO 2115.
    [0019] The viscosity mentioned is a Brookfield viscosity at 10 rpm according to the ISO 2555 standard. The dry extract of the aqueous dispersion is measured according to the ISO 3251 standard. The particle size is measured by Photon Correlation Spectroscopy (PCS). using Beckman Coulter N4 + equipment. The sample is diluted (3 to 5 drops of emulsion in 50 ml of water) in a polystyrene tank with deionized water on a 0.22 μm cellulose acetate filter. The particle size is measured at a temperature of 25 ° C, a measurement angle of 90 ° and a laser wavelength of 633 nm. The AFM microscopy image is produced on a device: AFM Nanoscope Illa (Veeco Digital Instrument) in film tapping mode obtained after depositing a drop of aqueous dispersion according to test 1, diluted 100 times on a slice of mica and drying of the film. at least 24 hours at room temperature. 2) Test procedure 1 Equipment used A glass reactor of 3 liters in internal capacity, equipped with a double jacket, equipped with an efficient stirring (vortex), a triple flow refrigerant, a control and a a regulation of the material temperature is used. The reactor comprises the number of introductions connections necessary for the separate introduction of the various components, as well as a dedicated introduction to the nitrogen inerting of the assembly (placing in an inert atmosphere of nitrogen). The tightness is checked before each synthesis.
    [0020] The installation is equipped with a system to control the introduction rates of the components. Preparation of the initial charge at the bottom of the tank 14.1 g of Disponil® FES 32 are solubilized in 327 g of demineralised water at the bottom of the tank. The temperature of the bottom of the tank is raised to 85 ° C. Preparation of the PO seed Mix 6.9 g MAM + 6.9 g ABu.
    [0021] Preparation of the Preemulsion 4.2 g of Aerosol® A102, 7.1 g of Disponil® FES 32 are dispersed in 44.1 g of demineralised water with good stirring. The following are added in succession and with good stirring: 130.9 g of MAM 18.5 g of ABu 4.2 g of HDDA 2.8 g of AMA The preemulsion thus formed is white and stable and it will be kept under slight agitation. It will be used for the synthesis of the P1 core of the particle, composed of PO and P'1 (P1 = PO + P'1). Preparation of Preemulsion P2 4.2 g of Aerosol® A102, 9.1 g of Tergitol® 15S9 are dispersed in 74.4 g of water with good stirring. The following are added in succession and with stirring: - 70 g of MAM - 135.7 g of ABu A white and stable pre-emulsion is obtained. 10% of this preemulsion, ie 29.3 g, will be taken and used to seed before P2 casting.
    [0022] Then, are added in the preemulsion, still with good stirring: - 42.4 g of AAEM - 8.5 g of AA - 1.06 g of MPP - 0.08 g of nDDM This preemulsion, P2, white and stable, will serve for the synthesis of the bark (P2) of the particle.
    [0023] Preparation of catalyst solutions 1.48 g of sodium persulfate are solubilized in 28.2 g of water. 0.42 g of sodium metabisulfite are solubilized in 3.8 g of water. 0.6 g of TBHP (70%) are solubilized in 2.65 g of water. 0.34 g of SFS are solubilized in 8.1 g of water. Polymerization Process i) Inoculation PO The stock base with the initial charge being stable at 85 ° C., the mixture specified above of MAM and ABu is introduced for PO seeding. Once the temperature is stabilized, 70% of the sodium persulfate solution is added. The maximum of exotherm marks the end of this step, the particle size is about 30 nm and the conversion is greater than 70%. ii) Synthesis of the P1 core The introduction of the P'1 preemulsion lasts 120 minutes, at a polymerization temperature of 85 ° C. iii) Thermal baking step and cooling The temperature is maintained for 60 minutes at 85 ° C. At the end of the thermal cooking, the reaction medium is cooled to 65 ° C. The conversion is then close to 100%. iv) Synthesis of Bark P2 At 65 ° C., the seeding consisting of 29.3 g of P2 fraction (without functional monomers or transfer agents) is introduced into the reactor. At least 5 min before the beginning of the separate introductions are mixed: - 100% remaining of the second preemulsion P2 - 30% remaining of the initiator solution (sodium persulfate) - 100% of the activator solution (metabisulfite of sodium) During castings lasting 150 minutes, the temperature of the medium is maintained at 65 ° C. This step is followed by a post-cure lasting 30 minutes at 65 ° C. v) Redox Treatment The TBHP and SFS solutions are added at 65 ° C in 30 minutes. This redox treatment is followed by baking at 65 ° C. for 30 minutes before cooling to room temperature. vi) Final additions At 30-35 ° C, the latex is neutralized by adding sodium hydroxide at pH 8 and post-addition of a biocide. It is then filtered on 100 μm canvas. The solids content is 44.5%. The final particle size is about 90 nm; the viscosity is less than 100 mPa.s; the measured TM F is 5 ° C. 3) Test procedure 2 Equipment used A reactor of 3 I (internal capacity) made of glass, equipped with a double jacket, equipped with an efficient stirring (vortex), a triple flow refrigerant, control and regulation of the material temperature is used. The reactor comprises the number of introductions connections necessary for the separate introduction of the various components, as well as a dedicated introduction to the nitrogen inerting of the assembly. The tightness is checked before each synthesis. The installation is equipped with a system to control the introduction rates of the components. Preparation of the initial charge at the bottom of the tank 33 g of Disponil® FES 32 are solubilized in 802 g of demineralised water at the bottom of the tank. The temperature of the bottom of the tank is raised to 85 ° C.
    [0024] Preparation of the PO seed Mix 17.9 g of MAM + 17.9 g of ABu. Preparation of the additional preemulsion P '11 g of Aerosol® A102, 29.3 g of Disponil® FES 32 and 23.6 g of Emulan® TO 4070 are dispersed in 316.7 g of demineralised water with good stirring. The following are added in succession and with good stirring: 356 g of MAM 565 g of ABu 110 g of AAEM 11 g of HDDA 5.5 g of AMA 16.5 g of AA The preemulsion P 'thus formed is white and stable and it will be kept under slight agitation. It will be used for the synthesis of the polymer particle P, composed of PO and P 'as defined for this test 2 (P = PO + P'). Preparation of catalyst solutions 3.9 g of sodium persulfate are solubilized in 73.2 g of water. 1.6 g of TBHP (70%) are solubilized in 6.9 g of water. 0.9 g of SFS are solubilized in 21.1 g of water. Polymerization Process i) Inoculation PO The stock base with the initial charge being stable at 85 ° C., the mixture specified above of MAM and ABu is introduced for PO seeding. Once the temperature is stabilized, 20% of the sodium persulfate solution is added. The maximum of exothermic marks the end of this stage. The particle size is about 40 nm and the conversion is greater than 70%. ii) Synthesis of the polymer particle P (unstructured) The introduction of the preemulsion P 'lasts 240 minutes at a polymerization temperature of 85 ° C. At the same time, 71.1% of the sodium persulfate solution is introduced during the same time. iii) Stage of consumption of the residual monomers, of thermal cooking and cooling After the end of the introduction of the preemulsion P ', the remaining 8.9% of the sodium persulfate solution is poured, still at 85 ° C. . The temperature is maintained for 20 minutes at 85 ° C. At the end of the thermal cooking, the reaction medium is cooled to 65 ° C. The conversion is then close to 100%. iv) Redox Treatment The TBHP and SFS solutions are added at 65 ° C in 30 minutes. This redox treatment is followed by baking at 65 ° C. for 30 minutes before cooling to room temperature. v) Final additions At 30-35 ° C, the latex is neutralized to pH 8 by adding sodium hydroxide and post-addition of a biocide. It is then filtered on 100 μm canvas. The dry extract is 45.5%. The final particle size is about 90 nm, the viscosity is less than 5,200 mPa.s, the measured TMF is 5 ° C. 4) Evaluation of the formaldehyde capture performance 4.1) Test method The performance of the tested product in reducing the formaldehyde concentration in the indoor air is measured using the ISO 16000-23 standard. ISO 16000-23 specifies a general laboratory test method to evaluate the reduction of formaldehyde concentration by sports building materials. It is based on the test chamber method as specified in ISO 16000-15 where the test chamber must simulate the parameters of the reference part. The sample to be tested is applied according to a specific load factor and placed in a test chamber (the sampling, transport and storage of the samples to be tested and the preparation of the samples to be tested being specified in ISO 1600011). The feed air is doped with formaldehyde to measure the sorption flux and the saturation mass per unit area. The first directly indicates the performance of the samples in relation to the reduction of formaldehyde concentration at a given time. The second (saturation mass per unit area) refers to the ability of a test sample to maintain that performance. Concretely, at selected time intervals, a known volume of air is taken from the test chamber. Formaldehyde is thus trapped and converted into a hydrazone derivative by a cartridge filled with silica gel impregnated with 2,4-DNPH (2,4-dinitrophenyl hydrazine). The stable hydrazone derivative formed is desorbed with acetonitrile and analyzed by HPLC with an ultraviolet detector (air sampling and methods of analysis for the determination of formaldehyde are specified in ISO 16000-3) . The results obtained are then expressed as a concentration of formaldehyde in the chamber in μg / m3 and / or as a sorption flux in 1 μg / m2 per hour. The performance of the test sample in its ability to reduce formaldehyde concentration is evaluated by comparing the amount of formaldehyde found in the chamber containing the test sample to that of the empty chamber (without sample). The consumption of FC formaldehyde by said test sample (in%) can then be calculated (see § 5.3) below for definitions of the measured quantities). 5.2) Operating conditions Test parameters in the emission chamber: Chamber volume: 119 I Temperature: 23 ± 1 ° C Relative humidity: 50 ± 5% Air change rate: 0.5 h-1 Factor of load: 1 m2 / m3 Preparation of the sample 1 layer of wet coating (aqueous dispersion) at 100 g / m2.
    [0025] Formaldehyde injection: constant concentration in the chamber during the test with an average chamber concentration of 78 pg / m3. Method of analysis: Method: ISO 16000-23, EN ISO 16000-3 Principle: HPLC-UV Detection limit formaldehyde: 3pg / m3 Uncertainty on detection / analysis of formaldehyde by HPLC detector UV: ± 22%. 5.3) Results Formaldehyde (CF) consumption results are presented in Table 3 below. FC formaldehyde consumption (in%) is calculated using the following formula: FC = (Centered - Ochambers) / Centered with the Center and Cchambre definitions being the same as below for flow calculation Table 3: FC formaldehyde consumption (%) Sample ref / 4 hours 8 hours 1 day 7 days Duration Test 1 76 56 42 26 Test 2 36 15 18 2 The F formal sorption flux results are presented in Table 1. Table 4 below. The sorption flux F is calculated according to the following formula: F = (Centered Chamber) * QC / A With: F: sorption flux in pg / m 2 per hour FC: formaldehyde consumption in%, as defined above Centered concentration at the entrance of the room, in pg / m3 Chamber: concentration in the chamber, in pg / m3 Qc: airflow doped with formaldehyde in the chamber = 0.06 m3 / h A = 0.119 m2 representing the surface of sample (coating) Table 4: Formaldehyde sorption flux F (in pg / m 2 per hour) Sample ref / 4 hours 8 hours 1 day 7 days Duration Test 1 31 23 18 8 Test 2 15 6 8 1
    权利要求:
    Claims (28)
    [0001]
    REVENDICATIONS1. Use of an aqueous dispersion of polymer, in particular the polymer resulting from said dispersion, for the irreversible capture and trapping of at least one volatile organic compound carrying a function of aldehyde, ketone or amine, preferably a volatile organic compound carrying an aldehyde function, with said dispersion having a minimum TMF filming temperature of 0 to 50 ° C, preferably 0 to 40 ° C measured according to ISO 2115 and comprising polymer particles structured in core / bark P1 / P2 hard / soft, with - P1 being the core hard polymer phase of said particle, with a glass transition temperature Tg1 ranging from 60 to 120 ° C, preferably from 60 to 100 ° C and said phase P1 comprising in its structure of units derived from at least one monomer M1 having at least two copolymerizable ethylenic unsaturations and having a crosslinking agent function and units derived from at least one monomer M2 ethylenically unsaturated compound bearing at least one carboxylic acid and / or carboxylic anhydride function P2 being the soft polymer phase in bark having a glass transition temperature Tg2 ranging from -20 to 40 ° C., preferably from -20 to 30 ° C. more preferably from -20 to 20 ° C with P2 representing from 40 to 85%, preferably from more than 50% and up to 85% by weight of the total weight of P1 + P2 and comprising in its structure, units from at least one monomer M3 carrying a polymerizable ethylenic unsaturation and in addition to a ureido functional group or a functional group having a mobile hydrogen alpha to a ketone carbonyl.
    [0002]
    2. Use according to claim 1, characterized in that said functional group of said monomer M3 is selected from ureido, acetoacetoxy or diacetone groups.
    [0003]
    3. Use according to claim 1 or 2, characterized in that said monomer M3 is selected from diacetone acrylamide (DAAM), acetoacetoxy ethyl (meth) acrylate (AAEM) or acetoacetoxy propyl (meth) acrylate (AAPM) N- (2- (meth) acryloyloxyethyl) ethylene urea (or ureido ethyl (meth) acrylate: UMA), in particular acetoacetoxyethyl (meth) acrylate (AAEM).
    [0004]
    4. Use according to one of claims 1 to 3, characterized in that the level of said monomer M3 carrying said functional group, preferably diacetone, acetoacetoxy or ureido, more preferably acetoacetoxy, varies from 50 to 1000 and preferably from 100 to 700 mmol per kg of said polymer (P1 + P2).
    [0005]
    5. Use according to one of claims 1 to 4, characterized in that said monomer M3 is present in said P2 phase at a level by weight of 1 to 25%, preferably from 2.5 to 25% and more preferably from 5 to 15% relative to the total weight of P1 + P2.
    [0006]
    6. Use according to one of claims 1 to 5, characterized in that said P2 phase further comprises at least one transfer agent selected from hydrophilic mercaptans, in particular carrying an ionic group.
    [0007]
    7. Use according to one of claims 1 to 6, characterized in that said P2 phase comprises at least a second transfer agent selected from hydrophobic mercaptans with a weight ratio of hydrophilic agent to hydrophobic agent greater than 1 and of preferably greater than 1.5.
    [0008]
    8. Use according to claim 7, characterized in that the overall rate of said first and second transfer agents represents, by weight, from 0.02 to 2% and preferably from 0.05 to 1.5% relative to the total weight of the phases P1 + P2.
    [0009]
    9. Use according to one of claims 1 to 8, characterized in that the difference between said Tgl and Tg2 ranges from 20 to 140 ° C and preferably from 30 to 115 ° C.
    [0010]
    10. Use according to one of claims 1 to 9, characterized in that said monomers M1 and M2 of the P1 phase represent an overall weight ratio ranging from 0.5 to 10% and preferably from 1 to 8% by weight. total of the phase P1 with said monomer M2 representing from 0.1 to 5% and preferably from 0.2 to 4% by weight of said phase P1.
    [0011]
    11. Use according to one of claims 1 to 10, characterized in that the phase P2 also comprises at least one monomer M2 as defined in claim 1, with respective levels by weight of M2 in the phases P1 and P2 selected so that the ratio of the weight ratio of M2 in P1 to the level of M2 in P2 ranges from 1/1 to 1/10 and preferably from 1/2 to 1/8.
    [0012]
    12. Use according to one of claims 1 to 11, characterized in that said P2 phase comprises, in addition, at least one monomer M4 bearing in addition to the polymerizable ethylenic unsaturation, at least one functional group selected from: hydroxy, amine, oxirane, phosphates, phosphonates or phosphinates, amide, sulphate or sulphonate, imide, aziridine, oxazoline or imidazole, provided that the choice of M4 monomers is made in such a way as to avoid a reaction between the different M4 monomer groups or between the groups of the M4 monomers and the groups of the other monomers.
    [0013]
    13. Use according to one of claims 1 to 12, characterized in that said phase P1 is obtained before said P2 phase and in that said P2 phase is obtained by polymerization at a temperature less than or equal to and preferably less than Tgl.
    [0014]
    14. Use according to one of claims 1 to 13, characterized in that said dispersion comprises in dispersion with the polymer particles, at least one compound comprising at least one hydrazine or hydrazide function.
    [0015]
    15. Use according to one of claims 1 to 14, characterized in that said volatile organic compound to be trapped or trapped has a boiling point at atmospheric pressure of less than 250 ° C, preferably less than 100 ° C.
    [0016]
    16. Use according to one of claims 1 to 15, characterized in that said volatile organic compound to be trapped or trapped is an aldehyde among C1 to C8 aldehydes and in particular formalin, acetaldehyde, propanal, acrolein (acrylaldehyde), butanal, pentanal, hexanal, heptanal or octanal, preferably formaldehyde, acetaldehyde, acrolein, hexanal and more preferably formalin.
    [0017]
    17. Use according to one of claims 1 to 16, characterized in that it is the polymer from said dispersion and said polymer is in film form or in the form of a coating, in particular in the form of varnish or paint, more particularly in the form of paint.
    [0018]
    18. Use according to one of claims 1 to 16, characterized in that it is the polymer from said dispersion and said polymer is used in the form of a thin layer or coating applied to a substrate, in particular on a porous or fibrous substrate.
    [0019]
    19. Use according to one of claims 1 to 16, characterized in that it is the polymer from said dispersion and said polymer is used in the form of a qualitative or quantitative probe for detecting said volatile compound, particularly aldehydes and more particularly formaldehyde.
    [0020]
    20. Use according to one of claims 1 to 18, characterized in that it applies to decorative coatings.
    [0021]
    21. Use according to one of claims 1 to 18, characterized in that it applies to industrial protective coatings.
    [0022]
    22. Use according to one of claims 1 to 21, characterized in that it relates to the capture of aldehydes, in particular formalin in the atmosphere in direct contact with the surface of said polymer, in particular in the form of a thin layer of polymer or coating.
    [0023]
    23. Use according to one of claims 1 to 18, characterized in that it relates to the capture of formaldehyde released by coatings applied in the underlayer or first layer relative to the sensor coating, in particular with said sensor coating used as surface coating.
    [0024]
    24. Use according to one of claims 1 to 16, characterized in that it relates to the capture of formaldehyde released by a substrate and that in this case it is coated or impregnated with a sensor coating from said polymer dispersion .
    [0025]
    25. Use according to claim 24, characterized in that said formalin-releasing substrate is chosen from: agglomerated wood or sandwich or plywood and glued by urea-formaldehyde or melamine-formaldehyde glues, treated textile or fibers treated with a composition of formalin-generating treatment.
    [0026]
    26. Use according to one of claims 1 to 16, characterized in that it relates to the capture of formaldehyde released by a first substrate "generator" and that in this case is applied in contact with said substrate "generator", a second "Sensor" substrate impregnated or coated with said aqueous dispersion of polymer or with the polymer resulting from said dispersion.
    [0027]
    27. Use according to claim 26, characterized in that said second "sensor" substrate in contact with said first "generator" substrate is chosen from: nonwovens, organic or mineral fiber fabrics, in particular glass fiber fabrics, for insulation or for renovation of interior walls.
    [0028]
    28. Use according to one of claims 1 to 16, characterized in that it relates to the impregnation of air filters or smoke filters by said aqueous dispersion of polymer.
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    同族专利:
    公开号 | 公开日
    PL3237093T3|2019-03-29|
    CN107106964A|2017-08-29|
    EP3237093B1|2018-10-31|
    US20170361263A1|2017-12-21|
    MX2017007911A|2017-09-05|
    CN107106964B|2021-03-30|
    DK3237093T3|2019-02-04|
    TWI574727B|2017-03-21|
    EP3237093A1|2017-11-01|
    TR201900048T4|2019-02-21|
    WO2016102794A1|2016-06-30|
    CA2971285A1|2016-06-30|
    ES2704908T3|2019-03-20|
    TW201627054A|2016-08-01|
    FR3030303B1|2016-12-30|
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    US4427836A|1980-06-12|1984-01-24|Rohm And Haas Company|Sequential heteropolymer dispersion and a particulate material obtainable therefrom, useful in coating compositions as a thickening and/or opacifying agent|
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    法律状态:
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    2016-06-24| PLSC| Publication of the preliminary search report|Effective date: 20160624 |
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    2021-11-15| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1463089A|FR3030303B1|2014-12-22|2014-12-22|USE OF COATINGS WITH AQUEOUS POLYMER DISPERSIONS HAVING A HEART / SKIN STRUCTURE FOR THE CAPTURE OF VOLATILE ORGANIC COMPOUNDS SUCH AS ALDEHYDES|FR1463089A| FR3030303B1|2014-12-22|2014-12-22|USE OF COATINGS WITH AQUEOUS POLYMER DISPERSIONS HAVING A HEART / SKIN STRUCTURE FOR THE CAPTURE OF VOLATILE ORGANIC COMPOUNDS SUCH AS ALDEHYDES|
    TR2019/00048T| TR201900048T4|2014-12-22|2015-12-03|Using coatings based on aqueous polymer dispersions with core-shell structure to capture volatile organic compounds such as aldehydes|
    CN201580070233.1A| CN107106964B|2014-12-22|2015-12-03|Use of coatings made of aqueous polymer dispersions having a core/shell structure for trapping volatile organic compounds such as aldehydes|
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    PCT/FR2015/053311| WO2016102794A1|2014-12-22|2015-12-03|Use of coatings made from aqueous polymer dispersions having a core/shell structure for capturing volatile organic compounds such as aldehydes|
    CA2971285A| CA2971285A1|2014-12-22|2015-12-03|Use of coatings made from aqueous polymer dispersions having a core/shell structure for capturing volatile organic compounds such as aldehydes|
    ES15817469T| ES2704908T3|2014-12-22|2015-12-03|Use of coatings based on aqueous dispersions of polymer with a core / shell structure for the uptake of volatile organic compounds such as aldehydes|
    EP15817469.8A| EP3237093B1|2014-12-22|2015-12-03|Use of coatings made from aqueous polymer dispersions having a core/shell structure for capturing volatile organic compounds such as aldehydes|
    MX2017007911A| MX2017007911A|2014-12-22|2015-12-03|Use of coatings made from aqueous polymer dispersions having a core/shell structure for capturing volatile organic compounds such as aldehydes.|
    US15/535,479| US20170361263A1|2014-12-22|2015-12-03|Use of coatings made from aqueous polymer dispersions having a core/shell structure for capturing volatile organic compounds such as aldehydes|
    DK15817469.8T| DK3237093T3|2014-12-22|2015-12-03|APPLICATION OF COATINGS MANUFACTURED OF Aqueous POLYMER DISTRIBUTIONS WITH A CORE / SHELL STRUCTURE TO COLLECT VOLATILE ORGANIC COMPOUNDS SUCH AS ALDEHYDES|
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