EP2768801A1 - Masked polyisocyanate and uses thereof - Google Patents

Masked polyisocyanate and uses thereof

Info

Publication number
EP2768801A1
EP2768801A1 EP12790594.1A EP12790594A EP2768801A1 EP 2768801 A1 EP2768801 A1 EP 2768801A1 EP 12790594 A EP12790594 A EP 12790594A EP 2768801 A1 EP2768801 A1 EP 2768801A1
Authority
EP
European Patent Office
Prior art keywords
masked
polyisocyanate
functions
prepolymer
polyol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12790594.1A
Other languages
German (de)
French (fr)
Inventor
Louis Durot
Pierre-Etienne Bindschedler
Virginie FRANCOIS BARSEGHIAN
Rémi Perrin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Soprema SAS
Original Assignee
Soprema SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Soprema SAS filed Critical Soprema SAS
Publication of EP2768801A1 publication Critical patent/EP2768801A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch

Definitions

  • the present invention describes a masked polyisocyanate which satisfies the ecological requirements for the emission of free monomers of diisocyanate.
  • This compound is intended to enter a polyurethane resin composition, especially in a stable one-component polyurethane resin composition, in order to bring the level of free monomers of diisocyanate at a rate consistent with and lower than the regulations in force.
  • This compound is also intended to react with a polyol to form a masked prepolymer which may also be introduced into a polyurethane resin composition, especially into a stable one-component polyurethane resin composition, in order to bring the content of the monomers free of diisocyanate to a rate that meets and is lower than the regulations in force.
  • the masked polyisocyanate and the masked prepolymer according to the invention also have the advantage of being less reactive than conventional polyisocyanates and prepolymers, which makes it possible to improve the stability of the compositions on storage.
  • the masked polyisocyanate is a good agent for hydrocarbon feedstocks and prepolymers in non-bituminous polyurethane resin and bituminous polyurethane resin compositions, preferably one-component, stable compositions.
  • a polyurethane resin comprises a prepolymer which is the reaction product between a di- and / or polyisocyanate and / or polyols, a solvent and / or diluent, optionally a catalyst for accelerating the polymerization and optionally a compatibilizing agent and a filler.
  • the agent is necessarily present when the resin is a bituminous resin or intended to be applied to a bituminous coating.
  • compositions containing diisocyanates may be considered harmful to health and the environment because they can release monomers free of diisocyanate, that is to say, not fixed on the prepolymer.
  • the regulation of certain states allows only a content of less than 1 ⁇ 6 in free monomers of diisocyanate in a final composition of polyurethane resin, preferably a stable monocomponent.
  • the present inventors have found that the free monomers of diisocyanate can be reduced or eliminated by using a monohydric alcohol-masked polyisocyanate and / or a masked prepolymer.
  • the present invention relates to liquid polyurethane resin compositions containing a monosaccharide-masked polyisocyanate and / or masked prepolymer, which are stable and non-toxic because having a content of diisocyanate-free monomers in accordance with regulatory requirements, on the using the masked polyisocyanate to form masked prepolymers as well as the use of a masked polyisocyanate and / or masked prepolymer in a polyurethane resin composition. Definitions
  • liquid composition is intended to mean a composition having a viscosity of between 1,000 and 40,000 centipoise, said viscosity being measured at 23 ° C. using a Brookfield viscometer (for viscosities less than 10,000 centipoise, the measurements are made with the R5 module at a speed of 30 rpm and for viscosities greater than 10,000 centipoise, measurements are made with the R6 module at a speed of 20 rpm. allows the application of the composition including a roller commonly called “rabbit leg roll” or a brush to form layers of 0.5 to 2 mm thick in a single application.
  • a Brookfield viscometer for viscosities less than 10,000 centipoise, the measurements are made with the R5 module at a speed of 30 rpm and for viscosities greater than 10,000 centipoise, measurements are made with the R6 module at a speed of 20 rpm.
  • one-component composition or “ready-to-use composition” is meant a composition which is intended to be applied as such by the end user, that is to say by the worker who will make the coating sealing.
  • a ready-to-use composition is conventionally referred to in the "one-component” art, as opposed to compositions which require the addition of a catalyst or hardener or other reactive agent prior to use or which are to be blended for limited time (a few hours) before being applied.
  • stable composition is meant a composition that can be stored for a minimum of 4 months without observing phase shift or caking.
  • Non-toxic composition means a polyurethane resin composition or bituminous polyurethane resin composition which contains less than 1% by weight of free diisocyanate monomers according to Directive 67/548 / EEC (30th ATP Directive 2008/58 / CE), the content of free monomers of diisocyanate being measured by gas chromatography coupled to a mass spectrometer (according to EN ISO 17734-1 / 2006).
  • Prepolymer means a reaction product of a polyol or a mixture of polyols having an OH number of functions of between 1.5 and 3 with a polyisocyanate or a mixture of polyisocyanates having an NCO number of functions inclusive between 1.6 and 3, in a ratio such that the number of NCO functions of the polyisocyanate or polyisocyanate mixture relative to the number of OH functions of the polyol or polyol mixture is from 1.5 to 2.5 approximately.
  • polyisocyanate is meant a compound having more than one isocyanate function, the diisocyanate may therefore also be referred to herein as polyisocyanate.
  • TDI toluene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • alkyl is meant a hydrocarbyl radical having 2 to 20 carbon atoms, corresponding to the general formula C n H2 n + 1 where n is greater than or equal to 2.
  • the alkyl groups may be linear or branched and may be substituted by the groups non-reactive radicals selected from halogen, alkyl, cycloalkyl, heterocycloalkyl, arylcycloalkyl, heteroarylcycloalkyl, aryl, heteroaryl, alkoxy, haloalkyl, arylalkyl, heteroaryl, hydrocarbyl having at least one unsaturation.
  • aryl a polyunsaturated hydrocarbyl group, aromatic, having a single ring (ie phenyl) or several fused rings (eg naphthyl) or several rings connected by a covalent bond (eg biphenyl), which typically contain 5 to 12 carbon atoms, preferably 6 to 10, and wherein at least one ring is aromatic.
  • the aromatic cycle can optionally include one to two additional cycles (ie cycloalkyl, heterocycloalkyl or heteroaryl) contiguous.
  • aryl also includes the partially hydrogenated derivatives of carbocyclic systems described above.
  • alkyl group defined above has two single bonds as a point of attachment to other groups.
  • arylalkyl or heteroaryl is meant a linear or branched alkyl substituent having a carbon atom attached to an aryl or heteroaryl ring.
  • heteroaryl is meant a ring or two rings contiguous or connected by a covalent bond, comprising 5 to 12 carbon atoms, preferably 5 to 6 carbon atoms, wherein at least one of the rings is aromatic and where at least one or more carbon atoms are replaced by oxygen, nitrogen and / or sulfur.
  • the nitrogen and / or sulfur atoms may optionally be oxidized and the nitrogen atom may optionally be quaternized.
  • heteroaryl also includes systems described above having an aryl, cycloalkyl, heteroaryl or heterocycloalkyl bonded group.
  • cycloalkyl is meant a monovalent, cyclic, unsaturated or saturated hydrocarbyl having one or two rings and having 3 to 10 carbon atoms.
  • heterocycloalkyl is meant a cycloalkyl in which at least one carbon atom is replaced by an oxygen, nitrogen and / or sulfur atom.
  • arylcycloalkyl or “heteroarylcycloalkyl” means a cycloalkyl attached to or linked by a covalent bond to an aryl or heteroaryl ring.
  • arylheterocycloalkyl or heteroaryl-heterocycloalkyl is meant an attached heterocycloalkyl or bound by a covalent bond to an aryl or heteroaryl ring.
  • hydrocarbyl is meant a hydrocarbon chain having 2 to 30 carbon atoms
  • Alkyl, aryl, arylalkyl, aryl, cyclohexyl, cyclohexyl, heteroaryl, heteroaryl, hydrocarbyl with at least 1 ky 1 e, hydrocarbyl with unsaturation may further comprise one or more conventional substituents selected from halogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, haloalkyl or arylalkyl.
  • the masked polyisocyanate used in the present invention is a polyisocyanate whose NCO function has been masked by a monoalcohol, that is to say a polyisocyanate adduct and monoalcohol, the two components being connected to each other by a urethane bond.
  • This masked polyisocyanate is an alkyl monourethane of polyisocyanate having a number of isocyanate functional groups of between 1.5 and 2.2, preferably between 1.5 and 2.1 and even more preferably between 1.5 and 2.
  • the masked polyisocyanate used in the composition according to the invention has the following:
  • A represents a group comprising a number of isocyanate functional groups of between 1.5 and 2.2, preferably between 1.5 and 2.1, and even more preferably between 1.5 and 2.
  • the number of isocyanate functions is estimated by calculation after NCO titration by back-dosing of the excess of dibutylamine with hydrochloric acid (according to EN ISO 14896-2006).
  • B is an optionally unsaturated C 2 -C 20 alkyl, preferably C 3 -C 12 alkyl, more preferably still C 4 -C 10 alkyl.
  • the "group" of A is:
  • each dashed line represents a point of attachment to an NCO function or the -NHCOO-B group of the masked polyisocyanate and provided that there is at least one dotted line which is a point of attachment to the group - NHCOO-B and that the remaining lines represent a point of attachment to an NCO function.
  • the masked polyisocyanate may especially be prepared by a process which comprises the gradual addition of a monoalcohol of formula B-OH to a polyisocyanate of formula A-NCO, A and B being as defined above.
  • the monoalcohol to the masking can in particular be an aliphatic monoalcohol C2-C20, preferably C3-C 1 2 and even more preferably C4-C 1 0.
  • the monoalcohol is chosen from the group comprising hexanol, 2-ethylhexanol, methylhexanol, butanol, terpenols, and mixtures thereof.
  • the polyisocyanate used to form the masked polyisocyanate is aromatic, aliphatic or cycloaliphatic and comprises between 2.5 and 3.2 NCO functions. It may especially be chosen from the group comprising a trimer of toluene diisocyanate (TDI), a diphenylmethane diisocyanate (MDI) polymer, a trimer of hexamethylene diisocyanate (HDI), a trimer of isophorone diisocyanate (IPDI), and their mixtures.
  • TDI trimer of toluene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI trimer of hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • the polyisocyanate used to form the masked polyisocyanate is a polymeric MDI having between 2.5 and 3.2 NCO functions or a TDI trimer.
  • aromatic polyisocyanate a polymeric MDI having 2.7 isocyanate functional groups, such as in particular Suprasec® 5025 marketed by Huntsman or a polymeric MDI having 2,9 isocyanate functional groups, such as in particular Suprasec® 2085 marketed by the company HUNTSMAN.
  • An example of an aliphatic polyisocyanate that can be used to form the masked polyisocyanate is a trimer of HDI having more or less 3 isocyanate functional groups, such as, in particular, Desmodur® N3300 or Desmodur® N100 sold by the company Bayer.
  • the masking of the polyisocyanate is primarily on the most reactive isocyanate function. As a result, the reactivity of the masked polyisocyanate is reduced which allows the compositions containing it to be more stable over time than compositions containing an unmasked polyisocyanate. In addition, the use of the masked polyisocyanate improves the compatibilization between the prepolymers and the bituminous mixtures using natural or synthetic bitumens, especially in the stable monocomponent bituminous polyurethane resin compositions.
  • the reaction between the monoalcohol and the polyisocyanate is an exothermic reaction.
  • the gradual addition of the monoalcohol is thus controlled so as to limit the rise in temperature to a value of less than 60 ° C, preferably less than 50 ° C and more preferably still less than 40 ° C.
  • This process is environmentally friendly, considering that it is conducted in the absence of any solvent and without heating and that it does not generate toxic fumes.
  • a first object of the invention is a polyurethane resin composition, preferably a stable one-component polyurethane resin composition, whose content of free diisocyanate monomers is in accordance with regulatory requirements and whose reactivity is controlled.
  • This composition may be a one-component polyurethane resin composition or a part of a multi-component polyurethane resin composition, more particularly the isocyanate part of a two-component composition, the other part conventionally comprising a polyol.
  • the polyurethane resin composition according to the invention is not a polyurethane foam composition. Therefore, according to a particular embodiment, the composition according to the invention will not be mixed with water to polymerize and give a polyurethane foam. In the same way the composition according to the invention is not intended to be mixed with a blowing agent such as in particular a gas, for example propane, butane, isobutane, carbon dioxide, carbon monoxide or dimethyl ether to form a polyurethane foam.
  • a blowing agent such as in particular a gas, for example propane, butane, isobutane, carbon dioxide, carbon monoxide or dimethyl ether to form a polyurethane foam.
  • the subject of the invention is therefore a polyurethane resin composition, preferably a stable monocomponent, more preferably a stable non-toxic one-component which comprises:
  • plasticizer optionally a plasticizer
  • the prepolymer (hereinafter referred to as the conventional prepolymer) may also be replaced by a mixture of a prepolymer with a masked prepolymer.
  • the composition according to the invention comprises the masked polyisocyanate as such, and not the reagents for forming the masked polyisocyanate.
  • the masked polyisocyanate must be synthesized before being introduced into the composition. Indeed, if a polyurethane resin composition is a monoalcohol, a polyisocyanate having between 2 and 3.2 NCO functions and a prepolymer, the prepolymer will react with the monoalcohol which is not desirable to obtain a coating elastic since the polymerization will be stopped at the end of the chain since the prepolymer will no longer have a reactive function once partially neutralized by the monoalcohol.
  • the masking of the polyisocyanate is a partial masking, that is to say that there remain free NCO functions to react with OH and / or NCO functions.
  • the partial masking of the polyisocyanate differs from the total masking, in which all the NCO functions of the polyisocyanate are masked.
  • the masked polyisocyanate according to the invention can always polymerize or react with a prepolymer via a urea bond while a completely masked polyisocyanate is not free to polymerize and it is necessary to use a thermal or chemical means to unlock some of the NCO functions before the composition can polymerize.
  • compositions according to the invention there is no need, for example, to heat the composition at high temperature in order to release the masked NCO functions nor to add a chemical compound that would allow the masked NCO functions to be unmasked. to initiate the polymerization.
  • the prepolymer used in the composition according to the invention may be a prepolymer conventionally used in polyurethane compositions (hereinafter referred to as a conventional prepolymer) or a masked prepolymer.
  • a masked prepolymer is the reaction product between a polyol and the masked polyisocyanate having a number of isocyanate functions of between 1.5 and 2.2 as described above or between a polyol and a mixture of a polyisocyanate and a polyisocyanate.
  • Conventional prepolymers are formed by reaction between: a polyol having between 1.5 and 3 OH functions; and a conventional di- and / or polyisocyanate having between 1.6 and 3 NCO functions;
  • the polyol used to form the conventional prepolymer may especially be of the polyether type such as a polyethylene glycol (PEG), a polypropylene glycol (PPG), a triol of glycerine polypropylene glycol or a polytetrahydrofuran (PTHF) or a polyol of polyester type, such that especially Priplast® 3196 marketed by the company CRODA or Krasol® LBH-p 3000 marketed by the company CRAYVALLEY or a polycaprolactone such as PCP 1000 sold by the company SOLVAY.
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • PTHF polytetrahydrofuran
  • the conventional di- and / or polyisocyanate used to form the conventional prepolymer may especially be MDI, polymeric MDI TDI, a TDI trimer, HDI, an HDI trimer, IPDI, an IPDI trimer, and their mixtures.
  • the conventional di- and / or polyisocyanate involved in the formation of the conventional prepolymer is MDI, polymeric MDI, TDI, a TDI trimer, and mixtures thereof.
  • a conventional polyisocyanate such as in particular MDI
  • a polyether such as in particular polypropylene glycol (PPG) or polytetrahydrofuran (PTHF); or with a polyester, such as in particular Priplast® 3196 marketed by the company CRODA or Krasol® LBH-p 3000 marketed by the company CRAYVALLEY.
  • Priplast® 3196 marketed by the company CRODA or Krasol® LBH-p 3000 marketed by the company CRAYVALLEY.
  • organometallic catalysts based on bismuth, vanadium or tin such as dibutyltin dilaurate or tertiary amines, such as Jeffcat® DMDLS marketed by the company Hunstman.
  • the fillers that can be introduced into the present composition are in particular liquid fillers which are aromatic plasticizing oils and exogenous plasticizers such as diisopropylnaphthalene, dioctyl phthalate (DOP), diisononyl phthalate (DINP), Mesamoll®, trimethylpentanediol diisobutyrate (TXIB) and butylbenzyl phthalate, natural or synthetic bitumens or a liquid bituminous mixture also called "cut-back”, and solid fillers such as pigments, calcium carbonate, titanium, or others.
  • aromatic plasticizing oils and exogenous plasticizers such as diisopropylnaphthalene, dioctyl phthalate (DOP), diisononyl phthalate (DINP), Mesamoll®, trimethylpentanediol diisobutyrate (TXIB) and butylbenzyl phthalate, natural or synthetic bitumens or a
  • composition according to the invention may be liquid, stable monocomponent or intended to be mixed before use.
  • this composition does not contain the masked polyisocyanate as such, but at least a part of the prepolymer is a masked prepolymer which is the reaction product between a polyol and the masked polyisocyanate having a number of isocyanate functional groups included. between 1.5 and 2.2 as described above.
  • polyurethane composition which comprises:
  • A represents a group comprising a number of isocyanate functional groups of between 1.5 and 2.2, preferably between 1.5 and 2.1, and even more preferably between 1.5 and 2;
  • plasticizer optionally a plasticizer
  • composition according to the invention comprises both the masked polyisocyanate and at least a part of the prepolymer is a masked prepolymer which is the reaction product between:
  • a polyol having between 1.5 and 3 OH functions and a molecular weight between 900 and 3000 g / mol, preferably between 1000 and 2800 g / mol and more preferably between 1500 and 2500 g / mol; and a masked polyisocyanate having a number of isocyanate functional groups of between 1.5 and 2.2 as previously described;
  • Said polyol having between 1.5 and 3 OH functions and a molecular weight between 900 and 3,000 g / mol involved in the formation of the masked prepolymer may in particular be a polyol of the polyether, polyester, polybutadiene, polycarbonate type and their mixtures.
  • the polyether type polyol may especially be a polypropylene glycol, a polyethylene glycol, a triol of glycerin polypropylene glycol, a triol of glycerin polyethylene glycol, or a polytetrahydrofuran.
  • the polyester-type polyol may especially be a polycaprolactone, a dimer fatty acid polyester comprising 34 to 36 carbon atoms, a polyadipate polyester or a polyester polyphthalate.
  • the polycarbonate polyol may in particular be a hexane-1,6-diol polycarbonate.
  • the polyol having between 1.5 and 3 OH functions and a molecular weight between 900 and 3000 g / mol forming the masked prepolymer is a polytetrahydrofuran, a hexane-1,6-diol polycarbonate, a polyester of dimeric fatty acids comprising 34 to 36 carbon atoms, a polycaprolactone or a hydroxylated polybutadiene.
  • the ready-to-use liquid composition according to the invention comprises:
  • the percentages being percentages by weight relative to the total weight of the composition.
  • the ready-to-use liquid composition according to the invention comprises:
  • plasticizer preferably of polymerizable plasticizer
  • solvent 0 to 80% of solvent, preferably 2 to 30% of solvent and more preferably 5 to 20% of solvent;
  • the percentages being percentages by weight of the total weight of the composition.
  • the prepolymer is either a conventional prepolymer or a mixture of conventional prepolymer and masked prepolymer.
  • plasticizer a polymerizable plasticizer which is the reaction product between:
  • an alcohol-type compound consisting of a hydrocarbon-based chain comprising and / or being substituted by an aromatic ring and / or an aliphatic ring and / or said hydrocarbon-based chain of the alcohol-type compound is substituted with at least two hydrocarbon-based chains which may comprise a unsaturation, and wherein said alcohol-type compound has a number of
  • a polyisocyanate comprising 2.1 to 3.2 isocyanate functional groups, preferably 2.5 to 3.1 isocyanate functional groups;
  • these compositions do not contain a masked polyisocyanate but at least a part of the prepolymer is a masked prepolymer which is the reaction product between a polyol and a masked polyisocyanate having an isocyanate functional number of between 1.5. and 2.2 as described above.
  • compositions comprise both the masked polyisocyanate and the masked prepolymer as defined above.
  • compositions are stable and have low toxicity since they comprise less than 5%, preferably less than 4%, more preferably less than 3%, more preferably still less than 2% and even more preferably less than 1% by weight of free diisocyanate monomers. They can be marketed without labeling "R40: carcinogenic effect suspected - insufficient evidence "given their low content of free monomers of diisocyanate.
  • compositions according to the invention are also storage-stable since the masked polyisocyanate and / or masked prepolymer described above have the advantage of being less reactive than conventional polyisocyanates and / or conventional prepolymers.
  • the masked polyisocyanate described above being a good compatibilizing agent for hydrocarbon feeds, such as natural or synthetic bitumen, and prepolymers, its use in bituminous polyurethane resin compositions makes it possible to reduce the amount of exogenous plasticizers and thus to avoid exogenous plasticizer exudation at the surface of the formed coating.
  • compositions do not include a solvent, they can be used indoors even in the countries where the legislation is the strictest.
  • the present compositions contain little or no solvent.
  • little solvent is meant a solvent content of less than 10%, preferably less than 5%, and more preferably less than 2% by weight.
  • compositions according to the invention do not contain a solvent.
  • the subject of the invention is also the use of the masked polyisocyanate as defined above, the number of isocyanate functional groups of which is between 1.5 and 2, 2 for the preparation of a masked prepolymer, by reaction of said masked polyisocyanate with a polyol having between 1.5 and 3 OH functions and a molecular weight between 900 and 3000 g / mol, preferably between 1000 and 2800 g / mol and more preferably between 1500 and 2500 g / mol, in a ratio such that the number of NCO functions of the polyisocyanate relative to the number of OH functions of the polyol is from 1.5 to 2.5 approximately.
  • the invention also relates to the use of the masked polyisocyanate and / or the masked prepolymer as defined above in polyurethane resin compositions, preferably in stable one-component polyurethane resin compositions.
  • the use of the masked polyisocyanate and / or the prepolymer masked in polyurethane resin compositions makes it possible to obtain a content of free monomers of diisocyanate of less than 5%, preferably less than 4%, more preferably less than 3%. more preferably still less than 2% and even more preferably less than 1% by weight of free diisocyanate monomers.
  • the use of the masked polyisocyanate in polyurethane resin compositions improves the compatibilization between the hydrocarbon feeds and the prepolymers, resulting in a stable composition.
  • the invention also relates to the use of the composition according to the invention for producing coatings, in particular sealing coatings, having no surface defects, such as bubbles, sufficiently resistant to the exterior, unprotected and possibly circulable.
  • the coatings obtained have a water recovery quite satisfactory, that is to say less than 8% after 28 days of immersion in water at 20 ° C.
  • the coatings obtained by the use of the composition according to the invention can cover horizontal, oblique, vertical, rough surfaces and / or with singular points.
  • the non-bituminous polyurethane resin compositions are preferably used for to waterproof horizontal surfaces that can be used outdoors, such as balconies, stadium stands, parking lots, courtyards, etc.
  • bituminous polyurethane resin compositions are preferably used to make readings, that is to say to achieve a tight coating between a bituminous surface and a vertical wall or a singular point or to renovate roofs.
  • the parts are expressed by weight. Viscosities are measured using a Brookfield Viscometer, mobile 5 or 6, at 20 rpm at 23 ° C, less than one week after manufacture of the product or composition.
  • Suprasec® 2385 Modified MDI having 2 isocyanate functional groups marketed by Huntsman.
  • Suprasec® 5025 polymeric MDI with 2.7 isocyanate functions marketed by the company HUNTSMAN.
  • Ruet as o lv® Di diisopropylnaphthalene plasticizing oil marketed by RKS.
  • Sovermol® 920 Polyether polyether polycarbonate having 2 OH functions marketed by Cognis.
  • Voranol® 2000 polypropylene glycol having a molecular weight of 2000 g / mol (CAS 025322-69-4) sold by the company DOW CHEMICAL.
  • Polybutadiene 3000 polybutadiene diol of molar mass 3000 g / mol.
  • Desmodur® L75 aromatic polyisocyanate based on 75% TDI in ethyl acetate marketed by Bayer.
  • PolyTHF® 2000 polytetrahydrofuran having 2 NCO functions and a molecular weight of 2,000 g / mol sold by the company BASF.
  • PTSI para-toluenesulfonyl isocyanate.
  • a viscosity of 5,000 centipoise is thus obtained as measured by the Brookfield viscometer at 23 ° C., with a module R5 at a speed of 20 rpm.
  • Ruetasolv® Di 12 parts of 2-ethylhexanol are gradually introduced, so that the temperature is below 50 ° C.
  • R5 module at a speed of 20tr / min.
  • a prepolymer was prepared by reacting 100 parts of PolyTHF 2000 with 75 parts of masked polyisocyanate prepared in Example 1. The mixture was stirred at 70 ° C. for 1 hour.
  • the content of free monomers of diisocyanate is less than 5%.
  • a prepolymer was prepared by reaction of 200 parts of Sovermol® 920, 45 parts of Suprasec® 2385 and 180 parts of masked polyisocyanate prepared in Example 2. The mixture was stirred at 70 ° C for 1 hr.
  • the content of free monomers of diisocyanate is 4.5%.
  • a prepolymer is prepared by reaction of 3000 parts of polybutadiene 3000, 135 parts of butane-1,4-diol, 540 parts of Suprasec® 2385, 800 parts of masked polyisocyanate prepared in Example 4. The mixture was stirred at 70 ° C for 1 hr.
  • the content of free monomers of diisocyanate is less than 5%.
  • a prepolymer is prepared by reacting 100 parts Voranol® 2000 and 54 parts Suprasec® 2385. The mixture is stirred at 80 ° C for 2 hours.
  • the composition can be applied as a primary.
  • the prepared composition has a viscosity
  • composition is stored for 4 months at 20 ° C. After 4 months, the composition quickly becomes homogeneous when mixing with a stick, no phase shift is observed.
  • the content of free monomers of diisocyanate is greater than 5%.
  • Such a product is labeled "R40: suspected carcinogenic effect - insufficient evidence” in Europe and “dangerous” in Asia.
  • a prepolymer was prepared by reacting 100 parts of Voranol® 2000 and 91 parts of the masked polyisocyanate prepared in Example 1. The mixture was stirred at 80 ° C for 2 hours.
  • a primer solution is prepared by mixing:
  • This one-component composition is stable and can be applied to the roll to make a primer outdoors.
  • the content of free monomers of diisocyanate is less than 1%. Such a composition may be marketed without labeling "R40: suspected carcinogenic effect - insufficient evidence”.
  • the 160/220 + PTSI cut-back is prepared. First heated 80 parts of bitumen grade 160/220 melted at 110 ° C which incorporates 20 parts of toluene. It is stirred at 1200 rpm for 4 minutes and the mixture is allowed to warm to room temperature. 1 part of PTSI is then added and the mixture is stirred at 1200 rpm for 4 minutes.
  • a liquid composition is obtained which can be used to make a waterproofing coating on a roof.
  • the composition has a diisocyanate free monomer content of less than 1%.
  • Such a composition may be marketed without labeling "R40: suspected carcinogenic effect - insufficient evidence”.
  • the 160/220 + PTSI cut-back is prepared. First heated 80 parts of bitumen grade 160/220 melted at 110 ° C which incorporates 20 parts of toluene. Stirred at 1200 rpm for 4 minutes and allow the mixture to come to room temperature. 1 part of PTSI is then added and the mixture is stirred at 1200 rpm for 4 minutes.
  • a liquid composition is obtained which can be used to make a waterproofing coating on a roof.
  • the composition has a diisocyanate free monomer content of less than 1%.
  • Such a composition may be marketed without labeling "R40: suspected carcinogenic effect - insufficient evidence”.

Abstract

The invention relates to polyurethane resin compositions and, in particular, stable, ready-to-use polyurethane resin compositions comprising: a masked polyisocyanate having formula (I), wherein B represents alkyl and A represents a group comprising a number of isocyanate functions of between 1.5 and 2.2, preferably between 1.5 and 2.1 and, more preferably, between 1.5 and 2; or a masked pre-polymer that is the product of a reaction between the above-mentioned masked polyisocyanate and a polyol having between 1.5 and 3 OH functions and a molecular mass of between 900 and 3,000 g/mol, in a ratio such that the number of NCO functions of the masked polyisocyanate in relation to the number of OH functions of the polyol is between 1.5 and 2.5 approximately; or a mixture of the aforementioned masked polyisocyanate and masked pre-polymer. The invention also relates to the use of the masked polyisocyanate in order to form a masked pre-polymer by reacting said masked polyisocyanate on a polyol, and to the use of a masked polyisocyanate and/or a masked pre-polymer in polyurethane resin compositions.

Description

POLYISOCYANATE MASQUE ET SES UTILISATIONS  MASK POLYISOCYANATE AND USES THEREOF
Domaine d' application Application domain
La présente invention décrit un polyisocyanate masqué qui permet de satisfaire les exigences écologiques en matière d'émission de monomères libres de diisocyanate . Ce composé est destiné à entrer dans une composition de résine polyuréthane, notamment dans une composition de résine polyuréthane monocomposante stable, afin d'amener le taux en monomères libres de diisocyanate à un taux conforme et inférieur aux réglementations en vigueur. Ce composé est également destiné à réagir avec un polyol afin de former un prépolymère masqué qui peut également être introduit dans une composition de résine polyuréthane, notamment dans une composition de résine polyuréthane monocomposante stable, afin d'amener le taux en monomères libres de diisocyanate à un taux conforme et inférieur aux réglementations en vigueur. Le polyisocyanate masqué et le prépolymère masqué selon l'invention présentent de plus l'avantage d'être moins réactifs que les polyisocyanates et prépolymères classiques, ce qui permet d'améliorer la stabilité des compositions au stockage. De surcroît, le polyisocyanate masqué est un bon agent c omp a t ib i 1 i s an t des charges hydrocarbonées et des prépolymères présents dans des compositions de résine polyuréthane non-bitumineuses et de résine polyuréthane bitumineuses, de préférence monocomposantes stables.  The present invention describes a masked polyisocyanate which satisfies the ecological requirements for the emission of free monomers of diisocyanate. This compound is intended to enter a polyurethane resin composition, especially in a stable one-component polyurethane resin composition, in order to bring the level of free monomers of diisocyanate at a rate consistent with and lower than the regulations in force. This compound is also intended to react with a polyol to form a masked prepolymer which may also be introduced into a polyurethane resin composition, especially into a stable one-component polyurethane resin composition, in order to bring the content of the monomers free of diisocyanate to a rate that meets and is lower than the regulations in force. The masked polyisocyanate and the masked prepolymer according to the invention also have the advantage of being less reactive than conventional polyisocyanates and prepolymers, which makes it possible to improve the stability of the compositions on storage. In addition, the masked polyisocyanate is a good agent for hydrocarbon feedstocks and prepolymers in non-bituminous polyurethane resin and bituminous polyurethane resin compositions, preferably one-component, stable compositions.
Art antérieur  Prior art
Les résines de polyuréthane sont très utiles dans de nombreux domaines, en particulier dans les ouvrages de travaux publics ou de bâtiments, où elles permettent de former des revêtements appliqués sur les structures, notamment pour en garantir l'étanchéité ou la protection. De façon classique, une résine de polyuréthane comprend un prépolymère qui est le produit de réaction entre un di-et/ou polyisocyanate et un et/ou des polyols, un solvant et/ou diluant, éventuellement un catalyseur permettant d'accélérer la polymérisation et éventuellement un agent compatibilisant et une charge. L'agent compa t ib i 1 i s an t est nécessairement présent lorsque la résine est une résine bitumineuse ou destinée à être appliquée sur un revêtement bitumineux. Polyurethane resins are very useful in many fields, especially in public works or buildings, where they make it possible to form coatings applied to the structures, in particular to guarantee their watertightness or protection. Typically, a polyurethane resin comprises a prepolymer which is the reaction product between a di- and / or polyisocyanate and / or polyols, a solvent and / or diluent, optionally a catalyst for accelerating the polymerization and optionally a compatibilizing agent and a filler. The agent is necessarily present when the resin is a bituminous resin or intended to be applied to a bituminous coating.
Cependant, ces compositions contenant des diisocyanates peuvent être considérées comme nocives pour la santé et l'environnement car elles peuvent libérer des monomères libres de diisocyanate, c'est-à-dire non fixés sur le prépolymère. Ainsi, la réglementation de certains Etats n'autorise qu'une teneur inférieure à 1 ~6 en monomères libres de diisocyanate dans une composition finale de résine de polyuréthane, de préférence monocomposante stable .  However, these compositions containing diisocyanates may be considered harmful to health and the environment because they can release monomers free of diisocyanate, that is to say, not fixed on the prepolymer. Thus, the regulation of certain states allows only a content of less than 1 ~ 6 in free monomers of diisocyanate in a final composition of polyurethane resin, preferably a stable monocomponent.
Les présents inventeurs ont trouvé qu'il était possible de diminuer, voire de supprimer, les monomères libres de diisocyanate à l'aide d'un polyisocyanate masqué par un monoalcool et/ou d'un prépolymère masqué. Ainsi, la présente invention porte sur des compositions de résine polyuréthane liquides contenant un polyisocyanate masqué par un monoalcool et/ou un prépolymère masqué, qui sont stables et non toxiques car ayant une teneur en monomères libres de diisocyanate conforme aux exigences réglementaires, sur l'utilisation du polyisocyanate masqué pour former des prépolymères masqués ainsi que sur l'utilisation d'un polyisocyanate masqué et/ou d'un prépolymère masqué dans une composition de résine de polyuréthane . Définitions The present inventors have found that the free monomers of diisocyanate can be reduced or eliminated by using a monohydric alcohol-masked polyisocyanate and / or a masked prepolymer. Thus, the present invention relates to liquid polyurethane resin compositions containing a monosaccharide-masked polyisocyanate and / or masked prepolymer, which are stable and non-toxic because having a content of diisocyanate-free monomers in accordance with regulatory requirements, on the using the masked polyisocyanate to form masked prepolymers as well as the use of a masked polyisocyanate and / or masked prepolymer in a polyurethane resin composition. Definitions
Dans la présente invention, par "composition liquide", on entend une composition ayant une viscosité comprise entre 1 000 et 40 000 centipoises, ladite viscosité étant mesurée à 23°C à l'aide d'un viscosimètre Brookfield (pour des viscosités inférieures à 10 000 centipoises, les mesures sont réalisées avec le module R5 à une vitesse de 30 tr/min et pour des viscosités supérieures à 10 000 centipoises, les mesures sont réalisées avec le module R6 à une vitesse de 20 tr/min. Une telle viscosité permet l'application de la composition notamment avec un rouleau communément appelé « rouleau à patte de lapin » ou une brosse pour former des couches de 0,5 à 2 mm d'épaisseur en une seule application.  In the present invention, the term "liquid composition" is intended to mean a composition having a viscosity of between 1,000 and 40,000 centipoise, said viscosity being measured at 23 ° C. using a Brookfield viscometer (for viscosities less than 10,000 centipoise, the measurements are made with the R5 module at a speed of 30 rpm and for viscosities greater than 10,000 centipoise, measurements are made with the R6 module at a speed of 20 rpm. allows the application of the composition including a roller commonly called "rabbit leg roll" or a brush to form layers of 0.5 to 2 mm thick in a single application.
Par "composition monocomposante" ou "composition prête-à-l'emploi" on entend une composition qui est destinée à être appliquée telle quelle par l'utilisateur final, c'est-à-dire par l'ouvrier qui va réaliser le revêtement d ' étanchéité . Une telle composition prête-à- l'emploi est classiquement appelée dans la technique "monocomposante", par opposition aux compositions qui nécessitent l'ajout d'un catalyseur ou durcisseur ou autre agent réactif avant l'emploi ou qui doivent être mélangées pour une durée limitée (quelques heures) avant d'être appliquées.  By "one-component composition" or "ready-to-use composition" is meant a composition which is intended to be applied as such by the end user, that is to say by the worker who will make the coating sealing. Such a ready-to-use composition is conventionally referred to in the "one-component" art, as opposed to compositions which require the addition of a catalyst or hardener or other reactive agent prior to use or which are to be blended for limited time (a few hours) before being applied.
Par "composition stable", on entend une composition qui peut-être stockée pendant un minimum de 4 mois sans observer de déphasage ou de prise en masse.  By "stable composition" is meant a composition that can be stored for a minimum of 4 months without observing phase shift or caking.
Par "composition non toxique", on entend une composition de résine polyuréthane ou composition de résine polyuréthane bitumineuse qui contient moins de 1% en poids de monomères libres de diisocyanate d'après la directive 67/548/CEE (30ème ATP directive 2008/58/CE), la teneur en monomères libres de diisocyanate étant mesurée par chromatographie en phase gazeuse couplée à un spectromètre de masse (selon la norme EN ISO 17734-1 / 2006) . "Non-toxic composition" means a polyurethane resin composition or bituminous polyurethane resin composition which contains less than 1% by weight of free diisocyanate monomers according to Directive 67/548 / EEC (30th ATP Directive 2008/58 / CE), the content of free monomers of diisocyanate being measured by gas chromatography coupled to a mass spectrometer (according to EN ISO 17734-1 / 2006).
Par "prépolymère", on entend un produit de réaction d'un polyol ou d'un mélange de polyols ayant un nombre de fonctions OH compris entre 1,5 et 3 avec un polyisocyanate ou un mélange de polyisocyanates ayant un nombre de fonctions NCO compris entre 1,6 et 3, dans un ratio tel que le nombre de fonctions NCO du polyisocyanate ou du mélange de polyisocyanates par rapport au nombre de fonctions OH du polyol ou mélange de polyols soit de 1,5 à 2,5 environ.  "Prepolymer" means a reaction product of a polyol or a mixture of polyols having an OH number of functions of between 1.5 and 3 with a polyisocyanate or a mixture of polyisocyanates having an NCO number of functions inclusive between 1.6 and 3, in a ratio such that the number of NCO functions of the polyisocyanate or polyisocyanate mixture relative to the number of OH functions of the polyol or polyol mixture is from 1.5 to 2.5 approximately.
Par "polyisocyanate" on entend un composé ayant plus d'une fonction isocyanate, le diisocyanate peut donc également être désigné dans la présente demande par polyisocyanate .  By "polyisocyanate" is meant a compound having more than one isocyanate function, the diisocyanate may therefore also be referred to herein as polyisocyanate.
Par "TDI" on entend le toluène diisocyanate.  By "TDI" is meant toluene diisocyanate.
Par "MDI" on entend le diphénylméthane diisocyanate. By "MDI" is meant diphenylmethane diisocyanate.
Par "HDI" on entend 1 ' hexaméthylène diisocyanate. By "HDI" is meant hexamethylene diisocyanate.
Par "IPDI" on entend l'isophorone diisocyanate.  By "IPDI" is meant isophorone diisocyanate.
Par alkyle on entend un radical hydrocarbyle ayant 2 à 20 atomes de carbone, répondant à la formule générale CnH2n+i où n est supérieur ou égale à 2. Les groupes alkyles peuvent être linéaires ou ramifiés et peuvent être substitués par les groupements non réactifs choisis parmi halogène, alkyle, cycloalkyle, hétérocycloalkyle, arylcycloalkyle, hétéroarylcycloalkyle, aryle, hétéroaryle, alcoxy, ha 1 o gé n o a 1 ky 1 e , arylalkyle, h é t é r o arylalkyle, hydrocarbyle ayant au moins une insaturation. By alkyl is meant a hydrocarbyl radical having 2 to 20 carbon atoms, corresponding to the general formula C n H2 n + 1 where n is greater than or equal to 2. The alkyl groups may be linear or branched and may be substituted by the groups non-reactive radicals selected from halogen, alkyl, cycloalkyl, heterocycloalkyl, arylcycloalkyl, heteroarylcycloalkyl, aryl, heteroaryl, alkoxy, haloalkyl, arylalkyl, heteroaryl, hydrocarbyl having at least one unsaturation.
Par aryle on entend un groupe hydrocarbyle polyinsaturé, aromatique, ayant un seul cycle (i.e. phényle) ou plusieurs cycles accolés (e. g. naphtyle) ou plusieurs cycles reliés par une liaison covalente (e.g. biphényle) , qui contiennent typiquement 5 à 12 atomes de carbone, préférentiellement 6 à 10, et où au moins un cycle est aromatique. Le cycle aromatique peut optionnellement comprendre un à deux cycles supplémentaires (soit cycloalkyle, hétérocycloalkyle ou hétéroaryle) accolés. Le terme aryle comprend également les dérivés partiellement hydrogénés de systèmes carbocycliques décrits ci-dessus. By aryl is meant a polyunsaturated hydrocarbyl group, aromatic, having a single ring (ie phenyl) or several fused rings (eg naphthyl) or several rings connected by a covalent bond (eg biphenyl), which typically contain 5 to 12 carbon atoms, preferably 6 to 10, and wherein at least one ring is aromatic. The aromatic cycle can optionally include one to two additional cycles (ie cycloalkyl, heterocycloalkyl or heteroaryl) contiguous. The term aryl also includes the partially hydrogenated derivatives of carbocyclic systems described above.
Lorsque les suffixes « ène » ou « diyl » sont employés en conjonction avec un groupement alkyle, cela veut dire que le groupe alkyle défini ci-dessus, présente deux liaisons simples comme point d'attache à d'autres groupes.  When the suffixes "ene" or "diyl" are used in conjunction with an alkyl group, this means that the alkyl group defined above has two single bonds as a point of attachment to other groups.
Par arylalkyle ou hé t é r o a r y 1 a 1 ky 1 e on entend un substituant alkyle linéaire ou ramifié ayant un atome de carbone attaché à un cycle aryle ou hétéroaryle.  By arylalkyl or heteroaryl is meant a linear or branched alkyl substituent having a carbon atom attached to an aryl or heteroaryl ring.
Par hétéroaryle on entend un cycle ou deux cycles accolés ou reliés par une liaison covalente, comprenant 5 à 12 atomes de carbone, préférentiellement 5 à 6 atomes de carbone, où au moins l'un des cycles est aromatique et où au moins un ou plusieurs atomes de carbone sont remplacés par de l'oxygène, de l'azote et/ou du soufre. Les atomes d'azote et/ou de soufre peuvent éventuellement être oxydés et l'atome d'azote peut éventuellement être quaternisé. Le terme hétéroaryle comprend également des systèmes décrits ci-dessus ayant un groupe aryle, cycloalkyle, hétéroaryle ou hétérocycloalkyle accolé.  By heteroaryl is meant a ring or two rings contiguous or connected by a covalent bond, comprising 5 to 12 carbon atoms, preferably 5 to 6 carbon atoms, wherein at least one of the rings is aromatic and where at least one or more carbon atoms are replaced by oxygen, nitrogen and / or sulfur. The nitrogen and / or sulfur atoms may optionally be oxidized and the nitrogen atom may optionally be quaternized. The term heteroaryl also includes systems described above having an aryl, cycloalkyl, heteroaryl or heterocycloalkyl bonded group.
Par cycloalkyle on entend un hydrocarbyle monovalent, cyclique, insaturé ou saturé, présentant un ou 2 cycles et comportant 3 à 10 atomes de carbone.  By cycloalkyl is meant a monovalent, cyclic, unsaturated or saturated hydrocarbyl having one or two rings and having 3 to 10 carbon atoms.
Par hétérocycloalkyle on entend un cycloalkyle dans lequel au moins un atome de carbone est remplacé par un atome d'oxygène, d'azote et/ou de soufre.  By heterocycloalkyl is meant a cycloalkyl in which at least one carbon atom is replaced by an oxygen, nitrogen and / or sulfur atom.
Par arylcycloalkyle ou hétéroarylcycloalkyle on entend un cycloalkyle accolé ou lié par une liaison covalente à un cycle aryle ou hétéroaryle.  The term "arylcycloalkyl" or "heteroarylcycloalkyl" means a cycloalkyl attached to or linked by a covalent bond to an aryl or heteroaryl ring.
Par arylhétérocycloalkyle ou hétéroaryl- hétérocycloalkyle on entend un hétérocycloalkyle accolé ou lié par une liaison covalente à un cycle aryle ou hétéroaryle . By arylheterocycloalkyl or heteroaryl-heterocycloalkyl is meant an attached heterocycloalkyl or bound by a covalent bond to an aryl or heteroaryl ring.
Par hydrocarbyle on entend une chaîne hydrocarbonée ayant 2 à 30 atomes de carbones  By hydrocarbyl is meant a hydrocarbon chain having 2 to 30 carbon atoms
Les groupes alkyle, aryle, arylalkyle, a r y 1 c yc 1 o a 1 ky 1 e , a r y 1 hé t é r o c y c 1 o a 1 ky 1 e , hétéroaryl, h é t é r o a r y 1 a 1 k y 1 e , hydrocarbyle avec au moins une insaturation peuvent en outre comporter un ou plusieurs substituants classiques choisis parmi halogène, alkyle, cycloalkyle, hétérocycloalkyle, aryle, hétéroaryle, alcoxy, halogénoalkyle ou arylalkyle.  Alkyl, aryl, arylalkyl, aryl, cyclohexyl, cyclohexyl, heteroaryl, heteroaryl, hydrocarbyl with at least 1 ky 1 e, hydrocarbyl with unsaturation may further comprise one or more conventional substituents selected from halogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, haloalkyl or arylalkyl.
Polyisocyanate masqué  Masked polyisocyanate
Le polyisocyanate masqué utilisé dans la présente invention est un polyisocyanate dont une fonction NCO a été masquée par un monoalcool, c'est-à-dire un adduit de polyisocyanate et de monoalcool, les deux composants étant reliés entre eux par une liaison uréthane.  The masked polyisocyanate used in the present invention is a polyisocyanate whose NCO function has been masked by a monoalcohol, that is to say a polyisocyanate adduct and monoalcohol, the two components being connected to each other by a urethane bond.
Ce polyisocyanate masqué est un alkyl monouréthane de polyisocyanate ayant un nombre de fonctions isocyanates compris entre 1,5 et 2,2, de préférence entre 1,5 et 2,1 et plus préférentiellement encore entre 1,5 et 2.  This masked polyisocyanate is an alkyl monourethane of polyisocyanate having a number of isocyanate functional groups of between 1.5 and 2.2, preferably between 1.5 and 2.1 and even more preferably between 1.5 and 2.
Le polyisocyanate masqué entrant dans la composition selon 1 ' invention présente suivante : The masked polyisocyanate used in the composition according to the invention has the following:
où :  or :
B représente alkyle,  B represents alkyl,
A représente un groupe comportant un nombre de fonctions isocyanates compris entre 1,5 et 2,2, de préférence entre 1,5 et 2,1, et plus préférentiellement encore entre 1,5 et 2.  A represents a group comprising a number of isocyanate functional groups of between 1.5 and 2.2, preferably between 1.5 and 2.1, and even more preferably between 1.5 and 2.
Le nombre de fonctions isocyanates est estimé par calcul après titrage NCO par dosage en retour de l'excès de dibutylamine par de l'acide chlorhydrique (selon la norme EN ISO 14896-2006) . The number of isocyanate functions is estimated by calculation after NCO titration by back-dosing of the excess of dibutylamine with hydrochloric acid (according to EN ISO 14896-2006).
De préférence B est un alkyle, éventuellement insaturé, en C2-C20, de préférence en C3-C12, plus préférentiellement encore en C4-C10. Preferably B is an optionally unsaturated C 2 -C 20 alkyl, preferably C 3 -C 12 alkyl, more preferably still C 4 -C 10 alkyl.
De préférence, le "groupe" de A est :  Preferably, the "group" of A is:
une chaîne polymérique (provenant du MDI polymérique) répondant à la formule (Al) : a polymeric chain (from the polymeric MDI) corresponding to the formula (Al):
(Al) , (Al),
un radical répondant à la formule (A2) ou à un radical apparenté 'un trimère de TDI :  a radical corresponding to formula (A2) or to a related radical, a trimer of TDI:
(A2) ,  (A2),
un radical répondant à l'une des formules (A3) et/ou (A4) ou à un radical apparenté d'un trimère de HDI :  a radical corresponding to one of the formulas (A3) and / or (A4) or to a related radical of a trimer of HDI:
(A3) (A4),  (A3) (A4),
un radical répondant à la formule (A5) ou à un radical apparenté d'un trimère d' IPDI : a radical having the formula (A5) or a related radical of an IPDI trimer:
(A5) ,  (AT 5) ,
où chaque trait en pointillé représente un point d'attache à une fonction NCO ou au groupe -NHCOO-B du polyisocyanate masqué et à la condition qu' il y ait au moins un trait en pointillé qui soit un point d'attache au groupe -NHCOO-B et que les traits restants représentent un point d' attache à une fonction NCO. where each dashed line represents a point of attachment to an NCO function or the -NHCOO-B group of the masked polyisocyanate and provided that there is at least one dotted line which is a point of attachment to the group - NHCOO-B and that the remaining lines represent a point of attachment to an NCO function.
Le polyisocyanate masqué peut notamment être préparé par un procédé qui comprend l'adjonction progressive d'un monoalcool de formule B-OH sur un polyisocyanate de formule A-NCO, A et B étant tels que définis ci-dessus.  The masked polyisocyanate may especially be prepared by a process which comprises the gradual addition of a monoalcohol of formula B-OH to a polyisocyanate of formula A-NCO, A and B being as defined above.
Le monoalcool permettant le masquage peut notamment être un monoalcool aliphatique en C2-C20, de préférence en C3-C12 et plus préférentiellement encore en C4-C10. The monoalcohol to the masking can in particular be an aliphatic monoalcohol C2-C20, preferably C3-C 1 2 and even more preferably C4-C 1 0.
Avantageusement, le monoalcool est choisi dans le groupe comprenant l'hexanol, le 2-éthylhexanol, le méthylhexanol , le butanol, les terpénols, et leurs mélanges .  Advantageously, the monoalcohol is chosen from the group comprising hexanol, 2-ethylhexanol, methylhexanol, butanol, terpenols, and mixtures thereof.
Le polyisocyanate utilisé pour former le polyisocyanate masqué est aromatique, aliphatique ou cycloaliphatique et comprend entre 2,5 et 3,2 fonctions NCO. Il peut notamment être choisi dans le groupe comprenant un trimère de toluène diisocyanate (TDI), un polymère de diphénylméthane diisocyanate (MDI), un trimère d' hexamé thylène diisocyanate (HDI), un trimère de diisocyanate d' isophorone (IPDI), et leurs mélanges. De préférence, le polyisocyanate utilisé pour former le polyisocyanate masqué est un MDI polymérique ayant entre 2,5 et 3,2 fonctions NCO ou un trimère de TDI . The polyisocyanate used to form the masked polyisocyanate is aromatic, aliphatic or cycloaliphatic and comprises between 2.5 and 3.2 NCO functions. It may especially be chosen from the group comprising a trimer of toluene diisocyanate (TDI), a diphenylmethane diisocyanate (MDI) polymer, a trimer of hexamethylene diisocyanate (HDI), a trimer of isophorone diisocyanate (IPDI), and their mixtures. Preferably, the polyisocyanate used to form the masked polyisocyanate is a polymeric MDI having between 2.5 and 3.2 NCO functions or a TDI trimer.
Plus particulièrement, pour former le polyisocyanate masqué, on peut utiliser comme polyisocyanate aromatique un MDI polymérique ayant 2,7 fonctions isocyanates, tel que notamment le Suprasec® 5025 commercialisé par la société HUNTSMAN ou un MDI polymérique ayant 2,9 fonctions isocyanates, tel que notamment le Suprasec® 2085 commercialisé par la société HUNTSMAN.  More particularly, to form the masked polyisocyanate, it is possible to use as aromatic polyisocyanate a polymeric MDI having 2.7 isocyanate functional groups, such as in particular Suprasec® 5025 marketed by Huntsman or a polymeric MDI having 2,9 isocyanate functional groups, such as in particular Suprasec® 2085 marketed by the company HUNTSMAN.
Un exemple de polyisocyanate aliphatique utilisable pour former le polyisocyanate masqué est un trimère de HDI ayant plus ou moins 3 fonctions isocyanates, tel que notamment le Desmodur® N3300 ou le Desmodur® N100 commercialisés par la société BAYER.  An example of an aliphatic polyisocyanate that can be used to form the masked polyisocyanate is a trimer of HDI having more or less 3 isocyanate functional groups, such as, in particular, Desmodur® N3300 or Desmodur® N100 sold by the company Bayer.
De façon à obtenir le nombre de fonctions isocyanates compris entre 1,5 et 2,2 sur le polyisocyanate masqué, on ajoute 0,60 mol à 1,50 mol, de préférence 0,80 mol à 1,3 mol, de monoalcool sur 1 mol de polyisocyanate. Si la teneur en monoalcool est trop faible, le nombre de fonctions isocyanates sera supérieur à 2,2 et les propriétés mécaniques, notamment l'élasticité, du revêtement obtenu à l'aide d'une composition contenant ce polyisocyanate masqué seraient altérées.  In order to obtain the number of isocyanate functions of between 1.5 and 2.2 on the masked polyisocyanate, 0.60 mol to 1.50 mol, preferably 0.80 mol to 1.3 mol, of monoalcohol are added. 1 mol of polyisocyanate. If the content of monoalcohol is too low, the number of isocyanate functions will be greater than 2.2 and the mechanical properties, including elasticity, of the coating obtained with a composition containing this masked polyisocyanate would be altered.
Le masquage du polyisocyanate se fait prioritairement sur la fonction isocyanate la plus réactive. De ce fait, la réactivité du polyisocyanate masqué est réduite ce qui permet aux compositions le contenant d'être plus stables dans le temps que des compositions contenant un polyisocyanate non masqué. De plus, l'utilisation du polyisocyanate masqué améliore la compatibilisation entre les prépolymères et les mélanges bitumineux utilisant des bitumes naturels ou synthétiques, notamment dans les compositions de résine polyuréthane bitumineuse monocomposantes stables. The masking of the polyisocyanate is primarily on the most reactive isocyanate function. As a result, the reactivity of the masked polyisocyanate is reduced which allows the compositions containing it to be more stable over time than compositions containing an unmasked polyisocyanate. In addition, the use of the masked polyisocyanate improves the compatibilization between the prepolymers and the bituminous mixtures using natural or synthetic bitumens, especially in the stable monocomponent bituminous polyurethane resin compositions.
La réaction entre le monoalcool et le polyisocyanate est une réaction exothermique. On contrôle donc l'adjonction progressive du monoalcool de façon à limiter l'élévation de température à une valeur inférieure à 60°C, de préférence inférieure à 50°C et plus préfèrentiellement encore inférieure à 40°C.  The reaction between the monoalcohol and the polyisocyanate is an exothermic reaction. The gradual addition of the monoalcohol is thus controlled so as to limit the rise in temperature to a value of less than 60 ° C, preferably less than 50 ° C and more preferably still less than 40 ° C.
Lorsque la température redevient la température ambiante (environ 20°C), la réaction est terminée.  When the temperature returns to room temperature (about 20 ° C), the reaction is complete.
Ce procédé est respectueux de l'environnement, compte tenu du fait qu'il est conduit en l'absence de tout solvant et sans chauffage et qu'il ne génère pas de vapeurs toxiques .  This process is environmentally friendly, considering that it is conducted in the absence of any solvent and without heating and that it does not generate toxic fumes.
Composition de polyuréthane  Polyurethane composition
Un premier objet de l'invention est une composition de résine polyuréthane, de préférence une composition de résine polyuréthane monocomposante stable, dont la teneur en monomères libres de diisocyanate est conforme aux exigences réglementaires et dont la réactivité est contrôlée .  A first object of the invention is a polyurethane resin composition, preferably a stable one-component polyurethane resin composition, whose content of free diisocyanate monomers is in accordance with regulatory requirements and whose reactivity is controlled.
Cette composition peut être une composition de résine polyuréthane monocomposante ou bien une partie d'une composition de résine polyuréthane multi-composante, plus particulièrement, la partie isocyanate d'une composition bi-composante, l'autre partie comprenant classiquement un polyol .  This composition may be a one-component polyurethane resin composition or a part of a multi-component polyurethane resin composition, more particularly the isocyanate part of a two-component composition, the other part conventionally comprising a polyol.
De préférence, la composition de résine polyuréthane selon l'invention n'est pas une composition de mousse de polyuréthane. De ce fait, selon un mode de réalisation particulier, la composition selon l'invention ne sera pas mélangée avec de l'eau pour polymériser et donner une mousse de polyuréthane. De la même façon la composition selon l'invention n'est pas destinée à être mélangée avec un agent de soufflage tel que notamment un gaz, par exemple le propane, butane, isobutane, dioxyde de carbone, monoxyde de carbone ou le diméthyléther pour former une mousse de polyuréthane . Preferably, the polyurethane resin composition according to the invention is not a polyurethane foam composition. Therefore, according to a particular embodiment, the composition according to the invention will not be mixed with water to polymerize and give a polyurethane foam. In the same way the composition according to the invention is not intended to be mixed with a blowing agent such as in particular a gas, for example propane, butane, isobutane, carbon dioxide, carbon monoxide or dimethyl ether to form a polyurethane foam.
L'invention a donc pour objet une composition de résine polyuréthane, de préférence monocomposante stable, plus préférentiellement encore monocomposante stable non- toxique qui comprend :  The subject of the invention is therefore a polyurethane resin composition, preferably a stable monocomponent, more preferably a stable non-toxic one-component which comprises:
au moins un polyisocyanate masqué tel que défini précédemment ;  at least one masked polyisocyanate as defined above;
au moins un prépolymère ;  at least one prepolymer;
éventuellement un plastifiant;  optionally a plasticizer;
éventuellement un catalyseur ;  optionally a catalyst;
éventuellement du solvant et/ou diluant ;  optionally solvent and / or diluent;
- éventuellement des charges.  - possibly loads.
Le prépolymère (appelé par la suite prépolymère classique) peut également être remplacé par un mélange d'un prépolymère avec un prépolymère masqué.  The prepolymer (hereinafter referred to as the conventional prepolymer) may also be replaced by a mixture of a prepolymer with a masked prepolymer.
Il est important de préciser que la composition selon l'invention comprend le polyisocyanate masqué en tant que tel, et non les réactifs permettant de former le polyisocyanate masqué. Ainsi, le polyisocyanate masqué doit être préalablement synthétisé avant son introduction dans la composition. En effet, si l'on met dans une composition de résine polyuréthane un monoalcool, un polyisocyanate ayant entre 2 et 3,2 fonctions NCO et un prépolymère, le prépolymère va réagir avec le monoalcool ce qui n'est pas souhaitable pour obtenir un revêtement élastique car la polymérisation sera stoppée en bout de chaîne puisque le prépolymère n'aura plus de fonction réactive une fois neutralisé partiellement par le monoalcool. Les chaînes polymères résultantes seront donc plus courtes ce qui nuit à l'élasticité et à la résistance du revêtement final. Il est également important de préciser que le masquage du polyisocyanate est un masquage partiel, c'est-à-dire qu'il reste des fonctions NCO libres pour réagir avec des fonctions OH et/ou NCO. Le masquage partiel du polyisocyanate se différencie du masquage total, où toutes les fonctions NCO du polyisocyanate sont masquées. En effet, le polyisocyanate masqué selon l'invention peut toujours polymériser ou réagir avec un prépolymère par l'intermédiaire d'une liaison urée alors qu'un polyisocyanate masqué totalement n'est pas libre de polymériser et il faut utiliser un moyen thermique ou chimique pour débloquer une partie des fonctions NCO avant que la composition puisse polymériser. Le masquage total des fonctions NCO d'un polyisocyanate suivi du démasquage par un moyen thermique ou chimique ne s'applique pas aux compositions que nous envisageons. Ainsi, dans les compositions selon l'invention, il n'y a pas besoin, par exemple, de chauffer la composition à haute température afin de libérer les fonctions NCO masquées ni d'ajouter un composé chimique qui permettrait le démasquage des fonctions NCO masquées pour initier la polymérisation. It is important to specify that the composition according to the invention comprises the masked polyisocyanate as such, and not the reagents for forming the masked polyisocyanate. Thus, the masked polyisocyanate must be synthesized before being introduced into the composition. Indeed, if a polyurethane resin composition is a monoalcohol, a polyisocyanate having between 2 and 3.2 NCO functions and a prepolymer, the prepolymer will react with the monoalcohol which is not desirable to obtain a coating elastic since the polymerization will be stopped at the end of the chain since the prepolymer will no longer have a reactive function once partially neutralized by the monoalcohol. The resulting polymer chains will therefore be shorter which affects the elasticity and strength of the final coating. It is also important to specify that the masking of the polyisocyanate is a partial masking, that is to say that there remain free NCO functions to react with OH and / or NCO functions. The partial masking of the polyisocyanate differs from the total masking, in which all the NCO functions of the polyisocyanate are masked. Indeed, the masked polyisocyanate according to the invention can always polymerize or react with a prepolymer via a urea bond while a completely masked polyisocyanate is not free to polymerize and it is necessary to use a thermal or chemical means to unlock some of the NCO functions before the composition can polymerize. The total masking of the NCO functions of a polyisocyanate followed by unmasking by a thermal or chemical means does not apply to the compositions that we envisage. Thus, in the compositions according to the invention, there is no need, for example, to heat the composition at high temperature in order to release the masked NCO functions nor to add a chemical compound that would allow the masked NCO functions to be unmasked. to initiate the polymerization.
Le prépolymère mis en œuvre dans la composition selon l'invention peut être un prépolymère classiquement utilisé dans des compositions de polyuréthane (appelé par la suite prépolymère classique) ou un prépolymère masqué.  The prepolymer used in the composition according to the invention may be a prepolymer conventionally used in polyurethane compositions (hereinafter referred to as a conventional prepolymer) or a masked prepolymer.
Un prépolymère masqué est le produit de réaction entre un polyol et le polyisocyanate masqué ayant un nombre de fonctions isocyanates compris entre 1,5 et 2,2 tel que décrit ci-dessus ou entre un polyol et un mélange d'un polyisocyanate et d'un polyisocyanate masqué ayant un nombre de fonctions isocyanates compris entre 1,5 et 2,2 tel que décrit ci-dessus.  A masked prepolymer is the reaction product between a polyol and the masked polyisocyanate having a number of isocyanate functions of between 1.5 and 2.2 as described above or between a polyol and a mixture of a polyisocyanate and a polyisocyanate. a masked polyisocyanate having a number of isocyanate functional groups of between 1.5 and 2.2 as described above.
Les prépolymères classiques sont formés par réaction entre : un polyol ayant entre 1,5 et 3 fonctions OH ; et un di- et/ou polyisocyanate classique ayant entre 1,6 et 3 fonctions NCO ; Conventional prepolymers are formed by reaction between: a polyol having between 1.5 and 3 OH functions; and a conventional di- and / or polyisocyanate having between 1.6 and 3 NCO functions;
dans un ratio tel que le nombre de fonctions NCO du polyisocyanate ou du mélange de polyisocyanates par rapport au nombre de fonctions OH du polyol ou mélange de polyols soit de 1,5 à 2,5 environ. in a ratio such that the number of NCO functions of the polyisocyanate or of the polyisocyanate mixture relative to the number of OH functions of the polyol or polyol mixture is from 1.5 to 2.5 approximately.
Le polyol utilisé pour former le prépolymère classique peut notamment être de type polyéther tel que un polyéthylène glycol (PEG), un polypropylène glycol (PPG), un triol de glycérine polypropylène glycol ou un polytétrahydrofurane (PTHF) ou un polyol de type polyester, tel que notamment le Priplast® 3196 commercialisé par la société CRODA ou le Krasol® LBH-p 3000 commercialisé par la société CRAYVALLEY ou un polycaprolactone tel que le PCP 1000 commercialisé par la société SOLVAY.  The polyol used to form the conventional prepolymer may especially be of the polyether type such as a polyethylene glycol (PEG), a polypropylene glycol (PPG), a triol of glycerine polypropylene glycol or a polytetrahydrofuran (PTHF) or a polyol of polyester type, such that especially Priplast® 3196 marketed by the company CRODA or Krasol® LBH-p 3000 marketed by the company CRAYVALLEY or a polycaprolactone such as PCP 1000 sold by the company SOLVAY.
Le di- et/ou polyisocyanate classique utilisé pour former le prépolymère classique peut notamment être le MDI, le MDI polymérique le TDI, un trimère de TDI, le HDI, une trimère de HDI, l'IPDI, un trimère d'IPDI, et leurs mélanges .  The conventional di- and / or polyisocyanate used to form the conventional prepolymer may especially be MDI, polymeric MDI TDI, a TDI trimer, HDI, an HDI trimer, IPDI, an IPDI trimer, and their mixtures.
De préférence, le di- et/ou polyisocyanate classique entrant dans la formation du prépolymère classique est le MDI, le MDI polymérique le TDI, un trimère de TDI, et leurs mélanges.  Preferably, the conventional di- and / or polyisocyanate involved in the formation of the conventional prepolymer is MDI, polymeric MDI, TDI, a TDI trimer, and mixtures thereof.
A titre d'exemple, on peut citer un prépolymère classique résultant de la réaction d'un polyisocyanate classique tel que notamment le MDI avec un polyéther, tel que notamment le polypropylène glycol (PPG) ou le polytétrahydrofurane (PTHF) ; ou avec un polyester, tel que notamment le Priplast® 3196 commercialisé par la société CRODA ou le Krasol® LBH-p 3000 commercialisé par la société CRAYVALLEY . Le catalyseur qui peut être introduit dans la composition selon l'invention est un catalyseur classiquement utilisé dans des compositions de polyuréthane . A titre d'exemple, on peut citer les catalyseurs organométalliques à base de bismuth, de vanadium ou d'étain, tels que le dilaurate de dibutylétain ou des aminés tertiaires, telles que Jeffcat® DMDLS commercialisée par la société HUNSTMAN. By way of example, mention may be made of a conventional prepolymer resulting from the reaction of a conventional polyisocyanate, such as in particular MDI with a polyether, such as in particular polypropylene glycol (PPG) or polytetrahydrofuran (PTHF); or with a polyester, such as in particular Priplast® 3196 marketed by the company CRODA or Krasol® LBH-p 3000 marketed by the company CRAYVALLEY. The catalyst that can be introduced into the composition according to the invention is a catalyst conventionally used in polyurethane compositions. By way of example, mention may be made of organometallic catalysts based on bismuth, vanadium or tin, such as dibutyltin dilaurate or tertiary amines, such as Jeffcat® DMDLS marketed by the company Hunstman.
Les charges qui peuvent être introduites dans la présente composition sont notamment des charges liquides qui sont des huiles plastifiantes aromatiques et des plastifiants exogènes tels que le diisopropylnaphthalène, le phthalate de dioctyle (DOP) , le phthalate de diisononyle (DINP) , le Mesamoll®, le diisobutyrate de triméthylpentanediol (TXIB) et le phthalate de butylbenzyle, des bitumes naturels ou synthétiques ou un mélange bitumineux liquide aussi appelé « cut-back », et des charges solides telles que des pigments, du carbonate de calcium, de l'oxyde de titane, ou autres.  The fillers that can be introduced into the present composition are in particular liquid fillers which are aromatic plasticizing oils and exogenous plasticizers such as diisopropylnaphthalene, dioctyl phthalate (DOP), diisononyl phthalate (DINP), Mesamoll®, trimethylpentanediol diisobutyrate (TXIB) and butylbenzyl phthalate, natural or synthetic bitumens or a liquid bituminous mixture also called "cut-back", and solid fillers such as pigments, calcium carbonate, titanium, or others.
La composition selon l'invention peut être liquide, monocomposante stable ou destinée à être mélangée avant emploi .  The composition according to the invention may be liquid, stable monocomponent or intended to be mixed before use.
Selon un mode de réalisation particulier, cette composition ne contient pas le polyisocyanate masqué en tant que tel mais au moins une partie du prépolymère est un prépolymère masqué qui est le produit de réaction entre un polyol et le polyisocyanate masqué ayant un nombre de fonctions isocyanates compris entre 1,5 et 2,2 tel que décrit ci-dessus.  According to a particular embodiment, this composition does not contain the masked polyisocyanate as such, but at least a part of the prepolymer is a masked prepolymer which is the reaction product between a polyol and the masked polyisocyanate having a number of isocyanate functional groups included. between 1.5 and 2.2 as described above.
Ainsi un autre objet de l'invention est une composition polyuréthane qui comprend :  Thus another object of the invention is a polyurethane composition which comprises:
au moins un prépolymère masqué formé par réaction entre : - un polyol ayant entre 1,5 et 3 fonctions OH et un poids moléculaire entre 900 et 3 000 g/mol, de préférence entre 1 000 et 2 800 g/mol et plus préférentiellement entre 1 500 et 2 500 g/mol, etat least one masked prepolymer formed by reaction between: a polyol having between 1.5 and 3 OH functions and a molecular weight between 900 and 3000 g / mol, preferably between 1000 and 2800 g / mol and more preferably between 1500 and 2500 g / mol, and
- un polyisocyanate masqué répondant à la formule suivante a masked polyisocyanate corresponding to the following formula
où  or
- B représente alkyle,  B represents alkyl,
- A représente un groupe comportant un nombre de fonctions isocyanates compris entre 1,5 et 2,2, de préférence entre 1,5 et 2,1, et plus préférentiellement encore entre 1,5 et 2 ;  A represents a group comprising a number of isocyanate functional groups of between 1.5 and 2.2, preferably between 1.5 and 2.1, and even more preferably between 1.5 and 2;
dans un ratio moléculaire s tœchiométrique de 1,5 à 2,5 environ de polyisocyanate masqué par rapport au polyol ;  in a tecchiometric molecular ratio of from about 1.5 to about 2.5 percent masked polyisocyanate relative to the polyol;
éventuellement un polyisocyanate ayant entre 1,5 et optionally a polyisocyanate having between 1.5 and
3 fonctions NCO ; 3 NCO functions;
éventuellement un plastifiant ;  optionally a plasticizer;
éventuellement un catalyseur;  optionally a catalyst;
éventuellement du solvant et/ou diluant.  optionally solvent and / or diluent.
Selon un autre mode de réalisation particulier, la composition selon l'invention comprend à la fois le polyisocyanate masqué et au moins une partie du prépolymère est un prépolymère masqué qui est le produit de réaction entre :  According to another particular embodiment, the composition according to the invention comprises both the masked polyisocyanate and at least a part of the prepolymer is a masked prepolymer which is the reaction product between:
un polyol ayant entre 1,5 et 3 fonctions OH et un poids moléculaire entre 900 et 3 000 g/mol, de préférence entre 1 000 et 2 800 g/mol et plus préférentiellement entre 1 500 et 2 500 g/mol ; et un polyisocyanate masqué ayant un nombre de fonctions isocyanates compris entre 1,5 et 2,2 tel que décrit précédemment ; a polyol having between 1.5 and 3 OH functions and a molecular weight between 900 and 3000 g / mol, preferably between 1000 and 2800 g / mol and more preferably between 1500 and 2500 g / mol; and a masked polyisocyanate having a number of isocyanate functional groups of between 1.5 and 2.2 as previously described;
dans un ratio tel que le nombre de fonctions NCO du polyisocyanate par rapport au nombre de fonctions OH du polyol soit de 1,5 à 2,5 environ. in a ratio such that the number of NCO functions of the polyisocyanate relative to the number of OH functions of the polyol is from 1.5 to 2.5 approximately.
Ledit polyol ayant entre 1,5 et 3 fonctions OH et un poids moléculaire entre 900 et 3 000 g/mol entrant dans la formation du prépolymère masqué peut notamment être un polyol de type polyéther, polyester, polybutadiène, polycarbonate et leurs mélanges.  Said polyol having between 1.5 and 3 OH functions and a molecular weight between 900 and 3,000 g / mol involved in the formation of the masked prepolymer may in particular be a polyol of the polyether, polyester, polybutadiene, polycarbonate type and their mixtures.
Le polyol de type polyéther peut notamment être un polypropylène glycol, un polyéthylène glycol, un triol de glycérine polypropylène glycol, un triol de glycérine polyéthylène glycol, ou un polytétrahydrofurane .  The polyether type polyol may especially be a polypropylene glycol, a polyethylene glycol, a triol of glycerin polypropylene glycol, a triol of glycerin polyethylene glycol, or a polytetrahydrofuran.
Le polyol de type polyester peut notamment être un polycaprolactone, un polyester d'acides gras dimères comprenant 34 à 36 atomes de carbone, un polyester polyadipate ou un polyester polyphthalate .  The polyester-type polyol may especially be a polycaprolactone, a dimer fatty acid polyester comprising 34 to 36 carbon atoms, a polyadipate polyester or a polyester polyphthalate.
Le polyol polycarbonate peut notamment être un polycarbonate d' hexane-1 , 6-diol .  The polycarbonate polyol may in particular be a hexane-1,6-diol polycarbonate.
De préférence, le polyol ayant entre 1,5 et 3 fonctions OH et un poids moléculaire entre 900 et 3 000 g/mol entrant dans la formation du prépolymère masqué est un polytétrahydrofurane, un polycarbonate d' hexane-1 , 6- diol, un polyester d'acides gras dimères comprenant 34 à 36 atomes de carbone, un polycaprolactone ou un polybutadiène hydroxylé .  Preferably, the polyol having between 1.5 and 3 OH functions and a molecular weight between 900 and 3000 g / mol forming the masked prepolymer is a polytetrahydrofuran, a hexane-1,6-diol polycarbonate, a polyester of dimeric fatty acids comprising 34 to 36 carbon atoms, a polycaprolactone or a hydroxylated polybutadiene.
Selon un mode de réalisation particulier, destiné à la préparation de couche d ' étanchéité, la composition liquide prête à l'emploi selon l'invention comprend:  According to a particular embodiment, intended for the preparation of a sealing layer, the ready-to-use liquid composition according to the invention comprises:
- 2 à 15%, de polyisocyanate masqué;  2 to 15% of masked polyisocyanate;
- 30 à 80%, préférentiellement de 25 à 65% en poids de prépolymère ; - 0 à 40%, préférentiellement de 20 à 30% en poids de plastifiant ; - 30 to 80%, preferably 25 to 65% by weight of prepolymer; 0 to 40%, preferably 20 to 30% by weight of plasticizer;
- 0 à 5%, préférentiellement de 0,02 à 1,5% en poids de catalyseur;  0 to 5%, preferably 0.02 to 1.5% by weight of catalyst;
- 0 à 20%, de préférence de 0 à 10%, et plus préférentiellement encore de 0 à 2% en poids de solvant ;  0 to 20%, preferably 0 to 10%, and more preferably 0 to 2% by weight of solvent;
- 0 à 50%, de préférence 0 à 40% et plus préférentiellement encore 0 à 30% en poids de charges ;  0 to 50%, preferably 0 to 40% and even more preferably 0 to 30% by weight of charges;
les pourcentages étant des pourcentages en poids par rapport au poids total de la composition. the percentages being percentages by weight relative to the total weight of the composition.
Selon un autre mode de réalisation particulier, destiné à la préparation de primaire, la composition liquide prête à l'emploi selon l'invention comprend:  According to another particular embodiment, intended for the preparation of primer, the ready-to-use liquid composition according to the invention comprises:
- 2 à 90%, préférentiellement de 5 à 70% de polyisocyanate masqué;  2 to 90%, preferably 5 to 70% of masked polyisocyanate;
- 10 à 80%, préférentiellement de 15 à 65% en poids de prépolymère ;  - 10 to 80%, preferably 15 to 65% by weight of prepolymer;
- 0 à 40%, préférentiellement de 20 à 30% en poids de plastifiant, de préférence de plastifiant polymérisable ;  0 to 40%, preferably 20 to 30% by weight of plasticizer, preferably of polymerizable plasticizer;
- 0 à 5%, préférentiellement de 0,02 à 1,5% en poids de catalyseur;  0 to 5%, preferably 0.02 to 1.5% by weight of catalyst;
- 0 à 80% de solvant, de préférence de 2 à 30% de solvant et plus préférentiellement encore de 5 à 20% de solvant;  0 to 80% of solvent, preferably 2 to 30% of solvent and more preferably 5 to 20% of solvent;
- 0 à 50%, de préférence 0 à 40% et plus préférentiellement encore 0 à 30% de charges;  0 to 50%, preferably 0 to 40% and more preferably 0 to 30% of charges;
les pourcentages étant des pourcentages en poids du poids total de la composition. the percentages being percentages by weight of the total weight of the composition.
Dans les compositions ci-dessus, le prépolymère est ou bien un prépolymère classique ou bien un mélange de prépolymère classique et de prépolymère masqué. dans les compositions ci-dessus, on peut également utilisé comme plastifiant, un plastifiant polymérisable qui est le produit de réaction entre : In the above compositions, the prepolymer is either a conventional prepolymer or a mixture of conventional prepolymer and masked prepolymer. in the above compositions, it is also possible to use as plasticizer a polymerizable plasticizer which is the reaction product between:
- un composé de type alcool constitué d'une chaîne hydrocarbonée comprenant et/ou étant substituée par un cycle aromatique et/ou un cycle aliphatique et/ou ladite chaîne hydrocarbonée du composé de type alcool est substituée par au moins deux chaînes hydrocarbonées pouvant comporter une insaturation, et où ledit composé de type alcool présente un nombre d'- an alcohol-type compound consisting of a hydrocarbon-based chain comprising and / or being substituted by an aromatic ring and / or an aliphatic ring and / or said hydrocarbon-based chain of the alcohol-type compound is substituted with at least two hydrocarbon-based chains which may comprise a unsaturation, and wherein said alcohol-type compound has a number of
OH compris entre 0,8% et 2,5% ; et OH between 0.8% and 2.5%; and
- un polyisocyanate comprenant 2,1 à 3,2 fonctions isocyanates, de préférence 2,5 à 3,1 fonctions isocyanates ;  a polyisocyanate comprising 2.1 to 3.2 isocyanate functional groups, preferably 2.5 to 3.1 isocyanate functional groups;
tel que décrit dans la demande n° PCT/FR2012/052369 déposée le 18 octobre 2012 au nom de la Demanderesse qui est incorporée par référence. as described in Application No. PCT / FR2012 / 052369 filed on October 18, 2012 in the name of the Applicant which is incorporated by reference.
Selon un mode de réalisation particulier, ces compositions ne contiennent pas de polyisocyanate masqué mais au moins une partie du prépolymère est un prépolymère masqué qui est le produit de réaction entre un polyol et un polyisocyanate masqué ayant un nombre de fonctions isocyanates compris entre 1,5 et 2,2 tel que décrit ci- dessus .  According to a particular embodiment, these compositions do not contain a masked polyisocyanate but at least a part of the prepolymer is a masked prepolymer which is the reaction product between a polyol and a masked polyisocyanate having an isocyanate functional number of between 1.5. and 2.2 as described above.
Selon un autre mode de réalisation particulier, ces compositions comprennent à la fois le polyisocyanate masqué et le prépolymère masqué tels que définis ci-dessus.  According to another particular embodiment, these compositions comprise both the masked polyisocyanate and the masked prepolymer as defined above.
Ces compositions sont stables et présentent une faible toxicité puisqu'elles comprennent moins de 5%, de préférence moins de 4%, plus préférentiellement moins de 3%, plus préf érent iel lement encore moins de 2% et de manière encore plus préférentielle moins de 1% en poids de monomères libres de di i socyanate . Elles peuvent être commercialisées sans étiquetage « R40 : effet cancérigène suspecté - preuves insuffisantes » compte tenu de leur faible teneur en monomères libres de diisocyanate . These compositions are stable and have low toxicity since they comprise less than 5%, preferably less than 4%, more preferably less than 3%, more preferably still less than 2% and even more preferably less than 1% by weight of free diisocyanate monomers. They can be marketed without labeling "R40: carcinogenic effect suspected - insufficient evidence "given their low content of free monomers of diisocyanate.
Les compositions selon l'invention sont en outre stables au stockage étant donné que le polyisocyanate masqué et/ou le prépolymère masqué décrits ci-dessus présentent l'avantage d'être moins réactifs que les polyisocyanates classiques et/ou les prépolymères classiques .  The compositions according to the invention are also storage-stable since the masked polyisocyanate and / or masked prepolymer described above have the advantage of being less reactive than conventional polyisocyanates and / or conventional prepolymers.
Le polyisocyanate masqué décrit ci-dessus étant un bon agent compatibilisant des charges hydrocarbonées, telles que le bitume naturel ou synthétique, et des prépolymères, son utilisation dans des compositions de résine polyuréthane bitumineuses permet de diminuer la quantité de plastifiants exogènes et donc d'éviter l'exsudation de plastifiant exogènes en surface du revêtement formé.  The masked polyisocyanate described above being a good compatibilizing agent for hydrocarbon feeds, such as natural or synthetic bitumen, and prepolymers, its use in bituminous polyurethane resin compositions makes it possible to reduce the amount of exogenous plasticizers and thus to avoid exogenous plasticizer exudation at the surface of the formed coating.
Lorsque les compositions ne comprennent pas de solvant, elles pourront être utilisées en intérieur même dans les pays où la législation est la plus stricte.  When the compositions do not include a solvent, they can be used indoors even in the countries where the legislation is the strictest.
Selon un mode de réalisation avantageux, les présentes compositions contiennent peu ou pas de solvant. Par peu de solvant on entend une teneur en solvant inférieure à 10%, de préférence inférieure à 5%, et plus préférentiellement inférieure à 2% en poids.  According to an advantageous embodiment, the present compositions contain little or no solvent. By little solvent is meant a solvent content of less than 10%, preferably less than 5%, and more preferably less than 2% by weight.
Selon un mode de réalisation préféré, les compositions selon l'invention ne contiennent pas de solvant.  According to a preferred embodiment, the compositions according to the invention do not contain a solvent.
Utilisation  use
L'invention a également pour objet l'utilisation du polyisocyanate masqué tel que défini précédemment et dont le nombre de fonctions isocyanate est compris entre 1,5 et 2 , 2 pour la préparation d'un prépolymère masqué, par réaction dudit polyisocyanate masqué sur un polyol ayant entre 1,5 et 3 fonctions OH et un poids moléculaire entre 900 et 3 000 g/mol, de préférence entre 1 000 et 2 800 g/mol et plus préférentiellement entre 1 500 et 2 500 g/mol, dans un ratio tel que le nombre de fonctions NCO du polyisocyanate par rapport au nombre de fonctions OH du polyol soit de 1,5 à 2,5 environ. The subject of the invention is also the use of the masked polyisocyanate as defined above, the number of isocyanate functional groups of which is between 1.5 and 2, 2 for the preparation of a masked prepolymer, by reaction of said masked polyisocyanate with a polyol having between 1.5 and 3 OH functions and a molecular weight between 900 and 3000 g / mol, preferably between 1000 and 2800 g / mol and more preferably between 1500 and 2500 g / mol, in a ratio such that the number of NCO functions of the polyisocyanate relative to the number of OH functions of the polyol is from 1.5 to 2.5 approximately.
L'invention a également pour objet l'utilisation du polyisocyanate masqué et/ou du prépolymère masqué tels que définis précédemment dans des compositions de résine polyuréthane, de préférence dans des compositions de résine polyuréthane monocomposante stables. L'utilisation du polyisocyanate masqué et/ou du prépolymère masqué dans des compositions de résine polyuréthane permet d'obtenir une teneur en monomères libres de diisocyanate inférieure à 5%, de préférence infér ï ΘΙΙΓΘ cL 4~6 # plus préférentiellement inférieure à 3%, plus préférentiellement encore inférieure à 2% et de manière encore plus préférentielle inférieure à 1% en poids de monomères libres de diisocyanate. De plus, l'utilisation du polyisocyanate masqué dans des compositions de résine polyuréthane améliore la compatibilisation entre les charges hydrocarbonées et les prépolymères, ce qui permet d'obtenir une composition stable.  The invention also relates to the use of the masked polyisocyanate and / or the masked prepolymer as defined above in polyurethane resin compositions, preferably in stable one-component polyurethane resin compositions. The use of the masked polyisocyanate and / or the prepolymer masked in polyurethane resin compositions makes it possible to obtain a content of free monomers of diisocyanate of less than 5%, preferably less than 4%, more preferably less than 3%. more preferably still less than 2% and even more preferably less than 1% by weight of free diisocyanate monomers. In addition, the use of the masked polyisocyanate in polyurethane resin compositions improves the compatibilization between the hydrocarbon feeds and the prepolymers, resulting in a stable composition.
L'invention porte également sur l'utilisation de la composition selon l'invention pour réaliser des revêtements, notamment des revêtements d ' étanchéité, ne présentant pas de défauts de surface, tels que des bulles, suffisamment résistants pour l'extérieur, non protégés et éventuellement circulables. Les revêtements obtenus présentent une reprise en eau tout à fait satisfaisante, c'est-à-dire inférieure à 8% après 28 jours d'immersion dans de l'eau à 20 °C. Les revêtements obtenus par l'utilisation de la composition selon l'invention peuvent recouvrir des surfaces horizontales, obliques, verticales, rugueuses et/ou comportant des points singuliers.  The invention also relates to the use of the composition according to the invention for producing coatings, in particular sealing coatings, having no surface defects, such as bubbles, sufficiently resistant to the exterior, unprotected and possibly circulable. The coatings obtained have a water recovery quite satisfactory, that is to say less than 8% after 28 days of immersion in water at 20 ° C. The coatings obtained by the use of the composition according to the invention can cover horizontal, oblique, vertical, rough surfaces and / or with singular points.
Les compositions de résine polyuréthane non- bitumineuses sont préférentiellement utilisées pour étanchéifier des surfaces horizontales circulables en extérieur, telles que des balcons, des gradins de stade, des parkings, des cours d'immeuble, etc.. The non-bituminous polyurethane resin compositions are preferably used for to waterproof horizontal surfaces that can be used outdoors, such as balconies, stadium stands, parking lots, courtyards, etc.
Les compositions de résine polyuréthane bitumineuses sont préférentiellement utilisées pour réaliser des relevés, c'est-à dire pour réaliser un revêtement étanche entre une surface bitumineuse et un mur vertical ou un point singulier ou encore pour rénover des toitures.  The bituminous polyurethane resin compositions are preferably used to make readings, that is to say to achieve a tight coating between a bituminous surface and a vertical wall or a singular point or to renovate roofs.
L'invention va être décrite plus en détails à l'aide des exemples suivants qui sont donnés à titre purement illustratif .  The invention will be described in more detail with the aid of the following examples which are given purely by way of illustration.
EXEMPLES  EXAMPLES
Dans les exemples, les parts sont exprimées en poids. Les viscosités sont mesurées à l'aide d'un viscosimètre Brookfield, mobile 5 ou 6, vitesse 20 tr/min à 23°C, moins d'une semaine après la fabrication du produit ou de la composition .  In the examples, the parts are expressed by weight. Viscosities are measured using a Brookfield Viscometer, mobile 5 or 6, at 20 rpm at 23 ° C, less than one week after manufacture of the product or composition.
Dans les exemples, les produits commerciaux suivants sont utilisés :  In the examples, the following commercial products are used:
Suprasec® 2385 : MDI modifié ayant 2 fonctions isocyanates commercialisé par la société HUNTSMAN.  Suprasec® 2385: Modified MDI having 2 isocyanate functional groups marketed by Huntsman.
Suprasec® 5025 : MDI polymérique ayant 2,7 fonctions isocyanates commercialisé par la société HUNTSMAN.  Suprasec® 5025: polymeric MDI with 2.7 isocyanate functions marketed by the company HUNTSMAN.
Ruet as o lv® Di : huile plastifiante diisopropylnaphthalène commercialisée par la société RKS.  Ruet as o lv® Di: diisopropylnaphthalene plasticizing oil marketed by RKS.
Sovermol® 920 : polyol polyéther polycarbonate ayant 2 fonctions OH commercialisé par la société Cognis.  Sovermol® 920: Polyether polyether polycarbonate having 2 OH functions marketed by Cognis.
Voranol® 2000 : polypropylèneglycol ayant un poids moléculaire de 2000 g/mol (CAS 025322-69-4) commercialisé par la société DOW CHEMICAL.  Voranol® 2000: polypropylene glycol having a molecular weight of 2000 g / mol (CAS 025322-69-4) sold by the company DOW CHEMICAL.
Polybutadiène 3000 : diol polybutadiène de masse molaire 3 000 g/mol. Desmodur® L75 : polyisocyanate aromatique à base de TDI à 75% dans l'acétate d' éthyle commercialisé par la société BAYER. Polybutadiene 3000: polybutadiene diol of molar mass 3000 g / mol. Desmodur® L75: aromatic polyisocyanate based on 75% TDI in ethyl acetate marketed by Bayer.
PolyTHF® 2000 : polytétrahydrofurane ayant 2 fonctions NCO et un poids moléculaire de 2 000 g/mol commercialisé par la société BASF.  PolyTHF® 2000: polytetrahydrofuran having 2 NCO functions and a molecular weight of 2,000 g / mol sold by the company BASF.
Jeffcat® DMDLS : aminé tertiaire commercialisée par la société HUNTSMAN.  Jeffcat® DMDLS: tertiary amine marketed by the company HUNTSMAN.
PTSI : para-toluènesulfonyle isocyanate.  PTSI: para-toluenesulfonyl isocyanate.
EXEMPLE 1 : préparation d'un polyisocyanate masqué  EXAMPLE 1 Preparation of a Masked Polyisocyanate
Sur 37 parties de Suprasec® 5025, on introduit progressivement 10,2 parties d'hexanol, de façon à ce que la température soit inférieure à 50°C.  On 37 parts of Suprasec® 5025, 10.2 parts of hexanol are gradually introduced so that the temperature is below 50.degree.
Lorsque l'ajout d'hexanol est terminé, on laisse le mélange revenir à la température ambiante.  When the addition of hexanol is complete, the mixture is allowed to warm to room temperature.
On obtient alors une viscosité de 5 000 centipoises telle que mesurée au viscosimètre Brookfield à 23°C, avec un module R5 à une vitesse de 20tr/min.  A viscosity of 5,000 centipoise is thus obtained as measured by the Brookfield viscometer at 23 ° C., with a module R5 at a speed of 20 rpm.
EXEMPLE 2 : préparation d'un polyisocyanate masqué  EXAMPLE 2 Preparation of a Masked Polyisocyanate
Sur 37 parties de Suprasec® 5025 dans 32,3 parties de On 37 parts of Suprasec® 5025 in 32.3 parts of
Ruetasolv® Di, on introduit progressivement 12 parties de 2-éthylhexanol , de façon à ce que la température soit inférieure à 50°C. Ruetasolv® Di, 12 parts of 2-ethylhexanol are gradually introduced, so that the temperature is below 50 ° C.
Lorsque l'ajout de 2-éthylhexanol est terminé, on laisse le mélange revenir à la température ambiante.  When the addition of 2-ethylhexanol is complete, the mixture is allowed to warm to room temperature.
On obtient alors une viscosité de 1 000 centipoises telle que mesurée au viscosimètre Brookfield à 23°C, avec un module R5 à une vitesse de 20tr/min.  This gives a viscosity of 1000 centipoise as measured by the Brookfield viscometer at 23 ° C, with a R5 module at a speed of 20tr / min.
EXEMPLE 3 : préparation d'un polyisocyanate masqué  EXAMPLE 3 Preparation of a Masked Polyisocyanate
Sur 900 parties de Desmodur® L75 on ajoute progressivement 100 parties d'hexanol, de façon à ce que la température soit inférieure à 50°C.  On 900 parts of Desmodur® L75, 100 parts of hexanol are gradually added, so that the temperature is below 50 ° C.
Lorsque l'ajout d'hexanol est terminé, on laisse le mélange revenir à la température ambiante. On obtient alors une viscosité de 2 600 centipoises telle que mesurée au viscosimètre Brookfield à 23°C, avec un module R5 à une vitesse de 20tr/min. When the addition of hexanol is complete, the mixture is allowed to warm to room temperature. A viscosity of 2,600 centipoise is thus obtained as measured by the Brookfield viscometer at 23 ° C., with a module R5 at a speed of 20 rpm.
module R5 à une vitesse de 20tr/min.  R5 module at a speed of 20tr / min.
EXEMPLE 4 : préparation d'un polyisocyanate masqué  EXAMPLE 4 Preparation of a Masked Polyisocyanate
Sur 37 parties de Suprasec® 5025 dans 30 parties de d'acétate de butyle, on introduit progressivement 130 parties de 2-éthylhexanol , de façon à ce que la température soit inférieure à 50°C.  On 37 parts of Suprasec® 5025 in 30 parts of butyl acetate, 130 parts of 2-ethylhexanol are gradually introduced, so that the temperature is below 50 ° C.
Lorsque l'ajout de 2-éthylhexanol est terminé, on laisse le mélange revenir à la température ambiante.  When the addition of 2-ethylhexanol is complete, the mixture is allowed to warm to room temperature.
On obtient alors une viscosité de 750 centipoises telle que mesurée au viscosimètre Brookfield à 23°C, avec un module R5 à une vitesse de 20tr/min.  This gives a viscosity of 750 centipoises as measured by Brookfield viscometer at 23 ° C, with a module R5 at a speed of 20tr / min.
EXEMPLE 5 : préparation d'un prépolymère avec un polyisocyanate masqué  EXAMPLE 5 Preparation of a Prepolymer with a Masked Polyisocyanate
On prépare un prépolymère par réaction de 100 parties de PolyTHF® 2000, 75 parties de polyisocyanate masqué préparé à l'exemple 1. On agite le mélange à 70 °C pendant lhl5.  A prepolymer was prepared by reacting 100 parts of PolyTHF 2000 with 75 parts of masked polyisocyanate prepared in Example 1. The mixture was stirred at 70 ° C. for 1 hour.
La teneur en monomères libres de diisocyanate est inférieure à 5%.  The content of free monomers of diisocyanate is less than 5%.
EXEMPLE 6 : préparation d' un prépolymère avec un polyisocyanate masqué  EXAMPLE 6 Preparation of a Prepolymer with a Masked Polyisocyanate
On prépare un prépolymère par réaction de 200 parties de Sovermol® 920, 45 parties de Suprasec® 2385 et 180 parties de polyisocyanate masqué préparé à l'exemple 2. On agite le mélange à 70°C pendant lhl5.  A prepolymer was prepared by reaction of 200 parts of Sovermol® 920, 45 parts of Suprasec® 2385 and 180 parts of masked polyisocyanate prepared in Example 2. The mixture was stirred at 70 ° C for 1 hr.
La teneur en monomères libres de diisocyanate est de 4,5%.  The content of free monomers of diisocyanate is 4.5%.
EXEMPLE 7 : préparation d' un prépolymère avec un polyisocyanate masqué  EXAMPLE 7 Preparation of a Prepolymer with a Masked Polyisocyanate
On prépare un prépolymère par réaction de 3000 parties de polybutadiène 3000, 135 parts de butane-1, 4-diol, 540 parts de Suprasec® 2385, 800 parties de polyisocyanate masqué préparé à l'exemple 4. On agite le mélange à 70°C pendant lhl5. A prepolymer is prepared by reaction of 3000 parts of polybutadiene 3000, 135 parts of butane-1,4-diol, 540 parts of Suprasec® 2385, 800 parts of masked polyisocyanate prepared in Example 4. The mixture was stirred at 70 ° C for 1 hr.
La teneur en monomères libres de diisocyanate est inférieure à 5%.  The content of free monomers of diisocyanate is less than 5%.
EXEMPLE 8 : composition de primaire (comparatif)  EXAMPLE 8: Primary composition (comparative)
On prépare un prépolymère par réaction de 100 parties de Voranol® 2000 et 54 parties de Suprasec® 2385. On agite le mélange à 80 °C pendant 2 heures.  A prepolymer is prepared by reacting 100 parts Voranol® 2000 and 54 parts Suprasec® 2385. The mixture is stirred at 80 ° C for 2 hours.
Puis on prépare la formulation de primaire suivante : Then the following primary formulation is prepared:
154 parties du prépolymère précédent, 154 parts of the previous prepolymer,
20 parties de Suprasec® 2385,  20 parts of Suprasec® 2385,
40 parties Xylène.  40 parts Xylene.
La composition peut être appliquée comme primaire.  The composition can be applied as a primary.
La composition préparée présente une viscosité The prepared composition has a viscosity
Brookfield module 5 à 23°C de 400 centipoises. Brookfield modulates 5 at 23 ° C of 400 centipoise.
La composition est stockée pendant 4 mois à 20°C. Après 4 mois, la composition devient rapidement homogène lorsqu'on la mélange avec un bâton, aucun déphasage n'est observé.  The composition is stored for 4 months at 20 ° C. After 4 months, the composition quickly becomes homogeneous when mixing with a stick, no phase shift is observed.
La teneur en monomères libres de diisocyanate est supérieure à 5%. Un tel produit est étiqueté « R40 : effet cancérigène suspecté - preuves insuffisantes » en Europe et "dangereux" en Asie.  The content of free monomers of diisocyanate is greater than 5%. Such a product is labeled "R40: suspected carcinogenic effect - insufficient evidence" in Europe and "dangerous" in Asia.
EXEMPLE 9 : composition de primaire  EXAMPLE 9: Primary composition
On prépare un prépolymère par réaction de 100 parties de Voranol® 2000 et 91 parties de polyisocyanate masqué préparé à l'exemple 1. On agite le mélange à 80 °C pendant 2 heures .  A prepolymer was prepared by reacting 100 parts of Voranol® 2000 and 91 parts of the masked polyisocyanate prepared in Example 1. The mixture was stirred at 80 ° C for 2 hours.
On prépare une solution de primaire en mélangeant :  A primer solution is prepared by mixing:
154 parties du prépolymère précédent,  154 parts of the previous prepolymer,
35 parties du polyisocyanate masqué préparé à 35 parts of the masked polyisocyanate prepared
1 ' exemple 1 , Example 1
70 parties de xylène. Cette composition monocomposante est stable et peut être appliquée au rouleau pour faire un primaire en extérieur. 70 parts of xylene. This one-component composition is stable and can be applied to the roll to make a primer outdoors.
La teneur en monomères libres de diisocyanate est inférieure à 1%. Une telle composition pourra être commercialisée sans étiquetage « R40 : effet cancérigène suspecté - preuves insuffisantes ».  The content of free monomers of diisocyanate is less than 1%. Such a composition may be marketed without labeling "R40: suspected carcinogenic effect - insufficient evidence".
EXEMPLE 10 : composition bitumineuse  EXAMPLE 10 Bituminous Composition
Dans un réacteur on prépare le cut-back 160/220 + PTSI. On chauffe tout d'abord 80 parts de bitume de grade 160/220 fondu à 110°C auquel on incorpore 20 parts de toluène. On agite à 1 200 tr/min pendant 4 minutes et on laisse le mélange revenir à température ambiante. On ajoute alors 1 part de PTSI et on agite à 1 200 tr/min pendant 4 minutes .  In a reactor, the 160/220 + PTSI cut-back is prepared. First heated 80 parts of bitumen grade 160/220 melted at 110 ° C which incorporates 20 parts of toluene. It is stirred at 1200 rpm for 4 minutes and the mixture is allowed to warm to room temperature. 1 part of PTSI is then added and the mixture is stirred at 1200 rpm for 4 minutes.
Dans un réacteur on mélange les ingrédients suivants afin de former la composition de résine polyuréthane  In a reactor the following ingredients are mixed to form the polyurethane resin composition
100 parts de prépolymère masqué synthétisé à l'exemple 100 parts of masked prepolymer synthesized with the example
5, 5
100 parts de cut-back 160/220 + PTSI synthétisé ci- dessus, et l'on agite ce mélange pendant 3 minutes.  100 parts of 160/220 + PTSI cut-back synthesized above, and this mixture is stirred for 3 minutes.
15 parts de xylène,  15 parts of xylene,
0,2 parts de Jeffcat® DMDLS .  0.2 parts of Jeffcat® DMDLS.
On agite pendant 3 minutes. On obtient une composition liquide pouvant être utilisée pour faire un revêtement d'étanchéité sur toiture. La composition a une teneur en monomères libres de diisocyanate inférieure à 1%. Une telle composition pourra être commercialisée sans étiquetage « R40 : effet cancérigène suspecté - preuves insuffisantes ».  Stirred for 3 minutes. A liquid composition is obtained which can be used to make a waterproofing coating on a roof. The composition has a diisocyanate free monomer content of less than 1%. Such a composition may be marketed without labeling "R40: suspected carcinogenic effect - insufficient evidence".
EXEMPLE 11 : composition bitumineuse  EXAMPLE 11 Bituminous Composition
Dans un réacteur on prépare le cut-back 160/220 + PTSI. On chauffe tout d'abord 80 parts de bitume de grade 160/220 fondu à 110°C auquel on incorpore 20 parts de toluène. On agite à 1 200 tr/min pendant 4 minutes et on laisse le mélange revenir à température ambiante. On ajoute alors 1 part de PTSI et on agite à 1 200 tr/min pendant 4 minutes . In a reactor, the 160/220 + PTSI cut-back is prepared. First heated 80 parts of bitumen grade 160/220 melted at 110 ° C which incorporates 20 parts of toluene. Stirred at 1200 rpm for 4 minutes and allow the mixture to come to room temperature. 1 part of PTSI is then added and the mixture is stirred at 1200 rpm for 4 minutes.
Dans un réacteur on mélange les ingrédients suivants afin de former la composition de résine polyuréthane  In a reactor the following ingredients are mixed to form the polyurethane resin composition
500 parts de prépolymère masqué synthétisé à l'exemple 500 parts of masked prepolymer synthesized with the example
7, 7
500 parts de cut-back 160/220 + PTSI synthétisé ci- dessus, et l'on agite ce mélange pendant 3 minutes.  500 parts of 160/220 + PTSI cut-back synthesized above, and this mixture is stirred for 3 minutes.
1 part de Jeffcat® DMDLS .  1 part of Jeffcat® DMDLS.
On agite pendant 3 minutes. On obtient une composition liquide pouvant être utilisée pour faire un revêtement d'étanchéité sur toiture. La composition a une teneur en monomères libres de diisocyanate inférieure à 1%. Une telle composition pourra être commercialisée sans étiquetage « R40 : effet cancérigène suspecté - preuves insuffisantes ».  Stirred for 3 minutes. A liquid composition is obtained which can be used to make a waterproofing coating on a roof. The composition has a diisocyanate free monomer content of less than 1%. Such a composition may be marketed without labeling "R40: suspected carcinogenic effect - insufficient evidence".

Claims

REVENDICATIONS
1. Composition polyuréthane qui comprend : 1. Polyurethane composition which comprises:
au moins un polyisocyanate masqué répondant à la formule suivante at least one masked polyisocyanate corresponding to the following formula
où :  or :
- B représente alkyle,  B represents alkyl,
- A représente un groupe comportant un nombre de fonctions isocyanates compris entre 1,5 et 2,2, de préférence entre 1,5 et 2,1, et plus préférentiellement encore entre 1,5 et 2 ;  A represents a group comprising a number of isocyanate functional groups of between 1.5 and 2.2, preferably between 1.5 and 2.1, and even more preferably between 1.5 and 2;
au moins un prépolymère ;  at least one prepolymer;
éventuellement un plastifiant ;  optionally a plasticizer;
éventuellement un catalyseur ;  optionally a catalyst;
éventuellement du solvant et/ou diluant ;  optionally solvent and / or diluent;
éventuellement une charge.  possibly a charge.
2. Composition polyuréthane qui comprend : 2. Polyurethane composition which comprises:
au moins un prépolymère masqué formé par réaction entre :  at least one masked prepolymer formed by reaction between:
- un polyol ayant entre 1,5 et 3 fonctions OH et un poids moléculaire entre 900 et 3 000 g/mol, de préférence entre 1 000 et 2 800 g/mol et plus préférentiellement entre 1 500 et 2 500 g/mol ; et  a polyol having between 1.5 and 3 OH functions and a molecular weight between 900 and 3000 g / mol, preferably between 1000 and 2800 g / mol and more preferably between 1500 and 2500 g / mol; and
- un polyisocyanate masqué répondant à la formule suivante a masked polyisocyanate corresponding to the following formula
où :  or :
- B représente alkyle, - A représente un groupe comportant un nombre de fonctions isocyanates compris entre 1,5 et 2,2, de préférence entre 1,5 et 2,1, et plus préférentiellement encore entre 1,5 et 2 ; B represents alkyl, A represents a group comprising a number of isocyanate functional groups of between 1.5 and 2.2, preferably between 1.5 and 2.1, and even more preferably between 1.5 and 2;
dans un ratio tel que le nombre de fonctions NCO du polyisocyanate masqué par rapport au nombre de fonctions OH du polyol ou mélange de polyols soit de 1,5 à 2,5 environ;  in a ratio such that the number of NCO functions of the masked polyisocyanate relative to the number of OH functions of the polyol or mixture of polyols is from 1.5 to about 2.5;
- éventuellement un polyisocyanate ayant entre 1,5 et optionally a polyisocyanate having between 1.5 and
3 fonctions NCO ; 3 NCO functions;
éventuellement un plastifiant ;  optionally a plasticizer;
éventuellement un catalyseur ;  optionally a catalyst;
éventuellement du solvant et/ou diluant.  optionally solvent and / or diluent.
3. Composition polyuréthane selon la revendication 2 comprenant, en outre, un polyisocyanate masqué répondant à la formule suivante ; The polyurethane composition of claim 2 further comprising a masked polyisocyanate having the following formula;
où :  or :
- B représente alkyle,  B represents alkyl,
- A représente un groupe comportant un nombre de fonctions isocyanates compris entre 1,5 et 2,2, de préférence entre 1,5 et 2,1, et plus préférentiellement encore entre 1,5 et 2.  - A represents a group comprising a number of isocyanate functions of between 1.5 and 2.2, preferably between 1.5 and 2.1, and more preferably between 1.5 and 2.
4. Composition polyuréthane selon l'une quelconque des revendications 1 à 3, caractérisée en ce que ladite composition comprend moins de 5%, de préférence moins de 4%, plus préférentiellement moins de 3%, plus préférentiellement encore moins de 2% et de manière encore plus préférentielle moins de 1% en poids de monomères libres de diisocyanate . 4. Polyurethane composition according to any one of claims 1 to 3, characterized in that said composition comprises less than 5%, preferably less than 4%, more preferably less than 3%, more preferably still less than 2% and even more preferably less than 1% by weight of free diisocyanate monomers.
5. Composition polyuréthane selon l'une quelconque des revendications 2 à 4 où le polyol entrant dans la formation du prépolymère masqué est un polyol de type polyéther, polyester, polybutadiène, polycarbonate et leurs mélanges. 5. Polyurethane composition according to any one of claims 2 to 4 wherein the polyol forming the masked prepolymer is a polyol polyether type, polyester, polybutadiene, polycarbonate and mixtures thereof.
6. Composition polyuréthane selon l'une quelconque des revendications 2 à 5 où le polyol est un polytétrahydrofurane, un polycarbonate d'hexane-1, 6-diol, un polyester d'acides gras dimères comprenant 34 à 36 atomes de carbone, un polycaprolactone ou un polybutadiène hydroxylé .  The polyurethane composition according to any one of claims 2 to 5 wherein the polyol is a polytetrahydrofuran, a hexane-1,6-diol polycarbonate, a dimer fatty acid polyester comprising 34 to 36 carbon atoms, a polycaprolactone or a hydroxylated polybutadiene.
7. Composition polyuréthane selon l'une quelconque des revendications 1 à 6 où B représente un alkyle, éventuellement insaturé, en C2-C20, de préférence en C3-C12, plus préférentiellement encore en C4-C10. 7. Polyurethane composition according to any one of claims 1 to 6 wherein B represents an optionally unsaturated C 2 -C 20 alkyl, preferably C 3 -C 12 , more preferably still C 4 -C 10.
8. Composition polyuréthane selon l'une quelconque des revendications 1 à 7 où le "groupe" de A est:  The polyurethane composition according to any one of claims 1 to 7 wherein the "group" of A is:
une chaîne polymérique (provenant du MDI polymérique) répondant à la formule (Al) : (Al), a polymeric chain (from the polymeric MDI) corresponding to the formula (Al): (Al),
un radical répondant à la formule (A2) ou à un radical apparenté d'un trimère de TDI :  a radical having the formula (A2) or a related radical of a TDI trimer:
(A2) ,  (A2),
- un radical répondant à l'une des formules (A3) et/ou (A4) ou à un radical apparenté d'un trimère de HDI : a radical corresponding to one of the formulas (A3) and / or (A4) or to a related radical of a trimer of HDI:
(A3) (A4),  (A3) (A4),
un radical répondant à la formule (A5) ou à un a radical of formula (A5) or a
'un trimère d' IPDI :  a trimer of IPDI:
(A5) ,  (AT 5) ,
où chaque trait en pointillé représente un point d'attache à une fonction NCO ou au groupe -NHCOO-B du polyisocyanate masqué et à la condition qu'il y ait au moins un trait en 0 pointillé qui soit un point d'attache au groupe -NHCOO-B et que les traits restants représentent un point d'attache à une fonction NCO.  where each dashed line represents a point of attachment to an NCO function or to the -NHCOO-B group of the masked polyisocyanate and provided that there is at least one dashed line that is a point of attachment to the group -NHCOO-B and the remaining lines represent a point of attachment to an NCO function.
9. Utilisation d'un polyisocyanate masqué répondant à la formule suivante 9. Use of a Masked Polyisocyanate Having the Following Formula
où :  or :
- B représente alkyle,  B represents alkyl,
- A représente un groupe comportant un nombre de fonctions isocyanates compris entre 1,5 et 2,2, de préférence entre 1,5 et 2,1, et plus préférentiellement encore entre 1,5 et 2 ;  A represents a group comprising a number of isocyanate functional groups of between 1.5 and 2.2, preferably between 1.5 and 2.1, and even more preferably between 1.5 and 2;
pour la préparation d'un prépolymère masqué, par réaction dudit polyisocyanate masqué sur un polyol ayant entre 1,5 et 3 fonctions OH et un poids moléculaire entre 900 et 3 000 g/mol, de préférence entre 1 000 et 2 800 g/mol et plus préférentiellement entre 1 500 et 2 500 g/mol, dans un ratio tel que le nombre de fonctions NCO du polyisocyanate masqué par rapport au nombre de fonctions OH du polyol soit de 1,5 à 2,5 environ. for the preparation of a masked prepolymer, by reacting said masked polyisocyanate with a polyol having between 1.5 and 3 OH functions and a molecular weight between 900 and 3000 g / mol, preferably between 1000 and 2800 g / mol and more preferably between 1500 and 2500 g / mol, in a ratio such as the number of functions NCO of the polyisocyanate masked with respect to the number of OH functions of the polyol is from 1.5 to 2.5 approximately.
10. Utilisation d'un polyisocyanate masqué et/ou d'un prépolymère masqué tels que définis à la revendication 1 et 2 dans des compositions de résine p o 1 yu r é t hane , de préférence dans des compositions de résine polyuréthane monocomposantes stables.  10. Use of a masked polyisocyanate and / or masked prepolymer as defined in claim 1 and 2 in resin compositions, preferably in stable one-component polyurethane resin compositions.
EP12790594.1A 2011-10-20 2012-10-18 Masked polyisocyanate and uses thereof Withdrawn EP2768801A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1159492A FR2981649B1 (en) 2011-10-20 2011-10-20 MASK POLYISOCYANATE AND USES THEREOF
PCT/FR2012/052372 WO2013057430A1 (en) 2011-10-20 2012-10-18 Masked polyisocyanate and uses thereof

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EP (1) EP2768801A1 (en)
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US20140243484A1 (en) 2014-08-28
US9518144B2 (en) 2016-12-13
FR2981649A1 (en) 2013-04-26
CA2850286A1 (en) 2013-04-25
WO2013057430A1 (en) 2013-04-25

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