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
  • C08G18/70—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
  • 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
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
  • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D317/34—Oxygen atoms
• • 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
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • 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
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/7806—Nitrogen containing -N-C=0 groups
  • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
  • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
• • 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
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• • 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
  • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
  • C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
• • 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
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/02—Polyureas

Definitions

• the present invention relates to novel modified isocyanate derivatives and compositions containing the same. It relates more particularly to novel isocyanate derivatives comprising at least one isocyanate function modified with a group having crosslinking functionality and to compositions containing the same.
• the invention also relates to a process for preparing these derivatives or compositions, and to the use of these derivatives and compositions in the manufacture of coatings.
• the present invention relates in particular to monomer, oligomer or polymer compounds and mixtures thereof bearing isocyanate functions, at least one of which is modified with a group with crosslinking functionality, the crosslinking functional group also being known as a crosslinking functional arm.
• the present invention relates more specifically to polyisocyanates in which at least one isocyanate functional group is modified with a group as defined above.
• the present invention also relates to processes for obtaining these novel derivatives of modified polyisocyanates. It is also directed towards the use of the above derivatives in compositions that are useful for preparing polymers, in particular polycondensates and reticulates derived from the reaction of said polyisocyanates with suitable nucleophilic co-reagents. This preparation is the one which is exploited in industrial applications, such as coatings of any kind, in particular those on textiles, glasses, papers, metals, building materials and paints.
• a “masking agent” for an isocyanate function is a compound that is capable of masking this function at low temperature to prevent it from reacting with a group, and that comes off at high temperature to restore the isocyanate function initially present.
• crosslinking modifier group of the present invention does not constitute such a group, since it does not come off under the conditions for crosslinking the isocyanate function with which the compound which bare it has reacted.
• this group is capable under suitable conditions of liberating a functional group which is in turn capable of reacting with a reactive function to give especially a crosslinking reaction.
• One object of the present invention is to provide novel isocyanate derivatives that are capable of reacting with a suitable nucleophilic group and of giving various foam reticulates without, however, having the drawbacks of the free isocyanate groups.
• Another aim of the present invention is to provide isocyanates comprising a crosslinking functional group or arm, which are nontoxic or only sparingly toxic.
• Another object of the invention is to provide novel modified isocyanate derivatives comprising at least one crosslinking functional group, which are economical to prepare.
• Another object of the invention is to provide novel isocyanates comprising a crosslinking functional group, giving access to optionally crosslinked polymers (or rather to polycondensates), which satisfy the specifications for the applications.
• Another object of the invention is to provide a process for preparing polymers and/or reticulates from said modified isocyanates, comprising a crosslinking group as defined above.
• cyclic carbonates obtained from organic polyisocyanates, in particular from aromatic polyisocyanates, is known from EP 0 419 114.
• the carbonates react with the isocyanate group of the polyisocyanate compounds, where necessary in the presence of a polyol, with concomitant release of CO 2 , which causes expansion of the foam, which may be of polyurethane type.
• EP 337 926 discloses, in the broad sense, aqueous emulsions of linear polymers, the polymers being of varied nature and comprising at least two chain-end cyclocarbonate groups intended to allow extension of the chain by reaction with an epoxy group.
• cyclic carbonates can produce, by reaction with polyisocyanates, not a foam but stable modified polyisocyanates bearing a cyclic carbonate group, which, by subsequent reaction with a compound bearing a reactive hydrogen, led to coatings for nonexpanded industrial structures, in particular paints or varnishes.
• the polyisocyanates thus modified can give, by reaction with a reactive nucleophilic molecule, crosslinking reactions with consumption of an alcohol function.
• isocyanates advantageously diisocyanates, preferably modified polyisocyanates, of formula I below:
• Iso is a (poly)isocyanate residue (after having disregarded an isocyanate function);
• X represents an atom or a group of atoms resulting from the reaction of a compound bearing a —X′H group, where X′ represents X or —OCOX, optionally after decarboxylation when X′ represents OCOX with the isocyanate function;
• A represents a bond or a linear, branched or cyclic hydrocarbon-based chain containing from 1 to 30, advantageously from 1 to 18 and preferably 1 to 5 carbon atoms;
• R 1 represents H or a C 1 -C 6 alkyl group
• Q is absent or represents an oxygen or sulfur atom or a hydrocarbon-based chain as defined for A;
• Z represents a bond or a hydrocarbon-based chain as defined for A
• Y represents a bond or a hydrocarbon-baaed chain as defined for A:
• W is absent or represents an oxygen or sulfur atom or a hydrocarbon-based chain as defined for A;
• the compounds as defined above are chemically stable for a period of more than one day, advantageously more than one week, preferably more than one month and more preferably more than three months under usual storage conditions and in the absence of reactive nucleophilic compounds.
• hydrocarbon-based chain means a chain comprising carbon and hydrogen atoms and optionally interrupted with one or more hetero atoms, especially from columns IV, V and VI and in particular IV A, V A and VI A of the Periodic Table of the Elements (O, S, Si, etc.) or hetero groups (—NH, —N(substituted)) or substituted with one or more groups selected in particular from aryl, cycloalkyl, heteroalkyl, halogen (in particular fluorine), a linear or branched halogenated (in particular fluorinated) or perhalogenated (in particular perfluorinated) carbon-based chain and a carboxyl, primary or secondary amino, NO 2 or CN group.
• hetero groups —NH, —N(substituted)
• the hydrocarbon-based chain may be linear or branched, or even cyclic.
• It may be saturated or unsaturated.
• X may in particular represent the following functions:
• R represents a hydrogen atom or a hydrocarbon-based group generally containing from 1 to 12 and preferably from 1 to 5 carbon atoms, optionally interrupted with hetero atoms or hetero groups as defined above or optionally bearing substituents as defined above,
• R′ represents a 4- to 10-membered hydrocarbon-based chain as defined above which is optionally interrupted with one or more hetero atoms (in particular from columns IV A, V A and VI A of the Periodic Table of the Elements) such as O, S or Si or hetero groups selected in particular from —N ⁇ and —NR— (R being as defined above) and/or substituted with one or more substituents as defined above, the chain R′ forming with NH a nitrogen ring, advantageously a polynitrogen and preferably a dinitrogen ring, such as a piperazino ring,
• a hydrocarbon-based, preferably a linear or branched alkylene chain comprising from 1 to 12, preferably from 1 to 7 carbon atoms, optionally interrupted with hetero atoms or hetero groups as defined above or bearing a substituents as defined above, or A′-COO—, where A′ is a hydrocarbon based chain preferably a linear or branched alkylene chain as defined above, the —COO— group being lined to the —A— group as defined above,
• R being as defined above.
• X represents an oxygen atom, or a C 1 -C 12 alkylene chain or a (C 1 -C 12 )alkylene-COO— chain,
• A represents a —CH 2 — group
• Y represents —CH 2 —
• Z represents a bond or —CH 2 —, preferably a bond
• R 1 represents H or a C 1 -C 6 linear or branched alkyl group.
• One crosslinking group which is preferred is the one obtained by reacting an isocyanate function with glyceryl carbonate.
• Another group which is preferred is the one obtained by reacting an isocyanate function with fatty acid carbonates or esters thereof, such as oleic acid 8,9-carbonate.
• the isocyanates concerned may be monoisocyanates, diisocyanates or even polyisocyanates.
• isocyanate compounds in particular polyisocyanates comprising an isocyanurate group, which are also known as trimers;
• isocyanate derivatives in particular polyisocyanates comprising at least one uretidinedione group, which are also known as dimers;
• isocyanate derivatives in particular polyisocyanates comprising at least one biuret group
• isocyanate derivatives in particular polyisocyanates comprising at least one carbamate group
• isocyanate derivatives in particular polyisocyanates comprising at least one allophanate group
• isocyanate derivatives in particular polyisocyanates comprising at least one ester group
• isocyanate derivatives in particular polyisocyanates comprising at least one amide group
• isocyanate derivatives in particular polyisocyanates comprising at least one urea function
• isocyanate derivatives in particular polyisocyanates comprising at least one iminocyclooxadiazinedione function;
• isocyanate derivatives in particular polyisocyanates comprising at least one cyclooxadiazinetrione function
• isocyanate derivatives in particular polyisocyanates comprising at least one masked isocyanate group
• isocyanate derivatives in particular polyisocyanates comprising a combination of one or more of the groups which have just been mentioned, in particular an isocyanurate group.
• polyfunctional isocyanate tricondensates will be used more generally to denote the products obtained by (cyclo)condensation, in particular cyclo(trimerization), of one or more identical or different isocyanate monomers and optionally of another monomer.
• these compounds comprise an isocyanurate group or a biuret group.
• the (poly)isocyanates of the invention have a molecular weight of less than 7 500, advantageously less than 3 500 and preferably less than 2 500.
• the isocyanate monomers forming part of the composition of the various modified compounds mentioned may be aliphatic, cycloaliphatic or arylaliphatic.
• modified polyisocyanates as defined above may consist of products of condensation of identical or different isocyanate molecules, in which case they will be referred to, respectively, as homopolyisocyanates and heteropolyisocyanates, or alternatively as mixtures of different homopolyisocyanates and/or of different heteropolyisocyanates.
• the preferred polyisocyanates targeted by the invention are those in which at least one, advantageously two and preferably three of the conditions below are satisfied:
• At least one and advantageously two of the free NCO functions which have reacted with the crosslinking group according to the invention are linked to a hydrocarbon-based skeleton via a saturated (sp 3 ) carbon;
• At least one and advantageously two of said saturated (sp 3 ) carbons bears at least one and advantageously two hydrogen(s) (in other words, it has been found that better results are obtained when the carbon bearing the isocyanate function bears a hydrogen and preferably two hydrogens); it is also even preferable for at least a third, advantageously at least a half and preferably at least two thirds of said saturated (sp 3 ) carbons to be linked to said skeleton via a carbon atom which itself bears at least one and preferably two hydrogen(s);
• all the carbons via which the isocyanate functions are linked to the hydrocarbon-based skeleton are saturated (sp 3 ) carbons, advantageously some and preferably all of which bear a hydrogen and preferably two hydrogens; it is also even preferable for at least a third, advantageously at least a half and preferably at least two thirds of said saturated (sp 3 ) carbons to be linked to said skeleton via a carbon atom which itself bears at least one and more preferably two hydrogen(s).
• the polyisocyanates whose NCO functions are modified with a crosslinking group as defined are selected from the products of homocondensation or of heterocondensation of alkylene diisocyanate, in particular comprising products of the “biuret” type and of the “trimer” types or even “prepolymers” containing isocyanate functions in particular comprising urea, urethane, allophanate, ester and amide functions, and from mixtures containing them.
• They may be, for example, polyisocyanates sold by the Applicant Company under the name “Tolonate”.
• polyisocyanates that are preferred are the products of homocondensation or of heterocondensation of the following isocyanate monomers:
• polymethylene diisocyanates and in particular 1,6-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 3,5,5-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate and isocyanato (4)-methyl-1,8-octylene diisocyanate (TTI or NTI);
• IPDI isophorone diisocyanate
• NBDI bis(isocyanato)methylnorbornane
• BIC 1,3-bis(isocyanatomethyl)cyclohexane
• H 12 -MDI cyclohexyl 1,4-diisocyanate
• arylenedialkylene diisocyanates such as OCN-CH 2 - ⁇ -CH 2 -NCO; or aromatics such as tolylene diisocyanate.
• Aromatic isocyanates are not preferred.
• the polyisocyanates are relatively heavy, i.e. when they comprise at least four isocyanate functions, at least one isocyanate function advantageously being modified with a crosslinking group as defined above, or when there is a mixture of several compounds bearing isocyanate function(s), the first conditions become;
• At least a third, advantageously two thirds and preferably four fifths of the NCO functions which are free or which comprise a crosslinking group as defined above are linked to a hydrocarbon-based skeleton via a saturated (sp 3 ) carbon,
• At least a third, advantageously two thirds and preferably four fifths of said saturated (sp 3 ) carbons bears at least one and advantageously two hydrogen(s) (in other words, it has been found that better results are obtained when the carbon bearing the isocyanate function bears a hydrogen and preferably two hydrogens).
• the unmodified isocyanate functions according to the present invention may be either free or masked with a common heat-labile masking group.
• the term “masking agent” refers to a group reacting with an isocyanate function such that the masked isocyanate compound shows at a temperature of at least 50° C., advantageously at least 60° C. and preferably at least 70° C. and of not more than 350° C., advantageously not more than 250° C. and preferably not more than 200° C., the highest temperatures being reserved for flash crosslinking processes, and after a period of heating of between a few seconds and a few hours, advantageously between 10 seconds and 20 minutes, a “liberation” of the masking group at least equal to 50%, in the octanol test, the procedure of which is described later.
• a masked isocyanate compound is considered as being any compound which leads to the liberation of the masking agent with regeneration of the isocyanate bond or conversion of this bond into a urethane bond if a primary or secondary aliphatic alcohol is present, or into a urea bond if a primary or secondary aliphatic amine function is present.
• the octanol test gives a degree of liberation of 50% with respective formation of 50% corresponding octyl carbamate at 80° C. and 100% at 100° C., 2-hydroxypyridine giving respective degrees of 90% and 100% at these temperatures.
• MKO methyl ethyl ketoxime
• MEPO methyl pyruvate oxime
• MEPO methyl pyruvate oxime
• cyclohexanone oxime cyclohexanone oxime
• the masking groups optionally comprise acidic ionic functions such as carboxylic acid or sulfonic acid functions or basic ionic functions such as tertiary amine functions. These ionic groups are of most particular advantage since they facilitate the preparation of certain types of formulation such as the production of powders, dispersions or aqueous solutions.
• [0109] is greater than 4/3, advantageously greater than 1.5 and preferably greater than 2.
• the masking groups may be, in particular, an oxime and triazole (1,2,3-triazole or 1,2,4-triazole), the oxime advantageously being methyl ethyl ketoxime, methyl amyl ketoxime, methyl pyruvate oxime or ethyl pyruvate oxime.
• the modified isocyanate derivatives according to the invention are in liquid form or in powder form.
• modified isocyanate derivatives according to the invention may be prepared by carrying out procedures that are well known to those skilled in the art, by condensing a compound of general formula (II):
• R 1 , A, Q, Y, Z and W have the same specifications as above, and X′ represents X or OCOX, X being at specified above with an isocyanate.
• the isocyanates are reacted, before or after reaction with a compound of general formula (II) as defined above, with a masking agent under suitable reaction conditions.
• the isocyanates may also be reacted with a mixture of compounds of general formula II and of masking agents under suitable reaction conditions, that are known to those skilled in the art.
• the compounds of the invention may also be prepared by mixing the isocyanate compounds with compounds that are precursors of the molecule (II) such as vicinal diols and activated carbonylating agents, the carbonyl-activating molecules, liberated after the carbonate-forming reaction, possibly serving where appropriate as agents for masking the isocyanate function.
• activated carbonyl compounds such as carbonyldiimidazole, carbonylbis(1,2,4-triazole), carbonylbis(methyl ethyl ketoxime) and N,N′-disuccinimidyl carbonate.
• the compounds liberated after reaction with the diol and formation of the carbonate, such as imidazole, 1,2,4-triazole or methyl ethyl ketoxime, are known as agents for masking isocyanate functions.
• modified isocyanates which is preferred according to the invention consists of the diisocyanate derivatives as mentioned above, comprising at least some of the isocyanate functions, preferably at least 100% to 1% and advantageously 100% to 30%, by weight, modified with a crosslinking group as defined above, at least 1%, advantageously at least 5% and preferably 10%, and up to 99%, advantageously up to 95% and preferably up to 70%, by weight, of the isocyanate functions, modified with a masking group as defined above.
• the polyisocyanate compositions that are the subject of the present invention may consist of a mixture comprising at least 1% and not more than 99%, preferably at least 10% and not more than 90%, of a polyisocyanate predominantly bearing the crosslinking group of the invention and at least 1% and not more than 99%, preferably at least 10% and not more than 90%, of another polyisocyanate predominantly bearing a crosslinking group and/or another molecule derived from a diisocyanate bearing free and/or masked isocyanate functions and containing no crosslinking groups.
• crosslinking group and the free and/or masked NCO group are borne by the same (poly)isocyanate molecule.
• the (poly)isocyanate composition of the invention comprises no carboxylic groups borne by a molecule of formula I as defined above.
• the agents for masking the isocyanate functions may bear ionic groups and in particular carboxylic or tertiary amine group, these ionic groups possibly being partially or totally salified.
• the compounds may retain free isocyanate functions, in particular at least 1%, advantageously at least 5% and preferably at least 10%, and up to 99% and advantageously up to 70%, by weight.
• a second group of modified isocyanates which is preferred according to the invention consists of mixtures of polyfunctional isocyanate tricondensates, which are preferably true isocyanates (derived from the theoretical (cyclo)trimerization of three isocyanate monomer molecules and optionally other monomers and comprising an isocyanurate and/or biuret ring) and of allophanates, and/or dimers and/or ureas, urethanes, biurets or carbamates comprising at least some, preferably at least 1% to 100% and advantageously 30% to 100% by weight of the isocyanate functions modified with a crosslinking group as defined above.
• polyfunctional isocyanate tricondensates which are preferably true isocyanates (derived from the theoretical (cyclo)trimerization of three isocyanate monomer molecules and optionally other monomers and comprising an isocyanurate and/or biuret ring) and of allophanates, and/or dimers and/or ureas, ure
• the compounds may retain free isocyanate functions, in particular from 1% to 99% and advantageously from 5% to 70% by weight.
• a third group of compounds which is preferred consists of physical mixtures of several polyfunctional isocyanate tricondensates, with allophanates, uretinediones or dimers, comprising from 100% to 1% and advantageously from 70% to 1% by weight of isocyanate groups modified with a crosslinking group according to the invention and from 1% to 99% and advantageously from 5% to 70% by weight of isocyanate functions masked with a masking group as defined above.
• a fourth group of modified isocyanate derivatives according to the invention consists of modified isocyanates comprising free isocyanate groups and/or masked isocyanate groups and also allophanate and/or uretinedione groups.
• the compounds may retain free isocyanate functions, in particular from 1% to 99% and advantageously from 5% to 70% by weight.
• the various polyfunctional compounds may be derived from the polycondensation of several identical or different monomers.
• the various polyfunctional isocyanates may be obtained from different isocyanates or from a mixture of different isocyanates.
• HDI isocyanates and butyl allophanates and HMDI may be used.
• mixtures derived from these crude isocyanate (cyclo)condensation mixtures may be used.
• the expression “derived mixture” means the product of reaction of the compounds of the crude mixture with nucleophilic compounds or compounds bearing hydroxyl, sulfhydryl or amine functions capable of reacting with the isocyanate functions of the compounds of the mixture.
• the isocyanate compositions used are mixtures of various molecules derived from polymerizations or from polycondensation, in which case the explanation which has just been given as to what is preferred above applies with fractional and random values.
• the isocyanate functions that are free or liberated by departure of the [lacuna] group may form by condensation with groups containing labile hydrogen, in particular polyols, or polyamines or polysulfhydryls, prepolymers containing pendent carbonate functions and terminal free isocyanate or alcohol or amine or sulfhydryl functions depending on the ratio NCO/XH, X being as defined above.
• groups containing labile hydrogen in particular polyols, or polyamines or polysulfhydryls, prepolymers containing pendent carbonate functions and terminal free isocyanate or alcohol or amine or sulfhydryl functions depending on the ratio NCO/XH, X being as defined above.
• the prepolymer thus obtained may be subsequently crosslinked.
• the functions which react with the crosslinking group according to the invention are alcohol functions, primary or secondary amine functions, heterocyclic nitrogen compounds containing a reactive hydrogen atom, oximes or phenols, preferably phenates or carboxylates.
• Aqueous ammonia, primary or secondary amines or nitrogen heterocycles, for example guanidines or salts thereof which react by opening the ring, will preferably be selected.
• these prepolymers may be reacted with amines, preferably diamines or polyamines, which are preferably primary or secondary.
• amines preferably diamines or polyamines, which are preferably primary or secondary.
• Networks are thus obtained containing pendent hydroxyl functions which may be either auto-crosslinked with NCOs present in the medium, or allow grafting or permit a crosslinking reaction with mixtures that are reactive with these functions.
• these products bearing free isocyanate and carbonate functions may be reacted with amines to give polyurea urethane networks containing pendent hydroxyl and/or carbonate functions. If the amount of isocyanate functions is greater than the amount of amines, then the alcohol functions liberated by opening the carbonate ring may react with the excess of isocyanate functions. The speed of opening of the carbonate ring depends on the amine and on the reactivity of the isocyanate with this amine.
• the amine will preferentially react with the carbonate function before the isocyanate function. There will thus be the possibility of having a reaction of the isocyanate function with the liberated alcohol functions.
• the alcohol function liberated may be tertiary, but, in this case, its reactivity is low and it is not preferred.
• the free OH function may in turn react at a given temperature with an isocyanate function, which is optionally blocked, with departure of the blocking group to give a network rapidly, in particular when the free or blocked isocyanate groups are borne by a polyfunctional isocyanate, a dimer, a trimer or a prepolymer.
• the hydroxyl function liberated may also react with other compounds which may be present in a formulation using the compounds of the invention. Examples which may thus be mentioned are acid anhydrides or acidic compounds which may react with the hydroxyl function liberated to give an ester or an acid ester.
• the isocyanate functions that are free or liberated by departure of the blocking group may react with any type of compound containing labile hydrogen, in particular alcohols, thiols, urethanes, etc., depending on the crosslinking temperature used.
• Another advantageous possibility consists in opening the ring of the crosslinking group with a polyalkoxylated amine, in particular a polyethoxylated amine, so as to obtain a condensation product which has good emulsifying properties.
• This type of compound is particularly advantageous in the context of subsequent emulsion polymerization reactions, in particular by reaction with an isocyanate group which is free or liberated by departure of a blocking group.
• Salts preferably amine salts, preferably of weak acids, also react with the isocyanate and/or carbamate functions depending on the temperature imposed by the crosslinking.
• a salt of a weak acid with a pKa of greater than 2.5 will preferably be selected if the crosslinking temperature is less than 80° C.
• acid salts with pKa values of less than 3 may be used.
• a compound capable of neutralizing the salt of the amine which is reactive with a base capable of exchanging ions and liberating the amine, which, since it is nucleophilic, is then capable of opening the ring, may be also be introduced.
• Bases which may be mentioned are metal hydroxides (sodium hydroxide, potassium hydroxide, etc.), tertiary amines (triethylamine, trio-cylamine, N,N,-dimethylaminoethanol, etc.), metal alkoxides (sodium methoxide, etc.) and alkaline salts of weak acids (sodium acetate, sodium hydrogen carbonate, potassium carbonate, etc.).
• Amine salts have the advantage of having an improved “pot-life” due to the decrease in reactivity of the corresponding amine.
• isocyanate compounds modified according to the invention also comprising free isocyanate groups are reacted, care will be taken to select the isocyanates so as to promote either the reaction of the amine with the isocyanate, or the reaction of the amine with the carbonate. This selectivity may be increased by varying the temperature, the catalyst or the steric bulk of the amine and/or of the isocyanate.
• amine-precursor compounds which may restore the amine by a chemical or physical process, such as, for example, imines, oxazolines or oxazolidines, which, on hydrolysis, liberate the amine which can then open the carbonate ring.
• isocyanate molecules which also constitute masked forms of amines and which can, on hydrolysis, restore the amine function.
• isocyanates may be simple isocyanates (only one isocyanate function per molecule).
• IPDI will advantageously be selected.
• nonexpanded coatings are, surprisingly, obtained, in particular coatings such as paints or varnishes, with a film thickness which is not greater than 100 ⁇ m, and which may have a matt, satin or glossy appearance depending on the implementation conditions.
• the modified isocyanates according to the invention give, at a high temperature above 100° C., oxetane compounds with release of CO 2 .
• oxetane compounds may be used as crosslinking agents with polyols or polyamines, preferably polyols, in situ in the film.
• derivatives are obtained containing at least two alcohol functions, which may be used to prepare polymers or to introduce particular properties into a polymer, for example to make it self-emulsifying if the carbonate functions have been opened with a polyoxyethylenated amine, or to give an “anti-graffiti” or “mar-resistance” coating if the carbonate functions have been opened with an aminosilicone or perfluoroamine.
• the isocyanate derivatives according to the invention can also give tetra-functional polyols which may be used as crosslinking agents, in particular on account of the double reactivity due to the presence of primary and secondary alcohol functions.
• the modified isocyanate derivatives according to the present invention have the advantage of high and controlled reactivity and high crosslinking power, the properties being obtained by adding an arm which provides only a small increase in the molecular weight of the starting isocyanate.
• polyisocyanate derivatives containing pendent urethanecarbonate functions may lead to the formation of allophanates containing pendent carbonate functions.
• novel polyisocyanates according to the invention may serve as a basis for the preparation of polymers and/or reticulates that are useful, for example, as main constituents of coatings of any kind, such as paints.
• the hardness qualities of the crosslinkable polymers are among the qualities that are desired from a technical and functional viewpoint.
• the polyisocyanates containing a crosslinking function of the invention may be emulsified by means of various compounds such as surfactants or polyols of emulsifiable nature or may be made water-soluble by grafting nonionic functions such as polyalkylene oxide or acidic ionic functions such as those of para-hydroxybenzoic acid (PHBA), dimethylolpropionic acid, sulfamic acid and phosphoric derivatives or of basic ionic functions such as N,N-dialkylhydroxylalkylamines, in particular N,N-dimethylethanolamine or guanidine derivatives.
• nonionic functions such as polyalkylene oxide or acidic ionic functions such as those of para-hydroxybenzoic acid (PHBA), dimethylolpropionic acid, sulfamic acid and phosphoric derivatives or of basic ionic functions such as N,N-dialkylhydroxylalkylamines, in particular N,N-dimethylethanolamine or guanidine
• the grafting may be carried out reversibly (PHBA) or irreversibly.
• reaction medium is then brought to the test temperature. It is then heated for a given period, generally for six hours, except where otherwise indicated, at the test temperature, so as to unblock the isocyanate functions and thus make them reactive. Once the reaction is complete, the solvent is removed by distillation under vacuum and the residue is analyzed by NMR, mass and infrared spectra.
• the NCO titer measured is 0.786 as opposed to 1.19 for the starting HDI.
• the excess HDI is removed by two successive distillations under a vacuum of 0.5 mmHg at 140° C., with a flow rate of between 400 and 1 000 g/hour.
• the distilled product has an NCO content of 0.405, i.e. 17% by weight, and a viscosity at 25° C. of 140 mPa.s ⁇ 1 .
• the HDI content is 0.4%.
• reaction mixture is heated such that it reaches 113° C. over 20 minutes.
• the 1,2,4-triazole is then completely consumed.
• the cold product is a viscous liquid which does not flow, indicating a viscosity of greater than 10 000 mPa.s ⁇ 1 at 25° C.
• the mixture is heated from the moment of addition of the 1,2,4-triazole.
• the mixture reaches a temperature of 99° C. after 45 minutes.
• the product is removed and then left to cool (product obtained: 524.2 g theoretical, 517 g measured).
• the cold product is a solid, which is then ground, and whose content of potential isocyanate functions is 7.35% by weight and whose content of carbonate functions (—O-C(O)-O) is 10.48% by weight.
• the modified NCO/O-C(O)-O molar ratio is 1.
• reaction medium is heated at 90° C. for 6 hours and at 120° C. for 2 hours and then stirred for 2 hours.
• a liquid extraction is then carried out on the cold reaction medium in a separating funnel. 500 ml of cold (10° C.) aqueous 0.5 M bicarbonate solution and then 200 ml of ethyl acetate are added. The organic phase is removed and washed twice with the same cold (10° C.) aqueous 0.5 M bicarbonate solution.
• the aqueous phase is then extracted three times with 500 ml of ethyl acetate.
• the organic phases are then dried over dry sodium sulfate. After filtration, the solvent is concentrated under vacuum to give a white solid.
• the melting point of the product is 102-103° C. (Kofler block).
• the HDT used is Tolonate® HDT sold by the company Rhodia, comprising a mixture of compounds of cyclopolycondensation of hexamethylene diisocyanate (HDI) with itself, having the following composition: Products TOLONATE HDT TOLONATE HDT LV2 HDI 0.2% 0.24% Butyl monocarbamate 0.5% 0.5% True HDI dimer 2.5% 14.2% True HDI trimer 50.1% 56% Bis trimer + 24% 20.6% trimer dimer Heavy fractions 18.7% 7.6% Biuret 4.0% 0.86%
• the true trimers consist of three HDI chains cyclocondensed on themselves into an isocyanurate ring.
• the true dimers consist of two HDI chains cyclocondensed into a uretidinedione ring.
• trimer oligomers plus heavy fractions consist of more than three cyclocondensed HDI chains and of more than one isocyanurate ring.
• Tolonate® HDT contains free isocyanate functions in a proportion of 22% by weight, generally of NCO functions per 100 g of product.
• Iso represents an isocyanurate-isocyanate group.
• reaction medium is heated for 1 hour 30 at 160° C. 10 g (1% by weight) of HMDZ (hexamethyldisilazane) are then added.
• the reaction medium is heated for 30 minutes at 140° C. and then cooled. When the temperature reaches 88° C., 5.5 g of n-butanol are added. After reaction for one hour, the product is purified by distillation under vacuum.
• HMDZ hexamethyldisilazane
• the heavy fractions are compatibilized into tris-trimer.
• the bis-trimer bulk (major compound) comprises tetramers (trimer-dimer) and imino-trimer.
• the resulting composition has a viscosity at 25° C. of 509 cps (509 mPa.s).
• Tolonate® HDT LV2 contains free isocyanate functions in a proportion of 0.544 mol of NCO function per 100 g of Tolonate® HDT LV2 product.
• IPDT is a solid product (melting point of 100-115° C.) obtained by cyclopolycondensation of isophorone diisocyanate (IPDI) with itself, containing isocyanurate units and free isocyanate functions.
• IPDI isophorone diisocyanate
• the titer of isocyanate functions is 0.409 mol of NCO functions per 100 g of product.
• the product obtained is indeed the expected reaction product, but it still contains unreacted isocyanate functions and free acid functions in a proportion of 20 mol % of the initial functions and has the following major characteristic bands:
• the process is performed as in the above example, using 15 g of Tolonate® HDT (cf. Example 6), 2.797 g of 1,2,4-triazole and 8.77 g of succinic acid glyceryl carbonate monoester.
• the molar ratio of COOH functions/NCO functions is 0.5
• the molar ratio of triazole functions/NCO functions is 0.5
• the molar ratio of Et 3 N functions/COOH functions is 1%.
• the product obtained thus has 50% of the isocyanate bands in the form temporarily masked with 1,2,4-triazole, which may be regenerated thermally at a temperature of about 130-140° C.
• the 50 mol % of remaining isocyanate functions were converted into amide bonds by reaction with the acid functions and form the link between the aliphatic chain ((CH 2 ) 6 ) borne by the isocyanurate unit and the succinylcarbonate chain.
• This compound is thus characterized by a molar ratio of NCO masked with 1,2,4-triazole/carbonate functions equal to 1.
• Glutaric acid glyceryl carbonate monoester is obtained in the form of a solid compound in a yield of 52% .
• This product has characteristic infrared bands that are identical to those of the derivative of the compound of Example 6.
• the infrared analysis of the product indicates that the expected product is indeed obtained, i.e. a polyisocyanurate resin in which about 2 ⁇ 3 of the isocyanate functions are blocked with imidiazole and about 1 ⁇ 3 of the isocyanate functions are blocked in the form of the carbamate of trimethylolpropane carbonate.
• thermally crosslinkable resin can be obtained in a single step using a carbonyl compound activated with leaving groups which may be used as temporary protecting groups for isocyanate functions.
• the product is then concentrated to dryness on a rotary evaporator under vacuum to remove 95% of the N,N-dimethylformamide.
• Tolonate® HDT 0.518 mol of NCO function per 100 g of product
• 12 g of 9,10-dihydroxystearic acid carbonate such that the molar ratio of NCO functions/COOH functions is equal to 1
• 1 mol % of triethylamine relative to the carboxylic acid COOH functions is added.
• the mixture is left stirring at 95° C. for 8 hours under a stream of nitrogen.
• reaction medium is then left to cool so as to give a viscous composition of a urethane resin which is characterized by the absence of free isocyanate functions and by the presence of isocyanate functions masked with imidazole, carbamate functions and predominantly cyclic carbonate functions.
• reaction medium is heated at 80° C. It is stirred under N 2 at 80° C. for five hours and the excess HDI is then removed by distillation under high vacuum.
• the product obtained is a urethane prepolymer containing isocyanate end functions which has an NCO titer of 0.22 mol NCO per 100 g, i.e. 9.24% NCO per 100 g of product.
• reaction medium is heated at 60° C., in the presence of 0.1% dibutyltin dilaurate, until the NCO titer is less than 1% (method of assaying the NCO functions by reaction with dibutylamine and assay of the residual amine with HCl).
• the mixture obtained is placed on a glass plate so as to form a film 50 ⁇ m thick, and is then placed in an oven at 50° C. for 30 minutes, then at 100° C. for 20 minutes and at 140° C. for 30 minutes.
• this derivative can be obtained in a single operation using a carbonyl derivative activated with leaving groups (imidazole, triazole, phenyl) which may subsequently serve as agents for masking the NCO function.

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