WO2002053613A1 - (cyclo)condensation de composes isocyanates - Google Patents
(cyclo)condensation de composes isocyanates Download PDFInfo
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- WO2002053613A1 WO2002053613A1 PCT/FR2001/004206 FR0104206W WO02053613A1 WO 2002053613 A1 WO2002053613 A1 WO 2002053613A1 FR 0104206 W FR0104206 W FR 0104206W WO 02053613 A1 WO02053613 A1 WO 02053613A1
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- WIPO (PCT)
- Prior art keywords
- compound
- nitrogen
- isocyanate
- heterocyclic
- use according
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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
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/027—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing urethodione 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
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
- C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
Definitions
- the invention relates to a method for promoting the opening of uretidiones cycles or the closure of isocyanate compounds in uretidiones cycles.
- the invention more particularly relates to the (cyclo) condensation of isocyanate compounds.
- dimers compounds with a uretidione ring also called dimers are obtained by dimerization of isocyanate compounds in the presence of a dimerization catalyst such as a trialkylphosphine, a tris- (N, N-dialkyl) phosphotriamide or an N, N , N ', N'-tetra-alkylguanidine.
- a dimerization catalyst such as a trialkylphosphine, a tris- (N, N-dialkyl) phosphotriamide or an N, N , N ', N'-tetra-alkylguanidine.
- WO 99/23128 describes a process for the catalytic trimerization of isocyanate using a catalyst based on a quaternary ammonium salt in which imidazole or one of its co-catalysts is used derivatives so as to increase the reactivity of isocyanates, in particular cycloaliphatic isocyanates and to control it effectively without it depending on the content of hydrolyzable chlorine contained in the starting isocyanate monomer.
- the document also describes that the use of imidazole as a cocatalyst for a trimerization reaction in which the catalyst is a quaternary ammonium salt results in the formation of dimeric compounds with a uretidione cycle.
- the amount of imidazole or its derivatives is such that the imidazole / quaternary ammonium molar ratio is of the order of 14 or more.
- imidazole and other nitrogen-containing cyclic compounds having a five-membered nitrogen heterocyclic group comprising at least two nitrogen atoms add up on the isocyanate function at room temperature in accordance with the reaction scheme:
- R being the residue of an isocyanate compound after removal of an isocyanate function and HET-H being a nitrogen heterocyclic compound as defined above, linked to the NCO group via the NH group of the heterocycle.
- the mechanism proposed by the inventors is based on the assumption that in the presence of isocyanate and an anionic compound, as defined above, the five-membered heterocyclic compound promotes the addition of the isocyanate function on the urea-HET compound (I) to give a biuret-HET compound or also designated by "pseudo-biuret" of formula (II):
- heterocyclic groups comprising an NH group
- the addition of the nitrogen heterocyclic group to the isocyanate function is carried out via this group, with subsequent release of a HET-H compound.
- the work of the inventors has shown that when the rate of NCO functions present in the reaction medium decreased and at a temperature of at least 40 ° C, the HET-H compound acted by opening the uretidione cycle and favored, in the presence of a monomeric isocyanate, the formation of a higher homologous cyclocondensation compound, in other words the cyclotimerization reaction.
- the present invention has made it possible to determine that the heterocyclic compounds defined above catalyzed the addition reaction of the nucleophilic compounds on the uretidione cycle.
- the reaction temperature for adding alcohol to the uretidione cycle is carried out at low temperature, generally around 80 to 100 ° C. instead of the high temperatures described below. - above.
- This property can be taken advantage of in a particularly advantageous way for the opening of uretidiones rings originating from the condensation of isocyanate monomers, that is to say monomers in which the NCO function is carried by a carbon atom having steric hindrance, for example the dimers of IPD1, the opening of which is more difficult than for the true dimers formed by cyclodimerization of isocyanates. sparingly congested monomers, such as HDI.
- the invention relates to the use of a compound comprising at least one heterocyclic nitrogen group having at least five atoms in the ring including at least two nitrogen atoms, to promote the closing reaction of uretidiones rings or of openings of uretidiones rings and their reaction with an isocyanate compound or a nucleophilic compound containing a mobile hydrogen atom, with the condition that, when the heterocyclic nitrogen group is imidazole, the opening / closing reaction is not not the closing reaction of isocyanate compounds in uretidiones cycles in the presence of a quaternary ammonium salt.
- the nitrogen-containing cyclic compound advantageously has 5 links and is advantageously preferably chosen from imidazole, triazole, tetrazole and their derivatives comprising one or more substituents, in particular from 1 to 4 substituents depending on the nature of the cycle.
- the substituents can, independently of one another, be chosen from the groups -R, -OR, -SR, -NRR ", -COR, -CONRR ', -NRCOR' and -NRCOOR ', R and R ', identical or different, being chosen from a hydrogen atom, a C 1 -C 4 alkyl, C 3 -C 8 cycloalkyl, C 5 -C 1 o aryl and a heterocycle comprising from 2 to 10 carbon atoms and from 1 to 4 identical or different heteroatoms chosen from O, S and N and the group -NR ", R” being a C 1 -C 4 alkyl or C 3 -C cycloalkyl group 8 , the alkyl, cycloalkyl, aryl or heteroaryl groups being optionally substituted by one or more groups chosen from OH, COOH, NH 2 , SH, alkoxy or alkoxycarbonyl.
- the heterocyclic nitrogen compound can also be an isocyanate masked by a masking agent meeting the definition of heterocyclic nitrogen compounds given above, in other words a precursor of a heterocyclic nitrogen compound as defined above.
- the nitrogenous heterocyclic compound is used to promote the closing reaction of a uretidione ring, starting from starting isocyanate monomers, these being in excess relative to the heterocyclic nitrogen compounds.
- the nitrogen heterocyclic compound is used to promote the opening reaction of a uretidione ring, in the presence of an anionic compound in particular derived from a strong base, said base being in particular a catalyst for cyclocondensation of isocyanates.
- a large number of cyclocondensation catalysts, in particular of cyclotrimerization, are anionic compounds within the meaning of the present invention.
- the anionic compound may consist in particular of an alcoholate, hydroxide, fluoride, acetate, carbonate, hydrogen carbonate, carboxylate or a silazane salt of mineral or organic cations.
- mineral cations there may be mentioned alkali metals, alkaline earth metals, transition metals, as well as rare earths.
- the "oniums” or the “iniums” are preferred.
- the oniums are chosen from the group of cations formed by the elements of columns Vb and Vlb (as defined in the table of the periodic classification of elements published in the supplement to the Bulletin of the departments Chimique de France in January 1966) with 4 (case of column Vb) or 3 (case of column Vlb) hydrocarbon chains.
- the organic salt of the invention is in this case a phosphonium, sulfonium, ammonium, oxonium or diazonium.
- the "iniums”, group to which the pyridiniums belong, are derived from oniums by the replacement of two substituents by a double substituent
- a first type of trimerization catalyst which is particularly suitable for the invention when it is combined with a cyclic nitrogen compound as described above, consists of the rare earth alcoholates.
- rare earth elements see the table on page B-208 of "Handbook of Chemistry and Physics", Editor Robert C. Weast, 67 th Ed.).
- lanthanides include the following elements: scandium, yttrium, lanthanum as well as the lanthanides (cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, ytterbium and lutetium).
- the rare earth alcoholate function can consist of any function obtained by substitution of an alcoholic OH group with a rare earth metal.
- propylates in particular isopropylates, in particular isopropylate of the following rare earth elements: Y, Sm, Yb and The.
- methylates ethylates and butylates
- poly (alkylene glycol) alcoholates of which preferably at least one of the alcohol functions at the chain end is substituted by an ether, ester function, etc.
- a second type of trimerization catalysts consists of alkali, alkaline earth, tin, zinc, or other metals of carboxylic acids such as acetic, propionic, octanoic or benzoic acids.
- a third type of catalyst is constituted by alkali, alkaline earth, tin, zinc, alcoholates or phenolates salts.
- a fourth type of catalyst is formed by hydroxides, carbonates, hydrogen carbonates or carboxylates of quaternary ammoniums.
- a fifth type of catalyst consists of silazane salts or silanolates of mineral or organic cations. These are in particular the compounds of formula (1) or (2):
- R 2 , R 3 , R 4 , R 5 and R 6 which are identical or different, represent a monovalent group of saturated or unsaturated, aliphatic, cycloaliphatic, aryl, aralkyl or alkylaryl nature, optionally substituted by halogen atoms, CN groups, or ester, or • in formula (1) one of R 1 ( R 2 , R 3 , R 4 , R 5 and R 6 represents a motif of formula:
- A being an alkylene group having from 1 to 30 atoms, advantageously from 2 to 20 carbon atoms, preferably (C ⁇ with n 'between 1 and 6, advantageously from 2 to 6, and R' 1 to R ' 5 identical or different representing a monovalent group of hydrocarbon, aliphatic, cycloaliphatic saturated or unsaturated, aryl, aralkyl or alkylaryl nature, optionally substituted by halogen atoms, CN groups, or ester, and n is an integer between 1 and 50, or
- At least one group chosen from Ri, R 2 and R 3 forms with at least one group from R 4 , R 5 and R 6 a divalent hydrocarbon group.
- alkyl, alkenyl, haloalkyl or haloalkenyl group having from 1 to 20, preferably from 1 to 6 carbon atoms, and optionally comprising chlorine and / or fluorine atoms,
- cycloalkyl, cycloalkenyl, halogenocycloalkyl or halogenocycloalkenyl group having from 3 to 30, preferably 3 to 10 carbon atoms and containing chlorine and / or fluorine atoms
- aryl, alkylaryl or haloaryl group having from 6 to 30, preferably 6 to 10 carbon atoms and containing chlorine and / or fluorine atoms
- Ri, R 2 and R 3 or R 3 , R and R5 together form a divalent radical comprising from 2 to 5 carbon atoms, - or two of Ri, R 2 and R 3 on the one hand and / or R 4 , R 5 and R ⁇ on the other hand, together constitute a divalent hydrocarbon group, or
- At least one group chosen from Ri, R 2 and R 3 forms, with at least one group from R 4 , R 5 and R ⁇ , a divalent hydrocarbon group comprising from 2 to 5 carbon atoms.
- Groups Ri to R 6 and R'i to R'5 which are particularly preferred are chosen from methyl, ethyl, propyl, linear or branched where appropriate, vinyl and phenyl, which may optionally be chlorinated and / or fluorinated.
- the salt of the compound of formulas (1) and (2) can be a mineral, monovalent or multivalent salt, or a mixture of these salts.
- the preferred mineral salts are those of K, Li, Na and Mg.
- the salt of the compound of formulas (1) and (2) can also be an organic, monovalent or multivalent salt or a mixture of these salts.
- the salts preferred organics are stable "oniums" or "iniums”.
- the salt according to the invention can comprise at least one ligand of formula (1) or (2) above and optionally one or more different ligands. Generally, it is preferred that all of the ligands are compounds of formula (1) or (2).
- the number of ligands is a function of the valence of the mineral or organic cation, as well as the number of nitrogen atoms in the compound of formula (1).
- the nucleophilic compound or the solvent is an alcohol
- the use of a catalyst of the silazane salt type is avoided.
- an anionic compound having a nitrogen group of the type described above There may be mentioned histidine in its metallic carboxylate form which act both by its imidazole heterocycle to bind to the NCO function and COO function "of the. Group amino acid to catalyze the cyclotrimerization of isocyanate monomers.
- a cyclic nitrogen compound as defined above allows, when added to a polycondensation catalyst, in particular of (cyclo) trimerization of isocyanates, of anionic type in a molar cyclic nitrogen compound / anionic catalyst ratio included between 0.1 and 10, in particular between 0.2 and 5, preferably 0.3 and 2.5, to obtain a reaction product comprising true dimer polyisocyanates and true trimer polyisocyanates in a ratio of true dimer polyisocyanates / trimer polyisocyanates true greater than 0.5, in particular greater than 0.6, preferably greater than 0.75, or even greater than 1.
- the invention also relates to a process for the preparation of a polyisocyanate composition
- a polyisocyanate composition comprising trimer polyisocyanates, in particular true trimer polyisocyanates and dimer polyisocyanates, in particular true dimer polyisocyanates, in which the polyisocyanate molar ratio true dimers / true trimer polyisocyanates is greater than 0.5, in particular greater than 0.6, preferably greater than " 0.75, or even greater than 1, in which polycondensation of isocyanate monomers is carried out, in the presence of a anionic type cyclotrimerization catalyst and of a nitrogen compound consisting of a five-membered heterocyclic compound, having at least two nitrogen atoms, the molar ratio of cyclic nitrogen compound / anionic catalyst being between 0.1 and 10, advantageously between 0.2 and 5, preferably between 0.3 and 2.5.
- true dimers denotes the compounds obtained by condensation of two molecules of starting isocyanate monomers comprising a single uretidione ring.
- true trimers denotes the compounds obtained by condensation of three starting isocyanate monomer molecules comprising a single isocyanurate ring.
- heavy compounds denotes the compounds obtained by condensation of more than three monomeric isocyanate molecules, in particular “bis-trimers”, “bis-dimers”, tris-trimers and “dimers-trimers ".
- Bis-trimers are polyisocyanate molecules comprising two isocyanurate rings, in which the connection between the two isocyanurate rings is ensured by a monomer unit, namely that two monomer units are engaged in each of the isocyanurate rings.
- Bis-dimers are polyisocyanate molecules comprising two uretidion cycles, in which the connection between the two uretidion cycles is ensured by a monomer unit, namely that two monomer units are engaged in each of the uretidion cycles.
- tris-trimers are the higher counterparts of the bis-trimers comprising three cycles of isocyanurates.
- monomers are diisocyanates
- tris-trimers are obtained by polycondensation of seven monomer chains and comprise three isocyanurate rings, two consecutive isocyanurate rings being linked in pairs by a monomer unit.
- the dimer-trimers are higher homologs of the above compounds comprising an isocyanurate function and a mono-uretidione function.
- the method according to the invention can be used for the cyclocondensation of any type of isocyanates, or mixture of isocyanates as defined above whether they are aliphatic, cycloaliphatic or aromatic, including the prepolymers having terminal isocyanate groups , in particular those described in US 5,115,071, the content of which is incorporated by reference in the present application. It can thus be used for the trimerization of isocyanates in the presence of various diols, triols and other polyols whose molecular weights are in a wide range, including polyols and aminopolyols comprising polyether and polyester groups, used for the production of polyurethane resins and polyisocyanurates. Diisocyanates are however preferred.
- the diisocyanates for which the invention is interesting are those whose nitrogen atom is linked to a sp 3 hybridization carbon, and more particularly the (cyclo) aliphatic diisocyanates. Mention may in particular be made of polymethylene diisocyanates, namely compounds having at least two isocyanate functions comprising a sequence (CH 2 ) ⁇ where ⁇ represents an integer from 2 to 10, advantageously from 4 to 8. When there are several sequences, these can be similar or different. In addition, it is desirable that at least one, preferably all of these sequences, are free to rotate and therefore exocyclic.
- polymethylene diisocyanates are TMDI (tetramethylene diisocyanate), HDI [hexamethylene diisocyanate,
- OCN- (CH 2 ) 6 -NCO] and MPDI (2-methylpentane-diisocyanate) and 3,3,5- or 3,5,5-trimethylhexamethylene-diisocyanates In the case of a mixture obtained from several (in general, two) types of monomers, it is preferable that the one or those of the monomers which meets the above conditions and in particular the condition on the presence of polymethylene sequences (CH 2 ) ⁇ , represents at least a third, advantageously a half, preferably two thirds of the masked isocyanate functions.
- Isocyanate monomers which are particularly suitable are cycloaliphatic monomers, that is to say those in which the backbone comprises an aliphatic cycle.
- these monomers are advantageously such that at least one, advantageously the two isocyanate functions, is distant from the nearest ring, at most one carbon and preferably is connected directly to it.
- these cycloaliphatic monomers advantageously have at least one, preferably two, isocyanate functions chosen from secondary, tertiary or neopentyl isocyanate functions.
- Arylenedialcylene diisocyanates such as OCN-CH 2 -0-CH 2 -NCO are also suitable for the process of the invention.
- the cyclic nitrogen compound / rare earth alcoholate molar ratio advantageously varies between 0.1 and 10, preferably between 0.2 and 5.
- the reaction temperature is the temperature usually used for catalytic trimerization and depends on the type of catalyst.
- the catalyst is a rare earth alcoholate, it is generally between 20 ° C, advantageously 50 ° C and 200 ° C, advantageously 150 ° C.
- the catalyst is a silazane salt
- it is generally between 20 ° C., advantageously 40 ° C. and 200 ° C., advantageously 150 ° C.
- the catalyst is a rare earth alcoholate
- the reaction is stopped at the rate of transformation of the desired NCO functions. This is generally between 5 and 100%, advantageously between 10 and 80%.
- the invention also relates to the use of a nitrogen heterocyclic compound as defined above to promote the opening of a uretidione cycle and its reaction with a nucleophilic compound.
- the nucleophilic compound is a compound having at least one function having a mobile hydrogen atom, reactive with the isocyanate function, such as phenol, amino alcohols, thiols, acids, amides, carbamates, ureas or releasing compounds.
- a mobile hydrogen function during the reaction in other words the precursors of the compounds listed above.
- the nucleophilic compound is advantageously chosen from amines, alcohols and thiols, preferably primary or secondary alcohols. It is also possible to use polyols, polyesters, polyethers, polyacrylics, polyurethanes, etc.
- the invention is also particularly advantageous for compositions for polyurethane powder paints.
- the polyol compounds are in this case powder compounds.
- dimers of IPDI or HDI or their derivatives are used in particular, or compositions for powder paints comprising uretidiones functions resulting from the condensation of aliphatic or cycloaliphatic isocyanates.
- the advantage of using a heterocyclic compound within the meaning of the invention makes it possible to lower the thermal threshold of the crosslinking which is generally between 80 and 150 ° C in the presence of the heterocyclic compound, whereas in absence of heterocyclic compound, the crosslinking temperatures are above 180 ° C., generally between 200 and 220 ° C.
- the compositions for powder paints are generally stable on storage at a temperature above 0 ° C, preferably above 20 ° C.
- Tg glass transition temperature
- the Tg is a function of the basic units of the polymer and therefore of the final structure of the polymer. It is generally between -20 ° C and 150 ° C, preferably between 0 and 100 ° C and advantageously between 20 and 80 ° C.
- the heterocyclic compound can be incorporated at different stages of the manufacture of the powder paint, either at the stage of synthesis of the dimeric compound, either in the polyol, or at the time of manufacture of powder paint in combination with the various constituents of the paint, for example at the time of extrusion.
- the extrusion temperature generally being around 100 ° C. with an extrusion time, less than 30 minutes.
- the nucleophilic function / uretidione ratio is between 10 and 0.05, preferably between 5 and 0.1, advantageously between 3 and 0.25, this ratio being obtainable at any stage of the reaction. crosslinking.
- dimer functions are preserved and can react subsequently with other subsequent nucleophilic functions.
- the nucleophilic functions are preserved and can react with other functions such as free isocyanate, masked isocyanate, anhydride or oxirane functions, etc.
- the heterocyclic compounds be solid, that is to say that they have a melting temperature above 25 ° C, preferably above 50 ° C. Preference is therefore given to preferably substituted heterocyclic compounds having an aliphatic chain the number of carbon atoms of which is between 1 and 10.
- nucleophilic compound participating in the opening of the uretidione cycle by the heterocyclic nitrogen compound it is not necessary for the nucleophilic compound participating in the opening of the uretidione cycle by the heterocyclic nitrogen compound to be an ionic compound. However, the presence of such a compound is not harmful to the opening reaction of the cycle and therefore the application of the final coating.
- trimerization catalyst / imidazole ratios are molar ratios.
- IPDI isophorone diisocyanate
- NCO isophorone diisocyanate
- the catalytic solution (1 g, or 2.75 10 "4 moles of imidazole and 2.75 10 "4 moles of lanthanum tris- (2-methoxyethylene glycolate)) is added to the reaction medium.
- the amounts of lanthanum alcoholate and imidazole are respectively 100 mg and 19 mg, ie a ratio metal / NCO of 1.5 10 "3 .
- the temperature of the reaction medium is brought to 60 ° C. and the reaction left under stirring for 5 hours then is blocked by adding paratoluene sulfonic acid (200 mg).
- the IPDI transformation rate is 54.7%.
- Example 2 The procedure is as in Example 1, replacing the lanthanum alcoholate with that of yttrium.
- IPDl isophorone diisocyanate
- NCO isophorone diisocyanate
- the catalytic solution is added to the reaction medium.
- the amounts of yttrium alcoholate and imidazole are respectively equal to 150 mg and 32 mg, ie a metal / NCO ratio of 2.6 ⁇ 10 ⁇ 3 .
- the temperature of the reaction medium is brought to 60 ° C. and the reaction left with stirring for 5 hours then is blocked by the addition of para-toluene sulfonic acid (200 mg)
- the IPDI transformation rate is 41%.
- IPDl isophorone diisocyanate
- NCO isophorone diisocyanate
- Example 3 The procedure is as in Example 3, replacing the alcoholate of Yttrium with that of neodymium.
- IPDl isophorone diisocyanate
- NCO isophorone diisocyanate
- IPDl isophorone diisocyanate
- NCO isophorone diisocyanate
- IPDl isophorone diisocyanate
- NCO N-methylimidazole
- 20 g of isophorone diisocyanate (IPDl), ie 0.09 moles, or 0.18 moles of NCO are added at ambient temperature, under a nitrogen stream, to a 50 ml three-neck reactor.
- 200 mg of yttrium tris (isopropylate) (7.5 ⁇ 10 ⁇ 4 moles) and 51 mg of N-methylimidazole are added, ie a metal / NCO ratio of 4 ⁇ 10 ⁇ 3 .
- the temperature of the reaction medium is brought to 60 ° C. and the reaction left under stirring for 5 hours then is blocked by addition of para-toluene sulfonic acid (150 mg). There is the presence of dimer and trimer bands.
- Example 2 The procedure is as for Example 1, except that a methoxybutanol solution containing 5% by weight of lanthanum tris- (2-methoxy-ethylene glycolate) is added.
- Example 2 The procedure is as for Example 2, except that a methoxyethylethylate solution containing 5% yttrium tris- (2-methoxy-ethylene glycolate) is added.
- Example 3 The procedure is as for Example 3, except that a solution containing 200 mg of yttrium tris (isopropylate) is added.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01989664A EP1358237A1 (fr) | 2000-12-29 | 2001-12-26 | (cyclo)condensation de composes isocyanates |
BR0116561-5A BR0116561A (pt) | 2000-12-29 | 2001-12-26 | (ciclo)condensação de compostos isocianatos |
US10/450,035 US6936677B2 (en) | 2000-12-29 | 2001-12-26 | (Cyclo)condensation of isocyanate compounds |
US11/062,579 US7524435B2 (en) | 2000-12-29 | 2005-02-23 | (Cyclo)condensation of isocyanate compounds |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR00/17322 | 2000-12-29 | ||
FR0017322A FR2818974B1 (fr) | 2000-12-29 | 2000-12-29 | (cyclo) condensation de composes isocyanates |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10450035 A-371-Of-International | 2001-12-26 | ||
US11/062,579 Continuation US7524435B2 (en) | 2000-12-29 | 2005-02-23 | (Cyclo)condensation of isocyanate compounds |
Publications (1)
Publication Number | Publication Date |
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WO2002053613A1 true WO2002053613A1 (fr) | 2002-07-11 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2001/004206 WO2002053613A1 (fr) | 2000-12-29 | 2001-12-26 | (cyclo)condensation de composes isocyanates |
Country Status (6)
Country | Link |
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US (2) | US6936677B2 (fr) |
EP (1) | EP1358237A1 (fr) |
CN (1) | CN1238393C (fr) |
BR (1) | BR0116561A (fr) |
FR (1) | FR2818974B1 (fr) |
WO (1) | WO2002053613A1 (fr) |
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US10604622B2 (en) | 2013-04-08 | 2020-03-31 | Allnex Netherlands B.V. | Composition crosslinkable by Real Michael Addition (RMA) reaction |
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US10767074B2 (en) | 2015-04-17 | 2020-09-08 | Allnex Netherlands B.V. | Process for the manufacture of a crosslinkable composition |
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FR2818974B1 (fr) * | 2000-12-29 | 2003-10-24 | Rhodia Chimie Sa | (cyclo) condensation de composes isocyanates |
US6905765B2 (en) | 2002-08-09 | 2005-06-14 | E.I. Du Pont De Nemours And Company | Polyether ester elastomers comprising poly(trimethylene-ethylene ether) ester soft segment and alkylene ester hard segment |
DE102004012903A1 (de) * | 2004-03-17 | 2005-10-06 | Bayer Materialscience Ag | Niedrigviskose Allophanate mit aktinisch härtbaren Gruppen |
JP5268934B2 (ja) * | 2006-12-04 | 2013-08-21 | ビーエーエスエフ ソシエタス・ヨーロピア | ポリイソシアネートを製造するための方法 |
EP2644270A1 (fr) * | 2012-03-29 | 2013-10-02 | Huntsman International Llc | Composition de catalyseur de trimérisation de polyisocyanate |
CN105061709B (zh) * | 2015-08-26 | 2018-02-27 | 华南理工大学 | 一种基于甲苯二异氰酸酯二聚体的聚氨酯固化剂及其制法 |
JP2019527247A (ja) | 2016-06-30 | 2019-09-26 | エレメンティス スペシャルティーズ,インコーポレイテッド., | ドーマントカルバメート開始剤が配合された架橋性コーティング組成物 |
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WO1999023128A1 (fr) * | 1997-11-04 | 1999-05-14 | Rhodia Chimie | Catalyseur et procede de trimerisation d'isocyanates |
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DE3930670A1 (de) * | 1989-09-14 | 1991-03-28 | Basf Ag | Verfahren zur herstellung von uretdiongruppen aufweisenden polyisocyanaten |
US5264572A (en) * | 1990-03-12 | 1993-11-23 | Asahi Denka Kogyo K.K. | Catalyst for isocyanate trimerization |
DE4218540A1 (de) * | 1992-06-05 | 1993-12-09 | Basf Ag | Verfahren zur Herstellung von Uretdiongruppen aufweisenden Polyisocanaten |
DE4320821A1 (de) * | 1993-06-23 | 1995-01-05 | Basf Ag | Verfahren zur Herstellung von Isocyanurat- und/oder Uretdiongruppen enthaltenden Polyisocyanaten mit reduzierter Farbzahl und verbesserter Lagerstabilität sowie nach diesem Verfahren hergestellte Produkte |
FR2803297B1 (fr) * | 1999-12-29 | 2002-10-25 | Rhodia Chimie Sa | Procede de polycondensation d'isocyanates |
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BR0116559A (pt) * | 2000-12-29 | 2004-02-17 | Rhodia Chimie Sa | Catalisador de condensação para isocianato, composição compreendendo o mesmo, processo de utilização, e composições obtidas |
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2001
- 2001-12-26 CN CNB01821410XA patent/CN1238393C/zh not_active Expired - Lifetime
- 2001-12-26 WO PCT/FR2001/004206 patent/WO2002053613A1/fr not_active Application Discontinuation
- 2001-12-26 BR BR0116561-5A patent/BR0116561A/pt not_active Application Discontinuation
- 2001-12-26 EP EP01989664A patent/EP1358237A1/fr not_active Withdrawn
- 2001-12-26 US US10/450,035 patent/US6936677B2/en not_active Expired - Lifetime
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US3252945A (en) * | 1962-06-26 | 1966-05-24 | Bayer Ag | Polymerization of isocyanates utilizing an amidine, tetrazole, cyanamide or a related compound as the catalyst |
US4697014A (en) * | 1985-03-25 | 1987-09-29 | Rhone-Poulenc Specialites Chimiques | Catalytic partial cyclotrimerization of polyisocyanates and product thereof |
WO1999023128A1 (fr) * | 1997-11-04 | 1999-05-14 | Rhodia Chimie | Catalyseur et procede de trimerisation d'isocyanates |
Cited By (14)
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EP2985308A1 (fr) * | 2010-04-07 | 2016-02-17 | Nuplex Resins B.V. | Composition réticulable |
US9534081B2 (en) | 2010-04-07 | 2017-01-03 | Nuplex Resins B.V. | Crosslinkable composition crosslinkable with a latent base catalyst |
US10647876B2 (en) | 2011-10-07 | 2020-05-12 | Allnex Netherlands B.V. | Crosslinkable composition cross-linkable by real Michael addition reaction and resins for use in said composition |
US10604622B2 (en) | 2013-04-08 | 2020-03-31 | Allnex Netherlands B.V. | Composition crosslinkable by Real Michael Addition (RMA) reaction |
US10774238B2 (en) | 2015-04-17 | 2020-09-15 | Allnex Netherlands B.V. | Method for curing a RMA crosslinkable resin coating, RMA crosslinkable compositions and resins for use therein |
US10767074B2 (en) | 2015-04-17 | 2020-09-08 | Allnex Netherlands B.V. | Process for the manufacture of a crosslinkable composition |
US10759962B2 (en) | 2015-04-17 | 2020-09-01 | Allnex Netherlands B.V. | Method for applying RMA crosslinkable coating on modified epoxy primer coating |
US10920101B2 (en) | 2015-04-17 | 2021-02-16 | Allnex Netherlands B.V. | RMA crosslinkable compositions and RMA crosslinkable resins for easy to clean coatings |
US11072724B2 (en) | 2015-04-17 | 2021-07-27 | Allnex Netherlands B.V. | Adhesion promotor for real michael addition crosslinkable compositions |
US11414565B2 (en) | 2015-04-17 | 2022-08-16 | Allnex Netherlands B.V. | Process for the manufacture of a crosslinkable composition |
US11674055B2 (en) | 2015-04-17 | 2023-06-13 | Allnex Netherlands B.V. | RMA crosslinkable compositions and RMA crosslinkable resins for easy to clean coatings |
US11674054B2 (en) | 2015-04-17 | 2023-06-13 | Allnex Netherlands B.V. | Method for curing a RMA crosslinkable resin coating, RMA crosslinkable compositions and resins for use therein |
US11713402B2 (en) | 2015-04-17 | 2023-08-01 | Allnex Netherlands B.V. | RMA crosslinkable compositions and RMA crosslinkable resins for easy to clean coatings |
US11814536B2 (en) | 2015-04-17 | 2023-11-14 | Allnex Netherlands B.V. | Floor coating compositions |
Also Published As
Publication number | Publication date |
---|---|
US7524435B2 (en) | 2009-04-28 |
CN1492887A (zh) | 2004-04-28 |
US20040030085A1 (en) | 2004-02-12 |
US20050143575A1 (en) | 2005-06-30 |
BR0116561A (pt) | 2004-02-03 |
US6936677B2 (en) | 2005-08-30 |
FR2818974A1 (fr) | 2002-07-05 |
EP1358237A1 (fr) | 2003-11-05 |
CN1238393C (zh) | 2006-01-25 |
FR2818974B1 (fr) | 2003-10-24 |
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