WO2003018662A1 - Catalyseurs et compositions durcissables - Google Patents

Catalyseurs et compositions durcissables Download PDF

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Publication number
WO2003018662A1
WO2003018662A1 PCT/GB2002/003896 GB0203896W WO03018662A1 WO 2003018662 A1 WO2003018662 A1 WO 2003018662A1 GB 0203896 W GB0203896 W GB 0203896W WO 03018662 A1 WO03018662 A1 WO 03018662A1
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compound
formula
alkoxide
alkyl
complexing
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PCT/GB2002/003896
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English (en)
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Matthew Gwilym Davidson
Matthew David Gwydion Lunn
Andrew Lee Johnson
Bruno Frederic Stengel
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Johnson Matthey Plc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • 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
    • 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
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/48—Ring-opening reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/31—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/49—Hafnium

Definitions

  • This application concerns catalyst compositions, curable materials containing catalyst compositions and methods for their preparation
  • Catalyst compositions comprising complexes of metals such as titanium are well known for catalysing the formation of polyurethanes, epoxides and polyolefins
  • catalyst composition for catalysing the curing of polyisocyanate materials is disclosed in PCT Application WO 97/17388
  • This composition comprises a Group IVB metal compound, preferably a titanium chelate, optionally in combination with a compatibihsing compound and/or conventional release agents
  • US-A-5846897 discloses zirconium compounds with diketones or alkylacetoacetates which catalyse the isocyanate - hydroxy reaction having the chemical structure
  • Me (X1 , X2, X3, X4) wherein Me is zirconium (Zr) or hafnium (Hf) and X1 , X2, X3, and X4, are the same or different and selected from the group consisting of a diketone and an alkylacetoacetate having the structures F ⁇ COCH ⁇ CORz and RiOCOCHzCORz wherein each of R ⁇ and R 2 is a branched or linear C1 -C20 hydrocarbon and at least one of X1 , X2, X3, and X4 is a diketone with structure (II) wherein the total number of carbons in R ⁇ + R 2 is at least 4
  • a compound suitable for use as a catalyst for the formation of urethanes, ureas and epoxy resins comprising the reaction product of (i) an alkoxide, condensed alkoxide or haloalkoxide of titanium zirconium, hafnium or aluminium or a mixture thereof, and
  • (n) a complexing compound having a hydroxy group which is capable of reacting with the metal compound of (i) and which is selected from the list comprising oximes, hydroxy-Schiff bases, 8-hydroxyqu ⁇ nol ⁇ ne derivatives, 10-hydroxybenzo-[h]-qu ⁇ nol ⁇ ne derivatives, hydrazones and substituted phenols
  • the compound is especially useful as a catalyst for the reaction of an isocyanate with an alcohol to form a urethane, especially for polyurethane synthesis or with an amine to form a urea or polyurea compound.
  • the compound is also useful to catalyse the reaction between epoxy groups and hydroxy or amine groups to form epoxy resins.
  • a catalyst composition comprising a compound comprising the reaction product of (i) an alkoxide, condensed alkoxide or halo-alkoxide of titanium zirconium, hafnium or aluminium or a mixture thereof, and
  • a complexing compound having a hydroxy group which is capable of reacting with the metal compound of (i) and which is selected from the list comprising oximes, hydroxy-Schiff bases, 8-hydroxyquinoline derivatives, 10-hydroxybenzo-[h]-quinoline derivatives, hydrazones and substituted phenols.
  • curable composition comprising at least one polyisocyanate compound, a compound which is capable of reacting with said polyisocyanate compound to form a polymer and a compound comprising the reaction product of
  • a complexing compound having a hydroxy group which is capable of reacting with the metal compound of (i) and which is selected from the list comprising oximes, hydroxy-Schiff bases, 8-hydroxyquinoline derivatives, 10-hydroxybenzo-[h]-quinoline derivatives, hydrazones and substituted phenols.
  • R contains 1 to 6 carbon atoms and particularly suitable alkoxides include tetra-methoxytitanium, tetra- ethoxytitanium, tetra-isopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, tetra-propoxyzirconium, tetra-butoxyzirconium, tetra-n-propoxyhafnium and tetra-n- butoxyhafnium.
  • Condensed alkoxides of titanium, zirconium or hafnium can be represented by the general formula RO[M(OR) 2 0] z R, wherein M and R have the same meaning as discussed above and z is an integer.
  • these condensed alkoxides consist of a mixture containing compounds of the above formula with z having a range of values.
  • z has an average value in the range 2 to 16 and, more preferably, in the range 2 to 8
  • a condensed alkoxide is usually prepared by the controlled addition of water to an alkoxide, followed by removal of alcohol which is displaced
  • Suitable condensed alkoxides include the compounds known as polybutyl titanate, polybutyl zirconate and polyisopropyl titanate
  • the oxime, hydroxy-Schiff base, 8-hydroxyqu ⁇ nol ⁇ ne derivative, 10-hydroxybenzo-[h]- qumoline derivatives, hydrazone or substituted phenol forms, following deprotonation, an anionic hgand which replaces one or more of the alkoxide groups
  • complexing compounds all have the capability of binding to the metal both covalently and also of forming a second covalent or coordinating bond to the metal, by means of a second hydroxyl group or an alternative electron donor, usually in the form of an N atom
  • Any alkoxide groups remaining on the metal may, optionally, be displaced by reacting the resulting complex with an alcohol, such as phenol for example to form a complex containing an alkoxy group which is different from the alkoxy groups in the metal alkoxide starting material
  • Preferred oximes are aryl-substituted (including polycyclic aryl-), aromatic or heterocychc oximes of Formula 1 or Formula 2,
  • X 1 , Y 1 and X 2 which may be the same or different, are selected from H, alkyl (preferably C, - C 6 alkyl, e g t-butyl), alkoxy, N0 2 , halogen, ammo (including alkylamino)
  • alkyl preferably C, - C 6 alkyl, e g t-butyl
  • alkoxy preferably C, - C 6 alkyl, e g t-butyl
  • N0 2 halogen, ammo (including alkylamino)
  • Formulas 1 and 2 are amended accordingly
  • Z 1 and Z 2 may be selected from H, or an alkyl aryl or pyridyl group, any of which may be substituted or unsubstituted
  • the hydroxy-Schiff bases useful in the invention are of general Formula 3 or 3a
  • Formula 3 Formula 3a where each X 3 and Y 3 may be the same or different, and is selected from H, alkyl (preferably C- - C 6 alkyl, e g t-butyl), alkoxy, N0 2 , halogen, ammo (including alkylammo) and R is substituted or unsubstituted alkyl (including cycloalkyl), aryl, aryloxy, alkoxy, or a polycyhc group such as qumolyl
  • R When R is substituted alkyl or aryl, the substituents may be selected from alkyl, alkoxy, nitro, halogen or an and there may be one or more than one subsituent which may be the same or different from each other
  • Some useful examples of R include isopropyl, adamantyl, ethyl phenyl, phenyl, perfluorophenyl, alkoxyphenyl, bisphenyl, 2,4,6-t
  • the Schiff bases of the invention include dime ⁇ c and trime ⁇ c Schiff bases, in which R in Formula 3 or 3a comprises a linking group which is linked to a second or third Schiff base moiety which is preferably of the same composition as the other Schiff base moieties in the molecule
  • the linking group preferably contains between 1 and 6 atoms which are normally selected from C, N and O
  • the linking group may be substituted or form part of a longer chain or ring structure Examples of dime ⁇ c and trime ⁇ c Schiff bases are shown in Formula 3b and 3c in which X and Y are selected from the groups listed for X 3 and Y 3
  • the 8-hydroxyqu ⁇ nol ⁇ ne derivatives useful in the invention have the general formula 4
  • X 4 and Y 4 are, independently H, halogen, N0 2 , alkyl or alkenyl and Z 4 is H or alkyl.
  • 8-hydroxyquinoline derivatives include 8-hydroxyquinoline, 8- hydroxyquinaldine, 5-chloro-8-hydroxyquinoline, 5,7-dichloro-8-hydroxyquinoline, 5-chloro- 8-hydroxy-7-iodoquinoline, 8-hydroxy-5-nitroquinoline, 5,7-dibromo-8-hydroxyquinoline, 5,7- dichloro-8-hydroxy-2-methylquinoline, 5J-dibromo-8-hydroxy-2-methylquinoline, 7-allyl-8- hydroxyquinoline.
  • the 10-hydroxybenzo-[h]-quinoline derivatives are of the general formula 5 in which X 5 and Y 5 are, independently H, halogen, N0 2 , alkyl or alkenyl.
  • Suitable hydrazones are aromatic hydrazones, which may be unsubstituted or substituted at either the aromatic ring or the N atom. Therefore these suitable hydrazones have the following general formula 6:
  • X" and Y" are selected from H, (optionally substituted) alkyl (e.g. Ci - C 6 alkyl, such as t- butyl or i-propyl), alkoxy, for example methoxy, aryl, N0 2 , or (optionally substituted) amino.
  • R ! and R 2 may be H , alkyl or aryl or may be together another hydrazone derivative. In this latter case the molecule is preferably symmetrical so that the two hydrazone derivatives are the same. An example of such a molecule is shown as Formula 7. Polycyclic analogues of these hydrazone derivatives are also included in the suitable hydrazone species for the invention.
  • substituted phenols having substituents which include a N, O or S group which can coordinate to a metal atom may also be used as complexing compounds for the invention
  • substituents include hydroxy, hydroxyalkyl, am o, aminoalkyl, oxazole and thiazole- containing groups
  • the phenol may additionally contain other substituents such as (optionally substituted) alkyl, (e g C-i - C 6 alkyl, such as t-butyl or i-propyl), alkoxy, for example methoxy, aryl or N0 2
  • Suitable substituted phenols therefore include but are not limited to 2,4-d ⁇ t butyl-6-am ⁇ no phenol, 2,4,6-hydroxymethylphenol, 2-benzoxazol-2-yl-phenol, 2-benzoth ⁇ azol-2-yl-phenol
  • the phenol may be substituted by a phenol derivative
  • the phenol substituent is of a similar composition to the substituted phenol itself or is joined to the substituted phenol by a symmetrical bridging group, so that the resulting molecule is symmetrical
  • Examples of such a substituted phenol is 4,4'-methylene-b ⁇ s(2,6- di'butylphenol), 2,2'methylene b ⁇ s(6-'butyl-4methylphenol), 2,2'ethyl ⁇ dene bis (4,6-d ⁇ -ferf- butyl phenol), and compounds of these bisphenols where the metal M is zirconium or hafnium have not been demonstrated in the prior art More than one such substituent may be present to provide tnsphenol-type compounds such as those illustrated in formulae 8 & 9
  • R and R 2 in Formula 9 are each, independently, selected from H, aryl, alkyl, N0 2 , ammo or a halogen
  • the compounds of the invention may be made by combining a solution of the complexing compound in an inert atmosphere with the alkoxide, condensed alkoxide or halo-alkoxide of titanium zirconium, hafnium or aluminium, with heating to reflux if necessary
  • the solid complexes may be purified and isolated by standard synthetic techniques such as crystallisation or precipitation and recrystal sed if necessary
  • the compounds of the invention may comprise one or more than one metal atom
  • the complexing compounds, being capable of forming more than one bond with a metal atom may form bridges between metal atoms to form larger molecules For example, in a complexing compound containing more than one hydroxy group, each may form a bond to the same or a different metal atom In this way the architecture of the compound of the invention may be controlled by careful selection of a complexing compound of appropriate functionality
  • the catalysts of the invention are useful catalysts for the formation of bonds between an isocyanate group and a group which is reactive with an isocyanate group such as a hydroxy group, especially urethane bonds, most especially as curing agents in polyisocyanate / polyol compositions for polyurethane manufacture
  • Isocyanate compositions which may be cured using catalysts of this invention may be any organic polyisocyanate compound or mixture of organic polyisocyanate compounds, provided said compounds have at least 2 isocyanate groups
  • Organic polyisocyanates include dnsocyanates, particularly aromatic dnsocyanates, and isocyanates of higher functionality
  • organic polyisocyanates include aliphatic isocyanates such as hexamethylene diisocyanate, and aromatic isocyanates such as m- and p-phenylene diisocyanate, tolylene- 2,4- and tolylene- 2,6-d ⁇ socyanate, d ⁇ phenylmethane-4,4'-d ⁇ socyanate, chlorophenylene- 2,4-d ⁇ socyanate, naphthylene-1 ,5-d ⁇ socyanate, d ⁇ phenylene-4,4'-d ⁇ socyanate, 4,4'- d ⁇ socyanate-3,3'-d ⁇ methyl-d ⁇ phenyl, 3-methyld ⁇ phenylmethane-4,4'-d ⁇ - isocyanate and diphenyl ether diisocyanate, and cycloahphatic dnsocyanates such as cyclohexane-2,4- and -2,3-d ⁇ socyanate, 1-methylcyclohe
  • Modified polyisocyanates containing isocyanurate, carbodiimide or uretonimine groups may be employed in conjunction with the organometallic complexes of the invention as well Further blocked polyisocyanates, like the reaction product of a phenol or an oxime and a polyisocyanate, may be used, having a deblocking temperature below the temperature applied when using a polyisocyanate composition
  • the organic polyisocyanate may also be an isocyanate-ended prepolymer made by reacting an excess of a diisocyanate or higher functionality polyisocyanate with a polyol
  • Water-em ulsifiable organic polyisocyanates like those described in GB-A-1444933, in EP- A-516 361 and in WO93/03082 can also be used.
  • isocyanates may be used in conjunction with the organometallic composition of the invention, for example a mixture of tolylene diisocyanate isomers such as the commercially available mixtures of 2,4- and 2,6-isomers and also the mixture of di- and higher polyisocyanates.
  • Polyisocyanate mixtures may optionally contain monofunctional isocyanates such as p-ethyl phenylisocyanate.
  • Such mixtures are well-known in the art and include the crude phosgenation products containing methylene bridged polyphenyl polyisocyanates, including diisocyanate, triisocyanate and higher polyisocyanates together with any phosgenation by-products.
  • Preferred isocyanates to be used in conjunction with the organometallic complexes of the present invention are those wherein the isocyanate is an aromatic diisocyanate or polyisocyanate of higher functionality such as a pure diphenylmethane diisocyanate or a mixture of methylene bridged polyphenyl polyisocyanates containing diisocyanates, triisocyanates and higher functionality polyisocyanates.
  • Methylene bridged polyphenyl polyisocyanates are well known in the art. They are prepared by phosgenation of corresponding mixtures of polyamines. For convenience, polymeric mixtures of methylene bridged polyphenyl polyisocyanates containing diisocyanate, triisocyanate and higher functionality polyisocyanates are referred to hereinafter as polymeric MDI.
  • Polyisocyanates suitable for use with the organometallic complexes of the invention include SUPRASECTM DNR, SUPRASECTM 2185, RUBINATETM M and RUBINATETM 1840, all available from Huntsman ICI Polyurethanes..
  • the polyisocyanate is liquid at room temperature.
  • the isocyanate reactive compound is preferably a polyol suitable for forming polyurethanes when reacted with an isocyanate compound in the presence of a catalyst of the invention including those polyols known to the skilled person for the manufacture of polyurethanes and like compounds. These include polymeric polyols such as polyether polyols, polyester polyols, polyolefin polyols, polycarbonate polyols and polymer modified polyols.
  • Useful polymeric polyols are those having at least two isocyanate-reactive groups and include those generally known in the art, such as polyols and polyamines.
  • the polymeric polyol composition preferably comprises about 50 to about 100% and preferably about 75 to about 90% of a polyoxyethylene-terminated polyoxypropylene polyol.
  • This polymeric polyol should have a nominal hydroxyl functionality of about 2 to 6, preferably 2 to 3 and a total oxyethylene content of about 10 to 21%, preferably about 12 to 20%
  • Useful polymeric polyols have a hydroxyl equivalent weight of about 700-3000, preferably about 1 ,500 to 2,500, and more preferably about 1 ,700 to 2,000
  • the polyoxyethylene- terminated polyoxypropylated polyol preferably also contains less than about 2% of internal oxyethylene units and should comprise at least 90% by weight of oxypropylene and oxyethylene units
  • Polyether polyols which may be used include products obtained by the polymerization of a cyclic oxide, for example ethylene oxide, propylene oxide, butylene oxide or tetrahydrofuran in the presence, where necessary, of polyfunctional initiators
  • Especially useful polyether polyols include polyoxypropylene diols and t ⁇ ols and poly(oxyethylene-oxypropylene) diols and tnols obtained by the simultaneous or sequential addition of ethylene and propylene oxides to di- or trifunctional initiators as fully described in the prior art Mixtures of the said diols and tnols can be particularly useful
  • Other particularly useful polyether polyols include polytetramethylene glycols obtained by the polymerization of tetrahydrofuran
  • Polyester polyols which may be used include hydroxyl-termmated reaction products of polyhydnc alcohols such ethylene glycol, propylene glycol, diethylene glycol, 1 ,4- butanediol, neopentyl glycol, 1 ,6-hexaned ⁇ ol, cyclohexane dimethanol, b ⁇ s(hydroxyethyl)terephthalate, glycerol, t ⁇ methylolpropane, pentaeryth ⁇ tol or polyether polyols or mixtures of such polyhydnc alcohols and polycarboxyhc acids, especially dicarboxy c acids or their ester-forming derivatives, for example succmic, glutanc and adipic acids or their dimethyl esters, sebacic acid, phtha c anhydride, tetrachlorophtha c anhydride, dimethyl terephthalate or mixtures thereof Polyesteramides may be obtained by the inclusion of ammo
  • Polycarbonate polyols which may be used include products obtained by reacting diols such as 1 ,3-propaned ⁇ ol, 1 ,4-butaned ⁇ ol, 1 ,6-hexaned ⁇ ol, diethylene glycol or tetraethylene glycol with diaryl carbonates, for example diphenyl carbonate, or with phosgene
  • Polyacetal polyols which may be used include those prepared by reacting glycols such as diethylene glycol, tnethylene glycol or hexanediol with formaldehyde or by polymerizing cyclic acetals
  • Suitable polyolefm polyols include hydroxy-terminated butadiene homo- and copolymers and suitable polysiloxane polyols include polydimethylsiloxane diols and tnols
  • modified polyols often referred to as "polymer" polyols
  • Polyoxyalkylene polyols containing from 5 to 50% of dispersed polymer are particularly useful Particle sizes of the dispersed polymer of less than 50 microns are preferred
  • isocyanate-reactive polymers include polymeric polyamines, especially diamines and tnamines, corresponding to the above-described polymeric polyols Suitable polyamines of polyether polyols are those described, for example, in U S Pat No 3,654,374 or are obtained by the cyanoethylation of polyols followed by hydrogenation Polyoxypropylene diammes and tnamines and mixtures thereof are preferred Also useful are polymers containing both ammo and hydroxyl groups obtained by the partial amination of polyols Further isocyanate-reactive polymers include imino-functional polymers, such as polymers described in U S Pat No 4,794,129 together with methods for their preparation and enamine functional polymers which may be prepared either from secondary amine terminated resins (i e polyethers) by reaction with ketones/aldehydes having one or more alpha hydrogens, or by reacting ketone/aldehyde terminated resins (bearing alpha hydrogens) with
  • a composition containing an organometallic composition of the present invention and a polyisocyanate and compounds reactive therewith may further comprise conventional additives such as diluents, flame retardants, blowing agents, release agents, water, coupling agents, gnocellulosic preserving agents, fungicides, waxes, sizing agents, fillers, colourants, impact modifiers, surfactants, thixotropic agents and other binders like formaldehyde condensate adhesive resins and lignin
  • the catalysts of the present invention are useful for the manufacture of polyurethane foams, flexible or rigid articles, coatings, adhesives, elastomers, sealants, thermoplastic polyurethanes, and binders e g for oriented strand board manufacture
  • the catalysts of the present invention may also be useful in preparing polyurethane prepolymers, i e urethane polymers of relatively low molecular weight which are supplied to end-users for curing into polyurethane articles or compositions of higher molecular weight
  • the catalysts are typically added to the isocyanate / alcohol mixture to give a concentration in the range 1 x 10 "6 to 5 x 10 "3 % by weight
  • the catalysts are also useful in epoxy resin manufacture
  • Example Kb preparation of b ⁇ s(sal ⁇ cylaldox ⁇ m ⁇ nato)octa ⁇ sopropoxy titanate
  • Dry Toluene (10ml) was added to a Schlenk containing salicylaldoxime (2 06g, 15mmol) under an inert atmosphere Titanium tetraisopropoxide (6ml, 20mmol) was added to the resulting suspension resulting in the formation of an orange solution
  • the volume of this solution was reduced in vacuo to approximately half of its original volume and left to stand After standing for 24 hours the solution yielded a crop of orange crystals of T ⁇ 3 (L) 2 (0'Pr) 8 b ⁇ s(sal ⁇ cylaldox ⁇ m ⁇ nato)octa ⁇ sopropoxy titanate
  • L represents the hgand derived from salicylaldoxime
  • the yield 1 86g (31 5%)
  • melting point 146-148°C
  • the structure of the crystalline product was confirmed using 1 H N
  • Salicyl aldehyde (10ml, 11 46g, 93 83mmol) and phenyl aniline (9ml, 9 20g, 98 75mmol) was dissolved in toluene (100ml) and a catalytic amount of para-toluene sulfonic acid was added After heating at reflux temperature on a Dean-Stark apparatus over night, the mixture was cooled down and the solvent removed in vacuo The remaining oil was dissolved in dichloromethane, the solution washed with water and dried over sodium sulphate Removal of the filtered solvent gave a yellow oil which solidified on standing The yield was 16 30g (88%) and the identity of the product was confirmed by 1 H- and 13 C-NMR spectroscopy
  • Example 3 Preparation of bis 8-hydroxyqu ⁇ nol ⁇ nate bis isopropanolate complex
  • Dry toluene (20ml) was added to a Schlenk tube containing 8-hydroxyqu ⁇ nol ⁇ ne (7 23g, 50mmol) under an inert atmosphere to give a suspension at room temperature
  • titanium tetraisopropoxide (7 5ml, 7 11g, 25mmol) under a positive pressure of argon using a dry syringe
  • Formation of a yellow suspension occurred immediately and this was stirred for approximately 1 hour
  • Melting Point 184-185°C
  • the structure of the crystalline product was confirmed using 1 H NMR at 400MHz in deuterated DMSO and by single-crystal X-ray diffraction studies
  • Example 4 Preparation of titanium- 8-hydroxyqu ⁇ nol ⁇ nate complex with replaced alkoxide
  • a model urethane reaction, between methylene diphenyldnsocyanate (MDI) and 2- methoxyethanol was used to determine and compare the catalytic activity of the titanium complexes of the invention
  • MDI was purified by dissolving in toluene and removing insoluble material by filtration and then removing the solvent
  • the MDI produced was found to be analytically pure by NMR and was stored at -80°C
  • a standard 0 75M solution of MDI was prepared by dissolving 4 69g of purified MDI in dry degassed C 6 D 6 in a 25 ml volumetric flask The resulting clear solution was stored under argon over molecular sieves 2-methoxyethanol was degassed and stored under argon over molecular sieves C 6 D 6 was dried over molecular sieves, degassed and stored under argon
  • a standard catalyst solution was prepared using inert atmosphere techniques First a solution was prepared in 5ml of C 6 D 6 to give an approximate molarity of 5x10 "2 mol I "1 , based on the concentration of titanium atoms This solution was then diluted in C 6 D 6 benzene to give an approximate molarity of 1 25x10 "3 mol I "1 The catalyst solution was stored under argon at -10°C
  • the percentage of MDI remaining at the time at which each spectrum was taken was determined by calculating the ratio of integral of the starting material peaks to the total integral of peaks due to both starting materials and products in both these regions
  • the natural log of the MDI concentration was plotted against time to give in all cases a straight line whose gradient was equal to -k o s
  • a plot of k obs versus catalyst concentration was then produced which gave a straight line
  • Comparison of the gradients of the lines obtained from these final plots of k obs vs [Ti] for each catalyst allowed the relative rates of each catalyst for these reactions to be assessed. The results are shown in Table 1
  • Dry toluene (10ml) was added to a Schlenk tube containing 2,2'methylene bis (6-fert-butyl- 4-methyl phenol) (3 41g, lOmmmol) under an inert atmosphere
  • titanium tetraisopropoxide (3 Oml, 10mmol) under a positive pressure of argon using a dry syringe
  • the structure of the crystalline product was confirmed using 1 H NMR at 400MHz in CDCI 3
  • Dry toluene (10ml) was added to a Schlenk tube containing 2,2'ethyl ⁇ dene bis (5,6-d ⁇ -ferf- butyl phenol) (4 39g, 10mmol) under an inert atmosphere
  • titanium tetraisopropoxide (3 Oml, 10mmol) under a positive pressure of argon using a dry syringe
  • the resulting orange suspension was heated with stirring until the solid had entirely entered solution
  • the structure of the crystalline product was confirmed using 1 H NMR at 400MHz in CD
  • Dry toluene (5ml) was added to a Schlenk tube containing 2,2'ethyl ⁇ dene bis (5,6-d ⁇ -tert- butyl phenol) (2 20g, 5mmol) under an inert atmosphere
  • zirconium tetra-n-propoxide (1 7ml, 5mmol) under a positive pressure of argon using a dry syringe. Precipitation occurred immediately and the solvent was removed in vacuo to leave a white solid.
  • Dry hexane (5ml) was added to a Schlenk tube containing 4,4' methylene bis (2,6-di-ferf- butyl phenol) (2.12g, 5mmol) under an inert atmosphere. Titanium tetraisopropoxide (3.0ml, 10mmol) was added to this suspension under a positive pressure of argon using a dry syringe. A yellow solution was formed immediately. Approximately 50% of the solvent was removed in vacuo and the remaining yellow solution was placed in the fridge.
  • Example 6(f) Complex between three equivalents of titanium isopropoxide and 1 ,3,5- trimethyl-2-4-6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene
  • Dry toluene (10ml) was added to a Schlenk tube containing 2,4-di-tert-butyl-salicylaldehyde hydrazone, 2 mmol, 0.5 g,) under an inert atmosphere to give a suspension at room temperature.
  • titanium tetraisopropoxide (1 mmol, 0.3 ml) under a positive pressure of argon using a dry syringe.
  • the resulting suspension was heated to reflux and then cooled to room temperature leaving a yellow solution. Solvent was removed in vacuo until the formation of a yellow precipitate.
  • Ti(OiPr) 4 (3.1 ml, 10mmol) was added dropwise by syringe, to a stirred suspension of H 3 L(Me/Me) ( 4.2g, 10mmol) in toluene (50ml) at 0 ° C.
  • the reaction mixture was allowed to warm to room temperature, with stirring, resulting in a yellow solution.

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Abstract

La présente invention concerne un composé qui peut être utilisé en tant que catalyseur employé dans la formation d'uréthanes et d'urées. Ce composé est formé du produit de réaction de (i) un alcoxyde, un alcoxyde condensé ou un halo-alcoxyde de titane zirconium, de hafnium ou d'aluminium ou d'un mélange de ces derniers et de (ii) un composé complexant sélectionné dans la liste comprenant les oximes, les bases hydroxy-Schiff, les dérivés 8-hydroxyquinoline, les dérivés 10-hydroxybenzo-[h]-quinoline, les hydrazones et phénols substitués.
PCT/GB2002/003896 2001-08-25 2002-08-23 Catalyseurs et compositions durcissables WO2003018662A1 (fr)

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Cited By (7)

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WO2004052980A1 (fr) * 2002-12-11 2004-06-24 Johnson Matthey Plc Reaction de polymerisation et catalyseur associe
WO2015111498A1 (fr) * 2014-01-21 2015-07-30 日東化成株式会社 Catalyseur pour fabrication de résine uréthane, composition de résine uréthane fabriquée en présence dudit catalyseur, et procédé de fabrication de ladite composition
WO2015111497A1 (fr) * 2014-01-21 2015-07-30 日東化成株式会社 Catalyseur pour fabrication de résine uréthane, composition de résine uréthane fabriquée en présence dudit catalyseur, et procédé de fabrication de ladite composition
US9199924B2 (en) 2010-08-12 2015-12-01 Bayer Intellectual Property Gmbh Process for the preparation of urethanes
CN114621470A (zh) * 2020-12-10 2022-06-14 柏瑞克股份有限公司 用于缩合反应的催化剂及合成催化剂的方法
CN116354807A (zh) * 2023-03-23 2023-06-30 昆明理工大学 一种非金属催化剂的无溶剂合成方法及其应用
WO2024104923A1 (fr) * 2022-11-16 2024-05-23 Basf Se Catalyseurs contenant du manganèse et du fer comprenant un ligand imine pour la synthèse de polyuréthanes

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004052980A1 (fr) * 2002-12-11 2004-06-24 Johnson Matthey Plc Reaction de polymerisation et catalyseur associe
US9199924B2 (en) 2010-08-12 2015-12-01 Bayer Intellectual Property Gmbh Process for the preparation of urethanes
WO2015111498A1 (fr) * 2014-01-21 2015-07-30 日東化成株式会社 Catalyseur pour fabrication de résine uréthane, composition de résine uréthane fabriquée en présence dudit catalyseur, et procédé de fabrication de ladite composition
WO2015111497A1 (fr) * 2014-01-21 2015-07-30 日東化成株式会社 Catalyseur pour fabrication de résine uréthane, composition de résine uréthane fabriquée en présence dudit catalyseur, et procédé de fabrication de ladite composition
JP5894705B2 (ja) * 2014-01-21 2016-03-30 日東化成株式会社 ウレタン樹脂製造用触媒、該触媒存在下で製造されるウレタン樹脂組成物、および該ウレタン樹脂組成物の製造方法
JP5894704B2 (ja) * 2014-01-21 2016-03-30 日東化成株式会社 ウレタン樹脂製造用触媒、該触媒存在下で製造されるウレタン樹脂組成物、および該ウレタン樹脂組成物の製造方法
CN114621470A (zh) * 2020-12-10 2022-06-14 柏瑞克股份有限公司 用于缩合反应的催化剂及合成催化剂的方法
WO2024104923A1 (fr) * 2022-11-16 2024-05-23 Basf Se Catalyseurs contenant du manganèse et du fer comprenant un ligand imine pour la synthèse de polyuréthanes
CN116354807A (zh) * 2023-03-23 2023-06-30 昆明理工大学 一种非金属催化剂的无溶剂合成方法及其应用
CN116354807B (zh) * 2023-03-23 2024-04-12 昆明理工大学 一种非金属催化剂的无溶剂合成方法及其应用

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