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WO2005058996A1 - Catalyseur et procede de fabrication de materiaux en polyurethanne - Google Patents

Catalyseur et procede de fabrication de materiaux en polyurethanne Download PDF

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Publication number
WO2005058996A1
WO2005058996A1 PCT/GB2004/005368 GB2004005368W WO2005058996A1 WO 2005058996 A1 WO2005058996 A1 WO 2005058996A1 GB 2004005368 W GB2004005368 W GB 2004005368W WO 2005058996 A1 WO2005058996 A1 WO 2005058996A1
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coch
alkyl
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Inventor
Bruno Frederic Stengel
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Johnson Matthey PLC
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Johnson Matthey PLC
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • 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
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic

Definitions

  • Catalyst and method of making polvurethane materials The present invention relates to catalyst compositions which are suitable for catalysing the reaction between a polyol and an isocyanate composition for i.e. for preparing and curing polyurethane materials.
  • the catalysts of choice in many applications have, for many years, been organic mercury compounds. This is because these catalysts provide a desirable reaction profile which offers an initial induction period in which the reaction is either very slow or does not take place, followed by a rapid reaction which continues for sufficient time to produce a relatively hard polymer article.
  • the induction time also known as the pot life, is desirable because it allows the liquid reaction mixture to be poured or moulded after addition of the catalyst and therefore gives the manufacturer more control over the manufacturing process.
  • the rapid and complete reaction after the pot life is important to provide finished articles which are not sticky and which develop their desired physical properties quickly to allow fast turnaround in the production facility.
  • Catalysts comprising compounds of titanium or zirconium are well known for use in many applications such as in esterification reactions and for curing reaction mixtures containing isocyanate and hydroxylic species to form polyurethanes.
  • catalysts comprise a metal alkoxide, such as titanium tetra isopropoxide, or a chelated species derived from the alkoxides.
  • titanium alkoxides provide very effective catalysts for polyurethane cure reactions, they may not produce a reaction profile with the desirable pot life and cure profile described above. In many cases the reaction may be very rapid but offers only a short induction period so that the polyurethane mixture tends to gel very quickly, often before it can be cast into its final shape.
  • a further problem is that, despite the rapid initial reaction, the resulting polyurethane does not achieve a satisfactory degree of cure within a reasonable time. This presents a particular problem when the polyurethane reaction mixture contains polyols having secondary terminal hydroxy groups, which are less readily catalysed using titanium catalysts. This results in finished articles which are sticky and difficult to handle and which may have inferior physical properties compared with articles made using a mercury catalyst.
  • US3714077 describes the use of organic bismuth and/or antimony compounds, optionally in the presence of certain tertiary amines, as catalyst systems for curing polyurethane foams.
  • US4584362 describes processes for preparing polyurethane elastomers by reacting a polyether or polyester polyol with a polyisocyanate in the presence of a catalytic amount of a bismuth salt of a carboxylic acid having from 2 to 20 carbon atoms.
  • US5011902 describes polyurethane elastomers prepared by reacting a polyether or polyester polyol with a polyisocyanate in the presence of a catalytic amount of a co-catalyst system comprising an organo-bismuth compound, preferably a bismuth salt of a carboxylic acid, and at least one organo-metallic compound, preferably a metal salt of a carboxylic acid, wherein the metal is selected from the group consisting of zinc, antimony and lithium.
  • a co-catalyst system comprising an organo-bismuth compound, preferably a bismuth salt of a carboxylic acid, and at least one organo-metallic compound, preferably a metal salt of a carboxylic acid, wherein the metal is selected from the group consisting of zinc, antimony and lithium.
  • US5,902,835 describes a range of catalysts for blowing polyurethane foams.
  • the catalysts are titanium, zirconium or hafnium compounds.
  • the use of a combination of such catalysts with other catalysts such as bismuth, zinc, cobalt etc compounds is mentioned.
  • US6,590,057 describes polyurethane materials formed in the presence of amine catalysts and a catalyst mixture comprising an organic titanium or zirconium compound and a lithium carboxylate, optionally also containing a bismuth compound.
  • the bismuth catalysts of these prior art processes are relatively non-toxic. However, bismuth catalysts are rather reactive leading to relatively short pot-life and cure reactions which may be difficult to control. Furthermore, we have found that mixtures of bismuth catalysts in polyols tend to become less reactive after storage for several days.
  • a catalyst composition suitable for use in catalysing the reaction between a polyol and an isocyanate composition comprising a) an organometallic compound which is a compound of titanium, zirconium, hafnium, iron (III), cobalt (III) or aluminium and b) a bismuth compound.
  • compositions comprising: a) either i) a compound having more than one hydroxy group which is capable of reacting with an isocyanate group -containing material to form a polyurethane or ii) a compound having more than one isocyanate group which is capable of reacting with a hydroxyl group-containing material to form a polyurethane, or iii) a mixture of (i) and (ii) b) a catalyst composition comprising an organometallic compound which is a mixture of a compound of titanium, zirconium, hafnium, iron (III), cobalt (III) or aluminium and a bismuth compound.
  • chain modifiers one or more further components selected from chain modifiers, diluents, flame retardants, blowing agents, release agents, water, coupling agents, lignocellulosic preserving agents, fungicides, waxes, sizing agents, fillers, colourants, impact modifiers, surfactants, thixotropic agents, flame retardants, plasticisers, and other binders.
  • a process for the manufacture of a polyurethane elastomer, adhesive or thermoplastic polyurethane comprising the steps of : a) forming a mixture by mixing together either i) a compound having more than one hydroxy group which is capable of reacting with an isocyanate group -containing material to form a polyurethane or ii) a compound having more than one isocyanate group which is capable of reacting with a hydroxyl group-containing material to form a polyurethane, with a catalyst composition comprising a mixture of (iii) an organometallic compound which is a compound of titanium, zirconium, hafnium, iron (III), cobalt (III) or aluminium and (iv)a bismuth compound, i b) adding to said mixture the other of the compound having more than one hydroxy group which is capable of reacting with an isocyanate group -containing material to form a polyurethane or the a compound having
  • the catalyst composition comprises an organometallic compound which is a compound of titanium, zirconium, hafnium, iron (III), cobalt (III) or aluminium and a bismuth compound, which are mixed together before the catalyst composition is added to the polyol or isocyanate component of the polyurethane-forming mixture.
  • the mixed catalyst composition may be added to a mixture of polyol and isocyanate compound.
  • the catalyst composition does not contain a lithium carboxylate in contrast to the catalyst systems used in US6,590,057.
  • the organometallic compound is preferably of general formula: M(L 1 ) w (L 2 ) x (L 3 ) y (L 4 ) z wherein M is a metal selected from titanium(IV), zirconium(IV), hafnium(IV), iron (III), cobalt (III) or aluminium;
  • R is alkyl or a hydroxy-alkyl, hydroxyalkoxyalkyl, or (hydroxy)polyoxyalkyl group
  • L 1 , L 2 , L 3 and L 4 are each independently selected from:- a) RO-, where R is selected from alkyl, hydroxy-alkyl, hydroxyalkoxyalkyl, or (hydroxy)polyoxyalkyl group, b) a ⁇ -diketonate, c) an ester or amide of acetoacetic acid, d) a hydroxycarboxylic acid or ester thereof, e) R 1 COO- where R 1 is substituted or unsubstituted C-, - C 30 branched or linear alkyl, f) substituted or unsubstituted aryl including polycyclic structures such as naphthyl or anthracyl, g) phosphate, phosphinate, phosphonate, siloxy or sulphonato or h) a substitute
  • the metal M is preferably selected from titanium(IV) and zirconium(IV).
  • M is titanium then it is believed that compounds containing three or four ⁇ -diketonate, acetoacetate ester or carboxylic acid, phosphate, phosphinate, phosphonate, siloxy or sulphonato ligands attached to one metal atom do not form and so such compounds are not included in the scope of the organometallic compounds shown above.
  • the organometallic compounds may form bridged structures so that a molecule of the compound may contain more than one metal atom.
  • the ligands L1 - L4 may exchange so that the composition is a dynamic mixture of components approximating, on average, to the composition represented by the general formulae shown .
  • At least one of 10- L 4 is preferably -OR.
  • the group OR is labile and provides an active site for catalysis. By labile, we mean that under the conditions of the reaction which is to be catalysed, the group OR may undergo substitution or insertion by one of the reactant molecules to facilitate the reaction mechanism.
  • R may be an alkyl group, such as a Ci - C 22 alkyl, more preferably a C ⁇ - C 8 alkyl.
  • R may be a hydroxy-alkyl group derived from a diol such as 1 ,4-butane diol or a polyoxyalkyl group (also known as a.glycol- ether group) such as a dialkylene glycol, polyalkylene glycol, for example diethylene glycol or polyethylene glycol.
  • Preferred R groups include ethyl, n-propyl, isopropyl, n-butyl, t- butyl, pentyl, hexyl or 2-ethyl-hexyl, hydroxybutyl, polyoxyethyl and 2-(2-hydroxyethoxy)- ethyl.
  • -OR is an alkoxide derived from a diol, e.g. 1 ,4-butane diol, diethylene glycol, ethylene glycol or a polyalkylene glycol.
  • a short-chain polyol normally a diol such as1 ,4-butane diol, is often used as a chain extender as part of a mixture of polyols to be reacted with a polyisocyanate.
  • labile OR group of the catalyst a functionalised alkoxide, which is capable of forming a bis or poly functional alcohol on leaving the organometallic compound and thereby functioning as a chain extender rather than forming a singly functional alcohol which may have a tendency to terminate the growing polymer chains.
  • the organometallic compound may, for example, be a titanium or zirconium tetraalkoxide of formula M(OR) 4 where R is alkyl or hydroxy alkyl , preferably Ci, - C 22 alkyl, more preferably Ci to C 8 alkyl.
  • R groups include ethyl, n-propyl, isopropyl, n-butyl, t- butyl, pentyl, hexyl or 2-ethyl-hexyl, hydroxybutyl, polyoxyethyl and 2-(2-hydroxyethoxy)- ethyl.
  • L 1 - L 4 may alternatively be derived from a ⁇ -diketone such as acetylacetone, an alkylacetoacetate or an N-alkylacetoacetamide (where alkyl is preferably a Ci, to C 8 alkyl group), such as ethylacetoacetate or N,N-diethylacetoacetamide, a hydroxycarboxylic acid or ester thereof,, such as salicylic acid, mandelic acid, levulinic acid, naphthalene dicarboxylic acid, citric acid, lactic acid, tartaric acid; substituted or unsubstituted aryloxy such as phenoxy or naphthoxy, an alkyl phenoxy, benzoic acid or a C 2 - C 30 carboxylic acid, preferably a C 6 - C 22 carboxylic acid such as stearic, isostearic or 2-ethyl- hexylcarboxylic acid.
  • ligands which form two covalent bonds with the metal atom include hydroxycarboxylic acids, such as salicylic acid or esters thereof, a bis- hydroxy compound such as 2-hydroxy-benzyl alcohol (salicyl alcohol), or esters thereof e.g.
  • a carboxylic acid having a ⁇ -carbonyl group such as 3-oxo-butyric acid for example
  • a substituted phenol especially a bisphenol compound where two phenol moieties are linked by a hydrocarbon or nitrogen-containing bridge such as 2,2'ethylidene bis (4,6-di-terf-butyl phenolate), symmetrical or unsymmetrical hydrazine- or amine-bridged phenol derivatives.
  • L 1 , L 2 , L 3 and L 4 may be capable of forming a coordinating bond with the metal atom in addition to a covalent bond so that the total number of bonds formed between M and the L groups is greater than V. This may occur, for example, when L 1 or L 2 is a diketonate such as acetylacetone or an alkyl acetoacetate or acetoacetamide which can react with the metal atom at the carbonyl group through the enolate form of the compound and also form a coordinating bond between the electron-donating ester or amide group and the metal.
  • M is titanium, for example, this leads to a stable complexed form of titanium.
  • the organometallic compound is of general formula
  • M is a metal selected from titanium, zirconium, hafnium, iron (III), cobalt (III) or aluminium;
  • R is alkyl or a hydroxy-alkyl, hydroxyalkoxyalkyl, or (hydroxy)polyoxyalkyl group
  • L 1 and L 2 are each independently selected from a ⁇ - diketonate, an ester or amide of acetoacetic acid, a hydroxycarboxylic acid or ester thereof or siloxy.
  • R is a hydroxy-alkyl hydroxyalkoxyalkyl, or (hydroxy)polyoxyalkyl group
  • L 1 and L 2 are preferably each independently selected from a diketonate, an ester or amide of acetoacetic acid, a hydroxycarboxylic acid or ester thereof, R 1 COO- where R 1 is substituted or unsubstituted C-, - C 30 branched or linear alkyl, substituted or unsubstituted aryl including polycyclic structures such as naphthyl or anthracyl, phosphate, phosphinate, phosphonate, siloxy or sulphonato.
  • L 3 is selected from substituted or unsubstituted aryloxy, R 2 COO- where R 2 is a linear or branched C- ⁇ - C 30 alkyl or a substituted or unsubstituted aryl, a polyoxyalkoxy or hydroxyalkoxyalkoxy group;
  • the bismuth compound may be inorganic, e.g. bismuth trioxide but is preferably an organobismuth compound, especially compounds of bismuth with C 2 - C 20 carboxylic acids, e.g. bismuth triacetate or more especially with C 8 - C ⁇ 2 carboxylic acids.
  • organobismuth catalysts are known for use as catalysts in polyurethane systems and typical examples include bismuth tris(neodecanoate) and bismuth tris(2-ethyl- hexylcarboxylate).
  • the bismuth compounds may be made by reacting a bismuth salt such as bismuth trioxide with a carboxylic acid.
  • the bismuth compound is preferably present as a solution in e.g. a carboxylic acid.
  • the catalyst composition preferably contains the organometallic compound and bismuth compound in a ratio of about 1 -10 :10 - 1 by weight more preferably about 1 :1 by weight.
  • the catalyst composition may additionally include an amine.
  • Amines are known catalysts for polyurethane reactions and any known amine for this purpose may be used. Secondary and especially tertiary amines are preferred. Suitable amines include morpholines, e.g.2,2'- dimorpholinodiethyl ether (DMDEE), n-alkyl-morpholines, alkyl or aryl amines, e.g.
  • the organometallic compound or its mixture with the bismuth compound may contain one or more additional components.
  • a liquid diluent or solvent may provide a benefit.
  • the liquid component may be selected from an acid, a diol or polyol, a ⁇ -diketonate or a ketone.
  • Suitable acids include alkyl carboxylic acids, for example a C 2 - C 30 carboxylic acid, especially a C - C 22 carboxylic acid such as butyric, stearic, isostearic, oleic or 2-ethyl-hexylcarboxylic acid.
  • Suitable diols or polyols include 1 ,2-ethanediol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,4-butane diol or a dihydric alcohol containing a longer chain such as diethylene glycol or a polyethylene glycol or polypropylene glycol.
  • Suitable ⁇ -diketonates include acetyl acetone, alkyl acetoacetates, especially ethylacetoacetate or 2-ethylhexylacetoacetate.
  • the additional liquid component may be mixed with the compound of the invention in all proportions, suitably the proportions of the catalyst composition : additional liquid used will be in the range 1 :99 - 99:1 , more usually 10:90 - 90:10 by weight, depending upon the molecular weight of the additional liquid and the catalyst composition.
  • the additional liquid is added at a ratio of from 0.1 to 10 moles of the liquid compound per mole of titanium or zirconium, e.g. from about 0.5 to 5, preferably from about 0.5 to 3 moles of the liquid compound per mole of titanium or zirconium.
  • catalysts for curing polyurethanes are supplied in a liquid form.
  • the organometallic compositions of the invention may be supplied neat (particularly when the composition is, itself a liquid) or as a solution in a suitable solvent, such as toluene, hexane, heptane etc. More preferably it is supplied in a liquid component which is already present in or which is compatible with the polyurethane reaction components, such as a diol or glycol e.g. butane diol or diethylene glycol.
  • the compound having more than one hydroxy group which is capable of reacting with an isocyanate group-containing material to form a polyurethane or the compound having more than one isocyanate group which is capable of reacting with a hydroxyl group-containing material to form a polyurethane may comprise a mixture of such compounds or a mixture of such compounds with different compounds, e.g. fillers or other additives etc.
  • the process of the invention is comprises the reaction between a hydroxy-functionalised molecule, such as a polyol, and an isocyanate-functionalised molecule, such as a polyisocyanate to form an elastomer, an adhesive or a thermoplastic mouldable material.
  • This reaction forms the basis of many commercially available two-component polyurethane systems.
  • the process is not intended to include the formation of polyurethane foams in which the catalyst is a blowing agent. Therefore the reactants preferably do not contain water in sufficient amounts as to produce a blown foam by reaction of the water with the isocyanate material.
  • the polyol component should contain less than 0.3%, more preferably less than 0.1 %, of water by weight.
  • the polyol component may be any suitable for the manufacture of polyurethanes and includes polyester-polyols, polyester-amide polyols, polyether-polyols, polythioetherpolyols; polycarbonate polyols, polyacetal polyols, polyolefin polyols polysiloxane polyols, dispersions or solutions of addition or condensation polymers in polyols of the types described above, often referred to as "polymer" polyols.
  • polyester-polyols polyester-amide polyols
  • polyether-polyols polythioetherpolyols
  • polycarbonate polyols polyacetal polyols
  • polyolefin polyols polysiloxane polyols dispersions or solutions of addition or condensation polymers in polyols of the types described above, often referred to as "polymer" polyols.
  • a very wide variety of polyols has been described in the prior
  • a mixture of polyols is used to manufacture polyurethane having particular physical properties.
  • the polyol or polyols is selected to have a molecular weight, backbone type and hydroxy functionality which is tailored to the requirements of the formulator.
  • the polyol includes a chain extender, which is often a relatively short-chain diol such as 1 ,4-butane diol or diethylene glycol or a low molecular weight polyethylene glycol.
  • chain extender in commercial use, such as diamines, e.g. MOCA (4,4- methylene bis (2-chloroaniline)) may also be used.
  • the isocyanate compositions used for polyurethane manufacture suitable for use with the catalysts of the present invention may be any organic polyisocyanate compound or mixture of organic polyisocyanate compounds which are commercially useful for the purpose.
  • the polyisocyanate is liquid at room temperature.
  • Suitable organic polyisocyanates include diisocyanates, particularly aromatic diisocyanates, and isocyanates of higher functionality.
  • suitable organic polyisocyanates include aliphatic isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate; and aromatic isocyanates such as m- and p-phenylene diisocyanate, tolylene- 2,4- and tolylene- 2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, chlorophenylene- 2,4-diisocyanate, naphthylene-1 ,5-diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'- diisocyanate-3,3'-dimethyl-diphenyl, 3-methyldiphenylmethane-4,4'-di- isocyanate and diphenyl ether diisocyanate; and cycloaliphatic diiso
  • Modified polyisocyanates containing isocyanurate, carbodiimide or uretonimine groups may be used.
  • the polyisocyanate may also be an isocyanate-ended prepolymer made by reacting an excess of a diisocyanate or higher functionality polyisocyanate with a polyol for example a polyether polyol or a polyester polyol.
  • a polyol for example a polyether polyol or a polyester polyol.
  • prepolymers is common in commercially available polyurethane systems. In these cases, polyols may already be incorporated in the isocyanate or prepolymer whilst further components such as chain extenders, polyols etc may be mixed with the isocyanate prepolymer mixture before polymerisation.
  • 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.
  • a mixture of di- and higher polyisocyanates, such as trimers (isocyanurates) or pre-polymers, may also be used.
  • Polyisocyanate mixtures may optionally contain monofunctional isocyanates such as p-ethyl phenylisocyanate.
  • the organometallic composition of the invention is typically added to the polyol prior to ⁇ mixing together the polyol component with the isocyanate component to form the polyurethane.
  • the organometallic composition may instead be added to the isocyanate component if required.
  • a composition containing a catalyst composition of the present invention and a polyisocyanate and compounds reactive therewith may further comprise conventional additives such as chain modifiers, diluents, flame retardants, blowing agents, release agents, water, coupling agents, lignocellulosic preserving agents, fungicides, waxes, sizing agents, fillers, colourants, impact modifiers, surfactants, thixotropic agents, flame retardants, plasticisers, and other binders.
  • chain modifiers such as chain modifiers, diluents, flame retardants, blowing agents, release agents, water, coupling agents, lignocellulosic preserving agents, fungicides, waxes, sizing agents, fillers, colourants, impact modifiers, surfactants, thixotropic agents, flame retardants, plasticisers, and other binders.
  • chain modifiers such as chain modifiers, diluents, flame retardants, blowing agents, release agents, water, coupling agents,
  • 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
  • the catalysts are typically present in the isocyanate and/or alcohol mixture to give a concentration in the range 1 x 10 "4 to 10% by weight, preferably up to about 4% by weight based upon the weight of the total reaction system, i.e. the total weight of the
  • the organotitanium compound is Ti(N,N-diethylacetoacetamido) 2 (2- 20 isopropylphenoxy)(isopropoxy).
  • the bismuth compound is CoscatTM 83, a commercially available bismuth trisneodecanoate in neodecanoic acid, containing 16.5% by weight of bismuth.
  • the amine is 2,2'-dimorpholinodiethyl ether (DMDEE).
  • 35 0.1g of the total catalyst composition (i.e of the polyol and catalyst composition mixture prepared as described above) was put in a cup, together with 75g of the polyol used to make up the catalyst composition.
  • the catalyst and polyol were mixed in a high-speed mixer at 3000 rpm for 30 seconds.
  • a gel-time of about 600s normally provides a convenient balance between providing a period in which the mixture may flow to enable a mould to be filled or a coating to flow on application whilst providing a sufficiently rapid cure for a fast throughput in the manufacture of polyurethane articles.
  • the cure and testing was also carried out using also a commercially available mercury-based catalyst, phenyl mercury neodecanoate, as a comparison. The results are shown in Table 1. Table 1
  • Example 2 A catalyst composition according to the invention was prepared by mixing together the following components in a glass vial:- (i) 40g of VertecTM TAA, available from Johnson Matthey Catalysts, a commercially available liquid titanium complex of di(isopropoxy)titanium bis(2,4-pentanedionate) in 2- propanol, containing about 10% Ti, (ii) 20g BiCATTM HM available from Shepherd Chemical, a commercially available bismuth 2-ethylhexanoate in 2-ethylhexanoic acid containing about 28% Bi and (iii) 40g of a solution of 25g triethylene diamine in 10Og of 1 ,4-butane diol.
  • a catalyst composition according to the invention was prepared by mixing together the following components in a glass vial:-
  • a catalyst composition according to the invention was prepared by mixing together the following components in a glass vial:-

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une composition de catalyseur utilisée en vue de catalyser la réaction entre un polyol et une composition d'isocyanate comprenant un mélange de a) un composé d'organotitane ou d'organozircon, b) un composé de bismuth, éventuellement en présence d'une amine. La composition de catalyseur est notamment utile dans le traitement de mélanges formant du polyuréthanne dans lequel le composant de polyol contient des groupes hydroxyle secondaires.
PCT/GB2004/005368 2003-12-18 2004-12-17 Catalyseur et procede de fabrication de materiaux en polyurethanne Ceased WO2005058996A1 (fr)

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GB0329272A GB0329272D0 (en) 2003-12-18 2003-12-18 Catalyst and method of making polyurethane materials
GB0329272.9 2003-12-18

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WO2005058996A1 true WO2005058996A1 (fr) 2005-06-30

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Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007003966A1 (fr) * 2005-07-04 2007-01-11 Johnson Matthey Plc Nouveau compose du zirconium, catalyseur et son utilisation pour la fabrication de polyurethanne
WO2007119078A1 (fr) * 2006-04-13 2007-10-25 Johnson Matthey Plc Promoteur d'adherence
WO2008144770A1 (fr) * 2007-05-23 2008-11-27 Huntsman International Llc Adhésifs, systèmes de réaction et procédés de production de composites lignocellulosiques
WO2009063245A3 (fr) * 2007-11-16 2009-07-16 Johnson Matthey Plc Procédé et catalyseur pour la fabrication d'un polyuréthanne
DE102008021980A1 (de) 2008-05-02 2009-11-05 Bayer Materialscience Ag Neue Katalysatoren und deren Einsatz bei der Herstellung von Polyurethanen
WO2011003529A1 (fr) 2009-07-07 2011-01-13 Bayer Materialscience Ag Polyuréthanne et son utilisation
DE102009051445A1 (de) 2009-10-30 2011-05-05 Bayer Materialscience Ag Verwendung spezieller Katalysatoren für die Herstellung von Polyurethanbeschichtungen
WO2011051465A2 (fr) 2009-10-30 2011-05-05 Tib Chemicals Ag Procédés de production de composés métalliques
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