Title of Invention

A PROCESS FOR THE PREPARATION OF AN ORGANOMETALLIC COMPOSITION

Abstract A PROCESS FOR THE PREPARATION OF AN ORGANOMETALLIC
Full Text FORM 2
THE PATENTS ACT, 1970 [39 OF 1970]
COMPLETE SPECIFICATION
[See Section 10; Rule 13]
"A PROCESS FOR THE PREPARATION OF AN ORGANOMETALLIC COMPOSITION"
JOHNSON MATTHEY PLC, a British company of 2-4 Cockspur Street, Trafalgar Square, London SW1Y 5BQ, United Kingdom,
The following specification particularly describes the nature of the invention and the manner in which it is to be performed:-
GRANTED
-6 MAY 2005 7-10-2004

This invention relates to a process for the preparation of an organometailic composition and more particularly to organometailic composition based on Group IVB metals and which are useful in polyisocyanate compositions especially compositions for binding lignocellulosic material.
The use of organic polyisocyanates as binders for lignocellulosic material in the manufacture of sheets or moulded bodies such as waferboard. chipboard, fibreboard and plywood is well known. In a typical process the organic polyisocyanate, optionally in the form of a solution, dispersion or aqueous emulsion, is applied to the lignocellulosic material which is then subjected to heat and pressure.
One suitable polyisocyanate composition 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 compatibilising compound and/or conventional release agents. Although these compositions perform well as binders for lignocellulosic material and provide good release performance, it is desirable to develop a more economical composition which provides improved stability on storage before use. together with good curing properties and excellent bonding strength wnen applied to the lignocellulosic material.
It has now been surprisingly found that certain compounds of Group IVB metals and acetoacetate esters can be used to cure poiyisocyanate compositions and these compositions are very stable on prolonged storage and economical when used for binding lignocellulosic material.
According to the invention, an organometailic composition comprises a complex of at least one metal selected from the group consisting of titanium, zirconium and hafnium and an acetoacetate ester in which the molar ratio of Ti or Hf to acetoacetate ester is in the range 1 : 2.5 to 1:10 or the molar ratio of Zr


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to acetoacetate ester is in the range 1 : 4.5 to 1 : 10 and said acetoacetate ester is an ester of an alcohol containing 1 to 6 carbon atoms.
The titanium, zirconium or hafnium composition of the invention is described herein as a "complex". It is believed that some of the acetoacetate ester will be chemically bound to the metal (Ti, Zr or Hf) but some can be described as "free" ester. The exact proportions which are bound and free will depend partly upon the exact molar ratios present in the complex and which metal, or metals, are used, but it has been shown that the "free" ester does influence the properties, particularly the stability on storage of polyisocyanate
compositions containing the complexes.
The molar ratio of titanium or hafnium to acetoacetate ester in the complex is in the range 1 : 2.5 to 1 : 10. When the metal is titanium, the molar ratio is preferably in the range 1 : 2.5 to 1 : 8 and more preferably in the range 1 : 3 to 1 : 6. Particularly preferred compounds have a molar ration in the range
1 : 4 to 1 : 6. In agreement with conventional theories about the co-ordination chemistry of titanium, it is believed that two molecules of acetoacetate ester will be chemically bound to a titanium atom and the remainder will be "free". When the metal is hafnium, the molar ratio is preferably 1 : 4.5 to 1 : 10 and more preferably 1 : 4.5 to 1 : 8, hafnium to acetoacetate ester. When the metal is
zirconium, the molar ratio is from 1 : 4.5 to 1 : 10 and preferably from 1 : 4.5 to 1 : 8, zirconium to acetoacetate ester. For hafnium or zirconium, again in accordance with conventional theory, it is believed that, for complexes which contain 4 or more moles of acetoacetate ester. 4 molecules of acetoacetate ester are chemically bound to each atom of zirconium or hafnium and the
remainder are "free".
Preferably, the complex is a complex of at least one of titanium and zirconium.




The preferred acetoacetate ester for preparing the complex is ethyl acetoacetate The complex can be prepared from more than one acetoacetate ester Put preferably only one acetoacetate ester is present in the complex.
Typically, the complexes of titanium, zirconium or hafnium are prepared from titanium, zirconium or hafnium alkoxides having the general formula M(OR)4 in which M is Ti, Zr or Hf and R is a substituted or unsubstituted, cyclic or linear, aikyl, alkenyl, aryl or alkyl-aryl group or mixtures thereof. Preferably, R contains up to 8 carbon atoms and, more preferably, up to 6 carbon atoms. Generally, all four OR groups will be identical but alkoxides derived from a
mixture of alcohols can be used and mixtures of alkoxides can be employed
when more than one metal is present in the complex. Suitable alkoxides include
tetramethoxytitanium, tetra-ethoxytitanium, tetra-isopropoxytitanium,
tetra-n-propoxytitanium, tetrabutoxytitanium, tetrakis(2-ethylhexoxy)titanium, tetrakis(2-ethoxyethoxy)titanium, tetracyclohexyloxytitanium, tetraphenoxy-
titanium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetra-n-propoxyhafnium and tetra-n-butoxyhafnium.
Alternatively, the complex can be prepared from condensed alkoxides of titanium, zirconium or hafnium. These compounds can be represented by the general formula RO[M(OR)20],R, wherein M and R have the same meaning as
discussed above and x is an integer. Generally, these condensed alkoxides consist of a mixture containing compounds of the above formula with x having a range of values. Preferably, x 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 potybutyl titanate, polybutyt zrrconate and polyisopropyl titanate. Complexes of condensed alkoxides can also be prepared by forming a complex

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of an acetoacetate ester with an alkoxide. adding water to the complex and removing any by-product alcohol.
Other titanium, zirconium or hafnium compounds, such as titanium, zirconium or hafnium tetrachloride or alkoxides which have been substituted with, for example, glycol or phosphorus substituents can be usea as raw materials for the formation of the complex used in the invention.
The complex can be readily prepared by mixing, for example, an alkoxide or condensed alkoxide with an appropriate amount of acetoacetate ester. Alcohol from the alkoxide will be displaced by the acetoacetate ester and,
preferably, the displaced alcohol is removed by, for example, distillation. In a preferred method, 2 moles of acetoacetate ester per atom of Ti or 4 moles of acetoacetate ester per atom of Zr or Hf are added to an alkoxide or condensed alkoxide and the displaced alcohol is removed by distillation. Any additional acetoacetate ester required is then added to the stripped product. This method
is advantageous because it provides a consistent product of known stoichiometry. It is possible to add all the acetoacetate ester in one charge and subsequently remove all the displaced alcohol but some of the "free" acetoacetate ester is usually accidentally removed during this process, leading to inconsistent products and contamination of the displaced alcohol.
Alternatively, when an organometallic composition according to the
invention is used in a polyisocyanate composition, a product containing, for example, 2 moles of acetoacetate ester per Ti atom or 4 moles of acetoacetate ester per Zr or Hf atom can be prepared according to the method outlined above and this can be mixed with a polyisocyanate. Any additional acetoacetate ester
required to produce the organometallic composition of the invention can be added to the polyisocyanate before or after the titanium, zirconium or hafnium compound has been added. This effectively results in the preparation of an

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organometallic composition according to this invention in situ in the poiyisocyanate composition. Other methods of preparing the composition of the invention will be apparent to a person skilled in this art
The organometallic complexes of the invention are particularly useful as curing agents in poiyisocyanate compositions and compositions suitable for use with the organometallic compositions of the present invention may be any organic poiyisocyanate compound or mixture of organic poiyisocyanate compounds, provided said compounds have at least 2 isocyanate groups. Organic polyisocyanates include diisocyanates, particularly aromatic
diisocyanates, and isocyanates of higher functionality.
Examples of organic polyisocyanates for which the organometallic complexes of the present invention are useful curing agents include aliphatic isocyanates such as hexamethyiene 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, diphenyiene-4,4"-diisocyanate,
4,4"-diisocyanate-3.3"-dimethyl-diphenyl, 3-methyldiphenylmethane-4,4"-di-
isocyanate and diphenyl ether diisocyanate; and cycloaliphatic diisocyanates such as cyclohexane-2.4- and -2,3-diisocyanate. 1-methyicyclohexyl-2,4- and
-2,6-diisocyanate and mixtures thereof and bis-(isocyanatocyclohexyl)methane and triisocyanates such as 2,4,6-triisocyanatotoluene and 2,4,4-tri-isocyanatodiphenylether.
Modified polyisocyanates containing isocyanurate. carbodiimide or uretonimine groups may be employed tn 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 poiyisocyanate, may be used.




having a deblocking temperature below the temperature applied when using a
polyisocyanate composition.
The organic polyisocyanate useful with the organometallic composition of
the invention may also be an isocyanate-ended prepolymer made by reacting an excess of a diisocyanate or higher functionality polyisocyanate with a polyol. Water-emulsifiable organic polyisocyanates like those described in UK
patent no. 1 444 933, in European patent publication no. 516 361 and in PCT
patent publication no. 91/03082 can also be used.
Mixtures of 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 phenyiisocyanate.
Such mixtures are well-known in the art and include the crude
phosgenation products containing methylene bridged poiyphenyl
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 poiyphenyl
polyisocyanates containing diisocyanates, triisocyanates and higher
functionality polyisocyanates.
Methylene bridged poiyphenyl polyisocyanates are well known in the art.
They are prepared by phosgenation of corresponding mixtures of polyamines.
For convenience, polymeric mixtures of methylene bridged poiyphenyl

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poiyisocyanates containing diisocyanate, triisocyanate and higher functionality polyisocyanates are referred to hereinafter as polymeric MD1. Poiyisocyanates suitable for use with the organometaliic complexes of the invention include SUPRASEC™ DNR. SUPRASEC™ 2185, RUBINATE™ M and RUBINATE™ 1840, all available from Imperial Chemical Industries
Preferably the polyisocyanate is liquid at room temperature. Conventional release agents can be added to or used in combination with a polyisocyanate composition containing a titanium, zirconium or hafnium complex of an acetoacetate ester according to the present invention.
In such compositions the conventional release agent is present in an
amount varying between 0.2 and 10 %, preferably between 0.5 and 6 % and most preferably between 1 and 3 % by weight based on the polyisocyanate whereas the titanium, zirconium or hafnium complex of an acetoacetate ester is preferably present in an amount varying between 0.2 and 4 %, most preferably
between 0.2 and 2 % by weight based on the polyisocyanate.
Examples of conventional release agents inciude polysiloxanes, saturated or unsaturated fatty acids (such as oleic acid) or fatty acid amides or fatty acid esters and polyolefin waxes.
Preferred conventional release agents to be used in polyisocyanate
compositions containing the organometaliic complexes according to the present invention are polyolefin waxes or mixtures of polyolefin waxes, especially functionalised polyolefin waxes, which are dispersible in an aqueous medium to form an aqueous emulsion. More preferably, the poiyolefin waxes are selected from oxidised polyethylene waxes and oxidised polypropylene waxes.
A preferred method for using the release agent is to apply the emulsion to
the surface of the polyisocyanate treated lignocellulosic material or to the press metal surface prior to hot pressing the combination.

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When used, an aqueous emulsion of the polyoiefin wax should normally contain a sufficient amount of the poiyolefin wax to provide a coverage of about 0.01 to about 1, and preferably about 0.02 to about 0 5 mg of the polyoiefin wax per cm: of lignocellulosic matenal or press metal surface. Generally, iower levels of poiyolefin wax are preferred as they are more cost effective. When taking the emulsifiers into account, the aqueous emulsions will usually contain about 0.2 to about 10 %, preferably about 0.3 to about 5 % by weight of total solids. The emulsions are usually prepared at 30 to 40 % total solids, transported to the point of use and then diluted with water to the desired
concentration.
It has been found that the poiyolefin wax emulsion, when used in combination with polyisocyanate compositions containing organometallic compositions of the present invention, may be usefully applied to the lignocellulosic material or press metal surface in an amount equivalent to 8 to
14 mg per cm".
A particularly preferred polyethylene wax emulsion which can be used in a process in combination with an organometallic composition of the present invention in combination with a poiyisocyanate is Rubilon™ 603 or Rubilon™ 605, both available from Imperial Chemical Industries.
A particularly preferred polypropylene wax emulsion which can be used in
a process in combination with an organometallic composition of the present invention in combination with a polyisocyanate is ME 42040 available from Michelman Inc. of Cincinnati, Ohio.
In order to further improve the storage stability of a polyisocyanate
composition containing an organometallic composition of the present invention a diluent may be added to the composition. Suitable diluents include plasticizers of the type mentioned in Taschenbuch der Kunststoff-Additive", Ed. by R.

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Gachter and H. Muller, Carl Hanser Verlag Munchen, third edition. 1989. Preferred diluents are phthalates, aliphatic carboxylates. fatty acid esters, linseed oil and soybean oil A particularly preferred diluent is Priolube 1403 available from Unichema being methyloleate. These diluents are added in amounts of from 1 to 40 parts by weight per 100 parts by weight of polyisocyanate and preferably in amounts of from 1 to 15 parts by weight per 100 parts by weight of polyisocyanate.
A composition containing an organometallic composition of the present invention and a polyisocyanate may further comprise conventional additives like
flame retardants, lignocellulosic preserving agents, fungicides, waxes, sizing agents, fillers, surfactants, thixotropic agents and other binders like formaldehyde condensate adhesive resins and lignin (optionally in combination with a iignin solvent such as described in PCT Patent Application No. EP96/00924).
A particularly preferred additive to be used in a polyisocyanate
composition containing an organometallic composition of the present invention is a coupling agent such as an organofunctional silane (for example, Dynasylan AMEO. available from Huels). Adding such a coupling agent to the polyisocyanate composition leads to improved board properties. The
organofunctional silane coupling agents are used in amounts ranging from 0.01 to 3 %, preferably from 0.1 to 2 % by weight based on the polyisocyanate.
The organometallic composition of present invention can be used in a process for preparing lignocellulosic bodies by bringing lignocellulosic parts into contact with a polyisocyanate composition containing the organometallic
composition of the present invention and pressing this combination.

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A typical process comprises the steps of a) bringing said lignoceiiulosic material in contact with a poiyisocyanate composition containing an organometallic composition of the present invention and, b) subsequently allowing said material to bind.
The lignoceiiulosic bodies are prepared by bringing the lignoceiiulosic parts into contact with a poiyisocyanate composition by means such as mixing, spraying and/or spreading the composition with/onto the lignoceiiulosic parts and by pressing the combination of the poiyisocyanate composition and the lignoceiiulosic parts, preferably by hot-pressing, normally at 150° C to 250°C and 2 to 6 MPa specific pressure.
Such binding processes are commonly known in the art.
In waferboard manufacture the lignoceiiulosic material and the poiyisocyanate composition may be conveniently mixed by spraying the present poiyisocyanate composition on the lignoceiiulosic material while it is being agitated.
As described hereinbefore, in a preferred process, a release agent, which is preferably an aqueous emulsion of a polyolefin wax, is applied to the surface of the poiyisocyanate treated lignoceiiulosic material or to the press metal surface prior to hot pressing the combination.
The iignocelluiosic material after treatment with the poiyisocyanate
composition containing an organometallic composition according to the
invention is placed on caul plates made of aluminium or steel which serve to
carry the furnish into the press where it is compressed to the desired extent
usually at a temperature between 150° C and 250° C.
While the process is particularly suitable for the manufacture of waferboard known
extensively as oriented strand board and will be largely used

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for such manufacture, the process may not be regarded as limited in this respect and can also be used in the manufacture of medium density fibreboard, particle board (also known as chipboard) and plywood.
Thus the lignocellulosic material used can include wood strands, woodchips, wood fibres, shavings, veneers, wood wool, cork, bark, sawdust and like waste products of the wood working industry as well as other materials having a lignocellulosic basis such as paper, bagasse, straw, flax, sisal, hemp, rushes, reeds, rice hulls, husks, grass, nutshells and the iike. Additionally, there may be mixed with the lignocellulosic materials other particulate or fibrous materials such as ground foam waste (for example, ground potyurethane foam waste), mineral fillers, glass fibre, mica, rubber, textile waste such as plastic fibres and fabrics.
When the polyisocyanate composition containing the organometallic
composition of the invention is applied to the lignocellulosic material, the weight
ratio of polyisocyanate/iignoceilulosic material will vary depending on the bulk
density of the lignocellulosic material employed. Therefore, the polyisocyanate
compositions may be applied in such amounts to give a weight ratio of
polyisocyanate/iignoceilulosic material in the range of 0.1 : 99.9 to 20 : 80 and
preferably in the range of 0.5 : 99.5 to 10 : 90.
If desired, other conventional binding agents, such as formaldehyde
condensate adhesive resins, may be used in conjunction with the polyisocyanate composition containing the organometallic composition.
More detailed descriptions of methods of manufacturing waferboard and
similar products based on lignocellulosic material are available in the prior art.
The tecnniques and equipment conventionally used can be adapted for use with
polyisocyanate compositions containing organometallic compositions of the
present invention.

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Poiyisocyanate compositions containing organometaliic compositions of the present invention are extremely effective in minimising unwanted adhesion to caul plates, press plates and other surfaces with which the treated lignocellulosic material may come into contact. Their storage stability and release performance is improved compared to poiyisocyanate compositions of the prior art, as well as the obtained board properties.
The sheets and moulded bodies produced from the poiyisocyanate compositions containing organometaliic compositions of the present invention have excellent mechanical properties and they may be used in any of the situations where such articles are customarily used.
The invention is illustrated but not limited by the following examples.
EXAMPLE 1
Preparation of Product A
A reactor was charged with tetraisopropyl titanate (1400 kg, Tilcom* TIPT
from ICI Vertec). Ethylacetoacetate (1282 kg) was then added with stirring. The
resulting product was a pale red liquid. The displaced alcohol (580 kg,
isopropanol) was then removed by evaporation to leave a red liquid, PRODUCT
A (2090 kg).
Product A was then diluted by addition of various amounts of methylacetoacetate. ethylacetoacetate and cetylacetoacetate in the following molar ratios.

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TABLE 1

Sample Moles Product A Moles
i Methylacetoacetate
Test 1 1.1
i | Test 2 i 1 2.2
I !
Test 3 4.4
Test 4 6.6
Test5 8.8
Test 6 1 I 11 I
TABLE 2

Sample Moles Product A Moles Ethylacetoacetate
Test 7 1-1
Test 8 2.2
Test 9 4.4
Test 10 6.6
Test 11 8.8
Test 12 11

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TABLE 3

Sample Moles Product A Moles Cetylacetoacetate
Comparison 1 1 1.1
Comparison 2 1 2.2
Comparison 3 1 4.4
Comparison 4 1 6.6
Comparison 5 1 8.8
Comparison 6 1 11
The products were evaluated by preparing a number of compositions comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR. available from Imperial Chemical Industries) and various amounts of the samples designated Test 1 to 12 (see Table 4 below). Each composition contained the same concentration of Product A. The compositions were then stored at 45° C and the viscosity tested by means of a Brookfield viscometer at various intervals.

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TABLE 4

Sample Parts by weight Parts by weight
Suprasec DNR
Test 1 0.78 100
i
Test 2 0.96 100
i
Test 3 1.32 100
Test 4 1.67 j 100
Test 5 i 2.03 ! 100
Test 6 i
2.38 ! 100
I
Test 7 0.80 100
Test 8 1.00 100
Test 9 1.40 100
Test 10 1.80 100
Test 11 2.20 100
Test 12 2.60 100
As a comparison a number of compositions comprising 100 parts by weight of polyisocyanate (polymeric MDl. SUPRASEC DNR, available from Imperial Chemical Industries) and various amounts of the samples designated Comparison 1 to 6 (see Table 5 below) were made up. All these compositions contained the same amount of Product A, this amount being the same as the amount of Product A in each of the compositions designated Test 1 to Test 12. These compositions were then stored at 45s C and the viscosity tested using a Brookfieid viscometer at the same intervals.

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TABLE 5

Sample Parts by weight Parts by weight Suprasec DNR
Comparison 1 1.1 100
Comparison 2 1.6 100
Comparison 3 2.6 100
Comparison 4 3.6 100
Comparison 5 4.6 100
Comparison 6 5.6 100
The following results were obtained for the systems based on Product A with various added amounts of methylacetoacetate and ethyiacetoacetate [all results are reported in Pa sj.
TABLE 6
Product A + Methylacetoacetate

Time (Days) Test 1 Test 2 Test 3 Test 4 Test 5 Test 6
0 0.292 0.288 0.274 0.272 0.267
i 0.267
14 0.828 0.548 0.632 0.678 0.746 0.806
25 1.208 0.734 0.840 1.007 1.078 1.153
30 n.m. 1.050 1.139 i
1.330 1.526
I 1.756
46 2.568 1.207 j 1.239
i 1.546 1.767 2.125
67 n.m. t
1.917 i 1.707
i i 2.209 2.579 3.392
n.m. = not measured

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TABLE 7
Product A + Ethylacetoacetate

Time (Days) Test 7 Test 8 Test 9 Test 10 Test 11 Test 12
0 0.305 0.293 0.280 ! 0.270
I 0.263 0.263
14 0.787 . 0.600 ... j
0.645 0.717 0.806 0.814
25 i 1.136 | 0.879 0.911 1.078 1.197 1.251
30 n.m. | 1.137 1.225 1.538 1.734 1.811
46 2.486 j 1.310
i 1.410 1.735 2.240 2.018
67 n.m. ! 2.028 1.943 2.440 3.275 3.192
n.m. = not measured
The foUowing results were obtained for the systems based on Product A with various added amounts of cetylacetoacetate [all results reported in Pa s].
TABLE 8
Product A + Cetylacetoacetate

Time (Days) Comparison 1 Comparison
2 Companson Comparison
3 i 4
i Comparison
5 Comparison
6
0 0.324 0.296 0.296 0.277 0.279 0.264
14 1.195 0.599 0.627 0.630 0.667 0.626
25 1.995 0.797 0.839 I 0.851
I 1.014 0.989
30 n.m. | 1.145 1.168 | 1.049 j 1.430 1.427
46 4.620 ! 1.396 i
1.281 | 1.162
j 1.608 1.620
67 n.m. 2.443 1.853 1.610 2.260 2.309
n. m. = not measured

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Generally, the most relevant period for storage stability at room temperature is the period 14 to 46 days after production of a poiyisocyanate composition. From Tables 6 to 8 above, it can be seen that the optimum (generally, lowest) viscosity after 46 days at 45° C (an accelerated test) is achieved in Test 2 (2.2 moles methylacetoacetate), Test 8 (2.2 moles ethylacetoacetate) and Comparison 4 (6.6 moles cetyiacetoacetate). The results demonstrate that the titanium complexes used in the composition of the invention provide a more economical means of stabilising the poiyisocyanate composition.
EXAMPLE 2
Preparation of Product B
A flask was charged with tetra-n-propyl zirconate (43.7g, Tilcom* NPZ [75% solution of Zr(On-C3H7)4 in n-propanol] from IGI Vertec) and placed in a cold water bath. Methylacetoacetate (46.5g) was added over a period of one
hour whilst the mixture was stirred. The resulting product was a pale yellow liquid. The displaced alcohol (35.3g, n-propanol) was then removed on a rotary evaporator to leave a yellow oil (54.8g). The oil was then mixed with additional methylacetoacetate (11.6g) to yield PRODUCT B.
To evaluate the product a composition comprising 100 parts by weight of
poiyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 2.09 parts by weight Product B was prepared in duplicate. The compositions were then stored at 45o C and the viscosity tested at various intervals using a Brookfield viscometer Results are reported in Table 9 below in Pa s.

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TABLE 9

Time (Days) Product B(i) | Product B(ii)
0 0.220 | 0.220
20 I
0.440 !
! 0.400
41 0.580 j 0.520
62 0.660
i 0.640
84 1.020 j 1.340
Preparation of Product C
A flask was charged with tetra-n-propyl zirconate (43.7g, Tilcom* NPZ [75% solution of Zr(On-C3H7), in n-propanol] from ICI Vertec) and placed in a cold water bath. Methylacetoacetate (46.5g) was added over a period of one hour whilst the mixture was stirred. The resulting product was a pale yellow liquid. The displaced alcohol (34.3g, n-propanol) was then removed on a rotary evaporator to leave a yellow oil (55.8g). The oil was then mixed with additional methylacetoacetate (23.2g) to yield PRODUCT C.
To evaluate the product a composition comprising 100 parts by weight of
polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 2.48 parts by weight Product C was prepared in duplicate. The compositions were then stored at 45° C and the viscosity tested at various intervals using a Brookfield viscometer. Results are reported in Table
10 below in Pa s.


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TABLE 10

Time (Days) Product C(i) Product C(ii)
0 0.220 0.220
20 0.460 i 0.500
I
41 0.500 i 0.500
62 0.720 0.620
84 1.280 0.980
Preparation of Product D
A flask was charged with tetra-n-propyl zirconate (87.3g, Tiicom* NPZ [75% solution of Zr(On-C3H7)4 in n-propanol] from ICI Vertec) and placed in a cold water bath. Ethyiacetoacetate (104g) was added over a period of one hour whilst the mixture was stirred. The resulting product was a pale yellow liquid. The displaced alcohol (67.1g, n-propanol) was then removed on a rotary evaporator to leave a yellow oil (124.3g). The oil was then mixed with additional ethyl acetoacetate (26g) to yield PRODUCT D.
To evaluate the product a composition comprising 100 parts by weight of
polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 2.21 parts by weight Product D was prepared in duplicate. The compositions were then stored at 45° C and the viscosity of the compositions tested at various intervals using a Brookfield viscometer. Results
are reported in Table 11 below in Pa s.

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TABLE 11

Time (Days) \ Product D(i) Product D(ii)
i 0 j 0.220 0.220
20 0.480 0.460
41 0.540 0.560
62 0.700 0.920
84 1.140 1.040
Preparation of Product E
A flask was charged with tetra-n-propyl zirconate (87.3g, Tilcom* NPZ [75% solution of Zr(On-C3H7)6 in n-propanol] from ICI Vertec) and placed in a cold water bath. Ethylacetoacetate (104g) was added over a period of one hour whilst the mixture was stirred. The resulting product was a paie yellow liquid. The displaced alcohol (70.0g, n-propanol) was then removed on a rotary evaporator to leave a yellow oil (121,4g). The oil was then mixed with additional ethylacetoacetate (52g) to yield PRODUCT E.
To evaluate the product a composition comprising 100 parts by weight of
polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 2.56 parts by weight Product E was prepared in duplicate. The compositions were then stored at 45° C and the viscosity of the compositions tested at various intervals using a Brookfield viscometer. Results
are reported in Table 12 below in Pa s.

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TABLE 12

Time (Days) i Product E(i) j Product E(ii)
i
0 0.220 0.220
20 0.560 0.580
41 0.620 0.600
62 0.860 0.780
84 1.060 0.960
The zirconium complexes (Products B, C, D E) show improved stability over a longer period of time than the titanium complexes of Comparison 1 to 6 (Table 8). EXAMPLE 3
Preparation of Product F
A flask was charged with tetraisopropyl titanate (71 g, Tilcom* TIPT from ICI Vertec) and placed in a cold water bath. Ethylacetoacetate (65g) was added over a period of one hour whilst the mixture was stirred. Following addition of
ethylacetoacetate, distilled water (1.1g, 0.25 moles per mole Ti) was added to the mixture with thorough stirring. The resulting product was a pale red liquid. The displaced alcohol (43.4g, isopropanoi) was then removed on a rotary evaporator to leave a red liquid (94.5g). This liquid was then mixed with additional ethyl acetoacetate (65g) to yield PRODUCT F
To evaluate the product a composition comprising 100 parts by weight of
poiyisocyanate (polymeric MDl. SUPRASEC DNR, available from Imperial Chemical Industries) and 0.88 parts by weight Product F was prepared. The

WO 00/02885

PCT/GB99/01982


composition was then stored at 45" C and the viscosity of the composition tested
at various intervals using a Brookfield viscometer.
Preparation of Product G
A flask was charged with tetraisopropyl titanate (71 g, Tilcom* TIPT from ICI Vertec) and placed in a cold water bath. Ethylacetoacetate (65g) was added
over a period of one hour whilst the mixture was stirred. Following addition of
ethylacetoacetate. distilled water (2.3g, 0.5 moles per moie of Ti) was added to
the mixture with thorough stirring. The resulting product was a pale red liquid.
The displaced alcohol (48.4g, isopropanol) was then removed on a rotary evaporator to leave a red liquid (93.3g). This liquid was then mixed with
additional ethyl acetoacetate (65g) to yield PRODUCT G.
To evaluate the product a composition comprising 100 parts by weight of
polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial
Chemical Industries) and 0.88 parts by weight Product G was prepared. The composition was then stored at 45° C and the viscosity of the composition tested
at various intervals using a Brookfield viscometer. Results are reported for
Product F and Product G in Table 13 below in Pa s.
TABLE 13

Time (Days) Product F Product G
0 0.220 0.220
10 0.485 0.520
40 0.760 0.760
60 1.100 1.200
80 1.140 1.220

WO 00/02885 PCT/GB99/01982

EXAMPLE 4
A flask was charged with tetraisopropyl titanate (71g, Tilcom* TIPT from ICI Vertec) and placed in a cold water bath. tert-Butylacetoacetate (79.1g) was added over a period of one hour whilst the mixture was stirred. The resulting product was a pale yellow liquid. The displaced alcohol (30.0g, isopropanol) was then removed on a rotary evaporator to leave a red liquid (120.0g). This liquid was then mixed with additional ethyl acetoacetate (65g) to yield PRODUCT H.
To evaluate the product a composition comprising 100 parts by weight of
polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 1.02 parts by weight Product H was prepared. The composition was then stored at 45° C and the viscosity of the composition tested at various intervals using a Brookfield viscometer. Results are reported in Table 14 below in Pa s.
TABLE 14

Time (Days) Viscosity
o - 0.220
10 0.480
40 1.160
60 1.800
80 2.160


00/02885

EXAMPLE 5
Preparation of Product I
A flask was charged with tetraisopropyl titanate (71g, Tilcom* TIPT from ICI Vertec) and placed in a cold water bath. Ethyiacetoacetate (65g) was added over a period of one hour whilst the mixture was stirred. Foilowing addition of ethyiacetoacetate, butyl acid phosphate (11.4g, 0.25 moles) was added to the mixture with thorough stirring. The resulting product was a pale red liquid. The displaced alcohol (38.2g, isopropanol) was then removed on a rotary evaporator to leave a red liquid (109.2g). This liquid was then mixed with additional ethyl
acetoacetate (65g) to yield PRODUCT I.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial Chemical Industries) and 0.97 parts by weight Product I was prepared in duplicate. The compositions were then stored at 45° C and the viscosity of the
compositions tested at various intervals using a Brookfield viscometer (see Table 15). Preparation of Product J
A flask was charged with tetraisopropyl titanate (71g, Tilcom* TIPT from ICI Vertec) and placed in a cold water bath. Ethyiacetoacetate (65g) was added
over a period of one hour whilst the mixture was stirred. Following addition of ethyiacetoacetate. butyl acid phosphate (22.8g, 0.5 moies) was added to the mixture with thorough stirring. The resulting product was a pale red liquid. The displaced alcohol (40.8g, isopropanol) was then removed on a rotary evaporator to leave a red liquid (118.0g). This liquid was then mixed with additional ethyl
acetoacetate (65g) to yield PRODUCT J.
To evaluate the product a composition comprising 100 parts by weight of polyisocyanate (polymeric MDI, SUPRASEC DNR, available from Imperial

WO 00/02885 PCT/GB99/0I982

Chemical Industries) and 1.02 parts by weight Product J was prepared. The
composition was then stored at 45° C and the viscosity of the composition tested
at various intervals using a Brookfield viscometer. Results are reported for
Product I and Product J in Table 15 below in Pa s.
TABLE 15

Time (Days) Product I J Product J
0 0.220 0.220
10 0.440 0.389
40 0.880 0.580
60 1.320 0.960
80 1.360 1.040

WE CLAIM:-
1. A process for the preparation of an organometallic composition comprising a
complex of at least one metal selected from the group consisting of titanium, zirconium
and hafnium and an acetoacetate ester in which the molar ratio of Ti or Hf to
acetoacetate ester is in the range 1 : 2.5 to 1:10 or the molar ratio of Zr to acetoacetate
ester is in the range 1 : 4.5 to 1 : 10 and said acetoacetate ester is an ester of an
alcohol containing 1 to 6 carbon atoms, said process comprising mixing a compound of
titanium, zirconium or hafnium with an acetoatetate ester.
2. A process as claimed in claim 1, wherein the compound of titanium, zirconium or hafnium is selected from an alkoxide, condensed alkoxide, substituted alkoxide or tetrachloride.
3. A process as claimed in claim 2 wherein the compound of titanium, zirconium or hafnium is a titanium, zirconium or hafnium alkoxide having the general formula M(OR)4 in which M is Ti, Zr or Hf and R is a substituted or unsubstituted, cyclic or linear, alky}, alkenyl, aryl or alkyl-aryl group.

4. A process as claimed in claim 3 in which R contains up to 6 carbon atoms.
5. A process as claimed in claim 1 or claim 2 wherein the compound of titanium, zirconium or hafnium is a condensed titanium, zirconium or hafnium alkoxide having the general formula RO[M(OR)20]xR in which M is Ti, Zr or Hf, x is an integer and R is a substituted or unsubstituted, cyclic or linear, alkyl, alkenyl, aryl or alkyl-aryl group.
6. A process as claimed in claim 5 wherein the average value of x is in the range 2 to 16.
7. A process as claimed in any one of claims 2 - 6, further comprising the step of removing an alcohol from the mixture.
8. A process as claimed in claim 7, wherein said alcohol is removed by distillation.
9. A process as claimed in any of the preceding claims, wherein a further quantity of acetoacetate ester is added to said mixture.


10. A process as claimed in any of the preceding claims, in which the complex is a complex of titanium having a molar ratio of Ti to acetoacetate ester in the range 1 : 2.5 to 1 :8.
11. A process as claimed in claim 10, in which the molar ratio of Ti to acetoacetate ester is in the range 1 : 3 to 1 : 6.
12. A process as claimed in any of the preceding claims, in which the complex is a complex of hafnium having a molar ratio of Hf to acetoacetate ester in the range 1 : 4.5 to 1 :10.
13. A process as claimed in any of the preceding claims, in which the molar ratio of Zr or Hf to acetoacetate ester is in the range 1 : 4.5 to 1 : 8.
14. A process as claimed in any of the preceding claims, in which the acetoacetate ester is ethyl acetoacetate.

15. A process for the preparation of an organometallic composition as claimed in any of the preceding claims wherein a product containing 2 moles of acetoacetate ester per Ti atom or 4 moles of acetoacetate ester per Zr or Hf atom is prepared by mixing a compound of titanium, zirconium or hafnium with an acetoacetate ester, then said product is mixed with a polyisocyanate containing any additional acetoacetate ester required to produce the organometallic composition.
16. A process for the preparation of an organometallic composition as claimed in any of the preceding claims wherein a product containing 2 moles of acetoacetate ester per Ti atom or 4 moles of acetoacetate ester per Zr or Hf atom is prepared by mixing a compound of titanium, zirconium or hafnium with an acetoacetate ester, then
such additional acetoacetate ester required to produce the organometallic composition is added to the polyisocyanate mixture after the titanium, zirconium or hafnium compound has been added thereto.
Dated this 5th day of January, 2001.
[SANJAY KUMAR]
OF REMFRY & SAGAR
ATTORNEY FOR THE APPLICANTS

Documents:

in-pct-2001-00030-mum-assignment(28-4-2003).pdf

in-pct-2001-00030-mum-assignment(7-10-2004).pdf

in-pct-2001-00030-mum-assignment-(7-10-2004).pdf

in-pct-2001-00030-mum-cancelled pages(5-1-2001).pdf

in-pct-2001-00030-mum-cancelled pages(6-5-2005).pdf

in-pct-2001-00030-mum-claims(complete)-(5-1-2001).pdf

in-pct-2001-00030-mum-claims(granted)-(07-10-2004).doc

in-pct-2001-00030-mum-claims(granted)-(31-10-2006).pdf

in-pct-2001-00030-mum-claims(granted)-(7-10-2004).pdf

IN-PCT-2001-00030-MUM-CORRESPONDENCE (23-7-2012).pdf

IN-PCT-2001-00030-MUM-CORRESPONDENCE(23-7-2012).pdf

in-pct-2001-00030-mum-correspondence(5-12-2005).pdf

in-pct-2001-00030-mum-correspondence(7-5-2005).pdf

in-pct-2001-00030-mum-correspondence(ipo)-(27-12-2006).pdf

in-pct-2001-00030-mum-correspondence(ipo)-(31-10-2006).pdf

in-pct-2001-00030-mum-description(granted)-(31-10-2006).pdf

in-pct-2001-00030-mum-descripton(complete)-(5-1-2001).pdf

in-pct-2001-00030-mum-form 1(5-1-2001).pdf

in-pct-2001-00030-mum-form 1(7-10-2004).pdf

in-pct-2001-00030-mum-form 1(7-4-2003).pdf

in-pct-2001-00030-mum-form 13(7-4-2003).pdf

IN-PCT-2001-00030-MUM-FORM 16(23-7-2012).pdf

in-pct-2001-00030-mum-form 19(29-3-2004).pdf

in-pct-2001-00030-mum-form 1a(7-10-2004).pdf

in-pct-2001-00030-mum-form 2(complete)-(5-1-2001).pdf

in-pct-2001-00030-mum-form 2(granted)-(31-10-2006).pdf

in-pct-2001-00030-mum-form 2(granted)-(7-10-2004).doc

in-pct-2001-00030-mum-form 2(granted)-(7-10-2004).pdf

in-pct-2001-00030-mum-form 2(title page)-(complete)-(5-1-2001).pdf

in-pct-2001-00030-mum-form 2(title page)-(granted)-(31-10-2006).pdf

in-pct-2001-00030-mum-form 3(29-3-2004).pdf

in-pct-2001-00030-mum-form 3(5-1-2001).pdf

in-pct-2001-00030-mum-form 3(7-10-2004).pdf

in-pct-2001-00030-mum-form 5(7-10-2004).pdf

in-pct-2001-00030-mum-form 6(28-4-2003).pdf

in-pct-2001-00030-mum-form-pct-ipea-409(5-1-2001).pdf

in-pct-2001-00030-mum-form-pct-isa-210(5-1-2001).pdf

in-pct-2001-00030-mum-general power of authority(9-5-2001).pdf

in-pct-2001-00030-mum-petition under rule 137(7-10-2004).pdf

in-pct-2001-00030-mum-petition under rule 138(7-10-2004).pdf

in-pct-2001-00030-mum-power of authority(28-4-2003).pdf

in-pct-2001-00030-mum-power of authority(5-1-2001).pdf

in-pct-2001-00030-mum-power of authority(9-5-2001).pdf

in-pct-2001-00030-mum-specification(amended)-(6-5-2005).pdf

in-pct-2001-00030-mum-wo international publication report (5-1-2001).pdf


Patent Number 203444
Indian Patent Application Number IN/PCT/2001/00030/MUM
PG Journal Number 19/2007
Publication Date 11-May-2007
Grant Date 31-Oct-2006
Date of Filing 05-Jan-2001
Name of Patentee JOHNSON MATTHEY PLC
Applicant Address A BRITISH COMANY, OF 2-4 COCKSPUR STREET, TRAFALGAR SQUARE, LONDON SW1Y 5BQ, UNITED KINGDOM.
Inventors:
# Inventor's Name Inventor's Address
1 CHRISTOPHER JOHN SKINNER A BRITISH COMANY, OF 2-4 COCKSPUR STREET, TRAFALGAR SQUARE, LONDON SW1Y 5BQ, UNITED KINGDOM.
PCT International Classification Number N/A
PCT International Application Number N/A
PCT International Filing date 1999-06-24
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 9815029.5 1998-07-11 U.K.