GB2303367A - Boron-containing metallocene complexes - Google Patents
Boron-containing metallocene complexes Download PDFInfo
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- GB2303367A GB2303367A GB9613933A GB9613933A GB2303367A GB 2303367 A GB2303367 A GB 2303367A GB 9613933 A GB9613933 A GB 9613933A GB 9613933 A GB9613933 A GB 9613933A GB 2303367 A GB2303367 A GB 2303367A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
NOVEL GROUP IVB METAL COMPLEXES
The present invention relates to novel Group IVB metal complexes and to their use as catalysts for the polymerisation of olefins.
Transition metal compounds have successfully been used as catalysts for the polymerisation of olefins. Conventional Ziegler-Natta catalysts are well known in the art. Metallocene catalysts based on Group IVB metals have also been used as olefin polymerisation catalysts. For example bis(cyclopentadienyl) zirconium dichlorides have been used in the presence of aluminoxane cocatalysts for a variety of polymerisation reactions.
More recently catalysts of the metallocene type have been developed in which substituents in the cyclopentadienyl nucleus have been used to modify the nature of the catalysts and the polymers produced.
We have now developed novel Group IVB transition metal complexes of the metallocene type in which the cyclopentadienyl ring is substituted with anionic substituents, in particular substituents having a borate structure.
Thus according to the present invention there is provided novel Group IVB transition metal complexes having the general formula I or II.
[(C5R5) (CsRs nLn) MQ2]- Y+ I [C5R4) R1 (C5Rq,nLn) MQ2]- Y+ II wherein M = Zr, Ti, Hf (CgRg) = substituted or unsubstituted cyclopentadienyl ring each R may be the
same or different and may be hydrogen, alkyl, alkenyl, aryl or two R
substituents together form a fused ring or may be silyl or similar, (C5R5.nLn) or (C5R4-nLn) = substituted cyclopentadienyl ring wherein each R is as defined
above,
L = B(C6FSyRy)3 in which R = hydrogen, alkyl, alkenyl, aryl
Y = cation
R1 = Cl-C4 alkylene radical, a dialkyl germanium or silicon or alkyl
phosphine or amine radical bridging two cyclopentadienyl rings,
Q = univalent anionic ligand for example alkyl, halide n = 1-5 in Formula I and 1-4 in Formula II, and
Y = 1-4
Preferred complexes are those of Formula I wherein M is zirconium, L is tris(pentafluoro)phenyl borate and n = 1. Preferred complexes may be illustrated by the following structures:
and their analogues in which M is hafnium and Q is methyl.
Preferred cations include [Li(THF)4](E3 [NR4]ffl [PR4]# [Ph3 P=N=PPh3 j in which R is alkyl
The novel complexes according to the present invention may be suitably prepared starting from the appropriate lithium cyclopentadienyl and the borate.
Full details of the methods of preparation of the complexes are given below in the
Examples accompanying this description.
The complexes according to the present invention are anionic in nature.
Neutral complexes may also be prepared having the general formula: (C5R5)(C5R5 nLn)MQ wherein Rn L, M, Q and n are as defined above.
Further complexes may also be prepared having the general formula: (C5R5)(c5RS-nLn)MM Q4 wherein R, L, M, Q and n are as defined above and M1 is a Group III metal e.g. B,
Al, Ga etc. M1 is preferably aluminium. A preferred compound of this type of
complex is [C5H3(SiMe3)2] [C5HqB(CgFg)3]HfMe2 AlMe2.
The particular complex exemplified may suitably be prepared by treatment of[C5H3(SiMe3)2][C5H4B(C6F5b]HfMe2 NEt4+ with [CPh3][B)CsFs)4] in the presence of one equivalent of AlMe3 per Hf in toluene at 20"C. The complex is a methyl bridged Hf=A1 dimer as indicated by 'HNMR.
The novel complexes according to the present invention may be used as catalysts or as components of catalyst compositions useful for the polymerisation of olefins in particular for the polymerisation of ethylene.
Thus according to another aspect of the present invention there is provided a catalyst or catalyst composition suitable for use in the polymerisation of olefins comprising a Group IVB metal complex as hereinbefore described.
The catalyst or catalyst composition comprising the novel Group IVB metal complex may be used in a process for preparing polymers of ethylene or copolymers of ethylene with alpha-olefin having 3 to 8 carbon atoms by contacting ethylene or a mixture of ethylene and at least one alpha-olefin with the aforementioned catalyst or catalyst composition in an inert solvent for example hexane or toluene.
Preferred alpha-olefins are butene, hexene or 4-methyl-l-pentene.
The catalyst or catalyst composition is most suitably used in the presence of a co-catalyst.
Suitably the co-catalyst is an organometallic compound having a metal of
Group IA, IIA, IIB or IIIB of the periodic table. Preferably, the metals are selected from the group including lithium, aluminium, magnesium, zinc and boron.
Such co-catalysts are known for their use in polymerisation reactions, especially the polymerisation of olefins, and include organo aluminium compounds such as trialkyl, alkyl hydride, alkyl halo and alkyl alkoxy aluminium compounds. Suitably each alkyl or alkoxy group contains 1 to 6 carbons. Examples of such compounds include trimethyl aluminium, triethyl aluminium, diethyl aluminium hydride, triisobutyl aluminium, tridecyl aluminium, tridodecyl aluminium, diethyl aluminium methoxide, diethyl aluminium ethoxide, diethyl aluminium phenoxide, diethyl aluminium chloride, ethyl aluminium dichloride, methyl diethyoxy aluminium and methyl aluminoxane (MAO). The preferred compounds are alkyl aluminoxanes, the alkyl group having 1 to 10 carbon atoms especially methyl aluminoxane.
Suitable co-catalysts also include Bronsted or Lewis acids.
The catalysts or catalyst compositions according to the present invention may suitably be supported on conventional olefin polymerisation catalyst supports for example silica, alumina, magnesium chloride. A preferred support is silica.
Polymerisations employing the catalysts or catalyst supports of the present invention may be performed under conventional conditions in the gas, solution or slurry phase.
The present invention will now be illustrated by reference to the following examples which describe the preparation of novel Group IVB metal complexes according to the present invention and polymerisation processes using such complexes.
Examples
In the following examples the following nomenclature will be used:
Complex
I Cp = cyclopentadienyl (C5Hg) Y = Cl
M = Zr
II Cp = C5H3 (SiMe3)2
Y = Cl
M = Zr
III Cp = C5H5 Y = Cl
M = Hf
IV Cp = C5H3 (SiMe3)2
Y = Cl
M = Hf
V Cp = C5H3 (SiMe3)2
Y = Me
M = Zr
VI Cp = C5H3 (SiMe3)2
Y = Me
M = Hf
NEt4+ as cation
VII
Cp = C5H5
Y = Cl
M = Zr
Example 1
Preparation of [Li(THF)4]2[(C6F5)3B(C5H4)]
A solution of lithium cyclopentadienyl in tetrahydrofyran (THF) was reacted with (C6Fs)3B at room temperature to give [Li(THF)4][C6F5)3B(C5H5)] in essentially quantitiative yield. The borate was readily deprotonated by treatment with butyllithiuym in tetrahydrofuran at -78 C to give the dianion [Li(THF)4]2[(C6F5)3B (C5H4)].
Example 2
Prepration of Complex I [(Li(THF)4]2[(C6F5)3(C6H4)] prepared according to Example 1 was reacted with
ZrCpC13 in tetrahydrofuran at -78" and warmed to room temperature to yield complex I (80-90%) Example 3
Preparation of complex II
The procedures described in Examples 1 and 2 were repeated using the appropriate lithium cyclopentadienyl starting material to yield complex II.
Example 4
Preparation of dimethyl analog V
A solution of complex I was alkylated by treatment with methyl lithium in ether/tetrahydroforum at -780C followed by warming to room temperature (yield 50-60%).
Example 5
Preparation of hafnium complexes III. IV VI
The procedures in Examples 1-4 were repeated using HfCpCl3 to obtain the hafnium analogues.
Example 6
Preparation of indenvl complex VII
The procedure described in example 2 was repeated with the appropriate indenyl compound.
Example 7
Polvmerisation
Into a 50 ml glass reactor containing 20 ml of toluene, warmed to 300C and stirred at about 1000 rpm under 1 bar of ethylene were injected 2 ml methylaluminoxane (MAO) in toluene (8.8 mmol Al) and 0.5 ml of a toluene solution of complex If (5 umol Zr). The reaction was quenched by methanol injection after 120 seconds. The mixture was poured into 50 ml methanol, filtered, and the resulting residue dried at 800C overnight, to give 176 mg polyethylene.
Example 8
The method described for Example 7 was repeated except that the reaction was carried out at 600C. 178 mg of polyethylene was obtained.
Example 9
The method described for Example 7 was repeated and ethylene was polymerised using MAO (8.8 mmol Al) and complex IV (5 ,umol) at 300C for a duration of 20 minutes. 134 mg polymer was obtained.
Example 10
The method described for Example 7 was repeated and ethylene was polymerised using MAO (8.8 mmol Al) and complex IV (5 umol) at 600C for a duration of 5 minutes. 115 mg polymer was obtained.
Example 11
The method described for Example 7 was repeated and ethylene was polymerised using MAO (8.8 mmol Al) and complex 1(5 pmol) at 20"C for a duration of2 minutes. 185 mg polymer was obtained.
Example 12
The method described for Example 7 was repeated and ethylene was polymerised using MAO (8.8 mmol Al) and complex 1(5 ,umol) at 600C for a duration of2 minutes. 190 mg polymer was obtained.
Example 13
The method described for Example 7 was repeated and ethylene was polymerised using MAO (8.8 mmol Al) and complex VII (511mol) at 20"C for a duration of2 minutes. 144 mg polymer was obtained.
Example 14
The method described for Example 7 was repeated and ethylene was polymerised using MAO (8.8 mmol Al) and complex VII (5 pmol) at 600C for a duration of2 minutes. 148 mg polymer was obtained.
Example 15
The method described for Example 7 was repeated and ethylene was polymerised using MAO (8.8 mmol Al) and complex VI (5 mol) at 600C for a duration of 5 minutes. 128 mg polymer was obtained.
Example 16
Into a 50 ml glass reactor containing 20 ml of toluene, warmed to 60"C and stirred at about 1000 rpm under 1 bar of ethene, were injected 40 pmol of triisobutylaluminium. 0.5 ml of a toluene solution of complex VI (5 pmol), and 1.0 ml of a toluene solution of[CPh3][B(C6F5)4] (5 mol). The reaction was quenched by methanol injection after 5 minutes. The mixture was worked up as described in Example 7 to give 114 mg polyethylene.
The polymerisation results show that the novel complexes of the present invention are active polymerisation catalysts in the presence of for example methyl aluminoxane (Al/Zr = 1800).
The catalyst composition polymerises ethylene at 1 bar and 20"C with a productivity of about 106 g PE (mol Zr)-1bar-1h-1.
Further details of the polymerisation results are given in the accompanying
Table 1.
TABLE 1
Example Temp OC Time (secs) Activity Mw MW/Mn 106g PE molZr -1 bar1H-1 x 103 7 30 120 1.1 207 5.5 8 60 120 1.1 92 5.6 9 30 1200 0.08 271 8.6 10 60 300 0.3 104 6.4 11 20 120 1.1 107 3.5 12 60 120 1.3 38 3.2 13 60 120 0.86 100 4.8 14 60 120 0.88 52 4.1 15 60 300 0.31 46 7.3 16 20 300 0.27 108 4.8 All reactions were carried out using 5 mmol of complex and 8.8 mmol of
MAO except for example 16 in which the activator was 40 mmol of triisobutylaluminium and 5 mmol of CPh3+.
Claims (11)
1. A complex having the general formula I or II
[(C5R5) (C5Rs nLn) MQ2]- Y+ I [C5R4) Rl (c5R4-nLn) MQ2]- Y+ II wherein M = Zr, Ti, Hf (C5R5) = substituted or unsubstituted cyclopentadienyl ring each R may be the
same or different and may be hydrogen, alkyl, alkenyl, aryl or two R
substituents together form a fused ring or may be silyl or similar, (CsRs nLn) or (C5R4 nLn) = substituted cyclopentadienyl ring wherein each R is as defined
above,
L = B (C6F5-yRy)3 in which R = hydrogen, alkyl, alkenyl, aryl
Y = cation
R1 = C 1 -C4 alkylene radical, a dialkyl germanium or silicon or alkyl
phosphine or amine radical bridging two cyclopentadienyl rings,
Q = univalent anionic ligand for example alkyl, halide n = 1-5 in Formula I and 1-4 in Formula II, and y = 1-4.
2. A complex according to claim 1 wherein M is zirconium, L is tris(pentafluro)phenyl borate and n is 1.
3. A catalyst composition comprising (a) a complex according to the general formula of claim 1 and (b) a cocatalyst.
4. A catalyst composition according to claim 4 wherein the cocatalyst is an organometallic compound having a metal of group IA, IIA, IIB or IIIB.
5. A catalyst composition according to claim 5 wherein the cocatalyst is methyl aluminoxane.
6. A catalyst composition according to claim 3 further comprising a support.
7. A catalyst composition according to claim 6 wherein the support is silica.
8. A process for polymerising ethylene or copolymerising ethylene and alphaolefins having 3 to 8 carbon atoms performed in the presence of a catalyst composition according to claims 3 to 7.
9. A complex having the general formula
(C5R5) (C5R5-nLn)MQ wherein R, L, M, Q and n are as defined in claim 1.
10. A complex having the general formula
(C5R5) (C5R5nLn)MM1 Q4 wherein R, L, M, Q and n are as defined in claim 1 and wherein M1 is a Group III metal.
11. A complex according to claim 10 wherein M1 is aluminium.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9513897.0A GB9513897D0 (en) | 1995-07-07 | 1995-07-07 | Novel group ivb metal complexes |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9613933D0 GB9613933D0 (en) | 1996-09-04 |
| GB2303367A true GB2303367A (en) | 1997-02-19 |
| GB2303367B GB2303367B (en) | 1998-01-21 |
Family
ID=10777300
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GBGB9513897.0A Pending GB9513897D0 (en) | 1995-07-07 | 1995-07-07 | Novel group ivb metal complexes |
| GB9613933A Expired - Fee Related GB2303367B (en) | 1995-07-07 | 1996-07-03 | Novel Group IVB Metal Complexes |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GBGB9513897.0A Pending GB9513897D0 (en) | 1995-07-07 | 1995-07-07 | Novel group ivb metal complexes |
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| Country | Link |
|---|---|
| GB (2) | GB9513897D0 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998028350A1 (en) * | 1996-12-20 | 1998-07-02 | Exxon Chemical Patents Inc. | High activity metallocene polymerization process |
| US6420299B1 (en) * | 1999-06-04 | 2002-07-16 | Dow Global Technologies Inc. | Boron-substituted cyclopentadienes and metal complexes thereof |
| WO2002076999A1 (en) * | 2001-03-23 | 2002-10-03 | Bayer Aktiengesellschaft | Catalysts characterized by a donor-acceptor interaction |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5496960A (en) * | 1994-11-23 | 1996-03-05 | University Of Guelph | Process for production of bis-(pentafluorophenyl) borane and use thereof for producition of base free zwitterionic homogeneous Ziegler-Natta olefin polymerization catalysts |
-
1995
- 1995-07-07 GB GBGB9513897.0A patent/GB9513897D0/en active Pending
-
1996
- 1996-07-03 GB GB9613933A patent/GB2303367B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5496960A (en) * | 1994-11-23 | 1996-03-05 | University Of Guelph | Process for production of bis-(pentafluorophenyl) borane and use thereof for producition of base free zwitterionic homogeneous Ziegler-Natta olefin polymerization catalysts |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998028350A1 (en) * | 1996-12-20 | 1998-07-02 | Exxon Chemical Patents Inc. | High activity metallocene polymerization process |
| AU723804B2 (en) * | 1996-12-20 | 2000-09-07 | Exxon Chemical Patents Inc. | High activity metallocene polymerization process |
| US6180736B1 (en) | 1996-12-20 | 2001-01-30 | Exxon Chemical Patents Inc | High activity metallocene polymerization process |
| US6420299B1 (en) * | 1999-06-04 | 2002-07-16 | Dow Global Technologies Inc. | Boron-substituted cyclopentadienes and metal complexes thereof |
| WO2002076999A1 (en) * | 2001-03-23 | 2002-10-03 | Bayer Aktiengesellschaft | Catalysts characterized by a donor-acceptor interaction |
| US6657027B2 (en) | 2001-03-23 | 2003-12-02 | Bayer Aktiengesellschaft | Catalysts with a donor-acceptor interaction |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2303367B (en) | 1998-01-21 |
| GB9513897D0 (en) | 1995-09-06 |
| GB9613933D0 (en) | 1996-09-04 |
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| Date | Code | Title | Description |
|---|---|---|---|
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20050703 |