CA1268753A - Supported polymerization catalyst - Google Patents
Supported polymerization catalystInfo
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- CA1268753A CA1268753A CA000511354A CA511354A CA1268753A CA 1268753 A CA1268753 A CA 1268753A CA 000511354 A CA000511354 A CA 000511354A CA 511354 A CA511354 A CA 511354A CA 1268753 A CA1268753 A CA 1268753A
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- bis
- ethylene
- catalyst
- olefin polymerization
- titanium
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Abstract
ABSTRACT OF THE DISCLOSURE
An olefin polymerization supported catalyst comprising (a) an alumoxane and (b) the reaction product of at least one metallocene and a support such as silica.
An olefin polymerization supported catalyst comprising (a) an alumoxane and (b) the reaction product of at least one metallocene and a support such as silica.
Description
1~68753 1 This invention relates to a transition metal containing
2 supported catalyst component useful in combination with a co-catalyst
3 for the polymerization and copolymerization of olefins and particu-
4 larly useful for the polymerization of ethylene and copolymerization of ethylene with l-olefins having 3 or more carbon atoms such as, for 6 example, propylene, i-butene, l-butene, l-pentene, l-hexene, l-octene, 7 dienes such as butadiene, 1,7-octadiene and 1,4-hexadiene. The inven-8 tion further relates to a heterogeneous catalyst system comprising the 9 transition metal containing supported catalyst component and as a co-catalyst, an alumoxane. The invention further generally relates to 11 a process for polymerization of ethylene alone or with other l-olefins 12 or diolefins in the presence of a catalyst system comprising the-sup-13 ported transition metal-containing catalyst component and an alumoxane.
14 Description of the Prior ~rt Traditionally, ethylene and l-olefins have been polymerized 16 or copolymerized in the presence of hydrocarbon insoluble catalyst 17 systems comprising a transition metal compound and an aluminum alkyl.
18 More recently, active homogeneous catalyst systems comprising a 19 bis-(cyclopentadienyl)titanium dialkyl or a bis(cyclopentadienyl)- :
zirconium dialkyl, an aluminum trialkyl and water have been found to 21 be useful for the polymerization of ethylene. Such catalyst systems 22 are generally referred to as Ziegler-type catalvsts 23 German Patent Application 2,608,86.~ (laid open August 9, 1977) 24 discioses the use of a 2s catalyst system for the polymerization of etnylene consisting of bis 26 (cyclopentadienyl) titanium dialkyl, aluminum trialkvl ~n~ water 27 German Patent Application 2,60~3,933 (laid open August 9, 1977) 28 discloses an ethylene 29 polymerization catalyst system consisting of zirconium metallocenes of the general formula (cyclopentadienyl)nZrY4 n wl~erein n stands 31 for a number in the range of 1 to 4, Y for R, CH2AlR2, CH2CH2AlR2 and 32 CH2CH(AlR2)2, wherein R stands for alkyl or metallo alkyl, and an 33 aluminum trialkyl co-catalyst and water.
34 European Patent Application No. 0035242 (published September 9, 1981) discloses a process 36 for preparing ethylene and atactic propylene polymers in the presence 37 of d halogen-free ~iegler catalyst system comprising (1) a cyclo-38 pentadienyl compound of the formul3 (cyclopentadielyl)nlleY4 n in 39 which n is an integer from 1 to 4, Me is~-a transition metal, especially zirconium, and Y is either hydrogen, a Cl-C5 alkyl or 41 r.::t2110 alkyl group or a radical llaving t~e follo~:i,ng general forlrl!la ~68753 1 CH2AlR2, CH2CH2AlR2 and CH2CH(AlR2)2 in which R represents a 2 Cl-C5 alkyl or metallo alkyl group, and (2) an alumoxane.
3 Additional teachings of homogeneous c,ata~lyst systems com-4 prising a metallocene and alumoxane are found in 7J.S. 4,404,344 issued Septe~ber 13, 1983 o~ Sinn et al.
7 In "Molecular Weight Distribution and Stereoregularity Of 8 Polypropylenes Obtained With Ti(OC4Hg)4tAl(C2H5)3 Catalyst System";
9 Polymer, Pg. 469-471, 1981, Vol. 22, April, Doi, et al disclose propylene polymerization with a catalyst which at about 41C obtains a 11 soluble catalyst and insol~ble cata7yst fraction, one with 12 "homogeneous catalytic centres" and the other with "heterogeneous 13 catalytic centres". The polymerization at that temperature obtains 14 polypropylene having a bimodal molecular weight distribution.
It is also ~nown to produce polymer blends by polymerizing 16 two or more polymerizable materials in two or more reactors arranged 17 in series. In accordance with such methods, a polymerizate is 18 produced in a first reactor which first polymerizate is passed to a 19 second reactor wherein a second polymerizate is produced thereby obtaining a blend of the first and second polymerizates.
21 An advantage of the metallocene-alumoxane homogeneous 22 catalyst system is the very high activity obtained for ethylene 23 polymerization. Another significant advantage is, unlike olefin 24 polymers produced in the presence of conventional heterogeneous Ziegler catalysts, terminal unsaturation is present in polymers 26 produced in the presence of these homogeneous catalysts. Never-27 theless, the catalysts suffer from a disadvantage, that-is, the ratio 28 of alumoxane to metallocene is high, for example, in the order of 29 1,000 to 1 or greater. Such voluminous amounts of alumoxane would require extensive treatment of polymer product obtained in order to 31 remove the undesirable aluminum. Another disadvantage of the 32 homogeneous catalyst system is that the polymer product produced 33 therefrom manifests small particle size and low bulk densitv.
34 In u.s. 4,530,914 issued July 23, 1985, a homogeneous catalyst system comprising two different metallocenes for 36 use in producing polyolefins having a broad molecular weight 3~ distribution and/or multi-modal molecular weight distribution is 38 desCri bed.
1~875;3 Other teachings are found in U.S. 4,522,982 issued June 11, 1985. James C. W.
Chien, in "Reduction of Ti(IV) Alkyls in Cab-0-Sils Surfaces", Jrnl.
of Catalysis 23, 71(1971); Dag Slotfeldt-Ellingsene et al. in "Heterogenization of Homogeneous Catalysts", Jrnl. Molecular Catalysis, 9, 423 (1980)disclose a supported titanocene in combination with alkyl aluminum halides as poor catalysts for olefin polyrnerization.
It would be-highly desirable to provide a metallocene based catalyst which is comrnercially useful for the polymerization of olefins wherein the aluminum to transition metal ratio is reduced compared with the known homogeneous systems, to provide a poly-merization catalyst system which produces polymer product having improved particle size and bulk density, and to prov~ide a catalyst system which evidences improved comonomer incorporation in the production of, for example, linear low density polyethylene (LLDPE).
It is particularly desirable to provide a catalyst system capable of producing polymers having a varied range of molecular weight distributions and/or compositional distributions.
Su1mary of the Invention In accordance with the present invention, a catalyst system comprising a metallocene supported catalyst component and an alumoxane co-catalyst is provided for olefin polymerization, and particularly for the production of linear low, medium and high density poly-ethylenes and copolymers of ethylene with alpha-olefins having 3 or more carbon atoms (C3-C18) and/or diolefins having up to 18 carbon atoms.
The supported catalyst component provided in accordance with one embodiment of this invention, comprises the product obtained by contacting at least one metallocene and a support material thereby providing a supported (rnulti)metallocene-olefin polymerization catalyst component.
8'~5;~
1 In accordance with another embodiment of the invention, a 2 catalyst system comprising a supported (multi) metallocene and an 3 alumoxane is provided which will polymerize olefins at commercially 4 respectable rates without an objectionable excess of alumoxane as required in the homogenous system.
6 In yet another embodiment of this invention there is provided 7 a process for the polymerization of ethylene and other olefins, and 8 particularly homopolymers of ethylene and copolymers of ethylene and 9 higher alpha-olefins and/or diolefins in the presence of the new catalyst system. The process, by means of the catalyst, provides the 11 capability of producing polymers having a varied range of molecular 12 weight distributions, i.e., from narrow molecular weight distribution 13 to a broad molecular weight distribution and/or multi-modal molecular 14 weight distribution. The process also provides the capability of producing reactor blends.
16 Reactor blends are mixtures of two or more (co)polymers of 17 different monomer composition and different physical properties 18 (density, melting point, etc.) produced simultaneously in a single 19 polymerization reactor.
The metallocenes employed in the production of the supported 21 catalyst component are organometallic coordination compounds which are 22 cyclopentadienyl derivatives of a Group 4b, 5b, or 6b metal of the 23 Periodic Table (56th Edition of Handbook of Chemistry and Physics, CRC
24 Press [1975]) and include mono, di and tricyclopentadienyls and their derivatives of the transition metals. Particularly desirable are the 26 metallocenes of Group 4b metals such as titanium and zirconium. The 27 alumoxanes employed as the co-catalyst with the metallocenes are 28 themselves the reaction products of an aluminum trialkyl with water.
29 The alumoxanes are well known in the art and comprise oligomeric, linear and/or cyclic alkyl alumoxanes represented by the 31 formulae:
1.
1 (I) R-(Al-O)n-AlR2 for oligomeric, linear alumoxanes, and 3 (II) (-Al-O-)m for oligomeric, cyclic alumoxanes, wherein n is l-40, preferably l-20, m is 3-40, preferably 3-20 and R
6 is a Cl-C8 alkyl group and preferably methyl. Generally, in the 7 preparation of alumoxanes from, for example, trimethylaluminum and 8 water, a mixture of linear and cyclic compounds is obtained.
9 The alumoxanes can be prepared in a variety of ways.
Preferably, they are prepared by contacting water with a solution of 11 aluminum trialkyl, soch as, for example, trimethylaluminum, in a 12 suitable organic solvent such as benzene or an aliphatic hydrocarbon.
13 For example, the aluminum alkyl is treated with water in the form of a 14 moist solvent. In a preferred method, the aluminum alkyl, such as trimethylaluminum, can be desirably contacted with a hydrated salt 16 such as hydrated ferrous sulfate. The method comprises treating a 17 dilute solution of trimethylaluminum in, for example, toluene with 18 ferrous sulfate heptahydrate.
Briefly, the supported (multi) transition metal containing 21 catalyst component of the present invention is obtained by contacting 22 at least one metallocene with a solid porous support material. The 23 supported product is employed as the transition metal-containing 24 catalyst component for the polymerization of olefins Typically, the support can be any solid, particularly porous ~6 supports such as talc or inorganic oxides, or resinous support 27 materials such as a polyolefin. Preferably, the support material is a 28 inorganic oxide in finely divided form.
29 Suitable inorganic oxide materials which are desirably employed in accordance with this invention include Group 2a, 3a, 4a or 31 4b metal oxides such as silica, alumina, and silica-alumina and 32 mixtures thereof. Other inorganic oxides that may be employed either 33 alone or in combination with the silica, alumina or silica-alumina are 7~
magnesia, titania, zirconia, and the like. Other suitable support 2 materials, however, can be employed, for example, finely divided 3 polyolefins such as finely divided polyethylene.
4 The metal oxides generally contain acidic surface hydroxyl groups which will react with the metallocene added to the reaction 6 slurry. Prior to use, the inorganic oxide support is dehydrated, 7 i. e., subjected to a thermal treatment in order to remove water and 8 reduce the concentration of the surface hydroxyl groups. The treat-g ment is carried out in vacuum or while purging with a dry inert gas such as nitrogen at a temperature of about lOOC to about lO00C, and 11 preferably, from about 300C to about 800C. Pressure considerations 12 are not critical. The duration of the thermal treatment can be from 13 about l to about 24 hours. However, shorter or longer times can be 14 employed provided equilibrium is established with the surface hydroxyl groups.
16 Chemical dehydration ac an alternative method of dehydration 17 of the metal oxide support material can advantageously be employed.
18 Chemical dehydration converts all water and hydroxyl groups on the l9 oxide surface to inert species. Useful chemical agents are for example; SiCl4; chlorosilanes, such as trimethylchlorosilane, 21 dime~hyaminotrimethylsilane and the like. The chemical dehydration is 22 accomplished by slurrying the inorganic particulate material, such as, 23 for example, silica in an inert low boiling hydrocarbon, such as, for 24 example, hexane. During the chemical dehydration reaction, the silica should be maintained in a moisture and oxygen-free atmosphere. To the 26 silica slurry is then added a low boiling inert hydrocarbon solution 27 of the chemical dehydrating agent, such as, for example, dichlorodi-28 methylsilane. The solution is added slowly to the slurry. The 29 temperature ranges during chemical dehydration reaction can be from about 25C to about 120C, however, higher and lower temperatures can 31 be employed. Preferably, the temperature will be about 50C to about 32 70C. The chernical dehydration procedure should be allowed to proceed 33 until all the moisture is removed from the particulate support 34 material, as indicated by cessation of gas evolution. Normally, the chemical dehydration reaction will be allowed to proceed from about 30 36 minutes to about l6 hours, preferably l to 5 hours. Upon completion 37 of the chemical dehydration, the solid particulate material is 38 filtered under a nitrogen atmosphere and washed one or more times ~X~8~753 1 with a dry, oxygen-free inert hydrocarbon solvent. The wash solvents, 2 as well as the diluents employed to form the slurry and the solution 3 of chemical dehydrating agent, can be any suitable inert hydrocarbon.
4 Illustrative of such hydrocarbons are heptane, hexane, toluene, isopentane and the like.
6 The normally hydrocarbon soluble metallocene is converted to 7 a heterogeneous supported catalyst by simply depositing said at least 8 one metallocene on the support material.
9 The treatment of the support material, as mentioned above, is conducted in an inert solvent. The same inert solvent or a different 11 inert solvent is also emp10yed to dissolve the metallocenes.
12 Preferred solvents include mineral oils and the various hydrocarbons 13 which are liquid at reaction temperatures and in which the metal-14 locenes are soluble. Illustrative examples of useful solvents include the alkanes such as pentane, iso-pentane, hexane, heptane, octane and 16 nonane; cycloalkanes such as cyclopentane and cyclohexane; and 17 aromatics such as benzene, toluene, ethylbenzene and diethy1benzene.
18 Preferably the support material is slurried in toluene and the 19 metallocenes and alumoxane are dissolved in toluene prior to addition to the support material. The amount of solvent to be employed is not 21 critical. Nevertheless, the amount should be employed so as to 22 provide adequate heat transfer away from the catalyst components 23 during reaction and to permit good mixing.
24 The supported (multi) metallocene catalyst component of this invention is prepared by simply adding the at least one metallocene in 26 the suitable solvent, preferably toluene to the support material 27 slurry, preferably silica slurried in toluene. The ingredients can be 28 added to the reaction vessel rapidly or slowly. The temperature 29 maintained during the contact of the reactants can vary widely, such as, for example, from 0 to lO0C. Greater or lesser temperatures can 31 also be employed. Preferably, the at least one metallocene is added 32 to the silica at room temperature. When two or more metallocenes are 33 added, the addition can be sequentially or simultaneously. The 34 reaction between the at least one metallocene and the support material is rapid, however, it is desirable that the at least one metallocene 36 be contacted with the support material for about one hour up to 37 eighteen hours or greater. Preferably, the reaction is maintained for 38 about one hour. The reaction of the at least one metallocene with the ~ 7 ~ 3 1 support material is evidenced by elemental analysis of the support 2 material for the transition metal contained in the metallocene(s).
3 At all times, the individual ingredients as well as the 4 recovered catalyst component are protected from oxygen and moisture.
Therefore, the reactions must be performed in an oxygen and moisture 6 free atmosphere and recovered in an oxygen and moisture free 7 atmosphere. Preferably, therefore, the reactions are performed in the 8 presence of an inert dry gas such as, for example, nitrogen. The 9 recovered solid catalyst is maintained in a nitrogen atmosphere.
Upon completion of the reaction of the at least one metal-11 locene with the support, the solid metallocene containing material can 12 be recovered by any well-known technique. For example, the solid 13 metallocene containing material can be recovered from the liquid by 14 vacuum evaporation, filtration or decantation. The solid is there-after dried under a stream of pure dry nitrogen or dried under 16 vacuum.
17 The total amount of metallocene usefully employed in 18 preparation of the solid supported catalyst component can vary over a 19 wide range. The concentration of the metallocene deposited on the essentially dry support can be in the range of about O.OOl to about 5 21 mmoles/g of support, however, greater or lesser amounts can be 22 usefully employed. Preferably, the metallocene concentration is in 23 the range of O.OlO to 2 mmoles/g of support and especially 0.03 to 24 l mmoles/g of support.
For the production of polymer product having a narrow 26 molecular weight distribution it is preferable to deposit only one 27 metallocene onto the porous support material and employ said support 28 metallocene together with the alumoxane as the polymerization 29 catalyst.
It is highly desirable to have for many applications, such as 31 extrusion and molding processes, polyethylenes which have a broad 32 molecular weight distribution of the unimodal and/or the multi-modal 33 type. Such polyethylenes evidence excellent processability, i.e., 34 they can be processed at a faster throughput rate with lower energy re4uirements and at the same time such polymers would evidence reduced 36 melt flow perturbations. Such polyethylenes can be obtained by 37 providing a catalyst component comprising at least two different ~87~3 1 metallocenes, each having different propagation ~nd termination rate 2 constants for ethylene polymerizations. Such rate constants are 3 readily determined by one of ordinary skill in the art.
4 The molar ratio of the metallocenes, such as for example, of
14 Description of the Prior ~rt Traditionally, ethylene and l-olefins have been polymerized 16 or copolymerized in the presence of hydrocarbon insoluble catalyst 17 systems comprising a transition metal compound and an aluminum alkyl.
18 More recently, active homogeneous catalyst systems comprising a 19 bis-(cyclopentadienyl)titanium dialkyl or a bis(cyclopentadienyl)- :
zirconium dialkyl, an aluminum trialkyl and water have been found to 21 be useful for the polymerization of ethylene. Such catalyst systems 22 are generally referred to as Ziegler-type catalvsts 23 German Patent Application 2,608,86.~ (laid open August 9, 1977) 24 discioses the use of a 2s catalyst system for the polymerization of etnylene consisting of bis 26 (cyclopentadienyl) titanium dialkyl, aluminum trialkvl ~n~ water 27 German Patent Application 2,60~3,933 (laid open August 9, 1977) 28 discloses an ethylene 29 polymerization catalyst system consisting of zirconium metallocenes of the general formula (cyclopentadienyl)nZrY4 n wl~erein n stands 31 for a number in the range of 1 to 4, Y for R, CH2AlR2, CH2CH2AlR2 and 32 CH2CH(AlR2)2, wherein R stands for alkyl or metallo alkyl, and an 33 aluminum trialkyl co-catalyst and water.
34 European Patent Application No. 0035242 (published September 9, 1981) discloses a process 36 for preparing ethylene and atactic propylene polymers in the presence 37 of d halogen-free ~iegler catalyst system comprising (1) a cyclo-38 pentadienyl compound of the formul3 (cyclopentadielyl)nlleY4 n in 39 which n is an integer from 1 to 4, Me is~-a transition metal, especially zirconium, and Y is either hydrogen, a Cl-C5 alkyl or 41 r.::t2110 alkyl group or a radical llaving t~e follo~:i,ng general forlrl!la ~68753 1 CH2AlR2, CH2CH2AlR2 and CH2CH(AlR2)2 in which R represents a 2 Cl-C5 alkyl or metallo alkyl group, and (2) an alumoxane.
3 Additional teachings of homogeneous c,ata~lyst systems com-4 prising a metallocene and alumoxane are found in 7J.S. 4,404,344 issued Septe~ber 13, 1983 o~ Sinn et al.
7 In "Molecular Weight Distribution and Stereoregularity Of 8 Polypropylenes Obtained With Ti(OC4Hg)4tAl(C2H5)3 Catalyst System";
9 Polymer, Pg. 469-471, 1981, Vol. 22, April, Doi, et al disclose propylene polymerization with a catalyst which at about 41C obtains a 11 soluble catalyst and insol~ble cata7yst fraction, one with 12 "homogeneous catalytic centres" and the other with "heterogeneous 13 catalytic centres". The polymerization at that temperature obtains 14 polypropylene having a bimodal molecular weight distribution.
It is also ~nown to produce polymer blends by polymerizing 16 two or more polymerizable materials in two or more reactors arranged 17 in series. In accordance with such methods, a polymerizate is 18 produced in a first reactor which first polymerizate is passed to a 19 second reactor wherein a second polymerizate is produced thereby obtaining a blend of the first and second polymerizates.
21 An advantage of the metallocene-alumoxane homogeneous 22 catalyst system is the very high activity obtained for ethylene 23 polymerization. Another significant advantage is, unlike olefin 24 polymers produced in the presence of conventional heterogeneous Ziegler catalysts, terminal unsaturation is present in polymers 26 produced in the presence of these homogeneous catalysts. Never-27 theless, the catalysts suffer from a disadvantage, that-is, the ratio 28 of alumoxane to metallocene is high, for example, in the order of 29 1,000 to 1 or greater. Such voluminous amounts of alumoxane would require extensive treatment of polymer product obtained in order to 31 remove the undesirable aluminum. Another disadvantage of the 32 homogeneous catalyst system is that the polymer product produced 33 therefrom manifests small particle size and low bulk densitv.
34 In u.s. 4,530,914 issued July 23, 1985, a homogeneous catalyst system comprising two different metallocenes for 36 use in producing polyolefins having a broad molecular weight 3~ distribution and/or multi-modal molecular weight distribution is 38 desCri bed.
1~875;3 Other teachings are found in U.S. 4,522,982 issued June 11, 1985. James C. W.
Chien, in "Reduction of Ti(IV) Alkyls in Cab-0-Sils Surfaces", Jrnl.
of Catalysis 23, 71(1971); Dag Slotfeldt-Ellingsene et al. in "Heterogenization of Homogeneous Catalysts", Jrnl. Molecular Catalysis, 9, 423 (1980)disclose a supported titanocene in combination with alkyl aluminum halides as poor catalysts for olefin polyrnerization.
It would be-highly desirable to provide a metallocene based catalyst which is comrnercially useful for the polymerization of olefins wherein the aluminum to transition metal ratio is reduced compared with the known homogeneous systems, to provide a poly-merization catalyst system which produces polymer product having improved particle size and bulk density, and to prov~ide a catalyst system which evidences improved comonomer incorporation in the production of, for example, linear low density polyethylene (LLDPE).
It is particularly desirable to provide a catalyst system capable of producing polymers having a varied range of molecular weight distributions and/or compositional distributions.
Su1mary of the Invention In accordance with the present invention, a catalyst system comprising a metallocene supported catalyst component and an alumoxane co-catalyst is provided for olefin polymerization, and particularly for the production of linear low, medium and high density poly-ethylenes and copolymers of ethylene with alpha-olefins having 3 or more carbon atoms (C3-C18) and/or diolefins having up to 18 carbon atoms.
The supported catalyst component provided in accordance with one embodiment of this invention, comprises the product obtained by contacting at least one metallocene and a support material thereby providing a supported (rnulti)metallocene-olefin polymerization catalyst component.
8'~5;~
1 In accordance with another embodiment of the invention, a 2 catalyst system comprising a supported (multi) metallocene and an 3 alumoxane is provided which will polymerize olefins at commercially 4 respectable rates without an objectionable excess of alumoxane as required in the homogenous system.
6 In yet another embodiment of this invention there is provided 7 a process for the polymerization of ethylene and other olefins, and 8 particularly homopolymers of ethylene and copolymers of ethylene and 9 higher alpha-olefins and/or diolefins in the presence of the new catalyst system. The process, by means of the catalyst, provides the 11 capability of producing polymers having a varied range of molecular 12 weight distributions, i.e., from narrow molecular weight distribution 13 to a broad molecular weight distribution and/or multi-modal molecular 14 weight distribution. The process also provides the capability of producing reactor blends.
16 Reactor blends are mixtures of two or more (co)polymers of 17 different monomer composition and different physical properties 18 (density, melting point, etc.) produced simultaneously in a single 19 polymerization reactor.
The metallocenes employed in the production of the supported 21 catalyst component are organometallic coordination compounds which are 22 cyclopentadienyl derivatives of a Group 4b, 5b, or 6b metal of the 23 Periodic Table (56th Edition of Handbook of Chemistry and Physics, CRC
24 Press [1975]) and include mono, di and tricyclopentadienyls and their derivatives of the transition metals. Particularly desirable are the 26 metallocenes of Group 4b metals such as titanium and zirconium. The 27 alumoxanes employed as the co-catalyst with the metallocenes are 28 themselves the reaction products of an aluminum trialkyl with water.
29 The alumoxanes are well known in the art and comprise oligomeric, linear and/or cyclic alkyl alumoxanes represented by the 31 formulae:
1.
1 (I) R-(Al-O)n-AlR2 for oligomeric, linear alumoxanes, and 3 (II) (-Al-O-)m for oligomeric, cyclic alumoxanes, wherein n is l-40, preferably l-20, m is 3-40, preferably 3-20 and R
6 is a Cl-C8 alkyl group and preferably methyl. Generally, in the 7 preparation of alumoxanes from, for example, trimethylaluminum and 8 water, a mixture of linear and cyclic compounds is obtained.
9 The alumoxanes can be prepared in a variety of ways.
Preferably, they are prepared by contacting water with a solution of 11 aluminum trialkyl, soch as, for example, trimethylaluminum, in a 12 suitable organic solvent such as benzene or an aliphatic hydrocarbon.
13 For example, the aluminum alkyl is treated with water in the form of a 14 moist solvent. In a preferred method, the aluminum alkyl, such as trimethylaluminum, can be desirably contacted with a hydrated salt 16 such as hydrated ferrous sulfate. The method comprises treating a 17 dilute solution of trimethylaluminum in, for example, toluene with 18 ferrous sulfate heptahydrate.
Briefly, the supported (multi) transition metal containing 21 catalyst component of the present invention is obtained by contacting 22 at least one metallocene with a solid porous support material. The 23 supported product is employed as the transition metal-containing 24 catalyst component for the polymerization of olefins Typically, the support can be any solid, particularly porous ~6 supports such as talc or inorganic oxides, or resinous support 27 materials such as a polyolefin. Preferably, the support material is a 28 inorganic oxide in finely divided form.
29 Suitable inorganic oxide materials which are desirably employed in accordance with this invention include Group 2a, 3a, 4a or 31 4b metal oxides such as silica, alumina, and silica-alumina and 32 mixtures thereof. Other inorganic oxides that may be employed either 33 alone or in combination with the silica, alumina or silica-alumina are 7~
magnesia, titania, zirconia, and the like. Other suitable support 2 materials, however, can be employed, for example, finely divided 3 polyolefins such as finely divided polyethylene.
4 The metal oxides generally contain acidic surface hydroxyl groups which will react with the metallocene added to the reaction 6 slurry. Prior to use, the inorganic oxide support is dehydrated, 7 i. e., subjected to a thermal treatment in order to remove water and 8 reduce the concentration of the surface hydroxyl groups. The treat-g ment is carried out in vacuum or while purging with a dry inert gas such as nitrogen at a temperature of about lOOC to about lO00C, and 11 preferably, from about 300C to about 800C. Pressure considerations 12 are not critical. The duration of the thermal treatment can be from 13 about l to about 24 hours. However, shorter or longer times can be 14 employed provided equilibrium is established with the surface hydroxyl groups.
16 Chemical dehydration ac an alternative method of dehydration 17 of the metal oxide support material can advantageously be employed.
18 Chemical dehydration converts all water and hydroxyl groups on the l9 oxide surface to inert species. Useful chemical agents are for example; SiCl4; chlorosilanes, such as trimethylchlorosilane, 21 dime~hyaminotrimethylsilane and the like. The chemical dehydration is 22 accomplished by slurrying the inorganic particulate material, such as, 23 for example, silica in an inert low boiling hydrocarbon, such as, for 24 example, hexane. During the chemical dehydration reaction, the silica should be maintained in a moisture and oxygen-free atmosphere. To the 26 silica slurry is then added a low boiling inert hydrocarbon solution 27 of the chemical dehydrating agent, such as, for example, dichlorodi-28 methylsilane. The solution is added slowly to the slurry. The 29 temperature ranges during chemical dehydration reaction can be from about 25C to about 120C, however, higher and lower temperatures can 31 be employed. Preferably, the temperature will be about 50C to about 32 70C. The chernical dehydration procedure should be allowed to proceed 33 until all the moisture is removed from the particulate support 34 material, as indicated by cessation of gas evolution. Normally, the chemical dehydration reaction will be allowed to proceed from about 30 36 minutes to about l6 hours, preferably l to 5 hours. Upon completion 37 of the chemical dehydration, the solid particulate material is 38 filtered under a nitrogen atmosphere and washed one or more times ~X~8~753 1 with a dry, oxygen-free inert hydrocarbon solvent. The wash solvents, 2 as well as the diluents employed to form the slurry and the solution 3 of chemical dehydrating agent, can be any suitable inert hydrocarbon.
4 Illustrative of such hydrocarbons are heptane, hexane, toluene, isopentane and the like.
6 The normally hydrocarbon soluble metallocene is converted to 7 a heterogeneous supported catalyst by simply depositing said at least 8 one metallocene on the support material.
9 The treatment of the support material, as mentioned above, is conducted in an inert solvent. The same inert solvent or a different 11 inert solvent is also emp10yed to dissolve the metallocenes.
12 Preferred solvents include mineral oils and the various hydrocarbons 13 which are liquid at reaction temperatures and in which the metal-14 locenes are soluble. Illustrative examples of useful solvents include the alkanes such as pentane, iso-pentane, hexane, heptane, octane and 16 nonane; cycloalkanes such as cyclopentane and cyclohexane; and 17 aromatics such as benzene, toluene, ethylbenzene and diethy1benzene.
18 Preferably the support material is slurried in toluene and the 19 metallocenes and alumoxane are dissolved in toluene prior to addition to the support material. The amount of solvent to be employed is not 21 critical. Nevertheless, the amount should be employed so as to 22 provide adequate heat transfer away from the catalyst components 23 during reaction and to permit good mixing.
24 The supported (multi) metallocene catalyst component of this invention is prepared by simply adding the at least one metallocene in 26 the suitable solvent, preferably toluene to the support material 27 slurry, preferably silica slurried in toluene. The ingredients can be 28 added to the reaction vessel rapidly or slowly. The temperature 29 maintained during the contact of the reactants can vary widely, such as, for example, from 0 to lO0C. Greater or lesser temperatures can 31 also be employed. Preferably, the at least one metallocene is added 32 to the silica at room temperature. When two or more metallocenes are 33 added, the addition can be sequentially or simultaneously. The 34 reaction between the at least one metallocene and the support material is rapid, however, it is desirable that the at least one metallocene 36 be contacted with the support material for about one hour up to 37 eighteen hours or greater. Preferably, the reaction is maintained for 38 about one hour. The reaction of the at least one metallocene with the ~ 7 ~ 3 1 support material is evidenced by elemental analysis of the support 2 material for the transition metal contained in the metallocene(s).
3 At all times, the individual ingredients as well as the 4 recovered catalyst component are protected from oxygen and moisture.
Therefore, the reactions must be performed in an oxygen and moisture 6 free atmosphere and recovered in an oxygen and moisture free 7 atmosphere. Preferably, therefore, the reactions are performed in the 8 presence of an inert dry gas such as, for example, nitrogen. The 9 recovered solid catalyst is maintained in a nitrogen atmosphere.
Upon completion of the reaction of the at least one metal-11 locene with the support, the solid metallocene containing material can 12 be recovered by any well-known technique. For example, the solid 13 metallocene containing material can be recovered from the liquid by 14 vacuum evaporation, filtration or decantation. The solid is there-after dried under a stream of pure dry nitrogen or dried under 16 vacuum.
17 The total amount of metallocene usefully employed in 18 preparation of the solid supported catalyst component can vary over a 19 wide range. The concentration of the metallocene deposited on the essentially dry support can be in the range of about O.OOl to about 5 21 mmoles/g of support, however, greater or lesser amounts can be 22 usefully employed. Preferably, the metallocene concentration is in 23 the range of O.OlO to 2 mmoles/g of support and especially 0.03 to 24 l mmoles/g of support.
For the production of polymer product having a narrow 26 molecular weight distribution it is preferable to deposit only one 27 metallocene onto the porous support material and employ said support 28 metallocene together with the alumoxane as the polymerization 29 catalyst.
It is highly desirable to have for many applications, such as 31 extrusion and molding processes, polyethylenes which have a broad 32 molecular weight distribution of the unimodal and/or the multi-modal 33 type. Such polyethylenes evidence excellent processability, i.e., 34 they can be processed at a faster throughput rate with lower energy re4uirements and at the same time such polymers would evidence reduced 36 melt flow perturbations. Such polyethylenes can be obtained by 37 providing a catalyst component comprising at least two different ~87~3 1 metallocenes, each having different propagation ~nd termination rate 2 constants for ethylene polymerizations. Such rate constants are 3 readily determined by one of ordinary skill in the art.
4 The molar ratio of the metallocenes, such as for example, of
5 a zirconocene to a titanocene~ can vary over d wide range and in
6 accordance with this invention the only limitation on the molar ratios
7 is the breadth of the MW distribution or the degree of bimodality
8 desired in the product polymer. Desirably, the metallocene to
9 metallocene molar ratio will be about 1:100 to about 100:1, and
10 preferably 1:10 to about 10:1.
11 The present invention also provides a process for producing
12 (co)polyolefin reactor blends comprising polyethylene and
13 copolyethylene-alpha-olefins. The reactor blends are obtained
14 directly during a single polymerization process, i.e., the blends of
15 this invention are obtained in a single reactor by simultaneously
16 polymerizing ethylene and copolymerizing ethylene with an alp-h~-olefin
17 thereby eliminating expensive blending operations. The process of
18 producing reactor blends in accordance with this invention can be G 19 employed in çonjunction with other prior art blending techniques, for 20 example the reactor blends produced in a first reactor can be 21 subjected to further blending in a second stage by use of the series 22 reactorS~
23 In order to produce reactor blends the supported metallocene 24 catalyst component comprises at least two different metallocenes each 25 having different reactivity ratios.
26 The reactivity ratios of the metallocenes in general are-27 obt-ained by methods well known such as, for example, as described in 28 "Linear Method for Dete)mining lfionomer Reactivity Ratios in 29 Copolymerization", M. Fineman and S. D. Ross, J. Polymer Science 5, 30 259 (1950) or "Copolymerization", F. R. Mayo and C. Walling, Chem.
31 Rev. 46, 191 (1950)-32 For examp1e, to determine reactivity ratios the most widely used 33 copolymerization model is based on the following equations:
:
~ .
~:
1 Ml* + Ml kll ~ Ml* (l) 2 Ml* + M2 kl2 ~ M2* (2) 3 M2* ~ Ml k2l ~Ml* ~3) 4 M2* + M2 k22 ~M2* (4) where Ml refers to a monomer molecule which is arbitrarily 6 designated i (where i = l, 2) and Mj* refers to a growing polymer 7 chain to which monomer i has most recently attached.
8 The kij values are the rate constants for the indicated 9 reactions. In this case, kll represents the rate at which an ethylene unit inserts into a growing polymer chain in which the 11 previously inserted monomer unit was also ethylene. The reactivity 12 rates follow as: rl=kll/kl2 and r2=k22/k2l wherein kll, 13 kl2, k22 and k2l are the rate constants for ethylene (l) or 14 comonomer (2) addition to a catalyst site where the last polymerized monomer is ethylene (klX) or comonomer(2) (k2X).
16 In Table I the ethylene-propylene reactivity rates rl and 17 r2 are listed for several metallocenes. It can be seen that with 18 increased steric interaction at the monomer coordination site rl
23 In order to produce reactor blends the supported metallocene 24 catalyst component comprises at least two different metallocenes each 25 having different reactivity ratios.
26 The reactivity ratios of the metallocenes in general are-27 obt-ained by methods well known such as, for example, as described in 28 "Linear Method for Dete)mining lfionomer Reactivity Ratios in 29 Copolymerization", M. Fineman and S. D. Ross, J. Polymer Science 5, 30 259 (1950) or "Copolymerization", F. R. Mayo and C. Walling, Chem.
31 Rev. 46, 191 (1950)-32 For examp1e, to determine reactivity ratios the most widely used 33 copolymerization model is based on the following equations:
:
~ .
~:
1 Ml* + Ml kll ~ Ml* (l) 2 Ml* + M2 kl2 ~ M2* (2) 3 M2* ~ Ml k2l ~Ml* ~3) 4 M2* + M2 k22 ~M2* (4) where Ml refers to a monomer molecule which is arbitrarily 6 designated i (where i = l, 2) and Mj* refers to a growing polymer 7 chain to which monomer i has most recently attached.
8 The kij values are the rate constants for the indicated 9 reactions. In this case, kll represents the rate at which an ethylene unit inserts into a growing polymer chain in which the 11 previously inserted monomer unit was also ethylene. The reactivity 12 rates follow as: rl=kll/kl2 and r2=k22/k2l wherein kll, 13 kl2, k22 and k2l are the rate constants for ethylene (l) or 14 comonomer (2) addition to a catalyst site where the last polymerized monomer is ethylene (klX) or comonomer(2) (k2X).
16 In Table I the ethylene-propylene reactivity rates rl and 17 r2 are listed for several metallocenes. It can be seen that with 18 increased steric interaction at the monomer coordination site rl
19 increases, i.e., the tendency for ethylene polymerization increases over propylene polymerization.
21 It can be seen from Table I that if one desires a blend 22 comprising HDPE/ethylene-propylene copolymer one would select bis-23 (pentamethylcyclopentadienyl)zirconium dichloride and bis(cyclopenta-24 dienyl)titaniumdiphenyl or dimethylsilyldicyclopentadienylzirconium dichloride in ratios of about 5:l to about l:l whereas if one desires 26 a blend comprising LLDPE/ethylene-propylene one would select bis-27 (cyclopentadienyl)zirconium dichloride and bis(cyclopentadienyl)-28 titanium diphenyl or dimethylsilyldicyclopentadienylzirconium 29 dichloride in ratios of about lO:l to about l:lO.
The molar ratio of the metallocenes can vary over a wide 31 range and in accordance with this invention the molar ratics are 32 controlled by the product polymer blend desired.
33 Desirably, the metallocene molar ratio on the support will be 34 about lOO:l to about l:lO0, and preferably lO:l to about l:lO. The specific metallocenes selected and their molar ratios are dependent 37~3 1 upon the molecular composition desired for the component polymers and 2 the overall composition desired for the blend. In general, the com-3 ponent catalyst used in a reactor blend catalyst mixture will each 4 have r values which are different in order to produce final polymer 5 compositions which comprise blends of two or more polymers.
7 Catalyst rl r2 8 CP2Ti=CH2 Al(Me)2Cl 24 0.0085 9 Cp2TiPh2 l9.5+l.5 0.0l5+.002 Me2SiCp2ZrCl2 24+2 0.029+.007 11 Cp~ZrCl2 48~2 0.015+.003 12 (MeCp)2ZrCl2 60 13 (Me5Cp)2ZrCl2 250+30 .002+0.00l 14 [Cp2ZrCl]20 50 0.007 The alumoxane which is used as the co-catalyst can be 16 employed in an amount in the range of l to lO0 moles of aluminum per 17 mole of transition metal on the support and preferably 2 to 50.
18 The present invention employs at least one metallocene compound in 19 the formation of the supported catalyst. Metallocene, i.e. a cyclopentadienylide, is a metal derivative of a cyclopentadiene. The 21 metallocenes usefully employed in accordance with this invention 22 contain at least one cyclopentadiene ring. The metal is selected from 23 Group 4b, 5b or 6b metals, preferably 4b and 5b metals, preferably 24 titanium, zirconium, hafnium, and vanadium, and especially titanium and zirconium. The cyclopentadienyl ring can be unsubstituted or 26 contain substituents such as, for example, hydrocarbyl substituents.
27 The metallocene can contain one, two, or three cyclopentadienyl ring 28 however two rings are preferred.
29 The metallocenes can be represented by the general formulas:
I- (Cp)mMRnXq 31 wherein Cp i~ a cyclopentadienyl ring, M is a Group 4b, 5b, or 6b 32 transition metal, R is a hydrocarbyl group having from l to 20 carbon 33 atoms, X is a halogen atom, m = 1-3, n = 0-3, q = 0-3 and the sum of 34 m+n+q is equal to the oxidation state of M.
II. (C5R'k)gRI's(C5R k)MQ3_9 and 36 III. R"s(C5R'k)2MQ' 87~3 - l2 -1 wherein (C5R'k) is a cyclopentadienyl or substituted 2 cyclopentadienyl, each R' is the same or different and is hydrogen or 3 a hydrocarbyl radical such as alkylS alkenyl, aryl, alkylaryl, or 4 arylalkyl radical containing from l to 20 carbon atoms or two carbon 5 atoms are joined together to form a C4-C6 ring, R" is a Cl-C4 6 alkylene radical, a dialkyl germanium or silicon, or a alkyl phosphine 7 or amine radical bridging two tC5R'k) rings, Q is a hydrocarbyl 8 radical such as aryl, alkyl, alkenyl, alkylaryl, or aryl alkyl radical 9 having from l-20 carbon atoms, hydrocarboxy radical having from l-20 10 carbon atoms or halogen and can be the same or different from each 11 other, Q' is an alkylidiene radical having from l to about 20 carbon t 12 atoms, s is 0 or l, 9 is 0,l or 2, s is 0 when 9 is 0, k is 4 when s 13 is l, and k is 5 when s is 0, and M is as defined above.
14 Exemplary hydrocarbyl radicals are methyl, ethyl, propyl, 15 butyl, amyl, isoamylj hexyl, isobutyl, heptyl, octyl, nonyl, decyl, 16 cetyl, 2-ethylhexyl, phenyl and the like.
17 Exemplary halogen atoms include chlorine, bromine, fluorine 18 and iodine and of these halogen atoms, chlorine is preferred.
19 Exemplary hydrocarboxy radicals are methoxy ethoxy, butoxy,
21 It can be seen from Table I that if one desires a blend 22 comprising HDPE/ethylene-propylene copolymer one would select bis-23 (pentamethylcyclopentadienyl)zirconium dichloride and bis(cyclopenta-24 dienyl)titaniumdiphenyl or dimethylsilyldicyclopentadienylzirconium dichloride in ratios of about 5:l to about l:l whereas if one desires 26 a blend comprising LLDPE/ethylene-propylene one would select bis-27 (cyclopentadienyl)zirconium dichloride and bis(cyclopentadienyl)-28 titanium diphenyl or dimethylsilyldicyclopentadienylzirconium 29 dichloride in ratios of about lO:l to about l:lO.
The molar ratio of the metallocenes can vary over a wide 31 range and in accordance with this invention the molar ratics are 32 controlled by the product polymer blend desired.
33 Desirably, the metallocene molar ratio on the support will be 34 about lOO:l to about l:lO0, and preferably lO:l to about l:lO. The specific metallocenes selected and their molar ratios are dependent 37~3 1 upon the molecular composition desired for the component polymers and 2 the overall composition desired for the blend. In general, the com-3 ponent catalyst used in a reactor blend catalyst mixture will each 4 have r values which are different in order to produce final polymer 5 compositions which comprise blends of two or more polymers.
7 Catalyst rl r2 8 CP2Ti=CH2 Al(Me)2Cl 24 0.0085 9 Cp2TiPh2 l9.5+l.5 0.0l5+.002 Me2SiCp2ZrCl2 24+2 0.029+.007 11 Cp~ZrCl2 48~2 0.015+.003 12 (MeCp)2ZrCl2 60 13 (Me5Cp)2ZrCl2 250+30 .002+0.00l 14 [Cp2ZrCl]20 50 0.007 The alumoxane which is used as the co-catalyst can be 16 employed in an amount in the range of l to lO0 moles of aluminum per 17 mole of transition metal on the support and preferably 2 to 50.
18 The present invention employs at least one metallocene compound in 19 the formation of the supported catalyst. Metallocene, i.e. a cyclopentadienylide, is a metal derivative of a cyclopentadiene. The 21 metallocenes usefully employed in accordance with this invention 22 contain at least one cyclopentadiene ring. The metal is selected from 23 Group 4b, 5b or 6b metals, preferably 4b and 5b metals, preferably 24 titanium, zirconium, hafnium, and vanadium, and especially titanium and zirconium. The cyclopentadienyl ring can be unsubstituted or 26 contain substituents such as, for example, hydrocarbyl substituents.
27 The metallocene can contain one, two, or three cyclopentadienyl ring 28 however two rings are preferred.
29 The metallocenes can be represented by the general formulas:
I- (Cp)mMRnXq 31 wherein Cp i~ a cyclopentadienyl ring, M is a Group 4b, 5b, or 6b 32 transition metal, R is a hydrocarbyl group having from l to 20 carbon 33 atoms, X is a halogen atom, m = 1-3, n = 0-3, q = 0-3 and the sum of 34 m+n+q is equal to the oxidation state of M.
II. (C5R'k)gRI's(C5R k)MQ3_9 and 36 III. R"s(C5R'k)2MQ' 87~3 - l2 -1 wherein (C5R'k) is a cyclopentadienyl or substituted 2 cyclopentadienyl, each R' is the same or different and is hydrogen or 3 a hydrocarbyl radical such as alkylS alkenyl, aryl, alkylaryl, or 4 arylalkyl radical containing from l to 20 carbon atoms or two carbon 5 atoms are joined together to form a C4-C6 ring, R" is a Cl-C4 6 alkylene radical, a dialkyl germanium or silicon, or a alkyl phosphine 7 or amine radical bridging two tC5R'k) rings, Q is a hydrocarbyl 8 radical such as aryl, alkyl, alkenyl, alkylaryl, or aryl alkyl radical 9 having from l-20 carbon atoms, hydrocarboxy radical having from l-20 10 carbon atoms or halogen and can be the same or different from each 11 other, Q' is an alkylidiene radical having from l to about 20 carbon t 12 atoms, s is 0 or l, 9 is 0,l or 2, s is 0 when 9 is 0, k is 4 when s 13 is l, and k is 5 when s is 0, and M is as defined above.
14 Exemplary hydrocarbyl radicals are methyl, ethyl, propyl, 15 butyl, amyl, isoamylj hexyl, isobutyl, heptyl, octyl, nonyl, decyl, 16 cetyl, 2-ethylhexyl, phenyl and the like.
17 Exemplary halogen atoms include chlorine, bromine, fluorine 18 and iodine and of these halogen atoms, chlorine is preferred.
19 Exemplary hydrocarboxy radicals are methoxy ethoxy, butoxy,
20 amyloxy and the like.
21 Exemplary of the alkylidiene radicals is methylidene,
22 ethylidene and propylidene.
23 Illustrative, but non-limiting examples of the metallocenes
24 represented by formula I are dialkyl metallocenes such as bis(cyclo-
25 pentadienyl)titanium dimethyl, bis(cyclopentadienyl)titanium diphenyl,
26 bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)-
27 zirconium diphenyl, bis(cyclopentadienyl)hafnium dimethyl and
28 diphenyl, bis(cyclopentadienyl)titanium dineopentyl, bis(cyclopenta-
29 dienyl)zirconium dineopentyl, bis(cyclopentadienyl)titanium dibenzyl,
30 bis(cyclopentadienyl)zirconium dibenzyl, bis(cyclopentadienyl)vanadium
31 dimethyl; the mono alkyl metallocenes such as bis(cyclopentadienyl)-
32 titanium methyl chloride, bis(cyclopentadienyl)titanium ethyl
33 chloride, bis(cyclopentadienyl)titanium phenyl chloride, bis(cyclo-
34 pentadienyl)zirconium methyl chloride, bis(cyclopentadienyl)zirconium
35 ethyl chloride, bis(cyclopentadienyl)zirconium phenyl chloride, bis-
36 (cyclo?entadienyl)titanium methyl bromide, bis(cyclopentadienyl)-
37 titanium methyl iodide, bis(cyclopentadienyl)titanium ethyl bromide,
38 bis(cyclopentadienyl)titanium ethyl iodide, bis(cyclopentadienyl)-. ..
1 titanium phenyl bromide, bis(cyclopentadienyl)titanium phenyl iodide, 2 bis(cyclopentadienyl)zirconium methyl bromide, bis(cyclopentadienyl)-3 zirconium methyl iodide, bis(cyclopentadienyl)zirconium ethyl bromide, 4 bis(cyclopentadienyl)zirconium ethyl iodide, bis(cyclopentadienyl)-zirconium phenyl bromide, bis(cyclopentadienyl)zirconium phenyl 6 iodide; the trialkyl metallocenes such as cyclopentadienyltitanium 7 trimethyl, cyclopentadienyl zirconium triphenyl, and cyclopentadienyl zirconium trineopentyl, cyclopentadienylzirconium trimethyl, cyclo-. 9 pentadienylhafnium triphenyl, cyclopentadienylhafnium trineopentyl, and cyclopentadienylhafnium trimethyl.
11 Illustrative, but non-limiting examples of II and III
12 metallocenes which can be usefully employed in accordance with this 13 invention are monocyclopentadienyls titanocenes such as, pentamethyl-14 cyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride, bis(pentamethylcyclopentadienyl) titanium 16 diphenyl, the carbene represented by the formula Cp2Ti=CH2 17 and derivatives of this reagent such as Cp~Ti=CH~ Al(CH3)3, 18 (Cp2TiCH2)2, and Cp2TiCH2CH(CH3)CH2, Cp2ti-CH2CH2CH2;
19 substituted bis(Cp)Ti(IV) compounds such as bis(indenyl)titanium diphenyl or dichloride, bis(methylcyclopentadienyl)titanium diphenyl 21 or dihalides; dialkyl, triaikyl, tetra-alkyl and pentaalkyl 22 cyclopentadienyl titanium compounds such as bis(l,2-dimethylcyclo-23 pentadienyl)titanium diphenyl or dichloride, bis(l,2-diethylcyclo-~4 pentadienyl)titanium diphenyl or dichloride and other dihalide com-plexes, silicon, phosphine, amine or carbon bridged cyclopentadiene 26 complexes, such as dimethyl silyldicyclopentadienyl titanium diphenyl 27 or dichloride, methyl phosphine dicyclopentadienyl titanium diphenyl 28 or dichloride, methylenedicyclopentadienyl titanium diphenyl or 29 dichloride and other dihalide complexes and the like.
Illustrative but non-limiting examples of the zirconocenes 31 of Formula II and III which can be usefully employed in accordance 32 with this invention are, pentamethylcyclopentadienyl zirconium tri-33 chloride, pentaethylcyclopentadienyl zirconium trichloride, the alkyl 34 substituted cyclopentadienes, such as bis(ethylcyclopentadienyl)-zirconium dimethyl, bis(~-phenylpropylcyclopentadienyl)zirconium 36 d-,methyl, bis(methylcyclopentadienyl)zirccnium dimethyl, bis(n-butyl-37 cyclopentadienyl)zirconium dimethyl, bis(cyclohexylmethylcyclopenta-38 dienyl)zirccnium dimethyl, bis(n-octyl-cyclopentadienyl)zirconium 687j3 - l4 -1 dimethyl, and haloalkyl and dihalide complexes of the above; dialkyl, 2 trialkyl, tetra-alkyl, and pentaalkyl cyclopentadienes, such as 3 bis(pentamethylcyclopentadienyl)zirconium diphenyl, bis(pentamethyl-4 cyclopentadienyl)zirconium dimethyl, bis(l,2-dimethylcyclopenta-dienyl)zirconium dimethyl and mono- and dihalide complexes of the 6 above, silicon, phosphorus, and carbon bridged cyclopentadiene 7 complexes such as dimethylsilyidicyclopentadienyl zirconium dimethyl, 8 methyl halide or dihalide, and methylene dicyclopentadienyl zirconium 9 dimethyl, methyl halide, or dihalide, carbenes represented by the formulae Cp?Zr=CH2P(C~H~)2CH3, and derivatives of these compounds 11 such as Cp2ZrCH2CH(CH3)CH2.
12 Bis(cyclopentadienyl)hafnium dichloride, bis(cyclopenta-13 dienyl)hafnium dimethyl, bis(cyclopentadienyl)vanadium dichloride and 14 the like are illustrative of other metallocenes.
The inorganic oxide support used in the preparation of the 16 catalyst may be any particulate oxide or mixed oxide as-previously 17 described which has been thermally or chemically dehydrated such that 18 it is substantially free of adsorbed moisture.
19 The specific particle size, surface area, pore volume, and number of surface hydroxyl groups characteristic of the inorganic 21 oxide are not critical to its utility in the practice of the 22 invention. However, since such characteristics determine the amount 23 of inorganic oxide that it is desirable to employ in preparing the 24 catalyst compositions, as well as affecting the properties of polymers formed with the aid of the catalyst compositions, these character-26 istics must frequently be taken into consideration in choosing an 27 inorganic oxide for use in a particular aspect of the invention. For 28 example, when the catalyst composition is to be used in a gas-phase 29 polymerization process - a type of process in which it is known that the polymer particle size can be varied by varying the particle size 31 of the support - the inorganic oxide used in preparing the catalyst 32 composition should be one having a particle size that is suitable for 33 the production of a polymer having the desired particle size. In 34 general, optimum results are usually obtained by the use of inorganic oxides having an average particle size in the range of about 30 to 600 36 microns, preferably about 30 to lO0 microns; a surface area of about '~tj~ 5 - l5 -1 50 to l,000 square meters per gram, preferably about lO0 to 400 square 2 meters per gram; and a pore volume of about 0.5 to 3.5 cc per gram;
3 preferably about 0.5 to 2cc per gram.
4 The polymerization may be conducted by a solution, slurry, or gas-phase technique, generally at a temperature in the range of about 6 0-160C or even higher, and under atmospheric, subatmospheric, or 7 superatmospheric pressure conditions; and conventional polymerization 8 adjuvants, such as hydrogen may be employed if desired. It is 9 generally preferred to use the catalyst compositions at a concentra-tion such as to provide about O.OOOOOl - 0.005%, most preferably about 11 O.OOOOl - 0.0003%, by weight of transition metal based on the weight 12 of monomer(s), in the polymerization of ethylene, alone or with one or 13 more higher olefins.
14 A slurry polymerization process can utilize sub- or super-atmospheric pressures and temperatures in the range of 40-110C. In a 16 slurry polymerization, a suspension of solid, particulate polymer is 17 formed in a liquid polymerization medium to which ethylene, alpha-18 olefin comonomer, hydrogen and catalyst are added. The liquid 19 employed as the polymerization medium can be an alkane or cycloalkane, such as butane, pentane, hexane, or cyclohexane, or an aromatic hydro-21 carbon, such as toluene, ethylbenzene or xylene. The medium employed 22 should be liquid under the conditions of the polymerization and rela-23 tively inert. Preferably, hexane or toluene is employed.
24 A gas-phase polymerization process utilizes superatmospheric pressure and temperatures in the range of about 50-l20C. Gas-phase 26 polymerization can be performed in a stirred or fluidized bed of 27 catalyst and product particles in a pressure vessel adapted to permit 28 the separation of product particles from unreacted gases. Thermo-29 stated ethylene, comonomer, hydrogen and an inert diluent gas such as nitrogen can be introduced or recirculated so as to maintain the 31 particles at a temperature of 50-120C. Triethylaluminum may be 32 added as needed as a scavenger of water, oxygen, and other adventi-33 tious impurities. Polymer product can be withdrawn continuously or 34 semi-continuously at a rate such as to maintain a constant product inventory in the reactor. After polymerization and deactivation of 36 the catalyst, the prcduct polymer can be recovered by any suitable 37 means. In commercial practice, the polymer product can be recovered 38 directly from the gas phase reactor, freed of residual monomer with a i8 753 1 nitrogen purge, and used without further deactivation or catalyst 2 removal. The polymer obtained can be extruded into water and cut into 3 pellets or other suitable comminuted shapes. Pigments, anti-oxidants 4 and other additives, as is known in the art, may be added to the polymer.
6 The molecular weight of polymer product obtained in accor-7 dance with this invention can vary over a wide range, such as low as 8 500 up to 2,000,000 or higher and preferably l,000 to about 500,000.
9 Since, in accordance with this invention~ one can produce high viscosity polymer product at a relatively high temperature, 11 temperature does not constitute a limiting parameter as with the prior 12 art homogeneous metallocene/alumoxane catalysts. The catalyst systems 13 described herein, therefore, are suitable for the polymerization of 14 olefins in solution~ slurry or gas phase polymerizations and over a lS wide range of temperatures and pressures. For example, such 16 temperatures may be in the range of about -60C to about 280C and 17 especially in the range of about 0C to about 160C. The pressures 18 employed in the process of the present invention are those well known, 19 for example, in the range of about l to 500 atmospheres, however, higher pressures can be employed.
21 The polydispersites (molecular weight distribution) expressed 22 as Mw/Mn are typically from l.5 to 4.0 or greater. The polymers can 23 contain up to l.0 chain end insaturation per molecule.
24 The polymers produced by the process of this present invention are capable of being fabricated into a wide variety of 26 articles, as is known for homopolymers of ethylene and copolymers of 27 ethylene and higher alpha-olefins.
28 In a slurry phase polymerization, tile alumoxane co-catalyst, 29 preferably methyl alumoxane, is dissolved in a suitable solvent, typically in an inert hydrocarbon solvent such as toluene, xylene, and 31 the like in a molar concentration of about 5x10-3M. However, 32 greater or lesser amounts can be used.
33 The present invention is illustrated by the following 34 examples.
Examples 36 In the Examples following, the alumoxane employed was 37 prepared by adding 45.5 grams of ferrous sulfate heptahydrate in 4 38 equally spaced increments over a 2 hour period to a rapidly stirred 2 ~875;~
1 liter round-bottom flask containing l liter of a lO.0 wt. percent 2 solution of trimethylaluminum (TMA) in hexane. The flask was 3 maintained at 50C and under a nitrogen atmosphere. Methane produce 4 was continuously vented. Upon completion of the addition of ferrous sulfate heptahydrate, the flask was continuously stirred and 6 maintained at a temperature of 50 for 6 hours. The reaction mixture 7 was cooled to room temperature and allowed to settle. The clear 8 solution was separated from the solids by decantation. The aluminum 9 containing catalyst prepared in accordance with this procedure contains 35 mole percent of aluminum present as methylalumoxane and 65 11 mole percent of aluminum present as trimethylaluminum.
12 Molecular weights were determined on a Water's Associates 13 Model No. l50C GPC (Gel Permeation Chromatography). The measurements 14 were obtained by dissolving polymer samples in hot trichlorobenzene and filtered. The GPC runs are performed at l45C in trichlorobenzene i6 at l.0 ml/min flow using styragel columns from Perkin Elmer, Inc. 300 17 microliters of a 3.l% solution in trichlorobenzene were injected and 18 the samples were run in duplicate. The integration parameters were 19 obtained with a Hewlett-Packard Data Module.
~ Melt index data for the polyethylene products were determined 21 at l90C according to ASTM Method Dl238.
22 Cataly5t Preparation 23 Catalyst A
24 lO grams of a high surface area (Davison 952) silica, dehydrated in a flow of dry nitrogen at 600C for 5 hours was slurried 26 with 50 cc of dry toluene at 30C under nitrogen in a 250 cc 27 round-botto~ flask using a magnetic stirrer. O.lO0 grams 28 bis(cyclopentadienyl) zirconium dichloride dissolved in 25 cc of 29 toluene was added dropwise to the silica slurry over l5 minutes with constant stirring. The suspension was stirred for 2 hours at 30C and 31 allowed to settle. The excess toluene was decanted. The recovered 32 solids were washed with three lO cc portions of toluene and dried in 33 vacuum for 4 hours. Analysis of the supported catalyst indicated that 34 it contained 0.3l wt. percent zirconium.
Catalyst B
36 Catalyst B was prepared identically as in Catalyst A with the 37 exception that 250 mg of bis(cyclopentadienyl) titanium diphenyl was 38 substituted for the zirconocene of Catalyst A. Analysis of the ~'~68753 1 supported catalyst indicated that it contained 0.48 wt. percent 2 titanium.
3 Catalyst C
4 Catalyst C was prepared identically as in Catalyst A with the exception that 100 mg of bis(pentamethylcyclopentadienyl) zirconium 6 dichloride was substituted for the zirconocene of Catalyst A.
7 Analysis of the supported catalyst indicated that it contained 0.21 8 wt. % zirconium.
9 Catalyst D
Catalyst D was prepared identically as in Catalyst A with the 11 exception that 10.0 grams of gamma alumina was substituted for the 12 silica and 0.100 grams of bis(cyclopentadienyl) zirconium dichloride 13 was employed. The high surface area gamma aluminum (Strem Co.) had 14 been dehydrated in a flow of dry nitrogen at 600C for 5 hours prior to use. Analysis of-the supported catalyst indicated that it 16 contained 0.31 wt % zirconium.
17 CatalYst E
18 Catalyst E was prepared as in Catalyst A with the exception 19 that 100 mg of bis(methylcyclopentadienyl)zirconium dichloride was substituted for the zirconocene of Catalyst A. Analysis of the 21 supported catalyst indicated that it contained 0.29 weight percent 22 zirconium.
23 Polymerizations 24 Example 1 A l-liter stainless steel pressure vessel, equipped with an 26 incline blade stirrer, an external water jacket for temperature 27 control, a septum inlet and vent line, and a regulated supply of dry 28 ethylene and nitrogen, was dried and deoxygenated with a nitrogen 29 flow. 500 cc of dry, degassed toluene was introduced directly into the pressure vessel. 10.0 cc of 0.850 molar (in total aluminum) 31 alumoxane in toluene was injected into the vessel by a gas-tight 32 syringe through the septum inlet and the mixture was stirred at 1,200 33 rpms and 85C for 5 minutes at 0 psig of nitrogen. 25 mg of Catalyst A
34 was injected into the vessel with a nitrogen flow. After 1 minute, hydrogen at 40 psig and ethylene at 200 psig was admitted while the 36 reaction vessel was maintained at 85C. The ethylene was passed into 37 the vessel for 5 minutes at 200 psig at which time the reaction was 38 stopped by rapidly venting and cooling. 10.6 grams of powdery white 1;26~3753 ,9 1 polyethylene was recovered having a melt index of 0.35 grams/lO min.
2 Specific polyrnerization activity is defined as the weight of polymer 3 produced by a given weight of transition metal contained in a catalyst 4 per hour and per atmosphere of absolute monomer pressure. i.e., 5Specific activity = g polymer 6 gZr x hr x atmospheres of monomer 7For Example l, 8Specific activity = 10.6 9 9 7.8 x lO 5gZr x 0.083 hr x lO.9 10 = 150,200 g/gZr. hr. atm.
11 Example 2 12 A l-liter stainless steel pressure vessel, equipped with an 13 incline blade stirrer, an external water jacket for temperature 14 control, a septum inlet and vent line, and a regulated supply of dry ethylene and nitrogen, was dried and deoxygenated with a nitrogen 16 flow. 500 cc of dry, degassed toluene was introduced directly into 17 the pressure vessel. lO.0 cc of alumoxane (.850 mmoles in total , 18 àluminum) was injected into the vessel by a gas-tight syringe through 19 the septum inlet and the mixture was stirred at l,200 rpms and 85C
for 5 minutes at 0 psig of nitrogen. 25 mg of Catalyst A was injected 21 into the reactor with a nitrogen stream. After l minute~ lO0 22 milliliters of l-butene was added and the vessel was pressured to l35 1, 23 psig with ethylene. Ethylene flow was maintained for 6 minutes while 24 maintaining the reaction vessel at 85C. The results of the polymerization are summarized in Table I.
26 Example 3 27 The polymerization was performed identically as in Example l 28 with the exception that 25 milligrams of Catalyst B were substituted 29 for Catalyst A. The results of the polymerization are summarized in Table I.
31 Example 4 32 The polymerization was performed identically as in Example 2 33 with the exception that 40 milligrams of Catalyst B were substituted 34 for Catalyst A. The results of the polymerization are summarized in Table I.
1 Examples 5 and 6 2 The polymerizations for Examples 5 and 6 were performed 3 identically as in Example l and 2 respectively with the exception that 4 lO0 milligrams of Catalyst C were substituted for Catalyst A. The results of the polymerizations are summarized in Table I.
6 Examples 7 and 8 7 The polymerizations for Examples 7 and 8 were performed 8 identically as in Example 1 and 2 respectively with the exception that 9 the polymerization temperature was maintained at lO0C. The results of the polymerizations are summarized in Table I.
11 Examples 9 and lO
, .
12 The polymerizations for Examples 9 and lO were performed 13 identically as in Example l and 2 respectively with the exception that 14 Catalyst D was substituted for Catalyst A. The results of the polymerizations are summarized in Table I.
16 Example ll 17 The polymerization was performed identically as in Example l 18 with the exception that lO mg of Catalyst E was substituted for 19 Catalyst A. The results of the polymerization is summarized in Table l.
21 ExamPle l2 22 The polymerization was performed identically as in Example 4 23 with the exception that 2.14 mg of pure, unsupported bis(cyclopenta-24 dienyl)titanium diphenyl dissolved in lO cc toluene was substituted for the supported Catalyst B. The results are summarized in Table l.
26 Example l3 27 Catalyst Preparation 28 lO grams of a high surface area (Davison 952) silica, 29 dehydrated in a flow of dry nitrogen at 800C for 5 hours was slurried with 50 cc of dry toluene under a nitrogen flow at 50C in a 250 cc 31 rouhd-bottom flask using a magnetic stirrer. O.lO0 grams each of 32 bis(cyclopentadienyl) titanium diphenyl and bis(pentamethyl-33 cyclopentadienyl) zirconium dichloride dissolved together in 25 cc of 34 toluene were added to the silica slurry dropwise over lS minutes under constant stirring. The suspension was stirred at 50C for 2 hours, 36 upon settling the excess toluene was decanted. The metallocene 37 treated silica was washed by stirring and decantation with three lO cc l~tj87~
~ - 2l -1 portions of toluene and dried in vacuum for 4 hours. Analysis of the 2 supported catalyst indicated that it contained 0.23 weight percent 3 zirconium and 0.l4 weight percent titanium on silica.
4 Polymerization A l-liter stainless steel pressure vessel, equipped with an 6 incline blade stirrer, an external water jacket for temperature 7 control, a septum inlet and vent line, and a regulated supply of dry 8 ethylene in nitrogen, was dried and deoxygenated with a nitrogen 9 flow. 500 cc of dry, degassed toluene was introduced directly into the pressure vessel. lO cc of alumoxane solution (0.9l molar in total 11 aluminum) was injected into the vessel by a gas-tight syringe through 12 the septum inlet and the mixture was stirred at 1,200 rpms at lO0 for 13 5 minutes at 0 psig nitrogen. 20 mg of the silica supported 14 metallocene catalyst was injected into the vessel under a nitrogen flow. After l minute, hydrogen at 40 psig and ethylene at 200 psig 16 were admitted into the reaction vessel which was maintained at lO0C.
17 Ethylene was passed into the vessel for 3 minutes in order to maintain 18 the pressure. The reaction was stopped by rapidly venting and cooling 19 the reactor. 7.5 grams of powdery white polyethylene were recovered having a weight average molecular weight of 59,400, a number average 21 molecular weight of 3,300, a molecular weight distribution of l8.l.
22 The GPC showed a bimodal molecular weight distribution. The product 23 had a melt index of 25 grams/lO minutes and a density of 0.960 g/cc.
24 The specific activity was 280,000 g/g metal hr. atm..
ExamPle l4 26 Polymerization 27 A l-liter stainless steel pressure vessel, equipped with an 28 incline blade stirrer, an external water jacket for temperature 29 control, a septum inlet and vent line, and a regulated supply of dry ethylene in nitrogen, was dried and deoxygenated with a nitrogen 31 flow. 400 cc of dry, degassed toluene was introduced directly into 32 the pressure vessel. lO cc of alumoxane solution (0.9l molar in total 33 aluminum) was injected into the vessel by a gas-tight syringe through 34 the septum inlet and the mixture was stirred at 1,200 rpms at 92 for 5 minutes at 0 psig nitrogen. lO mg of the catalyst as prepared in 36 Example l3 were injected into the vessel under a nitrogen flow. After 37 l minute, hydrogen at 80 psig and ethylene at 400 psig were admitted 38 into the reaction vessel which was maintained at lO0C. Ethylene was 1 passed into the vessel for 16 minutes while maintaining the reaction 2 vessel at 92C. The reaction was stopped by rapidly venting and 3 cooling the reactor. 12.8 grams of powdery white polyethylene were 4 recovered having a weight average molecular weight of 196,500, a S number average molecular weight of 8,800, a molecular weight 6 distribution of 22.3. The GPC showed a bimodal molecular weight 7 distribution. The product had 'd melt index of 0.09 grams/10 minutes 8 and a density of 0.967 g/cc. The specific activity was 130,000 9/9 9 metal. hr. atm..
Example 15 11 Gas-Phase Polymerization 12 A 1-liter stain7ess stee7 pressure vessel, equipped with a 13 paddle-blade stirrer, an external water jacket for temperatùre 14 control, a septum inlet and vent line, and a regulated supply of dry ethylene in nitrogen, was dried and deoxygenated with a nitrogen flow.
16 40 grams palystyrene granules (10 mesh) were introduced into 17 the pressure vessel. S.0 cc of alumoxane (9 mmoles in total aluminum) 18 were injected into the vessel by a gas-tight syringe through the 19 septum inlet and the mixture was stirred at 1,200 rpms at 85C for 5 minutes at 0 psig of nitrogen. 100 milligrams of the prepared solid 21 catalyst described in Example 13 was injected into the vessel with 22 nitrogen flow. After 1 minute, ethylene at 150 psig was admitted for 23 40 minutes while maintaining the reaction vessel at 85C. The 24 reaction was stopped by rapid venting and cooling. 4.5 grams of powdery white polyethylene was recovered having a weight average 26 molecular weigl-t of 39,500, a number average molecular weight of 27 3,600, a molecular weight distribution of 11Ø The GPC showeda 28 bimodal molecular weight distribution. The polyethylene had a melt 29 index of 50 grams/10 minutes and a density of 0.960 grams per cc. The specific activity was 4,200 9/9 metal. hr. atm.
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1 titanium phenyl bromide, bis(cyclopentadienyl)titanium phenyl iodide, 2 bis(cyclopentadienyl)zirconium methyl bromide, bis(cyclopentadienyl)-3 zirconium methyl iodide, bis(cyclopentadienyl)zirconium ethyl bromide, 4 bis(cyclopentadienyl)zirconium ethyl iodide, bis(cyclopentadienyl)-zirconium phenyl bromide, bis(cyclopentadienyl)zirconium phenyl 6 iodide; the trialkyl metallocenes such as cyclopentadienyltitanium 7 trimethyl, cyclopentadienyl zirconium triphenyl, and cyclopentadienyl zirconium trineopentyl, cyclopentadienylzirconium trimethyl, cyclo-. 9 pentadienylhafnium triphenyl, cyclopentadienylhafnium trineopentyl, and cyclopentadienylhafnium trimethyl.
11 Illustrative, but non-limiting examples of II and III
12 metallocenes which can be usefully employed in accordance with this 13 invention are monocyclopentadienyls titanocenes such as, pentamethyl-14 cyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride, bis(pentamethylcyclopentadienyl) titanium 16 diphenyl, the carbene represented by the formula Cp2Ti=CH2 17 and derivatives of this reagent such as Cp~Ti=CH~ Al(CH3)3, 18 (Cp2TiCH2)2, and Cp2TiCH2CH(CH3)CH2, Cp2ti-CH2CH2CH2;
19 substituted bis(Cp)Ti(IV) compounds such as bis(indenyl)titanium diphenyl or dichloride, bis(methylcyclopentadienyl)titanium diphenyl 21 or dihalides; dialkyl, triaikyl, tetra-alkyl and pentaalkyl 22 cyclopentadienyl titanium compounds such as bis(l,2-dimethylcyclo-23 pentadienyl)titanium diphenyl or dichloride, bis(l,2-diethylcyclo-~4 pentadienyl)titanium diphenyl or dichloride and other dihalide com-plexes, silicon, phosphine, amine or carbon bridged cyclopentadiene 26 complexes, such as dimethyl silyldicyclopentadienyl titanium diphenyl 27 or dichloride, methyl phosphine dicyclopentadienyl titanium diphenyl 28 or dichloride, methylenedicyclopentadienyl titanium diphenyl or 29 dichloride and other dihalide complexes and the like.
Illustrative but non-limiting examples of the zirconocenes 31 of Formula II and III which can be usefully employed in accordance 32 with this invention are, pentamethylcyclopentadienyl zirconium tri-33 chloride, pentaethylcyclopentadienyl zirconium trichloride, the alkyl 34 substituted cyclopentadienes, such as bis(ethylcyclopentadienyl)-zirconium dimethyl, bis(~-phenylpropylcyclopentadienyl)zirconium 36 d-,methyl, bis(methylcyclopentadienyl)zirccnium dimethyl, bis(n-butyl-37 cyclopentadienyl)zirconium dimethyl, bis(cyclohexylmethylcyclopenta-38 dienyl)zirccnium dimethyl, bis(n-octyl-cyclopentadienyl)zirconium 687j3 - l4 -1 dimethyl, and haloalkyl and dihalide complexes of the above; dialkyl, 2 trialkyl, tetra-alkyl, and pentaalkyl cyclopentadienes, such as 3 bis(pentamethylcyclopentadienyl)zirconium diphenyl, bis(pentamethyl-4 cyclopentadienyl)zirconium dimethyl, bis(l,2-dimethylcyclopenta-dienyl)zirconium dimethyl and mono- and dihalide complexes of the 6 above, silicon, phosphorus, and carbon bridged cyclopentadiene 7 complexes such as dimethylsilyidicyclopentadienyl zirconium dimethyl, 8 methyl halide or dihalide, and methylene dicyclopentadienyl zirconium 9 dimethyl, methyl halide, or dihalide, carbenes represented by the formulae Cp?Zr=CH2P(C~H~)2CH3, and derivatives of these compounds 11 such as Cp2ZrCH2CH(CH3)CH2.
12 Bis(cyclopentadienyl)hafnium dichloride, bis(cyclopenta-13 dienyl)hafnium dimethyl, bis(cyclopentadienyl)vanadium dichloride and 14 the like are illustrative of other metallocenes.
The inorganic oxide support used in the preparation of the 16 catalyst may be any particulate oxide or mixed oxide as-previously 17 described which has been thermally or chemically dehydrated such that 18 it is substantially free of adsorbed moisture.
19 The specific particle size, surface area, pore volume, and number of surface hydroxyl groups characteristic of the inorganic 21 oxide are not critical to its utility in the practice of the 22 invention. However, since such characteristics determine the amount 23 of inorganic oxide that it is desirable to employ in preparing the 24 catalyst compositions, as well as affecting the properties of polymers formed with the aid of the catalyst compositions, these character-26 istics must frequently be taken into consideration in choosing an 27 inorganic oxide for use in a particular aspect of the invention. For 28 example, when the catalyst composition is to be used in a gas-phase 29 polymerization process - a type of process in which it is known that the polymer particle size can be varied by varying the particle size 31 of the support - the inorganic oxide used in preparing the catalyst 32 composition should be one having a particle size that is suitable for 33 the production of a polymer having the desired particle size. In 34 general, optimum results are usually obtained by the use of inorganic oxides having an average particle size in the range of about 30 to 600 36 microns, preferably about 30 to lO0 microns; a surface area of about '~tj~ 5 - l5 -1 50 to l,000 square meters per gram, preferably about lO0 to 400 square 2 meters per gram; and a pore volume of about 0.5 to 3.5 cc per gram;
3 preferably about 0.5 to 2cc per gram.
4 The polymerization may be conducted by a solution, slurry, or gas-phase technique, generally at a temperature in the range of about 6 0-160C or even higher, and under atmospheric, subatmospheric, or 7 superatmospheric pressure conditions; and conventional polymerization 8 adjuvants, such as hydrogen may be employed if desired. It is 9 generally preferred to use the catalyst compositions at a concentra-tion such as to provide about O.OOOOOl - 0.005%, most preferably about 11 O.OOOOl - 0.0003%, by weight of transition metal based on the weight 12 of monomer(s), in the polymerization of ethylene, alone or with one or 13 more higher olefins.
14 A slurry polymerization process can utilize sub- or super-atmospheric pressures and temperatures in the range of 40-110C. In a 16 slurry polymerization, a suspension of solid, particulate polymer is 17 formed in a liquid polymerization medium to which ethylene, alpha-18 olefin comonomer, hydrogen and catalyst are added. The liquid 19 employed as the polymerization medium can be an alkane or cycloalkane, such as butane, pentane, hexane, or cyclohexane, or an aromatic hydro-21 carbon, such as toluene, ethylbenzene or xylene. The medium employed 22 should be liquid under the conditions of the polymerization and rela-23 tively inert. Preferably, hexane or toluene is employed.
24 A gas-phase polymerization process utilizes superatmospheric pressure and temperatures in the range of about 50-l20C. Gas-phase 26 polymerization can be performed in a stirred or fluidized bed of 27 catalyst and product particles in a pressure vessel adapted to permit 28 the separation of product particles from unreacted gases. Thermo-29 stated ethylene, comonomer, hydrogen and an inert diluent gas such as nitrogen can be introduced or recirculated so as to maintain the 31 particles at a temperature of 50-120C. Triethylaluminum may be 32 added as needed as a scavenger of water, oxygen, and other adventi-33 tious impurities. Polymer product can be withdrawn continuously or 34 semi-continuously at a rate such as to maintain a constant product inventory in the reactor. After polymerization and deactivation of 36 the catalyst, the prcduct polymer can be recovered by any suitable 37 means. In commercial practice, the polymer product can be recovered 38 directly from the gas phase reactor, freed of residual monomer with a i8 753 1 nitrogen purge, and used without further deactivation or catalyst 2 removal. The polymer obtained can be extruded into water and cut into 3 pellets or other suitable comminuted shapes. Pigments, anti-oxidants 4 and other additives, as is known in the art, may be added to the polymer.
6 The molecular weight of polymer product obtained in accor-7 dance with this invention can vary over a wide range, such as low as 8 500 up to 2,000,000 or higher and preferably l,000 to about 500,000.
9 Since, in accordance with this invention~ one can produce high viscosity polymer product at a relatively high temperature, 11 temperature does not constitute a limiting parameter as with the prior 12 art homogeneous metallocene/alumoxane catalysts. The catalyst systems 13 described herein, therefore, are suitable for the polymerization of 14 olefins in solution~ slurry or gas phase polymerizations and over a lS wide range of temperatures and pressures. For example, such 16 temperatures may be in the range of about -60C to about 280C and 17 especially in the range of about 0C to about 160C. The pressures 18 employed in the process of the present invention are those well known, 19 for example, in the range of about l to 500 atmospheres, however, higher pressures can be employed.
21 The polydispersites (molecular weight distribution) expressed 22 as Mw/Mn are typically from l.5 to 4.0 or greater. The polymers can 23 contain up to l.0 chain end insaturation per molecule.
24 The polymers produced by the process of this present invention are capable of being fabricated into a wide variety of 26 articles, as is known for homopolymers of ethylene and copolymers of 27 ethylene and higher alpha-olefins.
28 In a slurry phase polymerization, tile alumoxane co-catalyst, 29 preferably methyl alumoxane, is dissolved in a suitable solvent, typically in an inert hydrocarbon solvent such as toluene, xylene, and 31 the like in a molar concentration of about 5x10-3M. However, 32 greater or lesser amounts can be used.
33 The present invention is illustrated by the following 34 examples.
Examples 36 In the Examples following, the alumoxane employed was 37 prepared by adding 45.5 grams of ferrous sulfate heptahydrate in 4 38 equally spaced increments over a 2 hour period to a rapidly stirred 2 ~875;~
1 liter round-bottom flask containing l liter of a lO.0 wt. percent 2 solution of trimethylaluminum (TMA) in hexane. The flask was 3 maintained at 50C and under a nitrogen atmosphere. Methane produce 4 was continuously vented. Upon completion of the addition of ferrous sulfate heptahydrate, the flask was continuously stirred and 6 maintained at a temperature of 50 for 6 hours. The reaction mixture 7 was cooled to room temperature and allowed to settle. The clear 8 solution was separated from the solids by decantation. The aluminum 9 containing catalyst prepared in accordance with this procedure contains 35 mole percent of aluminum present as methylalumoxane and 65 11 mole percent of aluminum present as trimethylaluminum.
12 Molecular weights were determined on a Water's Associates 13 Model No. l50C GPC (Gel Permeation Chromatography). The measurements 14 were obtained by dissolving polymer samples in hot trichlorobenzene and filtered. The GPC runs are performed at l45C in trichlorobenzene i6 at l.0 ml/min flow using styragel columns from Perkin Elmer, Inc. 300 17 microliters of a 3.l% solution in trichlorobenzene were injected and 18 the samples were run in duplicate. The integration parameters were 19 obtained with a Hewlett-Packard Data Module.
~ Melt index data for the polyethylene products were determined 21 at l90C according to ASTM Method Dl238.
22 Cataly5t Preparation 23 Catalyst A
24 lO grams of a high surface area (Davison 952) silica, dehydrated in a flow of dry nitrogen at 600C for 5 hours was slurried 26 with 50 cc of dry toluene at 30C under nitrogen in a 250 cc 27 round-botto~ flask using a magnetic stirrer. O.lO0 grams 28 bis(cyclopentadienyl) zirconium dichloride dissolved in 25 cc of 29 toluene was added dropwise to the silica slurry over l5 minutes with constant stirring. The suspension was stirred for 2 hours at 30C and 31 allowed to settle. The excess toluene was decanted. The recovered 32 solids were washed with three lO cc portions of toluene and dried in 33 vacuum for 4 hours. Analysis of the supported catalyst indicated that 34 it contained 0.3l wt. percent zirconium.
Catalyst B
36 Catalyst B was prepared identically as in Catalyst A with the 37 exception that 250 mg of bis(cyclopentadienyl) titanium diphenyl was 38 substituted for the zirconocene of Catalyst A. Analysis of the ~'~68753 1 supported catalyst indicated that it contained 0.48 wt. percent 2 titanium.
3 Catalyst C
4 Catalyst C was prepared identically as in Catalyst A with the exception that 100 mg of bis(pentamethylcyclopentadienyl) zirconium 6 dichloride was substituted for the zirconocene of Catalyst A.
7 Analysis of the supported catalyst indicated that it contained 0.21 8 wt. % zirconium.
9 Catalyst D
Catalyst D was prepared identically as in Catalyst A with the 11 exception that 10.0 grams of gamma alumina was substituted for the 12 silica and 0.100 grams of bis(cyclopentadienyl) zirconium dichloride 13 was employed. The high surface area gamma aluminum (Strem Co.) had 14 been dehydrated in a flow of dry nitrogen at 600C for 5 hours prior to use. Analysis of-the supported catalyst indicated that it 16 contained 0.31 wt % zirconium.
17 CatalYst E
18 Catalyst E was prepared as in Catalyst A with the exception 19 that 100 mg of bis(methylcyclopentadienyl)zirconium dichloride was substituted for the zirconocene of Catalyst A. Analysis of the 21 supported catalyst indicated that it contained 0.29 weight percent 22 zirconium.
23 Polymerizations 24 Example 1 A l-liter stainless steel pressure vessel, equipped with an 26 incline blade stirrer, an external water jacket for temperature 27 control, a septum inlet and vent line, and a regulated supply of dry 28 ethylene and nitrogen, was dried and deoxygenated with a nitrogen 29 flow. 500 cc of dry, degassed toluene was introduced directly into the pressure vessel. 10.0 cc of 0.850 molar (in total aluminum) 31 alumoxane in toluene was injected into the vessel by a gas-tight 32 syringe through the septum inlet and the mixture was stirred at 1,200 33 rpms and 85C for 5 minutes at 0 psig of nitrogen. 25 mg of Catalyst A
34 was injected into the vessel with a nitrogen flow. After 1 minute, hydrogen at 40 psig and ethylene at 200 psig was admitted while the 36 reaction vessel was maintained at 85C. The ethylene was passed into 37 the vessel for 5 minutes at 200 psig at which time the reaction was 38 stopped by rapidly venting and cooling. 10.6 grams of powdery white 1;26~3753 ,9 1 polyethylene was recovered having a melt index of 0.35 grams/lO min.
2 Specific polyrnerization activity is defined as the weight of polymer 3 produced by a given weight of transition metal contained in a catalyst 4 per hour and per atmosphere of absolute monomer pressure. i.e., 5Specific activity = g polymer 6 gZr x hr x atmospheres of monomer 7For Example l, 8Specific activity = 10.6 9 9 7.8 x lO 5gZr x 0.083 hr x lO.9 10 = 150,200 g/gZr. hr. atm.
11 Example 2 12 A l-liter stainless steel pressure vessel, equipped with an 13 incline blade stirrer, an external water jacket for temperature 14 control, a septum inlet and vent line, and a regulated supply of dry ethylene and nitrogen, was dried and deoxygenated with a nitrogen 16 flow. 500 cc of dry, degassed toluene was introduced directly into 17 the pressure vessel. lO.0 cc of alumoxane (.850 mmoles in total , 18 àluminum) was injected into the vessel by a gas-tight syringe through 19 the septum inlet and the mixture was stirred at l,200 rpms and 85C
for 5 minutes at 0 psig of nitrogen. 25 mg of Catalyst A was injected 21 into the reactor with a nitrogen stream. After l minute~ lO0 22 milliliters of l-butene was added and the vessel was pressured to l35 1, 23 psig with ethylene. Ethylene flow was maintained for 6 minutes while 24 maintaining the reaction vessel at 85C. The results of the polymerization are summarized in Table I.
26 Example 3 27 The polymerization was performed identically as in Example l 28 with the exception that 25 milligrams of Catalyst B were substituted 29 for Catalyst A. The results of the polymerization are summarized in Table I.
31 Example 4 32 The polymerization was performed identically as in Example 2 33 with the exception that 40 milligrams of Catalyst B were substituted 34 for Catalyst A. The results of the polymerization are summarized in Table I.
1 Examples 5 and 6 2 The polymerizations for Examples 5 and 6 were performed 3 identically as in Example l and 2 respectively with the exception that 4 lO0 milligrams of Catalyst C were substituted for Catalyst A. The results of the polymerizations are summarized in Table I.
6 Examples 7 and 8 7 The polymerizations for Examples 7 and 8 were performed 8 identically as in Example 1 and 2 respectively with the exception that 9 the polymerization temperature was maintained at lO0C. The results of the polymerizations are summarized in Table I.
11 Examples 9 and lO
, .
12 The polymerizations for Examples 9 and lO were performed 13 identically as in Example l and 2 respectively with the exception that 14 Catalyst D was substituted for Catalyst A. The results of the polymerizations are summarized in Table I.
16 Example ll 17 The polymerization was performed identically as in Example l 18 with the exception that lO mg of Catalyst E was substituted for 19 Catalyst A. The results of the polymerization is summarized in Table l.
21 ExamPle l2 22 The polymerization was performed identically as in Example 4 23 with the exception that 2.14 mg of pure, unsupported bis(cyclopenta-24 dienyl)titanium diphenyl dissolved in lO cc toluene was substituted for the supported Catalyst B. The results are summarized in Table l.
26 Example l3 27 Catalyst Preparation 28 lO grams of a high surface area (Davison 952) silica, 29 dehydrated in a flow of dry nitrogen at 800C for 5 hours was slurried with 50 cc of dry toluene under a nitrogen flow at 50C in a 250 cc 31 rouhd-bottom flask using a magnetic stirrer. O.lO0 grams each of 32 bis(cyclopentadienyl) titanium diphenyl and bis(pentamethyl-33 cyclopentadienyl) zirconium dichloride dissolved together in 25 cc of 34 toluene were added to the silica slurry dropwise over lS minutes under constant stirring. The suspension was stirred at 50C for 2 hours, 36 upon settling the excess toluene was decanted. The metallocene 37 treated silica was washed by stirring and decantation with three lO cc l~tj87~
~ - 2l -1 portions of toluene and dried in vacuum for 4 hours. Analysis of the 2 supported catalyst indicated that it contained 0.23 weight percent 3 zirconium and 0.l4 weight percent titanium on silica.
4 Polymerization A l-liter stainless steel pressure vessel, equipped with an 6 incline blade stirrer, an external water jacket for temperature 7 control, a septum inlet and vent line, and a regulated supply of dry 8 ethylene in nitrogen, was dried and deoxygenated with a nitrogen 9 flow. 500 cc of dry, degassed toluene was introduced directly into the pressure vessel. lO cc of alumoxane solution (0.9l molar in total 11 aluminum) was injected into the vessel by a gas-tight syringe through 12 the septum inlet and the mixture was stirred at 1,200 rpms at lO0 for 13 5 minutes at 0 psig nitrogen. 20 mg of the silica supported 14 metallocene catalyst was injected into the vessel under a nitrogen flow. After l minute, hydrogen at 40 psig and ethylene at 200 psig 16 were admitted into the reaction vessel which was maintained at lO0C.
17 Ethylene was passed into the vessel for 3 minutes in order to maintain 18 the pressure. The reaction was stopped by rapidly venting and cooling 19 the reactor. 7.5 grams of powdery white polyethylene were recovered having a weight average molecular weight of 59,400, a number average 21 molecular weight of 3,300, a molecular weight distribution of l8.l.
22 The GPC showed a bimodal molecular weight distribution. The product 23 had a melt index of 25 grams/lO minutes and a density of 0.960 g/cc.
24 The specific activity was 280,000 g/g metal hr. atm..
ExamPle l4 26 Polymerization 27 A l-liter stainless steel pressure vessel, equipped with an 28 incline blade stirrer, an external water jacket for temperature 29 control, a septum inlet and vent line, and a regulated supply of dry ethylene in nitrogen, was dried and deoxygenated with a nitrogen 31 flow. 400 cc of dry, degassed toluene was introduced directly into 32 the pressure vessel. lO cc of alumoxane solution (0.9l molar in total 33 aluminum) was injected into the vessel by a gas-tight syringe through 34 the septum inlet and the mixture was stirred at 1,200 rpms at 92 for 5 minutes at 0 psig nitrogen. lO mg of the catalyst as prepared in 36 Example l3 were injected into the vessel under a nitrogen flow. After 37 l minute, hydrogen at 80 psig and ethylene at 400 psig were admitted 38 into the reaction vessel which was maintained at lO0C. Ethylene was 1 passed into the vessel for 16 minutes while maintaining the reaction 2 vessel at 92C. The reaction was stopped by rapidly venting and 3 cooling the reactor. 12.8 grams of powdery white polyethylene were 4 recovered having a weight average molecular weight of 196,500, a S number average molecular weight of 8,800, a molecular weight 6 distribution of 22.3. The GPC showed a bimodal molecular weight 7 distribution. The product had 'd melt index of 0.09 grams/10 minutes 8 and a density of 0.967 g/cc. The specific activity was 130,000 9/9 9 metal. hr. atm..
Example 15 11 Gas-Phase Polymerization 12 A 1-liter stain7ess stee7 pressure vessel, equipped with a 13 paddle-blade stirrer, an external water jacket for temperatùre 14 control, a septum inlet and vent line, and a regulated supply of dry ethylene in nitrogen, was dried and deoxygenated with a nitrogen flow.
16 40 grams palystyrene granules (10 mesh) were introduced into 17 the pressure vessel. S.0 cc of alumoxane (9 mmoles in total aluminum) 18 were injected into the vessel by a gas-tight syringe through the 19 septum inlet and the mixture was stirred at 1,200 rpms at 85C for 5 minutes at 0 psig of nitrogen. 100 milligrams of the prepared solid 21 catalyst described in Example 13 was injected into the vessel with 22 nitrogen flow. After 1 minute, ethylene at 150 psig was admitted for 23 40 minutes while maintaining the reaction vessel at 85C. The 24 reaction was stopped by rapid venting and cooling. 4.5 grams of powdery white polyethylene was recovered having a weight average 26 molecular weigl-t of 39,500, a number average molecular weight of 27 3,600, a molecular weight distribution of 11Ø The GPC showeda 28 bimodal molecular weight distribution. The polyethylene had a melt 29 index of 50 grams/10 minutes and a density of 0.960 grams per cc. The specific activity was 4,200 9/9 metal. hr. atm.
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Claims (24)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An olefin polymerization supported catalyst comprising (a) the reaction product of a porous support with at least one metallocene of a metal of Group 4b or 5b of the Periodic Table (b) an alumoxane.
2. The olefin polymerization supported catalyst in accordance with claim 1 wherein the support is a porous inorganic metal oxide of a Group 2a, 3a, 4a or 4b metal.
3. The olefin polymerization supported catalyst in accordance with claim 2 wherein the support is silica.
4. The olefin polymerization supported catalyst in accordance with claim 1 wherein the at least one metallocene is selected from a titanium, zirconium, hafnium or vanadium metallocene or mixtures thereof.
5. The olefin polymerization supported catalyst in accordance with claim 4 wherein the metallocene is selected from a titanium or zirconium metallocene or mixtures thereof.
6. The olefin polymerization supported catalyst in accordance with claim 1 wherein the concentration of metallocene deposited on the support is in the range of about 0.001 to 5 mmoles per gram of support.
7. The olefin polymerization supported catalyst in accordance with claim 6 wherein the concentration is in the range of 0.01 to 2.
8. The olefin polymerization supported catalyst in accordance with claim 1 wherein the metallocene is represented by the formulas (I) (Cp)mMRnXq (II) (C5R'k)gR''s(C5R'k)MQ3-g and (III) R''s(C5R'k)2MQ' wherein Cp is a cyclopentadienyl ring, M is a Group 4b, 5b, or 6b transition metal, X is a halogen, R is a hydrocarbyl or hydrocarboxy group having from 1 to 20 carbon atoms, m=1-3, n=0-3, q=0-3 and the sum of m + n + q is sufficient to saturate M, (C5R'k) is a cyclopentadienyl or a substituted cyclopentadienyl; each R' is the same or different and is hydrogen or a hydrocarbyl radical selected from alkyl, alkenyl aryl, alkylaryl or arylalkyl radicals containing from 1 to 20 carbon atoms, or two carbon atoms are joined together to form a C4-C6 ring, R" is a C1-C4 alkylene radical, a dialkyl germanium or silicon or an alkyl phosphine or amine radical bridging two (C5R'k) rings; Q is a hydrocarbyl radical selected from aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radicals having from 1-20 carbon atoms, hydrocarboxy radical having from 1-20 carbon atoms or halogen and can be the same or different from each other, Q' is an alkylidiene radical having from 1 to about 20 carbon atoms; s is 0 or 1; g is 0, 1, or 2; s is 0 when g is 0; k is 4 when s is 1 and k is 5 when s is 0; and M is defined as above.
9. The olefin polymerization supported catalyst in accord-ance with claim 8 wherein the at least one metallocene is selected from bis(cyclopentadienyl)zirconium dichloride, bis(cyclopenta-dienyl)zirconium methyl chloride, bis(cyclopentadienyl)zirconium dimethyl, bis(methylcyclopentadienyl)zirconium dichloride, bis(methyl-cyclopentadienyl)zirconium methyl chloride, bis(methylcyclopenta-dienyl)zirconium dimethyl, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium methyl chloride, bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(n-butylcyclo-pentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)-zirconium methyl chloride, bis(n-butylcyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)titanium diphenyl, bis(cyclopenta-dienyl)titanium dichloride, bis(cyclopentadienyl)titanium methyl chloride, bis(cyclopentadienyl)titanium dimethyl, bis(methylcyclo-pentadienyl)titanium diphenyl, bis(methylcyclopentadienyl)titanium dichloride, bis(methylcyclopentadienyl)titanium diphenyl, bis-(methylcyclopentadienyl)titanium methyl chloride, bis(mechylcyclo-pentadienyl)titanium dimethyl, bis(pentamethylcyclopentadienyl)-titanium dichloride, bis(pentamethylcyclopentadienyl)titanium diphenyl, bis(pentamethylcyclopentadienyl)titanium methyl chloride, bis(pentamethylcyclopentadienyl)titanium dimethyl, bis(n-butylcyclo-pentadienyl)titanium diphenyl, bis(n-butylcyclopentadienyl)titanium dichloride and mixtures thereof.
10. The olefin polymerization supported catalyst in accord-ance with claim 1 comprising at least two different metallocenes each having different propagation rates and termination rate constants for ethylene-alphaolefins copolymerizations.
11. The olefin polymerization supported catalyst in accordance with claim 1 comprising at least two different metallocenes each having different reactivity ratios.
12. The olefin polymerization supported catalyst in accordance with claim 1 wherein the alumoxane is methylalumoxane.
13. A method for preparing polymers of ethylene and copolymers of ethylene and alpha-olefins or diolefins said method characterized in that the polymerization is effected in the presence of the olefin polymerization catalyst of claim 1.
14. A method for preparing polymers of ethylene and copolymers of ethylene and alpha olefins or diolefins said method characterized in that the polymerization is effected in the presence of the olefin polymerizaticn catalyst of claim 2.
15. A method for preparing polymers of ethylene and copolymers of ethylene and alpha olefins or diolefins said method characterized in that the polymerization is effected in the presence of the olefin polymerization catalyst of claim 3.
16. A method for preparing polymers of ethylene and copolymers of ethylene and alpha olefins or diolefins said method characterized in that the polymerization is effected in the presence of the olefin polymerization catalyst of claim 4.
17. A method for preparing polymers of ethylene and copolymers of ethylene and alpha olefins or diolefins said method characterized in that the polymerization is effected in the presence of the olefin polymerization catalyst of claim 5.
18. A method for preparing polymers of ethylene and copolymers of ethylene and alpha olefins or diolefins said method characterized in that the polymerization is effected in the presence of the olefin polymerization catalyst of claim 6.
19. A method for preparing polymers of ethylene and copolymers of ethylene and alpha olefins or diolefins said method characterized in that the polymerization is effected in the presence of the olefin polymerization catalyst of claim 7.
20. A method for preparing polymers of ethylene and copolymers of ethylene and alpha olefins or diolefins said method characterized in that the polymerization is effected in the presence of the olefin polymerization catalyst of claim 8.
21. A method for preparing polymers of ethylene and copolymers of ethylene and alpha olefins or diolefins said method characterized in that the polymerization is effected in the presence of the olefin polymerization catalyst of claim 9.
22. A method for preparing polymers of ethylene and copolymers of ethylene and alpha olefins or diolefins said method characterized in that the polymerization is effected in the presence of the olefin polymerization catalyst of claim 10.
23. A method for preparing polymers of ethylene and copolymers of ethylene and alpha olefins or diolefins said method characterized in that the polymerization is effected in the presence of the olefin polymerization catalyst of claim 11.
24. A method for preparing polymers of ethylene and copolymers of ethylene and alpha olefins or diolefins said method characterized in that the polymerization is effected in the presence of the olefin polymerization catalyst of claim 12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US74761685A | 1985-06-21 | 1985-06-21 | |
| US747,616 | 1985-06-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1268753A true CA1268753A (en) | 1990-05-08 |
Family
ID=25005886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000511354A Expired CA1268753A (en) | 1985-06-21 | 1986-06-11 | Supported polymerization catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1268753A (en) |
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| US6111027A (en) * | 1997-10-01 | 2000-08-29 | Exxon Chemical Patents, Inc | Adhesives comprising copolymers of macromonomers and unsaturated acids or anhydrides |
| US6153551A (en) | 1997-07-14 | 2000-11-28 | Mobil Oil Corporation | Preparation of supported catalyst using trialkylaluminum-metallocene contact products |
| US6291611B1 (en) | 1993-11-05 | 2001-09-18 | Borealis Holding A/S | Supported olefin polymerization catalyst, its preparation and use |
| US6303688B1 (en) | 1995-09-22 | 2001-10-16 | Exxon Mobil Chemical Patents Inc. | Rubber toughened blends |
| US6383439B1 (en) | 1996-08-21 | 2002-05-07 | Exxonmobil Chemical Patents Inc. | Chemically modified elastomers and blends thereof |
| US6403743B1 (en) | 1999-09-14 | 2002-06-11 | Exxonmobil Chemical Patents Inc. | Petroleum resins and their production with supported catalyst |
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| WO2004046214A2 (en) | 2002-10-15 | 2004-06-03 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
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