CA1258061A - Polymerization catalyst, production and use - Google Patents
Polymerization catalyst, production and useInfo
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- CA1258061A CA1258061A CA000487742A CA487742A CA1258061A CA 1258061 A CA1258061 A CA 1258061A CA 000487742 A CA000487742 A CA 000487742A CA 487742 A CA487742 A CA 487742A CA 1258061 A CA1258061 A CA 1258061A
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Abstract
Abstract of the Disclosure Ethylene and alpha-olefins are homopolymerized or copolymer-ized with another olefin monomer in the presence of a catalyst system comprising an organo metal cocatalyst and a titanium-containing catalyst component, said titanium-containing catalyst component being obtained by reacting together a porous particulate material, an organic magnesium compound, an oxygen-containing compound, an acyl halide, titanium tetrachloride and Cl2, Br2 or an interhalogen compound and treating the solids with an organometallic compound of a Group IIa, IIb or IIIa metal.
Description
4 This invention rela~es to a novel cata1yst component to be employed with a cocatalyst for use in the polymerization of olefins to 6 polyolefins such as polyethylene, polypropylene and the like, or 7 copolymers such as ethylene copolymers with other alpha-olefins and 8 diolefins, which catalyst component imparts unusually high activity 9 and improved comonomer response and the polymer product obtained has a 'O desirable bulk density. The catalyst component is especially useful 11 for the production of linear polyethylenes such as high density and 12 l,near low density polyethylene. The polymer product obtained evi-13 dences an important balance of polymer properties, for example, the 14 catalyst system obtains a polymer with a narrow molecular weight distribution and an improved balance in polymer product machine direc-16 tion tear strength and transverse direction tear strength. As a 17 result, the film blown from resin produced from the catalyst manifests 18 an overall high strength.
19 The catalyst component comprises a solid reaction product obtaired by contacting a solid, particulate, porous support material 21 such as, for example, silica, alumina, magnesi~ or mixtures thereof, 22 for example, silica-alumina, in stages with an acyl halide, a tran-23 sition metal compound, an organometallic composition treated with an24 alcohol, a halogen containing compound, halogen or interhalogen and prereducing the solid in the presence of an organoaluminum compound.
26 The novel catalyst component, which when used with an aluminum alkyl 27 cocatalyst, provides the novel catalyst system of this invention which 28 can be usefully employed for the polymerization of olefins.
29 The catalyst system can be emp10yed in slurry, single-phase melt, solution or gas-phase polymerization processes and is particu-31 larly effective for the production of linear polyethylenes such as 32 high density polyethylene and linear low density polyethylene.
33 Recently, interest has arisen in the use of magnesium-34 titanium complex catalyst components for the polymerization of olefins. For e~ample, European Patent Application 27733, published 36 April 29, 1981 discloses a catalyst component obtained by reducing a 1 transition metal compound with an excess of organomagnesium compo~nd
19 The catalyst component comprises a solid reaction product obtaired by contacting a solid, particulate, porous support material 21 such as, for example, silica, alumina, magnesi~ or mixtures thereof, 22 for example, silica-alumina, in stages with an acyl halide, a tran-23 sition metal compound, an organometallic composition treated with an24 alcohol, a halogen containing compound, halogen or interhalogen and prereducing the solid in the presence of an organoaluminum compound.
26 The novel catalyst component, which when used with an aluminum alkyl 27 cocatalyst, provides the novel catalyst system of this invention which 28 can be usefully employed for the polymerization of olefins.
29 The catalyst system can be emp10yed in slurry, single-phase melt, solution or gas-phase polymerization processes and is particu-31 larly effective for the production of linear polyethylenes such as 32 high density polyethylene and linear low density polyethylene.
33 Recently, interest has arisen in the use of magnesium-34 titanium complex catalyst components for the polymerization of olefins. For e~ample, European Patent Application 27733, published 36 April 29, 1981 discloses a catalyst component obtained by reducing a 1 transition metal compound with an excess of organomagnesium compo~nd
2 in the presence of a support ~uch as silica and thereafter
3 deactivating the excess organo~agnesium compound with certain
4 deactivators including hydrogen chloride.
S U.SO Patent No. 4,136,058 discloses a cata7yst component 6 comprising an organomagnesium compound and d transition metal halide 7 compound, which catalyst component is thereafter deactivated with a 8 deactivating agent such as hydrogen chloride. This patent does not 9 teach the use of support material such as silica, but otherwise the la disclosure is similar to the above-discussed European paten~ applica-1 1 tionO
12 U.S. Pa~ent NoO 4,250,288 discloses a catalyst which is the 13 reaction product of a transition metal compound, an organomagnesium 14 component, and an active non-metallic halide such as HCl and organic halides containing a labile halogen. The ca~alyst reaction product 16 also contains some aluminum a1kyls.
17 Catalyst components comprising the reaction product ~f an 18 aluminum alkyl-magnesium alkyl complex plus titanium halide are d~s-lg closed in U.S~ Patent No. 4,0049071 and U.S. Patent No. 4,276,191.
U.S. Patent No. 4,173,547 and U.S. Patent No. 4,263,171, 21 respectively disclose a catalyst component comprising silica, an 22 aluminum-type titanium trichl~ride and dibutyl-magnesium and a 23 catalyst component comprising a magnesium alkylaluminum a~kyl complex 24 plus titanium halide on a silica support.
The use of chlorine gas in polymerization processes is taught 26 in U~S~ P~tent No~ 4,267,292 wherein it is disclosed that chlorine gas 27 is to be added to the polymerization reactor after polymerizat~on has 28 been initiated in the presence of a Ziegler catalyst. U.S. Patent No.
29 4,248,735 teaches subjecting a silica support to a treatment with bromine or iodine and thereafter incorporating a chromium compound 31 onto the support. U.S. Patent No. 3,513,150 discloses the treatment 32 of gamma alumina plus titanium tetrachloride with a yaseous chlori-33 nating agent and employing said treated material in combination with a 34 cocatalyst for the polymerization of ethylene.
European patent application 32,308 published July 36 22/81 discloses polymerizing ethylene in the presence of 37 a catalyst system comprising an organic metal compound and 38 a titanium-containing material which is obtained by reacting together an inert particulate material, an organic magnesium ?6:~
l compound, d titanium compound and a halogen containing compound such 2 d5 SiC14, PC13, 8C13, C12 and the like.
3 Each of U.S. 4,402,861, 4,378,304, 4,388,220, 4,301,029 and 4 4,385,161 disclose supported catalyst systems comprising an oxide support such d5 Si1iCd, an organomagnesium compound, a transition 6 meta7 comp~und and one or more catalyst co~ponent modifiers. These 7 patents do not disclose the catalyst of this invention.
8 In British 2,101,610 silica is treated with a magnesium 9 alkyl, an alcohol benzoyl chloride and TiC14. In each of 1~ Japanese Kokai 56-098206 published Aug. 7/81 and 57-070107 11 published April 30/82 acyl halides are employed during the 12 preparation of titanium supported catalysts.
13 The catalyst systems comprising magnesium alkyls and titanium ~ compounds, a~though generally usefùl for the po1ymerization of olefins such as ethylene and other l-olefins, do not show excellent respon-16 siveness to hydrogen during the polymerizdtion reaction for the 17 control of ~olecul~r weight, do not readily incorporate comonomers 18 such as butene-l for the production of ethylene copolyrners, do not 19 show an extremely high catalytic activity and obtain polymer product whose film properties are unbalanced under anisotropic conditions.
21 I~ U.S. Patent 4,451,574 issued May Z9, 1984, a catalyst 22 system obtained by treating an inert particula$e support, such dS
23 silica, with an organometallic compound, a titanium halide and a 24 halogen gas is disclosed. Although the catalyst obtains very high ac~civities, there is a need for improving the film properties of 26 poly~er product obtained by polym~rizing o~efins in the presence of 27 the catalyst and to improve the bulk density of polymer 28 product.
29 In our copending Canadian application serial nu~ber 487,246 filed July 22, 1985, we disclosed a 31 transition metal supported catalyst component obtained by 32 contacting an inert solid support with (a) the reaction 33 product of a dialkyl magnesium compound and an alcohol, 34 (b) an acyl halide, (c) TiC14, and (d) C12. In copending Canadian application serial number 487,479 filed 36 July 25, 1985, there is disclosed a transition metal 37 supported catalyst component obtained by contact:ing an 38 inert so1id support with (a) the reaction product of "~, 1 1 a dialkyl magnesium compound and an oxygen-containing 2 compound, (b) a transition metal halide such as TiC14, 3 (c) C12 and treating the resultant solid with an organo-4 m~tallic compound of a Group IIa, IIb or IIIa metal.
1 ~
~2 1 In accordance with this invention catalyst combinations have 2 been ~ound which have very high catalytic activities and excellent 3 hydrogen responsiveness for the control of molecular weight, excellent comonomer response and obtain polymer product with greatly improved film properties. The resins exhibit excellent melt strength along 6 with a decrease in extrusion power consumption9 resulting in increased 7 bubble stability in blown film production. In addition, the resins 8 exhibit an increase in extrusion rates. The invention is 9 distinguished over our copending application in that the catalyst of this invention unexpectedly obtains an improvement in catalytic 11 activity and the polymers produced therefrom have unexpectedly 12 improved bulk density.
13 The new catalyst components of this invention are obtained by 14 contacting an organometallic compound, an oxygen-containing compound such as a ketone, aldehyde, siloxane or alcohol, an acyl halide, a 16 transition metal compound, a halogen or interhalogen compound in the 17 presence of a oxide support and treating the obtained solid with an 18 organometall;c compound of a Group IIa, IIb or IIIa me-tal such as, for 19 example, an aluminum alkyl. The catalyst system comprising the tran-sition metal-containing catalyst component and an organoaluminum 21 cocatalyst is advantageously employed in a gas phase ethylene poly-22 merization process since there is a decrease in reactor fouling as 23 generally compared with catalytic prior art ethylene gas phase 24 polymerization processes thereby resulting in less frequent reactor shut downs for cleaning purposes.
26 Summary of the Invention 27 In accordance with the objectives of this invention there is 28 provided a transition metal-containing catalyst component for the 29 polymerization of alph~-olefins comprising a solid reaction product obtained by treating an inert solid support material in an inert 31 solvent with (A) an organometallic compound of a Group IIa, IIb or 32 IIIa metal of the Periodic Table wherein all the metal valencies are 33 satisfied with a hydrocarbon or substituted hydrocarbon group, (B) an 34 oxygen-containing compound selected from ketones, aldehydes, alcohols, siloxanes or mixtures thereof, (C) an acyl halide, (D) at least one 36 transition metal compound of a Group IVb, Vb, VIb or VIII metal of the 37 Periodic Table, (E) C12, Br2 or an interhalogen, and (F) treating 33 the transition metal-containing product w-ith an organometallic ~5~
1 compound of d Group Ila, lIb, or IIIa metal, with the proviso that the 2 (A) and (B) ingredients can be employed (i) simultaneously, (ii) as 3 the reaction product of (~) and (B), or (iii) treatment with (B) 4 immediately preceeds treatment with (A).
The solid transition metal-containing catalyst comp~nent when 6 employed in combination with a cocatalyst such as an alkyl aluminum 7 cocatalyst provides a catalyst system which demonstrates a number of 8 uninue properties that are of great importance in olefin polymeriza-9 tion technology such asa for example, extremely high catalytic activity, the ability to control the molecular weight during the 11 polymerization reaction as d result of the improved responsiveness to 12 hydrogen, improved comonomer response, increased polymer yield, and 13 reduced reactor foulingO A particular advan$age of the instant inven-14 tion is the ability of catalytically producing polymer product having improved bulk density.
16 In a preferred embodiment of the invention the (A) organo-17 metallic compound is a dihydrocarbyl magnesiurn compound represented by 18 RlMgR2 wherein Rl and R2 which can be the same or different 19 are selected from alkyl groups, aryl groups, cycloalkyl groups, aral-kyl groups, alkadienyl groups or alkenyl groups having from 1 to 20 21 carbon atoms, the (B) oxygen-containing compounds are selected from 22 alcohols and ketones represented by the formula R30H and R4CoR5 23 wherein R3 and each of R4 and R5 which may be the same or dif-24 ferent can be an alkyl group, aryl group, cycloalkyl group, aralkyl group, alkadienyl group or alkenyl group having from 1 to 20 carbon 26 atoms, the (C) acyl halide is represented by the formula R6COX
27 wherein R6 can be a Cl-C20 alkyl group, cycloalkyl group or aryl 28 group and X is halogen, the (D) transition metal compound is prefer-29 ably a transition meta~ compound or combination oF transition metal compounds represented by the Formulas TrX"4 q(OR8)q, 31 TrX"4 qRq, VO(OR )3 and VOX"3 ~herein Tr is a transition 32 metal of Groups IVb, Vb, VIb, and VIII and preferably titanium, 33 vanadium or zirconium, R8 is an alkyl group, aryl group, aralkyl 34 group, or substituted aralkyl group having from 1 to 20 carbon atoms and 1,3-cyclopentadienyls, X" is halogen and q is zero or a number 36 less than or equal to 4, and R9 is an alkyl group, aryl group or 37 aralkyl group having from 1-20 carbon atoms or a 1,3-cyclopentadienyl, 38 the (E) halogen is C12 and the (F) organometallic compound is an ~2~
1 aluminum alkyl represented by RnAlX'3 n wherein X' is a 2 halogen9 or hydride and R7 is a hydrocarbon group selected from 3 alkyl group, aryl group, cycloalkyl ~roup, aralkyl group, alkadienyl 4 grolJp or alkenyl group having from 1 to 20 carbon atoms and 1 ' n ~ 3.
All references to the Periodic Table are to the Periodic 6 Table of the Elements printed on page B-3 of the 56th Edition o~
7 Handbook of Chemistry and Physics, CRC Press (1975).
8 The catalyst component forming ingredien~s can be added in any 9 order to the support material (with the exception of (F) which must be last) in preparing the transition metal-containing catalyst component, 11 for example:
12 (B), (A), (C), (D), (E) and (F) 13 (A+B), (C), (D), (E) and (F) 14 (A~B), (C), (D), (E) and (F) (E), (B), (A), (C), (D) and (F) 16 (E), (A-~B), (C), (D) and (F) 17 (E), (A&B), (C), (D) and (F) 18 (C), (B), (A), (E), (D) and (F) 19 (C), (A~B), (E), (D) and (F) (C), (A&B), (E), (D) and (F) 21 (D), (C), (B), (A), (E) and (F) 22 (D), (C), (A+B), (E) and (F) 23 (D), (C), (A&B), (E) and (F) 24 (D), (E), (B), (A), (C) and (F) (D), (E), (A+B), (C) and (F) 26 (D), (E), (A~B), (C) and (F) 27 (D), (B), (A), (C), (E) and (F) 23 (D), (A~B), (C), (E) and (F) 29 (D), (A&B), (C), (E) and (F) (D), (B), (A), (E), (C) and (F) 31 (D), (A~B)9 (E), (C) and (F) 32 (D) 9 (A&B), (E), (C) and (F) 33 (B), ~A), (E), (D), (C) and (F) 34 (B+A), (E), (D), (C) and (F) (B&A), (E), (D), (C) and (F) 36 (B), (A), (C), (E), (D), and (F) 37 (B+A), (C), (E), (D), and (F) 1 (B~A), (C)9 (E), (D), and (F) 2 (B)~ (A), (E), (C), (D), and (F) 3 (B~A), (E)9 (C), (D), and (F) 4 (B~A)9 (E)9 (C), (D)9 and (F) and the like. In the above, (A+B) represents the reaction product of 6 (A) and (B) and (A&B) represents the simultaneous addition of (A) and 7 (B) to the reacting system.
8 Of the possible order of additions the preferred are (A+B), 9 (C), (D), (E) and (F); (E), (A+B), (C)~ (D) and (F); (A-~B)9 (E)9 (C), (D)9 and (F); or (C), (A-~B), (E), (D) and (F). More preferred are 11 (E), (A+B~, (C)9 (D) and (F); (A+B, (E), (C3, (D)9 and (F); or (A+B), 12 (C), (D), (E) and (F). The transition metal-containing catalyst 13 component especially preferred is prepared by first treating the 14 inert solid su~port with (E) C12, Br2 or an interhalogen or mixtures thereof followed by treatment with the reaction product of 16 (A) the organometallic compound with (B) the oxygen-containing 17 compound ancl thereafter treating the solid with the (C) acyl halide 18 followed by treatment with the (D) transition metal compound and 19 prereducing with (F).
In a second embodiment of this invention there is provided a 21 catalyst system comprising the transition metal-containing solid 22 catalyst component and an organoalum;num cocatalyst for the polymer-23 ization of alpha-olefins using the catalyst of this invention under 24 conditions characteristic of Ziegler polymerization.
In view of the high activity of the catalyst system prepared 26 in accordance with this invention as compared with conventional 27 Ziegler catalysts, it is generally not necessary to deash polymer ~8 product since polymer product will generally contain lower amounts of 29 catalyst residues than polymer product produced in the presence of conventional catalysts.
31 The catalyst system can be employed in a gas phase process, 32 single phase melt process, solvent process or slurry process. The 33 catalyst system is usefully employed in the polymerization of ethylene 34 and other alpha-olefins, particularly alpha-olefins having from 3 to 8 carbon atoms and copolymerization of these with other l-olefins or 36 diolefins having from 2 to 20 carbon atoms, such as propylene, butene, 37 pentene, hexene, butadiene9 1,4-pentadiene and the like, so as to form 38 copolymers of low and medium densities. The supported catalyst system 1 is particularly useful For the polymerization of ethylene and copoly-2 merization of ethylene with other alpha-olefins in gas phase processes.
3 Description of the Preferred Embodiments .
4 Briefly, the catalyst components of the present invention comprise the so7id reaction product obtained by contacting a solid 6 support material with (A) an organometallic composition, (B)-an 7 oxygen-containing compound, (C) an acyl halide~ (D) at least one 8 transition metal compound, (E) halogen or interhalogen compound which 9 is treated with (F~ an organometallic compound of a Group IIai IIb, IIIa metal, with the proviso that the (A) and (B) ingredients can be 11 added to the inert solid (i) simulaneously, (ii) as the reaction 12 product of (A) and (B), or (iii) treatment with (B) immediately 13 precedes treatment with (A).
14 The transition metal-containing catalyst component of this invention is preferably obtained by treating the inert solid support 16 material in an inert solvent in the steps selected from the group 17 consisting of 18 (a) first treating with ingredient (E) followed by 19 sequential treatment with ingredients (A), (B)~ (C), (D), and (F), (b) first treating with ingredients (A) and (B) followed by 21 the sequential treatment with ingredients (C), (D), (E), and (F), 22 or 23 (c) First treating with ingredient (C) followed by the 2~ sequential treatment with ingredients (A) and (B), (E), (D), and (F) 26 (d) first treating with ingredients (B) and (A) followed by 27 the sequential treatment with inyredients (E), (C), (D), and (F) 28 with the further proviso that the (A) and (B) ingredients can be added 2g (i) simultaneously, (ii) as the reaotion product o~ (A) and (B), or (iii) treatment with (B) immediately precedes treatment with (A).
31 Preferably, the transition metal-containing catalyst 32 component of this invention is obtained by (I) treating the inert 33 solid support material in an inert solvent with ingredient (E) 34 followed by sequential treatment with ingredients (A), (B), (C), (D), and (F) and that the (A) and (B) ingredients can be added (i) 36 simultaneously, (ii) as the reaction product of (A) and (B), or (iii) 37 treatment with (B) immediately precedes treatment with (A); or 6~
g 1 (~I) wherein the solid reaction product is obtained by 2 treating inert solid support material in an inert solvent with 3 ingredients (A) and (B), followed by sequential treatmen with 4 ingredients (C)~ (D), (E), and (F) and with the further proviso that the (A) and (B3 ingredients can be added to the inert solid (i) 6 simultaneously5 (ii) as the reaction product of (A) and (B),-or (iii) 7 treatment of the inert solid with (B) immediately precedes treatlnent 8 with (A). The method (I) is especially pre~erred.
9 According to the polymerization process of this invention, ethylene, at least one alpha-olefin having 3 or more carbon atoms or 11 ethylene and other olefins or diolefins having terminal unsaturation 12 are contacted with the catalyst under polymerizing conditions to form 13 a commercially useful polymeric product. Typically, the support can 14 be any of the solid particulate porous supports such as talc, zirconia, thoria, magnesia, and titania. Preferably the support 16 materia1 is a Group IIa, IIIa, IVa and I~b metal oxide in finely 17 divided form.
18 Suitable inorganic oxide materials which are desirably 19 employed in accordance with this invention include Group IIa, IIla, or IVa or IVb metal oxides such as silica, alumina, and silica-alumina 21 and mixtures thereof. Other inorganic oxides that may be employed 22 either alone or in combination with silica, alumina or silica-alumina 23 are magnesia~ titania, zirconia, and the like. Other suitable support 24 materials, however, can be employed, for example, finely divided polyolefins such as finely divided polyethylene.
26 The metal oxides generally contain acidic surface hydroxyl 27 groups which will react with the organometallic composition or transi-28 tion metal compound first added to the reaction solvent. Prior to 29 use, the inor~anic oxide support is dehydrated, i.e., subjected to a thermal treatment in order to remove water and reduce the 31 concentration of the surface hydroxyl groups. The treatment is 32 carried out in vacuum or while purging with a dry inert gas such as 33 nitrogen at a temperature of about 100 to about 1000C, and 34 preferably from about 300C to about 800~C. Pressure considerations are not critical. The duration of the thermal treatment can be from 36 about 1 to about 24 hours. However, shorter or longer times can be 37 employed provided equilibrium is established with the surface hydroxyl 38 groups.
~25~
1 Chemical dehydration as an alternative method of dehydration 2 of the metal oxide support material can advantageously be employed.
3 Chemical dehydration converts all water and hydroxyl groups on the 4 oxide surface to inert species. Useful chemical agents are, for example, SiC14, chlorosilanes, such as trimethylchlorisilane, 6 dimethyldichlorosilane, silylamines, such as hexamethyldisila~ane and 7 dimethylaminotrimethylsilane and the like. The chemical dehydration 8 is accomplished by slurrying the inorganic particulate material, such 9 as, for example, silica in an inert low boiling hydrocarbon, such as, for example, hexane. During the chemical dehydration reaction, the 11 silica should be maintained in a moisture and oxygen-free atmosphere.
12 To the silica slurry is then added a low boiling inert hydrocarbon 13 solution of the chemical dehydrating agent, such as, for example, 14 dichlorodimethylsilane. The solution is added slowly to the slurry.
The temperature ranges during chemical dehydration reaction can be 16 from about 25C to about 120C, however, higher and lower temperatures 17 can be employed. Preferably the temperature will be about 50C to 18 about 70C. The chemical dehydra-tion procedure should be allowed to 19 proceed until all the moisture is removed from the particulate support material, as indicated by cessation of gas evolution. Normally, the ~1 chemical dehydration reaction will be allowed to proceed from about 30 22 minutes to about 16 hours, preferably 1 to 5 hours. Upon completion 23 of the chemical dehydration, the solid particulate material is fil-24 tered under a nitrogen atmosphere and washed one or more times with a 25 dry, oxygen free inert hydrocarbon solvent. The wash solvents, as 26 well as the diluents employed to form the slurry and the solution of 27 chemical dehydrating agent, can be any suitable inert hydrocarbon.
28 Illustrative of such hydrocarbons are heptane, hexane, toluene, iso-29 pentane and the like.
The preferred (A) organometallic compounds employed in this 31 invention are the inert hydrocarbon soluble organomagnesium compounds 32 represented by the formula RlMgR2 wherein each of Rl and R2 33 which may be the same or different are alkyl groups, aryl groups, 34 cycloalkyl groups, aralkyl groups, alkadienyl groups or alkenyl groups. The hydrocarbon groups Rl or R can contain between 1 and 36 20 carbon atoms and preferably from 1 to about 10 carbon atoms.
37 Illustrative but non~limiting examples of magnesium compounds which 38 may be suitably employed in accordance with the invention are dialkyl-1 magnesiums such as diethylmagnesium, dipropylmagnesium, di-isopropyl-2 magnesium, di-n-butylmagnesium, di-isobutylmagnesium, diamylmagnesium, 3 di-n~octylmagnesium, di-n-hexylmagnesium, di-n-decylmagnesium, and 4 di-n-dodecylmagnesium; dicycloalkylmagnesiums, such as dicyclohexyl-magnesium; diaryl magnesiums such as dibenzylmagnesium, ditolylmag-6 nesium and dixylylmagnesium and the like. -7 Preferably the organomagnesium compounds will have from 1 to 8 6 carbon atoms and most preferably ~1 and R2 are different.
9 Illustrative examples of the preferred magnesium compounds are are ethyl-n-propylmagnesium, ethyl-n-butylmagnesium, amyl-n-hexylmag-11 nesium, n-butyl-s-butylmagnesium, n-butyl-n-octylmagnesium, and the 12 like. Mixtures of hydrocarbyl magnesium compounds may be suitably 13 employed such as for example di-n-butylmagnesium and ethyl-n-butyl-14 magnesium.
The magnesium hydrocarbyl compounds are generally obtained 16 from commercial sources as mixtures of the magnesium hydrocarbon 17 compounds with a minor amount of aluminum hydrocarbyl compound. The 18 minor amount of aluminum hydrocarbyl is present in order to facilitate 19 solublization and/or reduce the viscosity of -the organomagnesium compound in hydrocarbon solvent. The hydrocarbon solvent usefully 21 employed for the organomagnesium can be any of the well known hydro-22 carbon liquids, for example hexane, heptane, octane, decane, dodecane, 23 or mixtures thereof, as well as aromatic hydrocarbons such as benzene, 24 toluene, xylene, etc.
The organomagnesium complex with a minor amount of aluminum 26 alkyl can be represented by the formula (RlMgR2)p(R~oAl)s wherein 27 R1 and R2 are defined as above, R10 is defined as R and R and p is 28 greater than 0. The ratio of s/s+p is from O to 1, preferably from O
29 to about 0.7 and most desirably from about O to 0.1.
Illustrative examples of the organomagnesium-organoaluminum 31 complexes are [(n-C4Hg)(C2H5)M9][(c2H5)3Al]0.o2s 32 [(n-C4H9)2Mg][(c2Hs)3Al]o 013~ [(n~c4~l9)2 g][( 2 5 3 2.0 [( C6H13)2M9][(C2H5)3A130.01. A SUitable magnesium_alum;num 34 complex is Magala~ BEM manufactured by Texas Alkyls, Inc.
The hydrocarbon soluble organometallic compositions are known 36 ma-terials and can be prepared by conventional methods. One such 37 method involves, for example, the addition of an appropriate aluminum 38 alkyl to a solid dialkyl magnesium in the presence of an inert hydro-l carbon solvent. The ~rganomagnesium-argdnoaluminum compl~xes are, for 2 example, described in U.S. Patent No. 3,737,393 and 4,004~071.
3 However, any other suitable method for preparation of 4 organometallic compounds can be suitably employed.
s 6 The oxygen-containing compounds which may be usefully 7 employed in accordance with this in~ention are alcohols~ aldehydes7 8 siloxanes and ketones. Prefesrably the oxygen-containing compounds are 9 selected from alcohols and ketones represented by the for~ulas R OH
and R4CoR5 wherein R3 and each of R4 and R5, which may be the same or ll different9 can be alkyl groups, aryl groups, oycloalkyl groups, 12 aralkyl groups, alkadienyl groups, or alkenyl groups having from 2 to 13 20 carbon atoms. Preferably the R groups will have from 2 to lO
l~ oarbon ato~s. Most preferably the R groups are alkyl groups and will 15 have from 2 to 6 carbon atoms.
1~ Illus~rative, but non-limiting ex~mples o~ alcohols, which 17 may be usefully employed in accordance with this invention are alkyl 18 alcohols such as ethanol7 l-propanol, 2~propanol, l-butanol, l9 2-butanol, t-butanol, l-hexanol, 2-ethyl-l-hexanol, l-decanol; cylo-alkyl alsohols such as cyclobutanol, cyclohexanol; aryl alcohols, such 27 as pheno1, l-naphthol, 2-naphthol; aralkyl alcohols such as 22 benzylalcohol, p-cresol. m-cresol; alkenyl alcohols such as 23 allylalcohol, crotylalcohol~ 3-butene-l-ol; and alkadieny1 alcohols 24 such as 2,4-hexadiene-l-ol. The most preferred alcohol is l-butanol.
The ketones will preferably have from 3 to ll carbon atoms.
26 Illustrative, but non-limi~ing, ketones are alkyl ketones such as 27 acetone, 3-pentanone, 4-heptanone, methylethylketone, 28 methylhutylketone; cycloalkyl ketones such as cyclohexanone, cyclo-29 pentanone, 2-methylcycl~hexanone; ~ryl ketones such as benzophenone, acetophenone, propiophenone; alkenyl ketones such as methylvinylketone 31 and methylallylketone~ The most preferred ketone is acetone.
32 Illustrative, but non-limiting, aldehydes which can be use-33 fully employed in the preparation of the organomagnesium compound 34 include alkylaldehydes such dS formaldehyde, acetaldehyde9 propion-aldehyde, butandl, pentanal, hexanal, heptanal, octanal, 2-methyl-36 propanal, 3-methylbutanal; dryl aldehydes such as benzaldehyde;
37 alkenyl aldehydes such as acrolein, crotonaldehyde; aralkyl aldehydes 38 such as phenylacetaldehyde, o-tolualdehyde, m tolualdehyde5 l p-tolualdehyde. The most preferred aldehydes are acetaldehyde and 2 forma1dehyde.
3 Illustrative of the siloxanes which may be usefully employed 4 in the preparation of the organomagnesium compound include hexamethyl-disiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, 6 decamethylcyclopentasiloxane, sym-dihydrotetramethyldisiloxane, pen~
7 tamethyltrihydrotrisiloxane, methylhydrocyclotetrasilo~ane, both 8 linear and branched polydimethylsiloxanes, polymethylhydrosiloxanes, 9 polyethylhydrosiloxanes, polymethylethylsiloxanes, polymethyloctyl-siloxanes, and polyphenylhydrosiloxanes.
ll The preferred acyl halides can be represented by the formula l2 R6COX wherein R6 is a hydrocarbyl group containing l to 20 carbon 13 atoms. R6 can be an alkyl group, aryl group, aralkyl group, cyclo-l4 alkyl group, alkadienyl group or alkenyl group and X is a halogen.
The preferred halogen is chlorine. More preferably R6 is an alkyl l6 group having l to 6 carbon atoms or a phenyl or alkyl phenyl group 17 having 6 to lO carbon atoms. Most preferably R6 is a methyl or l8 phenyl group and X is chlorine.
l9 Illustra-tive, but non-limitin~, examples of the acyl halides which can be usefully employed in accordance with the invention are, 2l alkyl acyl halides such as acetylchloride, propanoylchloride, butyryl-22 chloride, butyrylbromide, isobutyrylchloride; aryl acyl halides such 23 as benzoylchloride, l-naphthoylchloride, 2-naphthoylchloride; cyclo-24 alkyl acyl halides such as ~yclopentane carbonylchloride, cyclahexane carbonylchloride; aralkyl acyl halides such as p-toluoylchloride, 26 m-toluoylchloride; alkenyl acyl halides such as acryloylchloride, 27 6-heptenoylchloride, crotonoylchloride. Acid chlorides based on 28 polyacids may also use~ully be employed such as, for example, dode-29 canedioyl, succinyl chloride, camphoryl chloride, terephthaloyl chloride and the like. The preferred acid halides are acetyl 31 chloride, benzoyl chloride, and p-methylbenzoyl chloride.
32 The transition metal compounds of a Group IVb, Vb, VIb or 33 VIII metal which can be usefully employed in the preparation of the 34 transition metal-containing catalyst component o~ this invention are well known in the art. The transition metals which can be employed in 36 accordançe with this invention may be represented by the formulas 37 TrX'4 q(OR8)q, TrX'4 qRq, VOX'3 and VO(OR8)3. Tr is a Group IVb3 38 Vb, VIb, and VIII metal, preferably Group IVb and Vb metals and ~2 ~ 76 ~
l preferably titanium~ vanadium or zirconium, q is 0 or a number equal 2 to or less than ~, X' is halogen and R8 is an alkyl group, aryl 3 group or cycloalkyl group having from l to 20 carbon atoms and R9 is 4 an alkyl group, aryl group, aralkyl group, substituted aralkyl group, 1,3-cyclopentadienyls and the like. The aryl, aralkyls and 6 substituted aralkyls contain from l to 20 carbon atoms preferably l to 7 lO carbon atoms~ When the transition metal compound contains a 8 hydrocarbyl group, R9, being an alkyl, cycloalkyl, aryl, or aralkyl 9 group, the hydrocarbyl group will preferably not contain a H atom in the position beta to the metal-carbon bond. Illustrative, but non-ll limiting, examples of alkyl groups are methyl, neo-pentyl, 12 2,2-dimethylbutyl, 2,2-dimethylhexyl, aryl groups such as phenyl, l3 naphthyl; aralkyl groups such as benzyl, cycloalkyl groups such as 14 l-norbornyl. Mixtures of the transition metal compounds can be employed if desired.
16 Illustrative examples of the transikion metal compounds 17 include TiC14, TiBr4, Ti(OC2H~)3Cl, Ti(OC2~15)C13, Ti(OC4~19)3Cl, ( 3 7)2Cl2~ Ti(OC6H13)2C12~ Ti(OCgH17)2Br2, and Ti(OC12H25)C13.
l9 As indicated above, mixtures of the transition metal com pounds may be usefully employed, no restriction being imposed on the 2l number of transition metal compounds which may be reacted with the 22 organometallic composition. Any halogenide and alkoxide transition 23 metal compound or mixtures thereof can be usefully employed. The 24 titanium tetrahalides are especially preferred with titanium tetra-chloride being most preferred.
26 The halogens (E) which can be suitably employed in accordance 27 with this invention are C12, Br2, I2 and mixtures thereof. Illustrative 28 interhalogen compounds are ClF, ClF37 BrF, BrF3, BrF5, ICl, IC13 and 29 IBr. The preferred halogens are Cl2 and Br2. The preferred interhalogens contain Br or Cl.
3l The transition metal-containing catalyst solid is treated 32 with an organometallic compound of a Group IIa, IIb or IIIa me-tal.
33 Preferably the organometallic compound employed in the treatment step 34 (F) is an aluminum alkyl represented by the structural formula RnAlX3 n wherein X is halogen or hydride and R7 is a hydrocarbyl 36 group selected from Cl to C18 satura-ted hydrocarbon radicals and 37 1 <n' 3.
l Illustrative of such compounds which can usefully be employed 2 in the treatment step of this invention are Al(C2H5)3, Al(C2H5)2Cl, 3 Al(i-C4Hg)3, Al2(C2~l5)3Cl3, Al(i-C4Hg)2H, ( 6 l3 3 4 Al(C8Hl7)3, Al(C2H5~2H. Preferably the organoaluminum compound is an aluminum trialkyl where the alkyl groups can have from l to lO carbon 6 atoms and most preferably from 2 to 8 carbon atoms. Tri-n-hexyl-7 aluminum and tri-n-octylaluminum being most preferred.
8 The treatment of the support material as mentioned above is 9 conducted in an inert solvent. The inert solvents can also be use-fully employed to dissolve the individual ingredients prior to the ll treatment step. Preferred solvents include mineral oils and the l2 various hydrocarbons which are liquid at reaction temperatures and in l3 which the individual ingredients are soluble. Illustrative examples 14 of useful solvents include the alkanes such as pentane, iso-pentane, hexane, heptane, octane and nonane; cycloalkanes such as cyclopentane 16 and cyclohexane; and aromatics such as benzene, toluene, ethylbenzene 17 and xylenes. The amount of solvent to be employed is not critical.
18 Nevertheless, the amount should be employed so as to provide adequate 19 heat transfer away ~rom the catalyst components during reaction and to permit good mixing.
21 The organometallic component (A) employed either as the 22 organometallic compound or its reaction product with (B) an oxygen-23 containing compound is preferably added to the inert solvent in the 24 form of a solution. Preferred solvents for the organometallic compositions are the alkanes such as hexane, heptane, octane and the 26 like. However, the same solvent dS employed for the slurrying inert 27 particulate support material can be employed for dissolving the 28 organo-metallic composition. The concentration of the organometallic 29 composition in the solvent is not critical and is limited only by handling needs.
31 The amount of materials usefully employed in the solid cata-32 lyst component can vary over a wide range. The concentration of 33 magnesium deposited on the essentially dry, inert support can be in 34 the range from about O.l to about 2.5 millimoles/g of support, how-ever, greater or lesser amounts can be usefully employed. Preferably, 36 the magnesium compound concentration is in the range of 0.5 to 2.0 37 millimoles/g of support and especially l.0 to l.8 millimoles/g of 38 support. The magnesium to oxygen-containing compound mole ratio can 1 range from about 0.01 to about 2Ø Preferably, the ratio is in the 2 range 0.5 to 1.5, and more preferably in the range 0.8 to 1.2. The 3 upper limit on this range is dependent on the choice of oxygen-containing compound and the mode of addition. When the oxygen-containing compound is not pre-mixed with the magnesium compound, that 6 is, when it is added to the support before the magnesium compound or 7 after the magnesium compound5 the ratio may range from 0.01 to 2Ø
8 ~hen premixed with the organomagnesium compound, the hydrocarbyl 9 groups on the oxygen-containing compound must be sufficiently larye to ensure solubility of the reaction product, otherwise the ratio of 11 oxygen-containing compound to organomagnesium compound ranges from 12 0.01 to 1.0~ most preferably 0.8 to 1Ø
13 The amount of acyl halide employed should be such as to 14 provide a mole ratio of about 0.1 to about 10 and preferably 0.5 to about 2.5 with respect to the magnesium compound. Preferably the mole 16 ratio will be about 1 to about 2. The transition metal compound is 17 added to the inert support at a concentration of about 0.01 to about 18 1.5 mmoles ri/g of dried support, preferably in the range of about 19 0.05 to about 1.0 mmoles Ti/g of dried support and especially in the range of about 0.1 to 0.8 mmoles Ti/g of dried support. The halogen 21 or interhalogen treatment is such as to provide an excess of the 22 halogen or interhalogen. Generally, the halogen employed, such as, 23 for example, C12, is employed in the form of a gas.
24 The halogen treatment of the catalyst can be accomplished, for example, by exposing the catalyst in either dry or slurry form to 26 gaseous chlorine at 1.0 to 10 atmospheres total pressure for about 10 27 minutes to 4 hours at temperatures ranging from about 0 to 100C~ A
28 mixture of C12 and an inert gas such as argon or nitrogen can be 29 used. The molar concentration of C12 in the inert gas can range from about 1 mole % to 100 mole %.
31 The treatment of the solids with the Group Ila, IIb or IIXa 32 metal alkyl can be accomplished, for example, by either adding the 33 Group IIa, IIb or IIIa metal hydrocarbyl to the solid mixture or by 34 slurrying the dried solid mixture in an inert solvent followed by the appropriate quantity of the organometallic treating agent.
36 The amount of treating agent (F~ to be employed should be 37 such as to provide a mole ratio of about 0.5 to about 50 and prefer-1 ably 1 to about 20 with respect to titanium. Most preferably the mole 2 ratio will be from about 3 to about 10.
3 Generally, the individual reaction steps can be conducted at 4 temperatures in the range of about -50C to about 150C. Preferred temperature ranges are from about -30C to about 60C with -10C to 6 about 50C being most preferred. The reaction time for the individual 7 treatment steps can range from about 5 minutes to about 24 hours.
8 Preferably the reaction time will be from about 1/2 hour to about 8 9 hours. During the reaction consta~t agitation is desirable.
In the preparation of the transition metal-containing cata-11 lyst component washing after the completion of any step may be 12 effected. However, it is generally found that the material advantages 13 of the catalyst system are diminished by washing until the completion 14 of step (F).
The transition metal-containing catalyst component prepared 16 in accordance with this invention are usefully employed with [the]
17 cocatalysts well known in the art of the Ziegler catalysis for poly-18 merization of olefins. Typically, the cocatalysts which are used 19 together with the transition metal-containing catalyst component are organometallic compounds of Group Ia, IIa, IIb, and IIIa metals such 21 as aluminum alkyls, aluminum alkyl hydrides, lithium aluminum alkyls, 22 zinc alkyls, magnesium alkyls and the like. The cocatalysts desirably 23 used are the organoaluminum compounds. The preferred alkylaluminum -24 compounds are represented by the formula AlR"'nX"3 n wherein 1 ' n ' 3 and R"' is hydrogen, hydrocarbyl or substituted hydrocarbyl 26 group and X" is halogen. Preferably R"' is an alkyl group having from 27 2 to 8 carbon atoms. Illustrative examples of the cocatalyst material 28 are ethylaluminum dichloride, ethylaluminum sesquichloride, 29 diethylaluminum chloride, triethylaluminum, tri-n-butylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide and the like.
31 Aluminum trialkyl compounds are most preferred with 32 triisobutylaluminum being highly desirable.
33 The catalyst system comprising the alkylaluminum cocatalyst 34 and the transition metal~-containing catalyst component is usefully employed for the polymerization of ethylene, other alpha-oleFins 36 having from 3 to 20 carbon atoms~ such as for example, propylene, 37 butene-l, pentene-l, hexene-l, 4-methylpentene-1, and the like and 38 ethylene copolymers with other alpha-olefins or diolefins such as 6~
1~ -1 1,4-pentadiene, l~hexadiene, butadiene, 2-methyl-1,3-butadiene and 2 the like. The polymerizable monomer o~ preFerence is ethytene~ The 3 catalyst may be usefully employed to produce high density polyethylene 4 or linear low density polyethylene by copolymerizing ethylene with other alpha-olefins or diolefins, particularly propylene, butene-l, 6 pentene-l, hexene-19 and octene-1. The olefins can be polymerized in 7 the presence of the catalyst of this invention by any suitable known 8 process such as9 for example, suspension, solution and gas-phase 9 polymerization processes.
The polymerization reaction employing catalytic amounts of 11 the above-described catalyst can be carried out under conditions well 12 known in the art of Ziegler polymerization, for example, in an inert 13 diluent at a temperature in the range of 50C to 120C and a pressure 14 of 1 and 40 atmospheres or in the gas phase at a temperature range of lS 70C to 100C at about 1 to about 50 atmospheres and upward.
16 Illustrative of the gas-phase processes are those disclosed in U.S.
17 4,302,565 and U.S. 4,302,566.
18 As indicated above, one advantageous property of the 19 catalyst system of this invention is the reduced amount of gas phase reactor fouling. The catalyst system can also be used to polymerize 21 olefin at single phase conditions, i.e., 150C to 320C and 1000 -22 30GO atmospheres. At these conditions the cat-alyst lifetime is short 23 but the activity sufficiently high that removal of catalyst residues 24 from the polymer is unnecessary. However9 it is preferred that the polymerization be done at pressures rdnging from 1 to 50 atmospheres, 26 preferably 5 to 25 atmospheres.
27 In the processes according to this invention it has been 2~ discovered that the catalyst system is highly responsive to hydrogen 29 for the control of molecular weight. Other well known molecular weight controlling agents and modifying agents, however, may be use-31 fully employed.
32 The polyolefins prepared in accordance with this invention 33 cdn be extruded, mechdnically melted, Cdst or molded as desired. They 34 can be used for plates, sheets, films and a variety of other objects.
While the invention is described in connection with the 36 specific examples below, i-t is understood thdt these are only for 37 illustrative purposes. Many alternatives, modifications and varia-38 tions will be ~pparent to those skilled in the art in light of the 3,. ~ F ~
_ 19 _ below examples and such dlternatives, modifications and variations 2 fall within the general scope of the claims.
3 In Examples 1 through 3 and Comparative Example 1, the silica 4 support was prepared by placing Davison Chemical Company G-95~ silica
S U.SO Patent No. 4,136,058 discloses a cata7yst component 6 comprising an organomagnesium compound and d transition metal halide 7 compound, which catalyst component is thereafter deactivated with a 8 deactivating agent such as hydrogen chloride. This patent does not 9 teach the use of support material such as silica, but otherwise the la disclosure is similar to the above-discussed European paten~ applica-1 1 tionO
12 U.S. Pa~ent NoO 4,250,288 discloses a catalyst which is the 13 reaction product of a transition metal compound, an organomagnesium 14 component, and an active non-metallic halide such as HCl and organic halides containing a labile halogen. The ca~alyst reaction product 16 also contains some aluminum a1kyls.
17 Catalyst components comprising the reaction product ~f an 18 aluminum alkyl-magnesium alkyl complex plus titanium halide are d~s-lg closed in U.S~ Patent No. 4,0049071 and U.S. Patent No. 4,276,191.
U.S. Patent No. 4,173,547 and U.S. Patent No. 4,263,171, 21 respectively disclose a catalyst component comprising silica, an 22 aluminum-type titanium trichl~ride and dibutyl-magnesium and a 23 catalyst component comprising a magnesium alkylaluminum a~kyl complex 24 plus titanium halide on a silica support.
The use of chlorine gas in polymerization processes is taught 26 in U~S~ P~tent No~ 4,267,292 wherein it is disclosed that chlorine gas 27 is to be added to the polymerization reactor after polymerizat~on has 28 been initiated in the presence of a Ziegler catalyst. U.S. Patent No.
29 4,248,735 teaches subjecting a silica support to a treatment with bromine or iodine and thereafter incorporating a chromium compound 31 onto the support. U.S. Patent No. 3,513,150 discloses the treatment 32 of gamma alumina plus titanium tetrachloride with a yaseous chlori-33 nating agent and employing said treated material in combination with a 34 cocatalyst for the polymerization of ethylene.
European patent application 32,308 published July 36 22/81 discloses polymerizing ethylene in the presence of 37 a catalyst system comprising an organic metal compound and 38 a titanium-containing material which is obtained by reacting together an inert particulate material, an organic magnesium ?6:~
l compound, d titanium compound and a halogen containing compound such 2 d5 SiC14, PC13, 8C13, C12 and the like.
3 Each of U.S. 4,402,861, 4,378,304, 4,388,220, 4,301,029 and 4 4,385,161 disclose supported catalyst systems comprising an oxide support such d5 Si1iCd, an organomagnesium compound, a transition 6 meta7 comp~und and one or more catalyst co~ponent modifiers. These 7 patents do not disclose the catalyst of this invention.
8 In British 2,101,610 silica is treated with a magnesium 9 alkyl, an alcohol benzoyl chloride and TiC14. In each of 1~ Japanese Kokai 56-098206 published Aug. 7/81 and 57-070107 11 published April 30/82 acyl halides are employed during the 12 preparation of titanium supported catalysts.
13 The catalyst systems comprising magnesium alkyls and titanium ~ compounds, a~though generally usefùl for the po1ymerization of olefins such as ethylene and other l-olefins, do not show excellent respon-16 siveness to hydrogen during the polymerizdtion reaction for the 17 control of ~olecul~r weight, do not readily incorporate comonomers 18 such as butene-l for the production of ethylene copolyrners, do not 19 show an extremely high catalytic activity and obtain polymer product whose film properties are unbalanced under anisotropic conditions.
21 I~ U.S. Patent 4,451,574 issued May Z9, 1984, a catalyst 22 system obtained by treating an inert particula$e support, such dS
23 silica, with an organometallic compound, a titanium halide and a 24 halogen gas is disclosed. Although the catalyst obtains very high ac~civities, there is a need for improving the film properties of 26 poly~er product obtained by polym~rizing o~efins in the presence of 27 the catalyst and to improve the bulk density of polymer 28 product.
29 In our copending Canadian application serial nu~ber 487,246 filed July 22, 1985, we disclosed a 31 transition metal supported catalyst component obtained by 32 contacting an inert solid support with (a) the reaction 33 product of a dialkyl magnesium compound and an alcohol, 34 (b) an acyl halide, (c) TiC14, and (d) C12. In copending Canadian application serial number 487,479 filed 36 July 25, 1985, there is disclosed a transition metal 37 supported catalyst component obtained by contact:ing an 38 inert so1id support with (a) the reaction product of "~, 1 1 a dialkyl magnesium compound and an oxygen-containing 2 compound, (b) a transition metal halide such as TiC14, 3 (c) C12 and treating the resultant solid with an organo-4 m~tallic compound of a Group IIa, IIb or IIIa metal.
1 ~
~2 1 In accordance with this invention catalyst combinations have 2 been ~ound which have very high catalytic activities and excellent 3 hydrogen responsiveness for the control of molecular weight, excellent comonomer response and obtain polymer product with greatly improved film properties. The resins exhibit excellent melt strength along 6 with a decrease in extrusion power consumption9 resulting in increased 7 bubble stability in blown film production. In addition, the resins 8 exhibit an increase in extrusion rates. The invention is 9 distinguished over our copending application in that the catalyst of this invention unexpectedly obtains an improvement in catalytic 11 activity and the polymers produced therefrom have unexpectedly 12 improved bulk density.
13 The new catalyst components of this invention are obtained by 14 contacting an organometallic compound, an oxygen-containing compound such as a ketone, aldehyde, siloxane or alcohol, an acyl halide, a 16 transition metal compound, a halogen or interhalogen compound in the 17 presence of a oxide support and treating the obtained solid with an 18 organometall;c compound of a Group IIa, IIb or IIIa me-tal such as, for 19 example, an aluminum alkyl. The catalyst system comprising the tran-sition metal-containing catalyst component and an organoaluminum 21 cocatalyst is advantageously employed in a gas phase ethylene poly-22 merization process since there is a decrease in reactor fouling as 23 generally compared with catalytic prior art ethylene gas phase 24 polymerization processes thereby resulting in less frequent reactor shut downs for cleaning purposes.
26 Summary of the Invention 27 In accordance with the objectives of this invention there is 28 provided a transition metal-containing catalyst component for the 29 polymerization of alph~-olefins comprising a solid reaction product obtained by treating an inert solid support material in an inert 31 solvent with (A) an organometallic compound of a Group IIa, IIb or 32 IIIa metal of the Periodic Table wherein all the metal valencies are 33 satisfied with a hydrocarbon or substituted hydrocarbon group, (B) an 34 oxygen-containing compound selected from ketones, aldehydes, alcohols, siloxanes or mixtures thereof, (C) an acyl halide, (D) at least one 36 transition metal compound of a Group IVb, Vb, VIb or VIII metal of the 37 Periodic Table, (E) C12, Br2 or an interhalogen, and (F) treating 33 the transition metal-containing product w-ith an organometallic ~5~
1 compound of d Group Ila, lIb, or IIIa metal, with the proviso that the 2 (A) and (B) ingredients can be employed (i) simultaneously, (ii) as 3 the reaction product of (~) and (B), or (iii) treatment with (B) 4 immediately preceeds treatment with (A).
The solid transition metal-containing catalyst comp~nent when 6 employed in combination with a cocatalyst such as an alkyl aluminum 7 cocatalyst provides a catalyst system which demonstrates a number of 8 uninue properties that are of great importance in olefin polymeriza-9 tion technology such asa for example, extremely high catalytic activity, the ability to control the molecular weight during the 11 polymerization reaction as d result of the improved responsiveness to 12 hydrogen, improved comonomer response, increased polymer yield, and 13 reduced reactor foulingO A particular advan$age of the instant inven-14 tion is the ability of catalytically producing polymer product having improved bulk density.
16 In a preferred embodiment of the invention the (A) organo-17 metallic compound is a dihydrocarbyl magnesiurn compound represented by 18 RlMgR2 wherein Rl and R2 which can be the same or different 19 are selected from alkyl groups, aryl groups, cycloalkyl groups, aral-kyl groups, alkadienyl groups or alkenyl groups having from 1 to 20 21 carbon atoms, the (B) oxygen-containing compounds are selected from 22 alcohols and ketones represented by the formula R30H and R4CoR5 23 wherein R3 and each of R4 and R5 which may be the same or dif-24 ferent can be an alkyl group, aryl group, cycloalkyl group, aralkyl group, alkadienyl group or alkenyl group having from 1 to 20 carbon 26 atoms, the (C) acyl halide is represented by the formula R6COX
27 wherein R6 can be a Cl-C20 alkyl group, cycloalkyl group or aryl 28 group and X is halogen, the (D) transition metal compound is prefer-29 ably a transition meta~ compound or combination oF transition metal compounds represented by the Formulas TrX"4 q(OR8)q, 31 TrX"4 qRq, VO(OR )3 and VOX"3 ~herein Tr is a transition 32 metal of Groups IVb, Vb, VIb, and VIII and preferably titanium, 33 vanadium or zirconium, R8 is an alkyl group, aryl group, aralkyl 34 group, or substituted aralkyl group having from 1 to 20 carbon atoms and 1,3-cyclopentadienyls, X" is halogen and q is zero or a number 36 less than or equal to 4, and R9 is an alkyl group, aryl group or 37 aralkyl group having from 1-20 carbon atoms or a 1,3-cyclopentadienyl, 38 the (E) halogen is C12 and the (F) organometallic compound is an ~2~
1 aluminum alkyl represented by RnAlX'3 n wherein X' is a 2 halogen9 or hydride and R7 is a hydrocarbon group selected from 3 alkyl group, aryl group, cycloalkyl ~roup, aralkyl group, alkadienyl 4 grolJp or alkenyl group having from 1 to 20 carbon atoms and 1 ' n ~ 3.
All references to the Periodic Table are to the Periodic 6 Table of the Elements printed on page B-3 of the 56th Edition o~
7 Handbook of Chemistry and Physics, CRC Press (1975).
8 The catalyst component forming ingredien~s can be added in any 9 order to the support material (with the exception of (F) which must be last) in preparing the transition metal-containing catalyst component, 11 for example:
12 (B), (A), (C), (D), (E) and (F) 13 (A+B), (C), (D), (E) and (F) 14 (A~B), (C), (D), (E) and (F) (E), (B), (A), (C), (D) and (F) 16 (E), (A-~B), (C), (D) and (F) 17 (E), (A&B), (C), (D) and (F) 18 (C), (B), (A), (E), (D) and (F) 19 (C), (A~B), (E), (D) and (F) (C), (A&B), (E), (D) and (F) 21 (D), (C), (B), (A), (E) and (F) 22 (D), (C), (A+B), (E) and (F) 23 (D), (C), (A&B), (E) and (F) 24 (D), (E), (B), (A), (C) and (F) (D), (E), (A+B), (C) and (F) 26 (D), (E), (A~B), (C) and (F) 27 (D), (B), (A), (C), (E) and (F) 23 (D), (A~B), (C), (E) and (F) 29 (D), (A&B), (C), (E) and (F) (D), (B), (A), (E), (C) and (F) 31 (D), (A~B)9 (E), (C) and (F) 32 (D) 9 (A&B), (E), (C) and (F) 33 (B), ~A), (E), (D), (C) and (F) 34 (B+A), (E), (D), (C) and (F) (B&A), (E), (D), (C) and (F) 36 (B), (A), (C), (E), (D), and (F) 37 (B+A), (C), (E), (D), and (F) 1 (B~A), (C)9 (E), (D), and (F) 2 (B)~ (A), (E), (C), (D), and (F) 3 (B~A), (E)9 (C), (D), and (F) 4 (B~A)9 (E)9 (C), (D)9 and (F) and the like. In the above, (A+B) represents the reaction product of 6 (A) and (B) and (A&B) represents the simultaneous addition of (A) and 7 (B) to the reacting system.
8 Of the possible order of additions the preferred are (A+B), 9 (C), (D), (E) and (F); (E), (A+B), (C)~ (D) and (F); (A-~B)9 (E)9 (C), (D)9 and (F); or (C), (A-~B), (E), (D) and (F). More preferred are 11 (E), (A+B~, (C)9 (D) and (F); (A+B, (E), (C3, (D)9 and (F); or (A+B), 12 (C), (D), (E) and (F). The transition metal-containing catalyst 13 component especially preferred is prepared by first treating the 14 inert solid su~port with (E) C12, Br2 or an interhalogen or mixtures thereof followed by treatment with the reaction product of 16 (A) the organometallic compound with (B) the oxygen-containing 17 compound ancl thereafter treating the solid with the (C) acyl halide 18 followed by treatment with the (D) transition metal compound and 19 prereducing with (F).
In a second embodiment of this invention there is provided a 21 catalyst system comprising the transition metal-containing solid 22 catalyst component and an organoalum;num cocatalyst for the polymer-23 ization of alpha-olefins using the catalyst of this invention under 24 conditions characteristic of Ziegler polymerization.
In view of the high activity of the catalyst system prepared 26 in accordance with this invention as compared with conventional 27 Ziegler catalysts, it is generally not necessary to deash polymer ~8 product since polymer product will generally contain lower amounts of 29 catalyst residues than polymer product produced in the presence of conventional catalysts.
31 The catalyst system can be employed in a gas phase process, 32 single phase melt process, solvent process or slurry process. The 33 catalyst system is usefully employed in the polymerization of ethylene 34 and other alpha-olefins, particularly alpha-olefins having from 3 to 8 carbon atoms and copolymerization of these with other l-olefins or 36 diolefins having from 2 to 20 carbon atoms, such as propylene, butene, 37 pentene, hexene, butadiene9 1,4-pentadiene and the like, so as to form 38 copolymers of low and medium densities. The supported catalyst system 1 is particularly useful For the polymerization of ethylene and copoly-2 merization of ethylene with other alpha-olefins in gas phase processes.
3 Description of the Preferred Embodiments .
4 Briefly, the catalyst components of the present invention comprise the so7id reaction product obtained by contacting a solid 6 support material with (A) an organometallic composition, (B)-an 7 oxygen-containing compound, (C) an acyl halide~ (D) at least one 8 transition metal compound, (E) halogen or interhalogen compound which 9 is treated with (F~ an organometallic compound of a Group IIai IIb, IIIa metal, with the proviso that the (A) and (B) ingredients can be 11 added to the inert solid (i) simulaneously, (ii) as the reaction 12 product of (A) and (B), or (iii) treatment with (B) immediately 13 precedes treatment with (A).
14 The transition metal-containing catalyst component of this invention is preferably obtained by treating the inert solid support 16 material in an inert solvent in the steps selected from the group 17 consisting of 18 (a) first treating with ingredient (E) followed by 19 sequential treatment with ingredients (A), (B)~ (C), (D), and (F), (b) first treating with ingredients (A) and (B) followed by 21 the sequential treatment with ingredients (C), (D), (E), and (F), 22 or 23 (c) First treating with ingredient (C) followed by the 2~ sequential treatment with ingredients (A) and (B), (E), (D), and (F) 26 (d) first treating with ingredients (B) and (A) followed by 27 the sequential treatment with inyredients (E), (C), (D), and (F) 28 with the further proviso that the (A) and (B) ingredients can be added 2g (i) simultaneously, (ii) as the reaotion product o~ (A) and (B), or (iii) treatment with (B) immediately precedes treatment with (A).
31 Preferably, the transition metal-containing catalyst 32 component of this invention is obtained by (I) treating the inert 33 solid support material in an inert solvent with ingredient (E) 34 followed by sequential treatment with ingredients (A), (B), (C), (D), and (F) and that the (A) and (B) ingredients can be added (i) 36 simultaneously, (ii) as the reaction product of (A) and (B), or (iii) 37 treatment with (B) immediately precedes treatment with (A); or 6~
g 1 (~I) wherein the solid reaction product is obtained by 2 treating inert solid support material in an inert solvent with 3 ingredients (A) and (B), followed by sequential treatmen with 4 ingredients (C)~ (D), (E), and (F) and with the further proviso that the (A) and (B3 ingredients can be added to the inert solid (i) 6 simultaneously5 (ii) as the reaction product of (A) and (B),-or (iii) 7 treatment of the inert solid with (B) immediately precedes treatlnent 8 with (A). The method (I) is especially pre~erred.
9 According to the polymerization process of this invention, ethylene, at least one alpha-olefin having 3 or more carbon atoms or 11 ethylene and other olefins or diolefins having terminal unsaturation 12 are contacted with the catalyst under polymerizing conditions to form 13 a commercially useful polymeric product. Typically, the support can 14 be any of the solid particulate porous supports such as talc, zirconia, thoria, magnesia, and titania. Preferably the support 16 materia1 is a Group IIa, IIIa, IVa and I~b metal oxide in finely 17 divided form.
18 Suitable inorganic oxide materials which are desirably 19 employed in accordance with this invention include Group IIa, IIla, or IVa or IVb metal oxides such as silica, alumina, and silica-alumina 21 and mixtures thereof. Other inorganic oxides that may be employed 22 either alone or in combination with silica, alumina or silica-alumina 23 are magnesia~ titania, zirconia, and the like. Other suitable support 24 materials, however, can be employed, for example, finely divided polyolefins such as finely divided polyethylene.
26 The metal oxides generally contain acidic surface hydroxyl 27 groups which will react with the organometallic composition or transi-28 tion metal compound first added to the reaction solvent. Prior to 29 use, the inor~anic oxide support is dehydrated, i.e., subjected to a thermal treatment in order to remove water and reduce the 31 concentration of the surface hydroxyl groups. The treatment is 32 carried out in vacuum or while purging with a dry inert gas such as 33 nitrogen at a temperature of about 100 to about 1000C, and 34 preferably from about 300C to about 800~C. Pressure considerations are not critical. The duration of the thermal treatment can be from 36 about 1 to about 24 hours. However, shorter or longer times can be 37 employed provided equilibrium is established with the surface hydroxyl 38 groups.
~25~
1 Chemical dehydration as an alternative method of dehydration 2 of the metal oxide support material can advantageously be employed.
3 Chemical dehydration converts all water and hydroxyl groups on the 4 oxide surface to inert species. Useful chemical agents are, for example, SiC14, chlorosilanes, such as trimethylchlorisilane, 6 dimethyldichlorosilane, silylamines, such as hexamethyldisila~ane and 7 dimethylaminotrimethylsilane and the like. The chemical dehydration 8 is accomplished by slurrying the inorganic particulate material, such 9 as, for example, silica in an inert low boiling hydrocarbon, such as, for example, hexane. During the chemical dehydration reaction, the 11 silica should be maintained in a moisture and oxygen-free atmosphere.
12 To the silica slurry is then added a low boiling inert hydrocarbon 13 solution of the chemical dehydrating agent, such as, for example, 14 dichlorodimethylsilane. The solution is added slowly to the slurry.
The temperature ranges during chemical dehydration reaction can be 16 from about 25C to about 120C, however, higher and lower temperatures 17 can be employed. Preferably the temperature will be about 50C to 18 about 70C. The chemical dehydra-tion procedure should be allowed to 19 proceed until all the moisture is removed from the particulate support material, as indicated by cessation of gas evolution. Normally, the ~1 chemical dehydration reaction will be allowed to proceed from about 30 22 minutes to about 16 hours, preferably 1 to 5 hours. Upon completion 23 of the chemical dehydration, the solid particulate material is fil-24 tered under a nitrogen atmosphere and washed one or more times with a 25 dry, oxygen free inert hydrocarbon solvent. The wash solvents, as 26 well as the diluents employed to form the slurry and the solution of 27 chemical dehydrating agent, can be any suitable inert hydrocarbon.
28 Illustrative of such hydrocarbons are heptane, hexane, toluene, iso-29 pentane and the like.
The preferred (A) organometallic compounds employed in this 31 invention are the inert hydrocarbon soluble organomagnesium compounds 32 represented by the formula RlMgR2 wherein each of Rl and R2 33 which may be the same or different are alkyl groups, aryl groups, 34 cycloalkyl groups, aralkyl groups, alkadienyl groups or alkenyl groups. The hydrocarbon groups Rl or R can contain between 1 and 36 20 carbon atoms and preferably from 1 to about 10 carbon atoms.
37 Illustrative but non~limiting examples of magnesium compounds which 38 may be suitably employed in accordance with the invention are dialkyl-1 magnesiums such as diethylmagnesium, dipropylmagnesium, di-isopropyl-2 magnesium, di-n-butylmagnesium, di-isobutylmagnesium, diamylmagnesium, 3 di-n~octylmagnesium, di-n-hexylmagnesium, di-n-decylmagnesium, and 4 di-n-dodecylmagnesium; dicycloalkylmagnesiums, such as dicyclohexyl-magnesium; diaryl magnesiums such as dibenzylmagnesium, ditolylmag-6 nesium and dixylylmagnesium and the like. -7 Preferably the organomagnesium compounds will have from 1 to 8 6 carbon atoms and most preferably ~1 and R2 are different.
9 Illustrative examples of the preferred magnesium compounds are are ethyl-n-propylmagnesium, ethyl-n-butylmagnesium, amyl-n-hexylmag-11 nesium, n-butyl-s-butylmagnesium, n-butyl-n-octylmagnesium, and the 12 like. Mixtures of hydrocarbyl magnesium compounds may be suitably 13 employed such as for example di-n-butylmagnesium and ethyl-n-butyl-14 magnesium.
The magnesium hydrocarbyl compounds are generally obtained 16 from commercial sources as mixtures of the magnesium hydrocarbon 17 compounds with a minor amount of aluminum hydrocarbyl compound. The 18 minor amount of aluminum hydrocarbyl is present in order to facilitate 19 solublization and/or reduce the viscosity of -the organomagnesium compound in hydrocarbon solvent. The hydrocarbon solvent usefully 21 employed for the organomagnesium can be any of the well known hydro-22 carbon liquids, for example hexane, heptane, octane, decane, dodecane, 23 or mixtures thereof, as well as aromatic hydrocarbons such as benzene, 24 toluene, xylene, etc.
The organomagnesium complex with a minor amount of aluminum 26 alkyl can be represented by the formula (RlMgR2)p(R~oAl)s wherein 27 R1 and R2 are defined as above, R10 is defined as R and R and p is 28 greater than 0. The ratio of s/s+p is from O to 1, preferably from O
29 to about 0.7 and most desirably from about O to 0.1.
Illustrative examples of the organomagnesium-organoaluminum 31 complexes are [(n-C4Hg)(C2H5)M9][(c2H5)3Al]0.o2s 32 [(n-C4H9)2Mg][(c2Hs)3Al]o 013~ [(n~c4~l9)2 g][( 2 5 3 2.0 [( C6H13)2M9][(C2H5)3A130.01. A SUitable magnesium_alum;num 34 complex is Magala~ BEM manufactured by Texas Alkyls, Inc.
The hydrocarbon soluble organometallic compositions are known 36 ma-terials and can be prepared by conventional methods. One such 37 method involves, for example, the addition of an appropriate aluminum 38 alkyl to a solid dialkyl magnesium in the presence of an inert hydro-l carbon solvent. The ~rganomagnesium-argdnoaluminum compl~xes are, for 2 example, described in U.S. Patent No. 3,737,393 and 4,004~071.
3 However, any other suitable method for preparation of 4 organometallic compounds can be suitably employed.
s 6 The oxygen-containing compounds which may be usefully 7 employed in accordance with this in~ention are alcohols~ aldehydes7 8 siloxanes and ketones. Prefesrably the oxygen-containing compounds are 9 selected from alcohols and ketones represented by the for~ulas R OH
and R4CoR5 wherein R3 and each of R4 and R5, which may be the same or ll different9 can be alkyl groups, aryl groups, oycloalkyl groups, 12 aralkyl groups, alkadienyl groups, or alkenyl groups having from 2 to 13 20 carbon atoms. Preferably the R groups will have from 2 to lO
l~ oarbon ato~s. Most preferably the R groups are alkyl groups and will 15 have from 2 to 6 carbon atoms.
1~ Illus~rative, but non-limiting ex~mples o~ alcohols, which 17 may be usefully employed in accordance with this invention are alkyl 18 alcohols such as ethanol7 l-propanol, 2~propanol, l-butanol, l9 2-butanol, t-butanol, l-hexanol, 2-ethyl-l-hexanol, l-decanol; cylo-alkyl alsohols such as cyclobutanol, cyclohexanol; aryl alcohols, such 27 as pheno1, l-naphthol, 2-naphthol; aralkyl alcohols such as 22 benzylalcohol, p-cresol. m-cresol; alkenyl alcohols such as 23 allylalcohol, crotylalcohol~ 3-butene-l-ol; and alkadieny1 alcohols 24 such as 2,4-hexadiene-l-ol. The most preferred alcohol is l-butanol.
The ketones will preferably have from 3 to ll carbon atoms.
26 Illustrative, but non-limi~ing, ketones are alkyl ketones such as 27 acetone, 3-pentanone, 4-heptanone, methylethylketone, 28 methylhutylketone; cycloalkyl ketones such as cyclohexanone, cyclo-29 pentanone, 2-methylcycl~hexanone; ~ryl ketones such as benzophenone, acetophenone, propiophenone; alkenyl ketones such as methylvinylketone 31 and methylallylketone~ The most preferred ketone is acetone.
32 Illustrative, but non-limiting, aldehydes which can be use-33 fully employed in the preparation of the organomagnesium compound 34 include alkylaldehydes such dS formaldehyde, acetaldehyde9 propion-aldehyde, butandl, pentanal, hexanal, heptanal, octanal, 2-methyl-36 propanal, 3-methylbutanal; dryl aldehydes such as benzaldehyde;
37 alkenyl aldehydes such as acrolein, crotonaldehyde; aralkyl aldehydes 38 such as phenylacetaldehyde, o-tolualdehyde, m tolualdehyde5 l p-tolualdehyde. The most preferred aldehydes are acetaldehyde and 2 forma1dehyde.
3 Illustrative of the siloxanes which may be usefully employed 4 in the preparation of the organomagnesium compound include hexamethyl-disiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, 6 decamethylcyclopentasiloxane, sym-dihydrotetramethyldisiloxane, pen~
7 tamethyltrihydrotrisiloxane, methylhydrocyclotetrasilo~ane, both 8 linear and branched polydimethylsiloxanes, polymethylhydrosiloxanes, 9 polyethylhydrosiloxanes, polymethylethylsiloxanes, polymethyloctyl-siloxanes, and polyphenylhydrosiloxanes.
ll The preferred acyl halides can be represented by the formula l2 R6COX wherein R6 is a hydrocarbyl group containing l to 20 carbon 13 atoms. R6 can be an alkyl group, aryl group, aralkyl group, cyclo-l4 alkyl group, alkadienyl group or alkenyl group and X is a halogen.
The preferred halogen is chlorine. More preferably R6 is an alkyl l6 group having l to 6 carbon atoms or a phenyl or alkyl phenyl group 17 having 6 to lO carbon atoms. Most preferably R6 is a methyl or l8 phenyl group and X is chlorine.
l9 Illustra-tive, but non-limitin~, examples of the acyl halides which can be usefully employed in accordance with the invention are, 2l alkyl acyl halides such as acetylchloride, propanoylchloride, butyryl-22 chloride, butyrylbromide, isobutyrylchloride; aryl acyl halides such 23 as benzoylchloride, l-naphthoylchloride, 2-naphthoylchloride; cyclo-24 alkyl acyl halides such as ~yclopentane carbonylchloride, cyclahexane carbonylchloride; aralkyl acyl halides such as p-toluoylchloride, 26 m-toluoylchloride; alkenyl acyl halides such as acryloylchloride, 27 6-heptenoylchloride, crotonoylchloride. Acid chlorides based on 28 polyacids may also use~ully be employed such as, for example, dode-29 canedioyl, succinyl chloride, camphoryl chloride, terephthaloyl chloride and the like. The preferred acid halides are acetyl 31 chloride, benzoyl chloride, and p-methylbenzoyl chloride.
32 The transition metal compounds of a Group IVb, Vb, VIb or 33 VIII metal which can be usefully employed in the preparation of the 34 transition metal-containing catalyst component o~ this invention are well known in the art. The transition metals which can be employed in 36 accordançe with this invention may be represented by the formulas 37 TrX'4 q(OR8)q, TrX'4 qRq, VOX'3 and VO(OR8)3. Tr is a Group IVb3 38 Vb, VIb, and VIII metal, preferably Group IVb and Vb metals and ~2 ~ 76 ~
l preferably titanium~ vanadium or zirconium, q is 0 or a number equal 2 to or less than ~, X' is halogen and R8 is an alkyl group, aryl 3 group or cycloalkyl group having from l to 20 carbon atoms and R9 is 4 an alkyl group, aryl group, aralkyl group, substituted aralkyl group, 1,3-cyclopentadienyls and the like. The aryl, aralkyls and 6 substituted aralkyls contain from l to 20 carbon atoms preferably l to 7 lO carbon atoms~ When the transition metal compound contains a 8 hydrocarbyl group, R9, being an alkyl, cycloalkyl, aryl, or aralkyl 9 group, the hydrocarbyl group will preferably not contain a H atom in the position beta to the metal-carbon bond. Illustrative, but non-ll limiting, examples of alkyl groups are methyl, neo-pentyl, 12 2,2-dimethylbutyl, 2,2-dimethylhexyl, aryl groups such as phenyl, l3 naphthyl; aralkyl groups such as benzyl, cycloalkyl groups such as 14 l-norbornyl. Mixtures of the transition metal compounds can be employed if desired.
16 Illustrative examples of the transikion metal compounds 17 include TiC14, TiBr4, Ti(OC2H~)3Cl, Ti(OC2~15)C13, Ti(OC4~19)3Cl, ( 3 7)2Cl2~ Ti(OC6H13)2C12~ Ti(OCgH17)2Br2, and Ti(OC12H25)C13.
l9 As indicated above, mixtures of the transition metal com pounds may be usefully employed, no restriction being imposed on the 2l number of transition metal compounds which may be reacted with the 22 organometallic composition. Any halogenide and alkoxide transition 23 metal compound or mixtures thereof can be usefully employed. The 24 titanium tetrahalides are especially preferred with titanium tetra-chloride being most preferred.
26 The halogens (E) which can be suitably employed in accordance 27 with this invention are C12, Br2, I2 and mixtures thereof. Illustrative 28 interhalogen compounds are ClF, ClF37 BrF, BrF3, BrF5, ICl, IC13 and 29 IBr. The preferred halogens are Cl2 and Br2. The preferred interhalogens contain Br or Cl.
3l The transition metal-containing catalyst solid is treated 32 with an organometallic compound of a Group IIa, IIb or IIIa me-tal.
33 Preferably the organometallic compound employed in the treatment step 34 (F) is an aluminum alkyl represented by the structural formula RnAlX3 n wherein X is halogen or hydride and R7 is a hydrocarbyl 36 group selected from Cl to C18 satura-ted hydrocarbon radicals and 37 1 <n' 3.
l Illustrative of such compounds which can usefully be employed 2 in the treatment step of this invention are Al(C2H5)3, Al(C2H5)2Cl, 3 Al(i-C4Hg)3, Al2(C2~l5)3Cl3, Al(i-C4Hg)2H, ( 6 l3 3 4 Al(C8Hl7)3, Al(C2H5~2H. Preferably the organoaluminum compound is an aluminum trialkyl where the alkyl groups can have from l to lO carbon 6 atoms and most preferably from 2 to 8 carbon atoms. Tri-n-hexyl-7 aluminum and tri-n-octylaluminum being most preferred.
8 The treatment of the support material as mentioned above is 9 conducted in an inert solvent. The inert solvents can also be use-fully employed to dissolve the individual ingredients prior to the ll treatment step. Preferred solvents include mineral oils and the l2 various hydrocarbons which are liquid at reaction temperatures and in l3 which the individual ingredients are soluble. Illustrative examples 14 of useful solvents include the alkanes such as pentane, iso-pentane, hexane, heptane, octane and nonane; cycloalkanes such as cyclopentane 16 and cyclohexane; and aromatics such as benzene, toluene, ethylbenzene 17 and xylenes. The amount of solvent to be employed is not critical.
18 Nevertheless, the amount should be employed so as to provide adequate 19 heat transfer away ~rom the catalyst components during reaction and to permit good mixing.
21 The organometallic component (A) employed either as the 22 organometallic compound or its reaction product with (B) an oxygen-23 containing compound is preferably added to the inert solvent in the 24 form of a solution. Preferred solvents for the organometallic compositions are the alkanes such as hexane, heptane, octane and the 26 like. However, the same solvent dS employed for the slurrying inert 27 particulate support material can be employed for dissolving the 28 organo-metallic composition. The concentration of the organometallic 29 composition in the solvent is not critical and is limited only by handling needs.
31 The amount of materials usefully employed in the solid cata-32 lyst component can vary over a wide range. The concentration of 33 magnesium deposited on the essentially dry, inert support can be in 34 the range from about O.l to about 2.5 millimoles/g of support, how-ever, greater or lesser amounts can be usefully employed. Preferably, 36 the magnesium compound concentration is in the range of 0.5 to 2.0 37 millimoles/g of support and especially l.0 to l.8 millimoles/g of 38 support. The magnesium to oxygen-containing compound mole ratio can 1 range from about 0.01 to about 2Ø Preferably, the ratio is in the 2 range 0.5 to 1.5, and more preferably in the range 0.8 to 1.2. The 3 upper limit on this range is dependent on the choice of oxygen-containing compound and the mode of addition. When the oxygen-containing compound is not pre-mixed with the magnesium compound, that 6 is, when it is added to the support before the magnesium compound or 7 after the magnesium compound5 the ratio may range from 0.01 to 2Ø
8 ~hen premixed with the organomagnesium compound, the hydrocarbyl 9 groups on the oxygen-containing compound must be sufficiently larye to ensure solubility of the reaction product, otherwise the ratio of 11 oxygen-containing compound to organomagnesium compound ranges from 12 0.01 to 1.0~ most preferably 0.8 to 1Ø
13 The amount of acyl halide employed should be such as to 14 provide a mole ratio of about 0.1 to about 10 and preferably 0.5 to about 2.5 with respect to the magnesium compound. Preferably the mole 16 ratio will be about 1 to about 2. The transition metal compound is 17 added to the inert support at a concentration of about 0.01 to about 18 1.5 mmoles ri/g of dried support, preferably in the range of about 19 0.05 to about 1.0 mmoles Ti/g of dried support and especially in the range of about 0.1 to 0.8 mmoles Ti/g of dried support. The halogen 21 or interhalogen treatment is such as to provide an excess of the 22 halogen or interhalogen. Generally, the halogen employed, such as, 23 for example, C12, is employed in the form of a gas.
24 The halogen treatment of the catalyst can be accomplished, for example, by exposing the catalyst in either dry or slurry form to 26 gaseous chlorine at 1.0 to 10 atmospheres total pressure for about 10 27 minutes to 4 hours at temperatures ranging from about 0 to 100C~ A
28 mixture of C12 and an inert gas such as argon or nitrogen can be 29 used. The molar concentration of C12 in the inert gas can range from about 1 mole % to 100 mole %.
31 The treatment of the solids with the Group Ila, IIb or IIXa 32 metal alkyl can be accomplished, for example, by either adding the 33 Group IIa, IIb or IIIa metal hydrocarbyl to the solid mixture or by 34 slurrying the dried solid mixture in an inert solvent followed by the appropriate quantity of the organometallic treating agent.
36 The amount of treating agent (F~ to be employed should be 37 such as to provide a mole ratio of about 0.5 to about 50 and prefer-1 ably 1 to about 20 with respect to titanium. Most preferably the mole 2 ratio will be from about 3 to about 10.
3 Generally, the individual reaction steps can be conducted at 4 temperatures in the range of about -50C to about 150C. Preferred temperature ranges are from about -30C to about 60C with -10C to 6 about 50C being most preferred. The reaction time for the individual 7 treatment steps can range from about 5 minutes to about 24 hours.
8 Preferably the reaction time will be from about 1/2 hour to about 8 9 hours. During the reaction consta~t agitation is desirable.
In the preparation of the transition metal-containing cata-11 lyst component washing after the completion of any step may be 12 effected. However, it is generally found that the material advantages 13 of the catalyst system are diminished by washing until the completion 14 of step (F).
The transition metal-containing catalyst component prepared 16 in accordance with this invention are usefully employed with [the]
17 cocatalysts well known in the art of the Ziegler catalysis for poly-18 merization of olefins. Typically, the cocatalysts which are used 19 together with the transition metal-containing catalyst component are organometallic compounds of Group Ia, IIa, IIb, and IIIa metals such 21 as aluminum alkyls, aluminum alkyl hydrides, lithium aluminum alkyls, 22 zinc alkyls, magnesium alkyls and the like. The cocatalysts desirably 23 used are the organoaluminum compounds. The preferred alkylaluminum -24 compounds are represented by the formula AlR"'nX"3 n wherein 1 ' n ' 3 and R"' is hydrogen, hydrocarbyl or substituted hydrocarbyl 26 group and X" is halogen. Preferably R"' is an alkyl group having from 27 2 to 8 carbon atoms. Illustrative examples of the cocatalyst material 28 are ethylaluminum dichloride, ethylaluminum sesquichloride, 29 diethylaluminum chloride, triethylaluminum, tri-n-butylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide and the like.
31 Aluminum trialkyl compounds are most preferred with 32 triisobutylaluminum being highly desirable.
33 The catalyst system comprising the alkylaluminum cocatalyst 34 and the transition metal~-containing catalyst component is usefully employed for the polymerization of ethylene, other alpha-oleFins 36 having from 3 to 20 carbon atoms~ such as for example, propylene, 37 butene-l, pentene-l, hexene-l, 4-methylpentene-1, and the like and 38 ethylene copolymers with other alpha-olefins or diolefins such as 6~
1~ -1 1,4-pentadiene, l~hexadiene, butadiene, 2-methyl-1,3-butadiene and 2 the like. The polymerizable monomer o~ preFerence is ethytene~ The 3 catalyst may be usefully employed to produce high density polyethylene 4 or linear low density polyethylene by copolymerizing ethylene with other alpha-olefins or diolefins, particularly propylene, butene-l, 6 pentene-l, hexene-19 and octene-1. The olefins can be polymerized in 7 the presence of the catalyst of this invention by any suitable known 8 process such as9 for example, suspension, solution and gas-phase 9 polymerization processes.
The polymerization reaction employing catalytic amounts of 11 the above-described catalyst can be carried out under conditions well 12 known in the art of Ziegler polymerization, for example, in an inert 13 diluent at a temperature in the range of 50C to 120C and a pressure 14 of 1 and 40 atmospheres or in the gas phase at a temperature range of lS 70C to 100C at about 1 to about 50 atmospheres and upward.
16 Illustrative of the gas-phase processes are those disclosed in U.S.
17 4,302,565 and U.S. 4,302,566.
18 As indicated above, one advantageous property of the 19 catalyst system of this invention is the reduced amount of gas phase reactor fouling. The catalyst system can also be used to polymerize 21 olefin at single phase conditions, i.e., 150C to 320C and 1000 -22 30GO atmospheres. At these conditions the cat-alyst lifetime is short 23 but the activity sufficiently high that removal of catalyst residues 24 from the polymer is unnecessary. However9 it is preferred that the polymerization be done at pressures rdnging from 1 to 50 atmospheres, 26 preferably 5 to 25 atmospheres.
27 In the processes according to this invention it has been 2~ discovered that the catalyst system is highly responsive to hydrogen 29 for the control of molecular weight. Other well known molecular weight controlling agents and modifying agents, however, may be use-31 fully employed.
32 The polyolefins prepared in accordance with this invention 33 cdn be extruded, mechdnically melted, Cdst or molded as desired. They 34 can be used for plates, sheets, films and a variety of other objects.
While the invention is described in connection with the 36 specific examples below, i-t is understood thdt these are only for 37 illustrative purposes. Many alternatives, modifications and varia-38 tions will be ~pparent to those skilled in the art in light of the 3,. ~ F ~
_ 19 _ below examples and such dlternatives, modifications and variations 2 fall within the general scope of the claims.
3 In Examples 1 through 3 and Comparative Example 1, the silica 4 support was prepared by placing Davison Chemical Company G-95~ silica
5 gel in a vertical column and fluidizing with an upward flow of N2.
6 The column was heated slowly to 600C and held at that temperature for
7 12 hours after which the silica was cooled to ambient temperature. In
8 Examples 4 through 9 and Comparative Example 2~ the silica support was
9 prepared from d microspheroidal silica gel having an average particle size of 45.7 microns as measured by a Leeds and Northrup Microtrac(3) 11 instrument, a surface area of 311 m2/g and a pore volume of l.S9 12 cc/g. The silica gel was dehydrated for five hours at 800C under 13 flowing nitrogen in a manner similar to the G-952 dehydration9 after 14 which the silica was cooled to ambien~ temperatures. In Examples 10 through 13, this silica was dehydrated for five hours at 500C under 16 flowing nitrogen. The melt index (MI) and melt index ratio (MIR) were 17 measured in accordance with ASIM Test D1238 (condition E). The resin 18 density was determined by density gradient column according to ASTM
19 Test D1505. The bulk density was determined by allowing approximately 120 cc of resin to fall from the bottom of a polyethylene funnel 21 across a gap of 1 inch into a tared 100 cc plastic cylinder (2.6 cm in 22 diameter by 19.0 cm high). The funnel bottom~was covered with a piece 23 of cardboard until the funnel was filled with the sample. The entire 24 sample was then allowed to fall into the cylinder. Without agitatirg the sample, excess resin was scraped away so that the container was 26 completely filled without excess. The weight of resin in the 100 cc 27 cylinder was determined. This measurement was repeated 3 times and 28 the average value reported.
2~ Example 1 Into a vial containing 20 ml of hexane there was injected 10 31 ml of butylethylmagnesium (BEM) (6.8 mmoles Mg)~ To the solution was 32 added 0.5 ml (6.8 mmoles) of n-butanol. The mixture was allowed to 33 react at room temperature for 105 hours. The solution was added to a 3q vial containing 3.5 9 of the Davison silica and reacted with the silica for 1 hour at room temperature. To the reaction mixture was 36 added 6.8 mmoles of benzoyl chloride ~BzCl) with stirring. The 37 reaction mixture was stirred at room temperature for 1 hour. To the 38 slurry there was then added 2.3 mmoles of titanium tetrachloride and * TM
~B~
1 the slurry mixture was maintained at room temperature for 1 hour~
2 Therea~ter the vial was connected to a chlorine gas cylinder and 3 pressured to 7.5 psig and allowed to react for 1 hour at room 4 temperature. The vial was purged with nitrogen and the material contained therein filtered. The solid material was washed 3 times 6 with hexane and vacuum dried. The catalyst was reslurried in 20 ml of 7 hexane and 15 ml of tri-n-octyl-aluminum (25 wt % in hexane9 0.47 8 mmole Al/ml) was added to obtain a 3 to 1 molar aluminum to titanium 9 ratio. The reaction mix-ture was maintained at room temperature for 1 hour, filtered, washed 3 times with hexane and driedO Final catalyst 11 contained 1 wt% titanium.
12 To a 1.8 liter reactor there was added 800 cc of hexane, 0.15 13 g of the titanium containing catalyst and 1.7 ml of triisobutyl-14 aluminum cocatalyst (25 wt % in heptane, 0.9 mmole Al/ml) to provide an aluminum to titanium molar ratio o~ 50. The vessel was pressured 16 to 30 psig with H2, and then pressured to 300 psig with ethylene.
17 The vessel was heated to 85C and polymerization was maintained for 90 18 minutes. The results are summarized in Table 1.
19 Examples ? and 3 These examples were run identically as Example 1 with the 21 exception that increased levels of treatment (F) with the aluminum 22 alkyl were employed, the polymerization reactor was pressured to 50 23 psiy with hydrogen and 300 psig total pressure with ethylene and 24 additionally 40 ml of butene-l was injected into the reactor. The polymerization time was maintained for 40 minu-tes at 85C. The 26 amounts of treatment (F) agent and results of the polymerizations are 27 summarized in Table 1.
28 Comparative Example 1 29 The catalyst was prepared identically as in Example 1 with the exception that the treatment with tri-n-octylaluminum was 31 omitted. The polymerization was performed as in Example 1. Results 32 are summarized in Table 1.
33 In Examples 4 through 7, the reaction product of butyl ethyl 34 magnesium (BEM) and 1 butanol was prepared by placing 50 ml of 9.6%
(w/w) BEM in heptane into a clean, dry oxygen-free 125 ml vial con-36 taining a stirring bar followed by the slow addition of 2.84 ml of 37 neat dehydrated 1-butanol added at room temperature with constant 38 stirring. The evolved gas was vented through a syringe needleO The 1 colorless solution was stirred for 3 hours at room temperature. 9.16 2 ml of hexane was added to produce a final concentration of 0.5 mmoles 3 Mg/ml of solution.
4 Example 4 Into a 50 ml vial containing 2 grams oF the dehydrated silica 6 gel in 30 ml of hexane was flowed a mixture of 10% chlorine by volume 7 in nitrogen. The chlorine flow was maintained at a rate of 0.014 8 grams~ minute for 40 minutes at ambient temperature while continuously 9 stirring the silica slurry. Excess C12 was flushed from the vial at the end of the chlorination by flowing pure N2 at the same flow rate 11 for 5 minutes. To the constantly stirred chlorine treated silica 12 slurry, 6.0 ml of the prepared BEM/butanol solution was slowly added 13 at ambient temperatures. The vial was maintained at ambient 14 temperature and stirred for 1 hour. To the slurry was then added dropwise 2 ml of a 0.5 mmole/rnl solution of benzoyl chloride in 16 hexane. Upon completion of the benzoyl chloride addition, the slurry 17 was stirred for 1 hour at ambient temperature. Thereafter 1.2 ml of a 18 0.5 mmole/ml solution oF TiC14 in hexane was added dropwise -to the 19 slurry. The slurry was stirred for 1 hour at ambient temperature.
18.8 ml of a 25.2% (w/w) solution of tri-n-hexyl aluminum in heptane 21 was added dropwise to the slurry and the slurry was stirred for 1 22 hour. The solid catalyst was recovered by decanting the solvent and 23 washed in 30 ml of fresh hexane for 30 minutes. The titanium-24 containing solids were recovered by decantation and drying under a stream of nitrogen at room temperature.
26 To a 1.8 liter polymerization reactor was added 850 ml of 27 hexane, 2.4 ml of 25% (w/w) tri-isobutyl aluminum in heptane. ~he 28 reaction vessel was pressured to 30 psig with hydrogen and then heated 29 to 85C. 20 ml o~ butene-l was pressured into the reactor with sufficient ethylene to bring the total reactor pressure to 150 psig.
31 25 mg of the dry titanium-containing solids was injected into the 32 reactor and polymerization was conducted for 60 minutes. The polymer-33 ization was ceased by shutting off ethylene flow and rapidly cooling 34 the reactor to room temperature. The results of the polymerization are summarized in Table 2. A comparison of the results in Table II
36 shows that the catalyst in accordance with the invention obtains 37 improved bulk density1 a generally narrower molecular weight 38 distribution and a better hydrogen response.
1 Example 5 2 The titanium-containing catalyst component was prepared as in 3 Example 4 with the exception that 4 ml of benzoyl chloride solution 4 was employed in the preparation of the solid catalyst component. The polymerization of ethylene was performed as in Example 4 with the 6 exception that 100 mg of the solid catalyst component was used in the 7 polymerization. The results of the polymerization are summarized in 8 Table 2.
9 Example 6 The titanium-containing catalyst component was prepared as in 11 Example 4 with the exception that 8 ml of benzoyl chloride solution 12 was employed in the preparation of the solid catalyst component. The 13 polymerization of ethylene was performed as in Example 4 with the 14 exception that 100 mg of the solid catalyst component ~as used in the polymerization. The results of the polymerization are summarized in 16 Table 2.
17 Example 7 18 The titanium-containing catalyst component was prepared as in 19 Example 4 with the exception that 8.4 ml of benzoyl chloride solution was employed in the preparation of the solid catalyst component. The 21 polymerization of ethylene was performed as in Example 4 with the 22 exception that 75 mg of the solid catalyst component was used in the 23 polymerization. The results of the polymerization are summarized in 24 Table 2.
Comparative Example 2 26 The titanium-containing catalyst component was prepared as in 27 Example 4 with the exception that benzoyl chloride addition was not 28 included in the preparation of the solid catalyst component. The 29 polymerization of ethylene was performed as in Example 4 with the exception that 25 mg of the solid catalyst component was used in the 31 polymerization. The results of the polymerization are summarized in 32 Table 2.
33 Example 8 34 903 9 of silica was slurried in 5000 ml of isopentane at 25C
under a nitrogen blanket. The slurry temperature was raised to 35C
36 and the reaction vessel was pressured to 11 psig with chlorine which 37 was ~lowed into the reactor at a constant flow rate of 1.2 standard 38 liters/ minute. The chlorine addition was maintained for 1.25 hours 1 a-fter which no further chlorine uptake was observed. The slurry was 2 stirred for an additional 0.75 hours under a chlorine pressure of 11 3 psig. The chlorine atmosphere was thereafter removed with nitrogen 4 flow. To the slurry was added 2,050 ml of a reaction mixture of butylethylmagnesium and butanol prepared by pre-reacting 10% BEM in 6 hexane with neat butanol to produce an alcohol/magnesium molar ratio 7 of 0.95 at a concentration of 0.62 mmole mg/ml. The reaction mixture 8 was added over a 29 minute period and thereafter stirred for 2 hours.
9 To the slurry was thereafter added 268 grams of neat benzoyl chloride over a 15 minute period while maintaining the temperature at 35~.
11 The reaction mixture was then stirred for an additional 45 minutes at 12 which time 51.4 grams of neat TiC14 was added with stirring at 35C
13 over 15 minutes; stirring was continued for 45 minutes. To the slurry 14 was added over a 15 minute period 2,350 ml of a 25% tri-n-hexyl alumi num solution in isopentane. The solution was stirred for an addi-16 tional 45 minutes while maintaining the reaction vessel at 35C. The 17 solvent was removed by decantation, the solids washed in 3,000 ml of 18 isopentane, and, finally, recovered by decantation followed by drying 19 for 4 hours at 60C under flowing nitrogen.
Gas-Phase Polymerization 21 A 36-inch diameter fluid bed reactor, operated in a 22 continuous manner, at 82C and at a total pressure of 300 psig was 23 employed to produce an ethylene-butene-l copolymer. A reaction 24 mixture comprising 31.4 mole percent ethylene, sufficient butene-l and hydrogen to provide a C4H8/C2H4 molar ratio of 0.390 and a H2/C2H4 26 molar ratio of 0.092 was circulated continuously through the bed at a 27 superficial velocity of ~8 cm/sec. The remainder of the reaction 28 mixture was nitrogen. The titanium-containing solid prepared above 29 was continuously pumped at a feed rate of 9.6 g/hr into the reactor and an ll~o triethylaluminum in isopentane solution was continuously 31 pumped into the reactor at a feed rate of 511 cc/hr. The production 32 rate was maintained at 76 kg/hr and an average residence time of 5.0 33 hr. Polymer product formed was removed periodically so as to main-34 tain an essentially constant weight of polymer in the reactor vessel. The results of the polymerization operating at a steady 36 state conditions are set out in Table 3.
~2~6:~
1 Example 9 2 872 grams of silica was slurried in 5,000 ml of isopentane 3 at 25C under a nitrogen blanketO The slurry temperature was raised 4 to 35C and a 1,980 ml~ aliquot of a butylethylmagnesium and butanol reaction product in hexane (prepared by pre-reacting sufficient 10%
6 butylethylmagnesium in hexane with l-butanol to produce an alcoho~lMg 7 molar ratio 0.95 at a concentration of 0.62 mmole Mg/ml~ was added, 8 with stirring over a 30 minute period. The reaction mixture was 9 stirred for two hours. To the reaction mixture was then added 257 grams of neat benzoyl chloride with constant stirring at 35C over a 11 15 minute period, followed by stirrinQ for an additional 45 minutes 12 while maintaining the temperature. Thereafter, 49.8 grams of neat 13 TiC14 was added over a 15 minute period with constant stirring 14 while maintaining the slurry at 35C. The mixture was thereafter stirred for one hour while maintaining the temperature at 35C at 16 which time chlorine gas was flowed into the slurry at approximately 17 1.2 standard liters per minute. The pressure in the reactor was kept 18 at 11 psig and excess chlorine was vented as necessary. Chlorine 19 addition was maintained for two hours at which time the atmosphere was replaced with nitrogen. To the chlorine-treated slurry was then 21 added 2,235 ml of 25~ tri-n-hexalaluminum in isopentane over a 15 22 minute period under constant stirring while maintaining the slurry at 23 35C. Upon completion of the addition, the reaction mixture was 24 stirred for an additional 45 minutes. The solvent was removed by decantation and the solids washed in 3,000 ml of isopentane. The 26 solids were recovered by decantation followed by drying at 60C under 27 a flowing nitrogen stream.
28 Polymerization was performed as in Example, with the 29 exception that H2/C2H4 ratio was 0.135, C4H8/C2H4 ratio was 0.415.
The catalyst feed rate was 11.1 g/hr and the aluminum/titanium molar 31 ratio was 22.8, to obtain a resin production rate of 63 ~g/hr with a 32 residence time of 3.6. The results of the polymerization are 33 summarized in Table III.
34 Example 10 _ Into a 50 ml vial containing 2 grams of -the 500C dehydrated 36 silica gel in 20 ml of hexane was flowed a mixture of 10% chlorine by 37 volume in ni-trogen. The chlorine flow was maintained at a rate of 38 0.014 grams/minute for 40 minutes at ambient temperature while 1 continuously stirring the silica slurry. Excess C12 was flushed 2 from the vial at the end of the chlorination by flowing pure N2 at 3 the same flow rate for 5 minutes. To the constantly stirred chlorine 4 treated silica slurry, 8.0 ml of a 0.5 mmole/ml solution of BEM/
butanol (1:1) was slowly added at ambient temperatures. The vial was 6 maintained at ambient temperature and stirred for 1 hour. To the-7 slurry was then added dropwise 4.8 ml of a 1.0 mmole/ml solution of 8 benzoyl chloride in hexane. Upon completion of the benzoyl chloride9 addition, the slurry was stirred for 1 hour at ambient temperature.
Thereafter 1.6 ml of a 0.5 mmol/ml solution of TiC14 in hexane was 11 added dropwise to the slurry. The slurry was stirred for 1 hour at 12 ambient temperature. 3.8 ml of a 0.629 mmole/ml solution of tri-n-13 hexyl aluminum in hexane/heptane was added dropwise to the slurry and 14 the slurry was stirred for 1 hour. The solid catalyst was recovered by removing the solvent in vacuo.
16 To a 2.0 liter polymerization reactor was added 850 ml of 17 hexane, 4.2 ml of 25~ (w/w) tri-isobutyl aluminum in hep-tane. The 18 reaction vessel was pressured to 30 psig with hydrogen and then 19 heated to 35C. 20 ml of butene-l was pressured in the reactor with sufficient ethylene to bring the total reactor pressure to 150 psig.
21 75 mg of the dry titanium-containing solids slurried in 3.0 ml of 22 white oil was injected into the reactor and polymerization was con-23 ducted for 40 minutes. The polymerization was ceased by shutting off 24 ethylene flow and rapidly cooling the reactor to room temperature.
The results of the polymerization are summarized in Table IV.
26 Example 11 27 The titanium-containing catalyst component was prepared as 28 in Example 10 with the exception that chlorine was added after the 29 addition of the BEM/butanol solution but prior to the benzoyl chlo-ride treatment. The polymerization of @thylene was performed as in 31 Example 10. The results of the polymerization are su~lmarized in 32 Table IV.
33 Example 12 34 The titanium-containing catalyst component was prepared as in Example 10 with the exception that chlorine was added after the 36 addition of the benzoyl chloride solution. The polymerization of 37 ethylene was performed as in Example 10. The results of the polymer-38 ization are summarized in Table IV.
~;~5~
.
1 Example 13 2 The titanium-containing catalyst component was prepared as 3 in Example 10 with the exception that chlorine was added after the 4 addition of the TiCl~ solution. The polymerization of ethylene was performed as in Example 10. The results of the polymeri7ation are 6 summari~ed in Table IV.
~.2~
_ ~ ~ , ~ t~.
~ t,, ~ ~ ~ t~
CQ C ~ C~l C~J C~l r~--t~
~ ~ t~ LS~ ~t t~l r--tn ~n ~ ~;t ~ ~ Cl~
a~ t~ cn a) ~ O O O O
C~
C~
_, O O O
C~:
~ 0 ~o m r~
o^ r~ r~
- o r~ o~
-- . O O O
~, ~_ ~ cn ~ CJ U- a~
r~ ¢ ~ t~ r~ . C 0 t o .
, ~ r~ o O a~
o ~ 4-cl ~ ~ o , ~ ~ s a~
~ n o o o a~
1~ ~ E
~ C~l ~ ~ ~7 + +~ +~ +~
, c~ ~ ~ o ,_ i-- 1-- ~ + E ' '~
E ~
r~ ~ r~l ~, ~ I
X r + r+ r+ E ¢ ~
_~ ~ ~ ~ ,- o I I I I '~I ~ ~
O O O O 't ~ '~ O
~ c~ rn ca o ~ ~, ~
+ + + + c v Q~ ~
~ orc ~ s 1:~ N ~ ~J ~ O ~ O
O O O O ~ N ~ U1 a~
~ E E o O o ^ ^
x ~ ~ r _ ~z _ 1 TABLE_ II
~ Resin Bulk 3 Exdmple Specific MI Density Density 4 Number ActivitY(l) ~ in) MIR(2) ~ (lb/ft ) 6 4 45.0 1.32 29.4 0.9420 25.0 7 5 31.2 1.87 2600 0.9427 25.6 8 6 21.4 -1.98 26.9 0.9429 25.5 9 7 11.5 1.13 26.5 0.9447 23.7 10Comp.2 53.8 1.09 31.7 0.9417 12.5 12 (1) Units of Specific Activity are KgPE/gTi-hr-atm of ethylene 13 (2) MIR is the ratio of HLMI to MI as measured by ASTM D1238 14 (condition E) 18 Example 8Example 9 19 Productivity (9/9) 8,000 5,700 Resin density (gtcc) 0.9195 0.9190 21 MI (dg/min) 1.29 0.98 22 MIR 30.7 33.4 23 Reactor Bulk Density (lb/ft3) 24.6 20.6 27 Bulk 28 Example Specific MI Density 29 Number Activi y(l~tgllO min)MIR(2) (lb/ft ) 157.3 0.4 ~0 19.3 31 11 272.5 0.7 34 22.5 32 12 157.9 0.7 29 20.6 33 13 395 0.6 24 19.3 (1) Units of Specific Activity are KgPE/gTi-hr-moles/L of ethylene.
36 (2) MIR is the ratio of HLMI to MI as measured by ASTM 1238 37 (Condition E).
19 Test D1505. The bulk density was determined by allowing approximately 120 cc of resin to fall from the bottom of a polyethylene funnel 21 across a gap of 1 inch into a tared 100 cc plastic cylinder (2.6 cm in 22 diameter by 19.0 cm high). The funnel bottom~was covered with a piece 23 of cardboard until the funnel was filled with the sample. The entire 24 sample was then allowed to fall into the cylinder. Without agitatirg the sample, excess resin was scraped away so that the container was 26 completely filled without excess. The weight of resin in the 100 cc 27 cylinder was determined. This measurement was repeated 3 times and 28 the average value reported.
2~ Example 1 Into a vial containing 20 ml of hexane there was injected 10 31 ml of butylethylmagnesium (BEM) (6.8 mmoles Mg)~ To the solution was 32 added 0.5 ml (6.8 mmoles) of n-butanol. The mixture was allowed to 33 react at room temperature for 105 hours. The solution was added to a 3q vial containing 3.5 9 of the Davison silica and reacted with the silica for 1 hour at room temperature. To the reaction mixture was 36 added 6.8 mmoles of benzoyl chloride ~BzCl) with stirring. The 37 reaction mixture was stirred at room temperature for 1 hour. To the 38 slurry there was then added 2.3 mmoles of titanium tetrachloride and * TM
~B~
1 the slurry mixture was maintained at room temperature for 1 hour~
2 Therea~ter the vial was connected to a chlorine gas cylinder and 3 pressured to 7.5 psig and allowed to react for 1 hour at room 4 temperature. The vial was purged with nitrogen and the material contained therein filtered. The solid material was washed 3 times 6 with hexane and vacuum dried. The catalyst was reslurried in 20 ml of 7 hexane and 15 ml of tri-n-octyl-aluminum (25 wt % in hexane9 0.47 8 mmole Al/ml) was added to obtain a 3 to 1 molar aluminum to titanium 9 ratio. The reaction mix-ture was maintained at room temperature for 1 hour, filtered, washed 3 times with hexane and driedO Final catalyst 11 contained 1 wt% titanium.
12 To a 1.8 liter reactor there was added 800 cc of hexane, 0.15 13 g of the titanium containing catalyst and 1.7 ml of triisobutyl-14 aluminum cocatalyst (25 wt % in heptane, 0.9 mmole Al/ml) to provide an aluminum to titanium molar ratio o~ 50. The vessel was pressured 16 to 30 psig with H2, and then pressured to 300 psig with ethylene.
17 The vessel was heated to 85C and polymerization was maintained for 90 18 minutes. The results are summarized in Table 1.
19 Examples ? and 3 These examples were run identically as Example 1 with the 21 exception that increased levels of treatment (F) with the aluminum 22 alkyl were employed, the polymerization reactor was pressured to 50 23 psiy with hydrogen and 300 psig total pressure with ethylene and 24 additionally 40 ml of butene-l was injected into the reactor. The polymerization time was maintained for 40 minu-tes at 85C. The 26 amounts of treatment (F) agent and results of the polymerizations are 27 summarized in Table 1.
28 Comparative Example 1 29 The catalyst was prepared identically as in Example 1 with the exception that the treatment with tri-n-octylaluminum was 31 omitted. The polymerization was performed as in Example 1. Results 32 are summarized in Table 1.
33 In Examples 4 through 7, the reaction product of butyl ethyl 34 magnesium (BEM) and 1 butanol was prepared by placing 50 ml of 9.6%
(w/w) BEM in heptane into a clean, dry oxygen-free 125 ml vial con-36 taining a stirring bar followed by the slow addition of 2.84 ml of 37 neat dehydrated 1-butanol added at room temperature with constant 38 stirring. The evolved gas was vented through a syringe needleO The 1 colorless solution was stirred for 3 hours at room temperature. 9.16 2 ml of hexane was added to produce a final concentration of 0.5 mmoles 3 Mg/ml of solution.
4 Example 4 Into a 50 ml vial containing 2 grams oF the dehydrated silica 6 gel in 30 ml of hexane was flowed a mixture of 10% chlorine by volume 7 in nitrogen. The chlorine flow was maintained at a rate of 0.014 8 grams~ minute for 40 minutes at ambient temperature while continuously 9 stirring the silica slurry. Excess C12 was flushed from the vial at the end of the chlorination by flowing pure N2 at the same flow rate 11 for 5 minutes. To the constantly stirred chlorine treated silica 12 slurry, 6.0 ml of the prepared BEM/butanol solution was slowly added 13 at ambient temperatures. The vial was maintained at ambient 14 temperature and stirred for 1 hour. To the slurry was then added dropwise 2 ml of a 0.5 mmole/rnl solution of benzoyl chloride in 16 hexane. Upon completion of the benzoyl chloride addition, the slurry 17 was stirred for 1 hour at ambient temperature. Thereafter 1.2 ml of a 18 0.5 mmole/ml solution oF TiC14 in hexane was added dropwise -to the 19 slurry. The slurry was stirred for 1 hour at ambient temperature.
18.8 ml of a 25.2% (w/w) solution of tri-n-hexyl aluminum in heptane 21 was added dropwise to the slurry and the slurry was stirred for 1 22 hour. The solid catalyst was recovered by decanting the solvent and 23 washed in 30 ml of fresh hexane for 30 minutes. The titanium-24 containing solids were recovered by decantation and drying under a stream of nitrogen at room temperature.
26 To a 1.8 liter polymerization reactor was added 850 ml of 27 hexane, 2.4 ml of 25% (w/w) tri-isobutyl aluminum in heptane. ~he 28 reaction vessel was pressured to 30 psig with hydrogen and then heated 29 to 85C. 20 ml o~ butene-l was pressured into the reactor with sufficient ethylene to bring the total reactor pressure to 150 psig.
31 25 mg of the dry titanium-containing solids was injected into the 32 reactor and polymerization was conducted for 60 minutes. The polymer-33 ization was ceased by shutting off ethylene flow and rapidly cooling 34 the reactor to room temperature. The results of the polymerization are summarized in Table 2. A comparison of the results in Table II
36 shows that the catalyst in accordance with the invention obtains 37 improved bulk density1 a generally narrower molecular weight 38 distribution and a better hydrogen response.
1 Example 5 2 The titanium-containing catalyst component was prepared as in 3 Example 4 with the exception that 4 ml of benzoyl chloride solution 4 was employed in the preparation of the solid catalyst component. The polymerization of ethylene was performed as in Example 4 with the 6 exception that 100 mg of the solid catalyst component was used in the 7 polymerization. The results of the polymerization are summarized in 8 Table 2.
9 Example 6 The titanium-containing catalyst component was prepared as in 11 Example 4 with the exception that 8 ml of benzoyl chloride solution 12 was employed in the preparation of the solid catalyst component. The 13 polymerization of ethylene was performed as in Example 4 with the 14 exception that 100 mg of the solid catalyst component ~as used in the polymerization. The results of the polymerization are summarized in 16 Table 2.
17 Example 7 18 The titanium-containing catalyst component was prepared as in 19 Example 4 with the exception that 8.4 ml of benzoyl chloride solution was employed in the preparation of the solid catalyst component. The 21 polymerization of ethylene was performed as in Example 4 with the 22 exception that 75 mg of the solid catalyst component was used in the 23 polymerization. The results of the polymerization are summarized in 24 Table 2.
Comparative Example 2 26 The titanium-containing catalyst component was prepared as in 27 Example 4 with the exception that benzoyl chloride addition was not 28 included in the preparation of the solid catalyst component. The 29 polymerization of ethylene was performed as in Example 4 with the exception that 25 mg of the solid catalyst component was used in the 31 polymerization. The results of the polymerization are summarized in 32 Table 2.
33 Example 8 34 903 9 of silica was slurried in 5000 ml of isopentane at 25C
under a nitrogen blanket. The slurry temperature was raised to 35C
36 and the reaction vessel was pressured to 11 psig with chlorine which 37 was ~lowed into the reactor at a constant flow rate of 1.2 standard 38 liters/ minute. The chlorine addition was maintained for 1.25 hours 1 a-fter which no further chlorine uptake was observed. The slurry was 2 stirred for an additional 0.75 hours under a chlorine pressure of 11 3 psig. The chlorine atmosphere was thereafter removed with nitrogen 4 flow. To the slurry was added 2,050 ml of a reaction mixture of butylethylmagnesium and butanol prepared by pre-reacting 10% BEM in 6 hexane with neat butanol to produce an alcohol/magnesium molar ratio 7 of 0.95 at a concentration of 0.62 mmole mg/ml. The reaction mixture 8 was added over a 29 minute period and thereafter stirred for 2 hours.
9 To the slurry was thereafter added 268 grams of neat benzoyl chloride over a 15 minute period while maintaining the temperature at 35~.
11 The reaction mixture was then stirred for an additional 45 minutes at 12 which time 51.4 grams of neat TiC14 was added with stirring at 35C
13 over 15 minutes; stirring was continued for 45 minutes. To the slurry 14 was added over a 15 minute period 2,350 ml of a 25% tri-n-hexyl alumi num solution in isopentane. The solution was stirred for an addi-16 tional 45 minutes while maintaining the reaction vessel at 35C. The 17 solvent was removed by decantation, the solids washed in 3,000 ml of 18 isopentane, and, finally, recovered by decantation followed by drying 19 for 4 hours at 60C under flowing nitrogen.
Gas-Phase Polymerization 21 A 36-inch diameter fluid bed reactor, operated in a 22 continuous manner, at 82C and at a total pressure of 300 psig was 23 employed to produce an ethylene-butene-l copolymer. A reaction 24 mixture comprising 31.4 mole percent ethylene, sufficient butene-l and hydrogen to provide a C4H8/C2H4 molar ratio of 0.390 and a H2/C2H4 26 molar ratio of 0.092 was circulated continuously through the bed at a 27 superficial velocity of ~8 cm/sec. The remainder of the reaction 28 mixture was nitrogen. The titanium-containing solid prepared above 29 was continuously pumped at a feed rate of 9.6 g/hr into the reactor and an ll~o triethylaluminum in isopentane solution was continuously 31 pumped into the reactor at a feed rate of 511 cc/hr. The production 32 rate was maintained at 76 kg/hr and an average residence time of 5.0 33 hr. Polymer product formed was removed periodically so as to main-34 tain an essentially constant weight of polymer in the reactor vessel. The results of the polymerization operating at a steady 36 state conditions are set out in Table 3.
~2~6:~
1 Example 9 2 872 grams of silica was slurried in 5,000 ml of isopentane 3 at 25C under a nitrogen blanketO The slurry temperature was raised 4 to 35C and a 1,980 ml~ aliquot of a butylethylmagnesium and butanol reaction product in hexane (prepared by pre-reacting sufficient 10%
6 butylethylmagnesium in hexane with l-butanol to produce an alcoho~lMg 7 molar ratio 0.95 at a concentration of 0.62 mmole Mg/ml~ was added, 8 with stirring over a 30 minute period. The reaction mixture was 9 stirred for two hours. To the reaction mixture was then added 257 grams of neat benzoyl chloride with constant stirring at 35C over a 11 15 minute period, followed by stirrinQ for an additional 45 minutes 12 while maintaining the temperature. Thereafter, 49.8 grams of neat 13 TiC14 was added over a 15 minute period with constant stirring 14 while maintaining the slurry at 35C. The mixture was thereafter stirred for one hour while maintaining the temperature at 35C at 16 which time chlorine gas was flowed into the slurry at approximately 17 1.2 standard liters per minute. The pressure in the reactor was kept 18 at 11 psig and excess chlorine was vented as necessary. Chlorine 19 addition was maintained for two hours at which time the atmosphere was replaced with nitrogen. To the chlorine-treated slurry was then 21 added 2,235 ml of 25~ tri-n-hexalaluminum in isopentane over a 15 22 minute period under constant stirring while maintaining the slurry at 23 35C. Upon completion of the addition, the reaction mixture was 24 stirred for an additional 45 minutes. The solvent was removed by decantation and the solids washed in 3,000 ml of isopentane. The 26 solids were recovered by decantation followed by drying at 60C under 27 a flowing nitrogen stream.
28 Polymerization was performed as in Example, with the 29 exception that H2/C2H4 ratio was 0.135, C4H8/C2H4 ratio was 0.415.
The catalyst feed rate was 11.1 g/hr and the aluminum/titanium molar 31 ratio was 22.8, to obtain a resin production rate of 63 ~g/hr with a 32 residence time of 3.6. The results of the polymerization are 33 summarized in Table III.
34 Example 10 _ Into a 50 ml vial containing 2 grams of -the 500C dehydrated 36 silica gel in 20 ml of hexane was flowed a mixture of 10% chlorine by 37 volume in ni-trogen. The chlorine flow was maintained at a rate of 38 0.014 grams/minute for 40 minutes at ambient temperature while 1 continuously stirring the silica slurry. Excess C12 was flushed 2 from the vial at the end of the chlorination by flowing pure N2 at 3 the same flow rate for 5 minutes. To the constantly stirred chlorine 4 treated silica slurry, 8.0 ml of a 0.5 mmole/ml solution of BEM/
butanol (1:1) was slowly added at ambient temperatures. The vial was 6 maintained at ambient temperature and stirred for 1 hour. To the-7 slurry was then added dropwise 4.8 ml of a 1.0 mmole/ml solution of 8 benzoyl chloride in hexane. Upon completion of the benzoyl chloride9 addition, the slurry was stirred for 1 hour at ambient temperature.
Thereafter 1.6 ml of a 0.5 mmol/ml solution of TiC14 in hexane was 11 added dropwise to the slurry. The slurry was stirred for 1 hour at 12 ambient temperature. 3.8 ml of a 0.629 mmole/ml solution of tri-n-13 hexyl aluminum in hexane/heptane was added dropwise to the slurry and 14 the slurry was stirred for 1 hour. The solid catalyst was recovered by removing the solvent in vacuo.
16 To a 2.0 liter polymerization reactor was added 850 ml of 17 hexane, 4.2 ml of 25~ (w/w) tri-isobutyl aluminum in hep-tane. The 18 reaction vessel was pressured to 30 psig with hydrogen and then 19 heated to 35C. 20 ml of butene-l was pressured in the reactor with sufficient ethylene to bring the total reactor pressure to 150 psig.
21 75 mg of the dry titanium-containing solids slurried in 3.0 ml of 22 white oil was injected into the reactor and polymerization was con-23 ducted for 40 minutes. The polymerization was ceased by shutting off 24 ethylene flow and rapidly cooling the reactor to room temperature.
The results of the polymerization are summarized in Table IV.
26 Example 11 27 The titanium-containing catalyst component was prepared as 28 in Example 10 with the exception that chlorine was added after the 29 addition of the BEM/butanol solution but prior to the benzoyl chlo-ride treatment. The polymerization of @thylene was performed as in 31 Example 10. The results of the polymerization are su~lmarized in 32 Table IV.
33 Example 12 34 The titanium-containing catalyst component was prepared as in Example 10 with the exception that chlorine was added after the 36 addition of the benzoyl chloride solution. The polymerization of 37 ethylene was performed as in Example 10. The results of the polymer-38 ization are summarized in Table IV.
~;~5~
.
1 Example 13 2 The titanium-containing catalyst component was prepared as 3 in Example 10 with the exception that chlorine was added after the 4 addition of the TiCl~ solution. The polymerization of ethylene was performed as in Example 10. The results of the polymeri7ation are 6 summari~ed in Table IV.
~.2~
_ ~ ~ , ~ t~.
~ t,, ~ ~ ~ t~
CQ C ~ C~l C~J C~l r~--t~
~ ~ t~ LS~ ~t t~l r--tn ~n ~ ~;t ~ ~ Cl~
a~ t~ cn a) ~ O O O O
C~
C~
_, O O O
C~:
~ 0 ~o m r~
o^ r~ r~
- o r~ o~
-- . O O O
~, ~_ ~ cn ~ CJ U- a~
r~ ¢ ~ t~ r~ . C 0 t o .
, ~ r~ o O a~
o ~ 4-cl ~ ~ o , ~ ~ s a~
~ n o o o a~
1~ ~ E
~ C~l ~ ~ ~7 + +~ +~ +~
, c~ ~ ~ o ,_ i-- 1-- ~ + E ' '~
E ~
r~ ~ r~l ~, ~ I
X r + r+ r+ E ¢ ~
_~ ~ ~ ~ ,- o I I I I '~I ~ ~
O O O O 't ~ '~ O
~ c~ rn ca o ~ ~, ~
+ + + + c v Q~ ~
~ orc ~ s 1:~ N ~ ~J ~ O ~ O
O O O O ~ N ~ U1 a~
~ E E o O o ^ ^
x ~ ~ r _ ~z _ 1 TABLE_ II
~ Resin Bulk 3 Exdmple Specific MI Density Density 4 Number ActivitY(l) ~ in) MIR(2) ~ (lb/ft ) 6 4 45.0 1.32 29.4 0.9420 25.0 7 5 31.2 1.87 2600 0.9427 25.6 8 6 21.4 -1.98 26.9 0.9429 25.5 9 7 11.5 1.13 26.5 0.9447 23.7 10Comp.2 53.8 1.09 31.7 0.9417 12.5 12 (1) Units of Specific Activity are KgPE/gTi-hr-atm of ethylene 13 (2) MIR is the ratio of HLMI to MI as measured by ASTM D1238 14 (condition E) 18 Example 8Example 9 19 Productivity (9/9) 8,000 5,700 Resin density (gtcc) 0.9195 0.9190 21 MI (dg/min) 1.29 0.98 22 MIR 30.7 33.4 23 Reactor Bulk Density (lb/ft3) 24.6 20.6 27 Bulk 28 Example Specific MI Density 29 Number Activi y(l~tgllO min)MIR(2) (lb/ft ) 157.3 0.4 ~0 19.3 31 11 272.5 0.7 34 22.5 32 12 157.9 0.7 29 20.6 33 13 395 0.6 24 19.3 (1) Units of Specific Activity are KgPE/gTi-hr-moles/L of ethylene.
36 (2) MIR is the ratio of HLMI to MI as measured by ASTM 1238 37 (Condition E).
Claims (71)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A transition metal-containing catalyst component comprising the solid reaction product obtained by treating an inert solid support material in an inert solvent with (A) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbon or substituted hydrocarbon group, (B) an oxygen-containing compound selected from ketones, aldehydes, alcohols, siloxanes or mixtures thereof, (C) an acyl halide (D) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal, (E) Cl2, Br2 or an interhalogen, and (F) prereducing the transition metal-containîng product with an organometallic compound of a Group IIa, IIb or IIIa metal, with the proviso that the (A) and (B) ingredients can be added to the inert solid (i) simultaneously, (ii) as the reaction product of (A) and (B), or (iii) treatment with (B) immediately precedes treatment with (A).
2. The transition metal-containing catalyst component of claim 1 wherein the solid reaction product is obtained by treating the inert solid support material in an inert solvent in the orders selected from the group consisting of (a) first treating with ingredient (E) followed by sequential treatment with ingredients (A), (B), (C), (D), and (F), (b) first treating with ingredients (A) and (B) followed by the sequential treatment with ingredients (C), (D), (E), and (F), or (c) first treating with ingredient (C) followed by the sequential treatment with ingredients (A) and (B), (E), (D), and (F), (d) first treating with ingredients (B) and (A) followed by the sequential treatment with ingredients (E), (C), (D), and (F).
with the further proviso that the (A) and (B) ingredients can be added (i) simultaneously, (ii) as the reaction product of (A) and (B), or (iii) treatment with (B) immediately precedes treatment with (A).
with the further proviso that the (A) and (B) ingredients can be added (i) simultaneously, (ii) as the reaction product of (A) and (B), or (iii) treatment with (B) immediately precedes treatment with (A).
3. The transition metal-containing catalyst component of claim 2 wherein the solid reaction product is obtained by treating the inert solid support material in an inert solvent with ingredient (E) followed by sequential treatment with ingredients (A), (B), (C), (D), and (F) and that the (A) and (B) ingredients can be added (i) simultaneously, (ii) as the reaction product of (A) and (B), or (iii) treatment with (B) immediately precedes treatment with (A).
4. The transition metal-containing catalyst component of claim 2 wherein the solid reaction product is obtained by treating inert solid support material in an inert solvent with ingredients (A) and (B), followed by sequential treatmen with ingredients (C), (D), (E), and (F) and with the further proviso that the (A) and (B) ingredients can be added to the inert solid (i) simultaneously, (ii) as the reaction product of (A) and (B), or (iii) treatment of the inert solid with (B) immediately precedes treatment with (A).
5. The transition metal-containing catalyst component of claim 2 wherein comprising the solid reaction product is obtained by treating the inert solid support material in an inert solvent with ingredient (C) followed by sequential treatment with ingredients (A), (B), (E), (D), and (F) and that the (A) and (B) ingredients can be added (i) simultaneously, (ii) as the reaction product of (A) and (B), or (iii) treatment with (B) immediately precedes treatment with (A).
6. The transition metal-containing catalyst component of claim 1 wherein the (A) organometallic compound is d dihydrocarbyl magnesium compound represented by R1MgR2, wherein R1 and R2, which can be the same or different, contain 1 to 20 carbon atoms and are selected from alkyl groups, aryl groups, cycloalkyl groups, aralkyl groups, alkadienyl groups or alkenyl groups, the (B) oxygen-containing compounds are selected from alcohols and ketones repre-sented by the formula R3OH and R4COR5 wherein R3 and each of R4 and R5 which may be the same or different groups containing 1 to 20 carbon atoms and can be an alkyl group, aryl group, cycloalkyl group, aralkyl group, alkadienyl group or alkenyl group, the (C) acyl halide is represented by the formula R6COX wherein R6 can be a C1 to C12 alkyl group, cycloalkyl group, aryl group or substituted aryl group and X is halogen, the (E) halogen is Cl2 and the (F) organometallic compound is an aluminum alkyl represented by R?AlX'3-n wherein X' is a halogen or hydride and R7 is a hydrocarbyl group selected from C1 to C18 hydrocarbon radicals and 1 ? n ? 3.
7. The transition metal-containing catalyst component of claim 6 wherein the inert solid support material is one of silica, alumina, magnesia or mixtures thereof.
8. The transition metal-containing catalyst component of claim 6 wherein R1, R2, R3, R4, R5, R6 and R7 are alkyl or aryl groups having from 1 to 10 carbon atoms.
9. The transition metal-containing catalyst component of claim 6 wherein R1 and R2 are different.
10. The transition meta1-containing cata1yst component of claim 9 wherein R1, R2 and R3 are alkyl groups having from 1 to 6 carbon atoms.
11. The transition metal-containing catalyst component of claim 10 wherein R1 is butyl.
12. The transition metal-containing catalyst component of claim 11 wherein R2 is ethyl.
13. The transition metal-containing catalyst component of claim 12 wherein the oxygen-containing component is an alcohol.
14. The transition metal-containing catalyst component of claim 13 wherein R3 is butyl.
15. The transition metal-containing catalyst component of claim 6 wherein n is 3 and R7 is an alkyl group containing from 1 to 8 carbon atoms.
16. The transition metal-containing catalyst component of claim 6 wherein the (D) transition metal compound or mixtures thereof is represented by the formula TrX"4-q(OR8)q9 TrX"4-qR?, VOX"3 or VO(OR8)3 wherein Tr is a transition metal, R8 is a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms, R9 is an alky1 group, aryl group or aralkyl group having from 1 to 20 carbon atoms or a 1,3-cyclopentadienyl, X" is halogen and q is 0 or a number equal to or less than 4.
17. The transition metal-containing catalyst component of claim 16 wherein Tr is titanium, vanadium or zirconium.
18. The transition metal-containing catalyst component of claim 17 wherein the transition metal compound is TiCl4.
19. The transition metal-containing catalyst component of claim 6 wherein R6 is a C1 to C12 alkyl group, cycloalkyl group, aryl group or substituted aryl group and X is chlorine.
20. The transition metal-containing catalyst component of claim 19 wherein R6 is an methyl or phenyl group.
21. The transition metal-containing catalyst component of claims 1, 2, or 3 in which the (A) organomagnesium compound is ethyl-n-butyl magnesium and the (B) oxygen-containing compound is an alcohol having from 1 to 4 carbon atoms and are reacted together.
22. The transition metal-containing catalyst component of claim 6 wherein the aluminum compound is a trialkyl aluminum wherein the alkyl group has from 1 to 10 carbon atoms.
23. The transition metal-containing catalyst component of claim 22 wherein the aluminum alkyl is tri-n-hexyl aluminum.
24. The transition metal-containing component of claims 3, 4, or 5 in which the inert support is silica, the (A) and (B) ingredients are added as the reaction product of n-butyl-ethyl-magnesium with butanol, (C) is benzoyl chloride, (D) is TiCl4, (E) is Cl2 and (F) is tri-n-hexylaluminum.
25. A catalyst system for the polymerization or copoly-merization of ethylene and alpha-olefins having from 3 to 12 carbon atoms comprising (a) an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbon or substituted hydrocarbon having from 1 to 20 carbon atoms, X
is halogen and n is a number from 1 to 3, and (b) a transition metal-containing catalyst component comprising the solid reaction product obtained by treating an inert solid support material in an inert solvent with (A) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbyl or substituted hydrocarbyl group, (B) an oxygen-containing compound selected from ketones, aldehydes, alcohols or mixtures thereof, (C) an acyl halide, (D) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal , (E) Cl2, Br2 or an interhalogen, and (F) prereducing the transition metal-containing product with an organometallic compound of a Group IIa, IIb or IIIa metal, with the proviso that the (A) and (B) ingredients can be added to the inert solid (i) simultaneously, (ii) as the reaction product of (A), and (B) or (iii) treatment with (B) immediately precedes treatment with (A).
is halogen and n is a number from 1 to 3, and (b) a transition metal-containing catalyst component comprising the solid reaction product obtained by treating an inert solid support material in an inert solvent with (A) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbyl or substituted hydrocarbyl group, (B) an oxygen-containing compound selected from ketones, aldehydes, alcohols or mixtures thereof, (C) an acyl halide, (D) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal , (E) Cl2, Br2 or an interhalogen, and (F) prereducing the transition metal-containing product with an organometallic compound of a Group IIa, IIb or IIIa metal, with the proviso that the (A) and (B) ingredients can be added to the inert solid (i) simultaneously, (ii) as the reaction product of (A), and (B) or (iii) treatment with (B) immediately precedes treatment with (A).
26. The catalyst system of claim 25 wherein the transition metal-containing catalyst component comprises the solid reaction product obtained by treating the inert solid support material in an inert solvent in the orders selected from the group consisting of (a) first treating with ingredient (E) followed by sequential treatment with ingredients (A), (B), (C), (D), and (F), (b) first treating with ingredients (A) and (B) followed by the sequential treatment with ingredients (C), (D), (E), and (F), or (c) first treating with ingredient (C) followed by the sequential treatment with ingredients (A) and (B), (E), (D), and (F), (d) first treating with ingredients (B) and (A) followed by the sequential treatment with ingreclients (E), (C), (D), and (F).
with the further proviso that the (A) and (B) ingredients can be added (i) simultaneously, (ii) as the reacton product of (A) and (B) or (iii) treatment with (B) immediately precedes treatment with (A).
with the further proviso that the (A) and (B) ingredients can be added (i) simultaneously, (ii) as the reacton product of (A) and (B) or (iii) treatment with (B) immediately precedes treatment with (A).
27. The catalyst system of claim 26 wherein the transition metal-containing catalyst component comprises the solid reaction product obtained by treating the inert solid support material in an inert solvent with ingredient (E) followed by seqential treatment with ingredients (A) and (B), (C), (D), and (F) and that the (A) and (B) ingredients can be added (i) simultaneously, (ii) as the reacton product of (A) and (B) or (iii) treatment with (B) immediately precedes treatment with (A).
28. The catalyst system of claim 26 wherein the transition metal-containing catalyst component comprises the solid reaction product obtained by treating the inert solid support material in an inert solvent with ingredients (A) and (B), followed by the sequential treatment with ingredients (C), (D), (E), and (F) and with the further proviso that the (A) and (B) ingredients can be added to the inert solid (i) simultaneously, (ii) as the reacton product of (A) and (B) or (iii) treatment of the inert solid with (B) immediately precedes treatment with (A).
29. The catalyst system of claim 26 wherein the transition metal-containing catalyst component comprises the solid reaction product obtained by treating the inert solid support material in an inert solvent with ingredient (C) followed by sequential treatment with ingredients (A) and (B), (E), (D), and (F) and that the (A) and (B) ingredients can be added (i) simultaneously, (ii) as the reacton product of (A) and (B) or (iii) treatment with (B) immediately precedes treatment with (A).
30. The catalyst system of claim 25 wherein the (A) organo-metallic compound is a dihydrocarbyl magnesium compound represented by R1MgR2, wherein R1 and R2, which can be the same or different; are selected from C1 to C20 alkyl groups, aryl groups, cycloalkyl groups, aralkyl groups, alkadienyl groups or alkenyl groups, the (B) oxygen-containing compounds are selected from alcohols and ketones represented by the formula R3OH and R4COR5 wherein R3 and each of R4 and R5 which may be the same or different can be a C1 to C20 alkyl group, aryl group, cycloalkyl group, aralkyl group, alkadienyl group or alkenyl group, the (C) acyl halide is represented by the formula R6COX wherein R6 can be a C1 to C12 alkyl group, cycloalkyl group, aryl group or substituted aryl group and X is halogen, the (E) halogen is Cl2 and the (F) organometallic compound is an aluminum alkyl represented by Rn7AlX'3-n wherein X' is a halogen, or hydride and R7 is a hydrocarbyl group selected from C1 to C18 saturated hydrocarbon radicals and 1 ? n ? 3.
31. The catalyst system of claim 30 wherein the inert solid support material is one of silica, alumina, magnesia or mixtures thereof.
32. The catalyst system of claim 30 wherein R1, R2, R3, R4, R5, R6 and R7 are alkyl or aryl groups having from 1 to 10 carbon atoms.
33. The catalyst system of claim 30 wherein R1 and R2 are different.
34. The catalyst system of claim 33 wherein R1, R2 and R3 are alkyl groups having from 1 to 6 carbon atoms.
35. The catalyst system of claim 34 wherein R1 is butyl.
36. The catalyst system of claim 35 wherein R2 is ethyl.
37. The catalyst system of claim 36 wherein the oxygen-containing component is an alcohol.
38. The catalyst system of claim 37 wherein R3 is butyl.
39. The catalyst system of claim 30 wherein n is 3 and R7 is an alkyl group containing from 1 to 8 carbon atoms.
40. The catalyst system of claim 30 wherein the transition metal compound or mixtures thereof is represented by the formula TrX"4-q(OR8)q, TrX"4-qR?, VOX"3 or VO(OR8)3 wherein Tr is a transition metal, R8 is a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms, R9 is an alkyl group, aryl group or aralkyl group having from 1 to 20 carbon atoms or a 1,3-cyclo-pentadienyl, X' is halogen and q is 0 or d number equal to or less than 4.
41. The catalyst system of claim 40 wherein Tr is titanium, vanadium or zirconium.
42. The catalyst system of claim 41 wherein the transition metal compound is TiCl4.
43. The catalyst system of claims 25, 26 or 27 in which the (A) the organomagnesium compound is ethyl-n-butyl magnesium and the (B) oxygen-containing compound is an alcohol having from 1 to 4 carbon atoms and are reacted together.
44. The catalyst system of claim 25 wherein the aluminum compound is a trialkyl aluminum wherein the alkyl group has from 1 to 10 carbon atoms.
45. The catalyst system of claim 40 wherein the aluminum alkyl is tri-n-hexyl aluminum.
46. The catalyst system of claims 27, 28, or 29 in which the inert support is silica, the (A) and (B) ingredients are added as the reaction product of n-butylethylmagnesium with butanol, (C) is benzoyl chloride, (D) is TiCl4, (E) is Cl2, and (F) is tri-n-hexylaluminum.
47. A process for the polymerization of ethylene and alpha-olefins having from 1 to 20 carbon atoms or mixtures of ethylene, alpha-olefins and diolefins which process comprises polymerizing in the presence of a catalyst system comprising (a) an organo aluminum compound of the formula AlR"'nX"'3-n wherein R"' is hydrogen, hydrocarbyl or substitute hydrocarbyl having from 1 to 20 carbon atoms, X"' is halogen and n is a number from 1 to 3, and (b) a transition metal-containing catalyst component comprising the solid reaction product obtained by treating an inert solid support material in an inert solvent with (A) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbyl or substituted hydrocarbyl group, (B) an oxygen-containing compound selected from ketones, aldehydes, alcohols or mixtures thereof, (C) an acyl ha1ide, (D) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal , (E) Cl2, Br2 or an interhalogen, and (F) prereducing the transition metal-containing product with an organometallic compound of a Group IIa, IIb or IIIa metal, with the proviso that the (A) and (B) ingredients can be added to the inert solid (i) simultaneously, (ii) as the reaction product of (A), and (B) or (iii) treatment with (B) immediately precedes treatment with (A).
48. The process as in claim 47 wherein the transition metal-containing catalyst component comprises the solid reaction product obtained by treating the inert solid support material in an inert solvent in the orders selected from the group consisting of (a) first treating with ingredient (E) followed by sequential treatment with ingredients (A), (B), (C), (D), and (F), (b) first treating with ingredients (A) and (B) followed by the sequential treatment with ingredients (C), (D), (E), and (F), or (c) first treating with ingredient (C) followed by the sequential treatment with ingredients (A) and (B), (E), (D), and (F), (d) first treating with ingredients (B) and (A) followed by the sequential treatment with ingredients (E), (C), (D), and (F).
with the further proviso that the (A) and (B) ingredients can be added (i) simultaneously, (ii) as the reacton product of (A) and (B) or (iii) treatment with (B) immediately precedes treatment with (A).
with the further proviso that the (A) and (B) ingredients can be added (i) simultaneously, (ii) as the reacton product of (A) and (B) or (iii) treatment with (B) immediately precedes treatment with (A).
49. The process as in claim 48 wherein the transition metal-containing catalyst component comprises the solid reaction product obtained by treating the inert solid support material in an inert solvent with ingredient (E) followed by seqential treatment with ingredients (A) and (B), (C), (D), and (F) and that the (A) and (B) ingredients can be added (i) simultaneously, (ii) as the reacton product of (A) and (B) or (iii) treatment with (B) immediately precedes treatment with (A).
50. The process as in claim 48 wherein the transition metal-containing catalyst component comprises the solid reaction product obtained by treating the inert solid support material in an inert solvent with ingredients (A) and (B), followed by the sequential treatment with ingredients (C), (D), (E), and (F) and with the further proviso that the (A) and (B) ingredients can be added to the inert solid (i) simultaneously, (ii) as the reacton product of (A) and (B) or (iii) treatment of the inert solid with (B) immediately precedes treatment with (A).
51. The catalyst system of claim 48 wherein the transition metal-containing catalyst component comprises the solid reaction product obtained by treating the inert solid support material in an inert solvent with ingredient (C) followed by sequential treatment with ingredients (A) and (B), (E), (D), and (F) and that the (A) and (B) ingredients can be added (i) simultaneously, (ii) as the reacton product of (A) and (B) or (iii) treatment with (B) immediately precedes treatment with (A).
52. The process as in claim 47 wherein the (A) organo-metallic compound is a dihydrocarbon magnesium compound represented by R1MgR2, wherein R1 and R2, which can be the same or different, are selected from C1 to C20 alkyl groups, aryl groups, cycloalkyl groups, aralkyl groups, alkadienyl groups or alkenyl groups, the (B) oxygen-containing compounds are selected from alcohols and ketones represented by the formula R3OH and R4COR5 wherein R3 and each of R4 and R5 which may be the same or different can be a C1 to C20 alkyl group, aryl group, cycloalkyl group, aralkyl group, alkadienyl group or alkenyl group, the (C) acyl halide is represented by the formula R6COX wherein R6 can be a C1 to C12 alkyl group, cycloalkyl group, aryl group, or substituted aryl group and X is halogen, the (E) halogen is C12 and the (F) organometallic compound is an aluminum alkyl represented by R?AlX'3-n wherein X' is a halogen or hydride and R7 is a hydrocarbyl group selected from C1 to C18 saturated hydrocarbon and 1 ? n ? 3.
53. The process as in claim 52 wherein the inert solid support material is one of silica, aluminum, magnesium or mixtures thereof.
54. The process as in claim 52 wherein R1, R2, R3, R4, R5, R6 and R7 are alkyl or aryl groups having from 1 to 10 carbon atoms.
55. The process as in claim 52 wherein R1 and R2 are different.
56. The process as in claim 55 wherein R1, R2 and R3 are alkyl groups having from 1 to 6 carbon atoms.
57. The process as in claim 56 wherein R1 is butyl.
58. The process as in claim 57 wherein R2 is ethyl.
59. The process as in claim 58 wherein the oxygen-contain-ing component is an alcohol.
60. The process as in claim 59 wherein R3 is butyl.
61. The process as in claim 52 wherein n is 3 and R7 is an alkyl group containing from 1 to 8 carbon atoms.
62. The process as in claim 52 wherein the transition metal compound or mixtures thereof is represented by the formula TrX"4-q(OR8)q, TrX"4-qR?, VOX"3 or VO(OR8)3 wherein Tr is a transi-tion metal, R8 is a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms, R9 is an alkyl group, aryl group or aralkyl group having from 1 to 20 carbon atoms or a 1,3-cyclopentadienyl, X' is halogen and q is 0 or a number equal to or less than 4.
63. The process as in claim 62 wherein Tr is titanium, vanadium or zirconium.
64. The process as in claim 63 wherein the transition metal compound is TiCl4.
65. The process as in claims 47, 48, or 49 in which the (A) organomagnesium compound is ethyl-n-butylmagnesium and the (B) oxygen-containing compound is an alcohol having from 1 to 4 carbon atoms and are reacted together.
66. The process as in claim 52 wherein the aluminum compound is a trialkyl aluminum wherein the alkyl group has from 1 to 10 carbon atoms.
67. The process as in claim 66 wherein the aluminum alkyl is tri-n-hexyl aluminum.
68. The catalyst system of claims 49,50 and 51 in which the inert support is silica, the (A) and (B) ingredients are added as the reaction product of n-butyl-ethylemagnesium with butanol, (C) is benzoyl chloride, (D) is TiCl4, (E) is Cl2, and (F) is tri-n-hexylaluminum.
69. The transition metal containing catalyst component of claims 4 or 5 in which the (A) organomagnesium oompound is ethyl-n-butyl magnesium and the (B) oxygen-oontaining ccmpound is an alcohol having from 1 to 4 carbon atoms and are reacted together.
70. The catalyst system of claims 28 or 29 in which the (A) organomagnesium compound is ethyl-n-butyl magnesium and the (B) oxygen-containing compound is an alcohol having from 1 to 4 carbon atoms and are reacted together.
71. The process as in claims 50 or 51 in which the (A) organomagnesium compound is ethyl-n-butylmagnesium and the (B) oxygen-containing compound is an alcohol having from 1 to 4 carbon atoms and are reacted together.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63798584A | 1984-08-06 | 1984-08-06 | |
| US637,985 | 1984-08-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1258061A true CA1258061A (en) | 1989-08-01 |
Family
ID=24558181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000487742A Expired CA1258061A (en) | 1984-08-06 | 1985-07-30 | Polymerization catalyst, production and use |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1258061A (en) |
| ZA (1) | ZA855853B (en) |
-
1985
- 1985-07-30 CA CA000487742A patent/CA1258061A/en not_active Expired
- 1985-08-02 ZA ZA855853A patent/ZA855853B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA855853B (en) | 1987-04-29 |
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