CA1187862A - Polymerization catalyst - Google Patents
Polymerization catalystInfo
- Publication number
- CA1187862A CA1187862A CA000412442A CA412442A CA1187862A CA 1187862 A CA1187862 A CA 1187862A CA 000412442 A CA000412442 A CA 000412442A CA 412442 A CA412442 A CA 412442A CA 1187862 A CA1187862 A CA 1187862A
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- CA
- Canada
- Prior art keywords
- alpha
- olefins
- ethylene
- diolefins
- catalyst component
- Prior art date
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Abstract
ABSTRACT OF THE DISCLOSURE
An organometallic-transition metal compound com-plex either without support or supported on a support ma-terial such as silica, alumina or silica-alumina is treated with a halogen or interhalogen compound to produce a poly-merization catalyst component which when employed in com-bination with an aluminum alkyl co-catalyst obtains high activity and excellent molecular weight control.
An organometallic-transition metal compound com-plex either without support or supported on a support ma-terial such as silica, alumina or silica-alumina is treated with a halogen or interhalogen compound to produce a poly-merization catalyst component which when employed in com-bination with an aluminum alkyl co-catalyst obtains high activity and excellent molecular weight control.
Description
This invention relates to a novel~ highly active catalyst cornponent to
2 be employed with a co-catalyst for producing polyolefins such as
3 polyethylene, polypropylene and the like or copolymers such as ethylene
4 copolymers ~vith other alpha-olefins and diolefins, which catalyst compo-nent shows unusually high activity and excellent hydrogen response for the 6 control o~ polymer molecular weight. The catalyst connponent comprises 7 the reaction product of a transition metal compound with an organo-8 metallic composition obtained either in the presence or absence of a 9 support material such as, for example, silica, alumina, or silica-alumina 10 and thereafter treated with a halogen to provide the novel catalyst 11 component which when used in combination with the co-~atalyst, provides 12 the novel catalyst system of this invention.
13 The catalyst systems can be usefully employed in slurry, single phase 14 melt, solution and gas phase polymerization processes and is particularly 15 effective for the production of high-density polyethy]ene and linear low 16 density polyethylene.
17 Recently, interest has arisen in the use of magnesium-titanium 18 comp~ex catalyst components for the polymerization of olefins. These l9 magnesium-titaniurn complex catalyst components have been prepared in 20 the presence of support material such as silica or in the absence of support 21 material. For example, European Patent Application 27733, p~lblished April 22 29, 1~81 discloses a catalyst component obtained by reducing a trarLsition 23 metal compound with an excess of organomagnesium compound in the 24 presence of a support such as silica and thereafter deactivating the excess 25 organomagnesium compound with certain deactivators including hydrogen 26 chloride. I~.S. Patent No. 4,136,058 discloses a cstalyst component 27 comprising an organomagnesium compound and a transition metal halide 23 compound, which cntalyst component is thereafter deactivated with a 29 deactivating agent such as hydrogen chloride. This patent does not teach 30 the use of support material such as silica but otherwise the disclosure is 31 similar to the above-discussed European patent application.
32 U.S. Patent No. ~,250,288 discloses a catalyst which is the reaction 33 product of a compound of a transition metal and an organomagnesium 34 component and an active non-metallic hal;de such as HCl and organic 35 halides containing a labile halogen. l'he catalyst reaction product also 36 contain~s some alunninum alkyls~
~ 2 --Catalyst cornponents comprising the reaction product of an aluminum 2 alkyl-magnesium alkyl complex plus titanium halide are disclosed in U.S.
3 Patent No. 4,004,071 and U.S. Patent No. 4,276,191.
A IJ.S. Patent No. 4,173,547 and U.S. Patent No. 4,263,171, respectively
13 The catalyst systems can be usefully employed in slurry, single phase 14 melt, solution and gas phase polymerization processes and is particularly 15 effective for the production of high-density polyethy]ene and linear low 16 density polyethylene.
17 Recently, interest has arisen in the use of magnesium-titanium 18 comp~ex catalyst components for the polymerization of olefins. These l9 magnesium-titaniurn complex catalyst components have been prepared in 20 the presence of support material such as silica or in the absence of support 21 material. For example, European Patent Application 27733, p~lblished April 22 29, 1~81 discloses a catalyst component obtained by reducing a trarLsition 23 metal compound with an excess of organomagnesium compound in the 24 presence of a support such as silica and thereafter deactivating the excess 25 organomagnesium compound with certain deactivators including hydrogen 26 chloride. I~.S. Patent No. 4,136,058 discloses a cstalyst component 27 comprising an organomagnesium compound and a transition metal halide 23 compound, which cntalyst component is thereafter deactivated with a 29 deactivating agent such as hydrogen chloride. This patent does not teach 30 the use of support material such as silica but otherwise the disclosure is 31 similar to the above-discussed European patent application.
32 U.S. Patent No. ~,250,288 discloses a catalyst which is the reaction 33 product of a compound of a transition metal and an organomagnesium 34 component and an active non-metallic hal;de such as HCl and organic 35 halides containing a labile halogen. l'he catalyst reaction product also 36 contain~s some alunninum alkyls~
~ 2 --Catalyst cornponents comprising the reaction product of an aluminum 2 alkyl-magnesium alkyl complex plus titanium halide are disclosed in U.S.
3 Patent No. 4,004,071 and U.S. Patent No. 4,276,191.
A IJ.S. Patent No. 4,173,547 and U.S. Patent No. 4,263,171, respectively
5 disclose a catalyst component comprising silica, an aluminum-type titanium
6 tetrachloride and dibutyl magnesiurm and a catalyst component comprising
7 a magnesium alkyl-aluminum alkyl complex plus titanium halide on a silica
8 support.
9 The use of chlorine gas in polymerization processes is taught in U.~.
10 Patent No. 4,267,292 wherein it is disclosed that chlorine gas is to be
11 added to the polymerization reactor after polymerization has been initiated
12 in the presence of a Ziegler catalyst. U.S. Patent No. 4,~48,735 teaches
13 subjecting a silica support to a treatment with bromine or iodine and
14 thereafter incorporating a chromium compound onto the support. U.S.
15 Patent No. 3,513,150 discloses the treatment of gamma alumina plus
16 titanium tetrachloride with a gaseous chlorinating agent and employing said
17 treated material in combination with a co-catalyst for the polymeri~ation
18 of ethylene.
~ ~he catalyst systems comprising magnesium alkyls and titanium compounds, altholJgh useful for the polymerization of olefins such as 21 ethylene and other l-olefins, do not show excellent responsiveness to 22 hydrogen during the polymerization reaetion for the control of molecular 23 weight and do not show an extremely high catalytic activity.
24 In accordance with this invention catalyst combinations have been found which have extremely high catalytic activities and excellent 26 hydrogen responsiveness for the control of molecular weight. The new 27 catalysts and catalyst component of this invention are obtained by treating 28 an organometallic composition-transition metal compound complex with a 29 halogen or interhalogen compound.
In accordance with the objectives of this invention there is provided 31 a catalyst component which is obtained by treating an organometallic-32 transition metal compound complex either in the absence of a support or 33 supported on a support material such as, for example, silica, alumina and 34 silica-alumina or a finely divided polyolefin with a halogen or interhalogen 35 compound. The catalyst component when employed in cormbination with a 36 co-catalyst such as an alkyl aluminum co-catalyst provides a catalyst 37 system which demonstrates a number of unique properties that are of great æ
irnportance in the olefin polymerization technology such as, for example, 2 extremely high catalytic activity, the ability to control the molecular 3 weight during the polymerization reaction as a result of the improved 4 responsiveness to hydrogen, increased polymer yield and improved bull<
density of polymer product.
6 The catalyst components of this invention useful for the polymeriza-7 tion of alpha-monoolefins comprises the product of (l) reacting in an inert 8 solvent (a) an organometallic composition represented by the formula 9 Me~ MelIIyR2x2x+3y-z~ wherein MeII is a Group IIA or IIB
(Mendeleev's Periodic Table of Elements as shown in The Chemical 11 R~bber Cc~any's ~L~ndbook of Chemistry and Physics, 48th Edition) 12 n~ta1 or mlxtures thereof and MeIII is a Group III~ metal or mix-13 tures thereof, R is a hydrocarbyl or substituted hydrocarbyl grou~
14 having from 1 to 20 carbon atoms, X is a halogen or alkoxide or mix-tures thereof, the ratio of y/x+y is from 0 to about 1, z has a 16 value within the range of 1 to 2x+3y and (b) a transltion metal com-17 pound or co~ination of transition metal compounds represented by the 18 formula TrX'ds_q(OR')q, TrX'4 qRIIq~ VO(OR')3 and VOX'3 wherein Tr is
~ ~he catalyst systems comprising magnesium alkyls and titanium compounds, altholJgh useful for the polymerization of olefins such as 21 ethylene and other l-olefins, do not show excellent responsiveness to 22 hydrogen during the polymerization reaetion for the control of molecular 23 weight and do not show an extremely high catalytic activity.
24 In accordance with this invention catalyst combinations have been found which have extremely high catalytic activities and excellent 26 hydrogen responsiveness for the control of molecular weight. The new 27 catalysts and catalyst component of this invention are obtained by treating 28 an organometallic composition-transition metal compound complex with a 29 halogen or interhalogen compound.
In accordance with the objectives of this invention there is provided 31 a catalyst component which is obtained by treating an organometallic-32 transition metal compound complex either in the absence of a support or 33 supported on a support material such as, for example, silica, alumina and 34 silica-alumina or a finely divided polyolefin with a halogen or interhalogen 35 compound. The catalyst component when employed in cormbination with a 36 co-catalyst such as an alkyl aluminum co-catalyst provides a catalyst 37 system which demonstrates a number of unique properties that are of great æ
irnportance in the olefin polymerization technology such as, for example, 2 extremely high catalytic activity, the ability to control the molecular 3 weight during the polymerization reaction as a result of the improved 4 responsiveness to hydrogen, increased polymer yield and improved bull<
density of polymer product.
6 The catalyst components of this invention useful for the polymeriza-7 tion of alpha-monoolefins comprises the product of (l) reacting in an inert 8 solvent (a) an organometallic composition represented by the formula 9 Me~ MelIIyR2x2x+3y-z~ wherein MeII is a Group IIA or IIB
(Mendeleev's Periodic Table of Elements as shown in The Chemical 11 R~bber Cc~any's ~L~ndbook of Chemistry and Physics, 48th Edition) 12 n~ta1 or mlxtures thereof and MeIII is a Group III~ metal or mix-13 tures thereof, R is a hydrocarbyl or substituted hydrocarbyl grou~
14 having from 1 to 20 carbon atoms, X is a halogen or alkoxide or mix-tures thereof, the ratio of y/x+y is from 0 to about 1, z has a 16 value within the range of 1 to 2x+3y and (b) a transltion metal com-17 pound or co~ination of transition metal compounds represented by the 18 formula TrX'ds_q(OR')q, TrX'4 qRIIq~ VO(OR')3 and VOX'3 wherein Tr is
19 a transition metal of Groups IVB, VB, VIB, VIIE~ and VIII and preEer-ably selected from titanium, vanadium and ~irconium, R' is a hydro-21 carbyl or substituted hydrocarby1 group having from 1 to 20 carbon 22 a~ams, R" is an aryl group, aralky1 group, substituted aralkyl gr~up 23 h~ving from 1 to 20 carkon atc~ns and 1,3-cyclopentadienyls, X' is 24 h~logen and q is zero or a n~nber less than or equa1 to 4, (2) treating the reaction product of (1) either in an inert solvent or in the dry state 26 with a halogen or interhalogen compound and (3) recovering the halogen or 27 interhalogen treated reaction product.
28 The catalyst component can also be prepared by reacting the 29 organometallic compound and the transition metal compound in the presence of a support material of a Group IIA, IIIA, IVA and IVB metal 31 (Mendeleev's Periodic Table of Elements as shown in The Chemical Rubber 32 Company's Handbook of Chemistry and Physics, 48th Edition) oxide, a 33 finely divided polyolefin or other suitable support material. Preferably, 34 the support material is one of silica, alumina or silica-alumina.
In the preparation of the unsupported catalyst component according 36 to this invention the order of addition of the reactants to the inert solvent 37 can be varied, for example, the transition metal comFound and the 38 organometa11ic composition can be contacted in an inert so1vent sirr~
taneously, the transition metal compound can be added to the organo-2 metallic composition or alternatively the organometallic composition can 3 be added to the transition metal compound.
4 In the case where the catalyst component is prepared in the presence 5 of a support material it is desirable that the reactants be added 6 sequentially, for example, the organometallic composition can be added to 7 the support material in an inert solvent containing the support and 8 thereafter the transition metal compound added thereto or in the 9 alternative, the transition metal compound can be added to the inert 10 solvent containing support material and thereafter the organometallic 11 composition added thereto.
12 In other aspects of this invention there is provided a catalyst system 13 comprising the catalyst component and an organoaluminum co-catalyst and 14 a process for the polymerization of alpha-olefins under conditions charac-15 teristic of Ziegler polymerization wherein the catalyst system of 1 his 16 invention is employed as the catalyst.
17 A further aspect of this invention is the process of increasing 18 catalytic activity of transition metal containing catalyst systems by ~ treatment of the catalyst prior to its use in a polymerization reactor with
28 The catalyst component can also be prepared by reacting the 29 organometallic compound and the transition metal compound in the presence of a support material of a Group IIA, IIIA, IVA and IVB metal 31 (Mendeleev's Periodic Table of Elements as shown in The Chemical Rubber 32 Company's Handbook of Chemistry and Physics, 48th Edition) oxide, a 33 finely divided polyolefin or other suitable support material. Preferably, 34 the support material is one of silica, alumina or silica-alumina.
In the preparation of the unsupported catalyst component according 36 to this invention the order of addition of the reactants to the inert solvent 37 can be varied, for example, the transition metal comFound and the 38 organometa11ic composition can be contacted in an inert so1vent sirr~
taneously, the transition metal compound can be added to the organo-2 metallic composition or alternatively the organometallic composition can 3 be added to the transition metal compound.
4 In the case where the catalyst component is prepared in the presence 5 of a support material it is desirable that the reactants be added 6 sequentially, for example, the organometallic composition can be added to 7 the support material in an inert solvent containing the support and 8 thereafter the transition metal compound added thereto or in the 9 alternative, the transition metal compound can be added to the inert 10 solvent containing support material and thereafter the organometallic 11 composition added thereto.
12 In other aspects of this invention there is provided a catalyst system 13 comprising the catalyst component and an organoaluminum co-catalyst and 14 a process for the polymerization of alpha-olefins under conditions charac-15 teristic of Ziegler polymerization wherein the catalyst system of 1 his 16 invention is employed as the catalyst.
17 A further aspect of this invention is the process of increasing 18 catalytic activity of transition metal containing catalyst systems by ~ treatment of the catalyst prior to its use in a polymerization reactor with
20 a halogen or interhalogen compound.
21 In view of the extreme activity of the catalyst system prepared in
22 accordance with this invention as compared with conventional Ziegler
23 cat~lysts, it is generally unnecessary to deash polymer product since
24 polymer product will generally contain lower amounts of catalyst residues
25 than polymer product produced in the presence of conventional catalysts.
26 The catalyst systems can be employed in a gas phase process, single
27 phase melt process, solvent process or slurry process. The catalyst system
28 is usefully employed in the polymerization of ethylene and other alpha-
29 olefins, particularly alpha-olefins having from 3 to ~ carbon atoms and
30 copolymerization of these with l-olefins having from 2 to ~û carbon atoms,
31 such as propylene, butene, pentene and hexene so as to form copolymers
32 of low and medium densities. The supported catalyst system is particularly
33 useful for the polymerization of ethylene in gas phase processes.
34 Brieîly, the catalyst components of the present invention comprise
35 the reaction product of (a) an organometallic composition and (b) at least
36 one transition metal compound which reaction product is thereafter treated
37 with a halogen or interhalogen compound. According to the polymerization process o:E -this invention, ethylene, at least one alpha-olefin having 2 3 or r,~ore carbon atc~ns or ethylene and other olefins or diolefins ha~-3 ing terminal unsaturation is contacted with the ca~lyst under poly-4 n~erizing conditions to form a ccqr~merically useful product.
The organc~netalllc compositions T,~7hich are soluble in a suitable 6 inert hydrocarbon solvent are represented by the formula 7 Me xMe yRzX2x+3y z wherein Me is at least one Group IIA or IIB
8 metal or ~ture thereof and Me is a Group IIIA metal or mixture 9 thereof, R is a hydrocarbyl or substituted hydrocarbyl group or mixture 10 thereof having from 1 -to about 20 carbon at~s, X is a halogen or 11 aL'coxide or mixture thereof, the ratio of y/x-~y if fr~m 0 to 1, z has 12 a value within the range of 1 to 2x~3y. I~e hydrocarbyl group repre-13 sented by R rnay be al~yl radicals, a~yl radic~ls, cycloalJsyl radicals, ~ aralkyl radicals, aLkenyl radicals or alkadienyl radicals. Preferably 15 the hydrocarbyl radicals are alkyl - or cycloalkyl radicals.
16 Especially preferred are alkyl radicals having from 2 to 8 7 carbon atoms, especially ethyl, propyl, bu~l or hexyl radicals.
18 'rhe me~als represented by the symbol MeIl, as indicated above, are 19 from Group IIA or IIB or mixtures thereof, preferably magnesium. The o MeIIl metal is from Group IIIA, such as boron and aluminum and preferably 21 aluminum.
~2 Most desirably the organometallic compositions employed in this 23 invention are represented by the formula (R2Mg)XtRnAlX3_n)y wherein R
24 and X are defined above and n is a number from 1 to 3 with the further 25 proviso that x is greater than zero~
26 l'he ratio of y/x+y is from 0 to 1, preferably from 0 to about 0.7 and 27 especially most desirably from about 0 to about 0.3. The preferred 28 organcq~ llic c~npositions which can be employed in accordance 29 with this invention contain magnesium. Illustrative examples of the suitable magnesium compounds include butylethyl magnesium, di-n 31 butyl or diisobutyl magnesium, diamyl magnesium, di-n-hexyl 32 rnagnesium, and the like, as well as dicycloalkyl magnesium 33 compounds. The solution of the magnesium component will generally 34 contain some alkylaluminum compound in order to reduce the 3S viscosity of the solution. Illustrative examples of Mg-Al compositions 36 are: [(n-C4Hg)(C2Hs)Mg] [(C2H5)3Al]0.01~ [(nC4H9)2Mg][~C2H5)3Al]0 013 37 [~nC~H9)2Mg][(C2H5)3A1]2.0 arld [(nC6H13)2Mg] 1(C2H5)3AI]O.O1~
The organc~netalllc compositions T,~7hich are soluble in a suitable 6 inert hydrocarbon solvent are represented by the formula 7 Me xMe yRzX2x+3y z wherein Me is at least one Group IIA or IIB
8 metal or ~ture thereof and Me is a Group IIIA metal or mixture 9 thereof, R is a hydrocarbyl or substituted hydrocarbyl group or mixture 10 thereof having from 1 -to about 20 carbon at~s, X is a halogen or 11 aL'coxide or mixture thereof, the ratio of y/x-~y if fr~m 0 to 1, z has 12 a value within the range of 1 to 2x~3y. I~e hydrocarbyl group repre-13 sented by R rnay be al~yl radicals, a~yl radic~ls, cycloalJsyl radicals, ~ aralkyl radicals, aLkenyl radicals or alkadienyl radicals. Preferably 15 the hydrocarbyl radicals are alkyl - or cycloalkyl radicals.
16 Especially preferred are alkyl radicals having from 2 to 8 7 carbon atoms, especially ethyl, propyl, bu~l or hexyl radicals.
18 'rhe me~als represented by the symbol MeIl, as indicated above, are 19 from Group IIA or IIB or mixtures thereof, preferably magnesium. The o MeIIl metal is from Group IIIA, such as boron and aluminum and preferably 21 aluminum.
~2 Most desirably the organometallic compositions employed in this 23 invention are represented by the formula (R2Mg)XtRnAlX3_n)y wherein R
24 and X are defined above and n is a number from 1 to 3 with the further 25 proviso that x is greater than zero~
26 l'he ratio of y/x+y is from 0 to 1, preferably from 0 to about 0.7 and 27 especially most desirably from about 0 to about 0.3. The preferred 28 organcq~ llic c~npositions which can be employed in accordance 29 with this invention contain magnesium. Illustrative examples of the suitable magnesium compounds include butylethyl magnesium, di-n 31 butyl or diisobutyl magnesium, diamyl magnesium, di-n-hexyl 32 rnagnesium, and the like, as well as dicycloalkyl magnesium 33 compounds. The solution of the magnesium component will generally 34 contain some alkylaluminum compound in order to reduce the 3S viscosity of the solution. Illustrative examples of Mg-Al compositions 36 are: [(n-C4Hg)(C2Hs)Mg] [(C2H5)3Al]0.01~ [(nC4H9)2Mg][~C2H5)3Al]0 013 37 [~nC~H9)2Mg][(C2H5)3A1]2.0 arld [(nC6H13)2Mg] 1(C2H5)3AI]O.O1~
38 ~rhe hydrocarbon soluble organometallic compositions are known
39 materials and can be prepared by conventional methods. One such method 'L1~7~iZ
involves, for example, the addition of an appropriate aluminum alkyl to a 2 solid dialkyl magnesium in the presence of an inert hydrocarbon solvent.
3 The organomagnesium-organoaluminum complex will form at a reasonable 4 rate under ambient conditions. However, lower temperatures or higher 5 temperatures can be suitably employed. A method for preparing 6 organomagnesium-organoaluminum complexes is described in U.S. Patent 7 No. 3,737,393. ~ ~ever, any other suitable method for preparation 8 of organometallic compounds can be suitably employed.
9 Transition metal compounds which can be employed ln accordance 10 with this invention are represented by the formula TrX'4_q(OR')q, 11 TrX'4 qR~q~ VOX'~ and VO(OR')3. Tr is a Group IVB, VB, VIB, VIIB and VIII
12 rnetal prefexably Group IVB and VB metals and most pxeferably ~ nium, 13 vanadium and zirconium, q is 0 or a numker equal to or less than 4, 14 X' is halogerl and R' is a hydrocaxbyl or substituted hydrocarbyl group, for example, alkyl, axyl or cycloalkyl having from 1 to 20 carbon 16 aboms and R" is an aryl group, aralkyl group, substituted araIkyl, 17 1,3-cyclopentadienyls and the like. The aryl, aralkyls and substituted 18 aralkyls contain from 1 to 20 carbon atoms and preferably 1 to 10 19 carbon atcms. Mixtures of the transition metal oompounds can be em-ployed if desired.
21 Illustrative examples of the well known transition metal cornpounds 22 include TiC14, TiBr4, Ti(OCH3)3Cl, Ti(OC2H5)C13, Ti(OC4H933Cl, 23 Ti(OC3H7)2C12- Ti(C6H13)2Cl~ Ti(O C~17)2Br2 and Ti(ocl2H25~cl3.
2~i Other well known transition metal compounds are VCL~, VOC13, ZrC14, zirconium tetrabenzyl and ~/O(OC2Hs)3.
26 As indicated above, mixtures of the transition metal compounds may 27 be us~fully employed, no restriction being imposed on the number of 2~ transition metal compounds which may be reacted with the organometallic 2? composition. Any halogenide, R" and alkoxide transition metal compound 30 or mixtures thereof can be usefully employed. The titanium tetrahalides 31 are especially preferred with titanium tetrachloride being most preferred.
32 In the preparation of the reaction product of an organometallic 33 composition and the transition metal compound the organometallic com-34 position is employed in amounts such that the atomic ratio of the metals 35 in the organometallic composition to the transition me~al in the 36 transition metal co~ound is in the range of about 0.2:1 to about 37 100:1, preferably about 0.5:1 to about 20:1.
~'78fi%
The reaction between the organometallic composition and the transi-2 tion metal compound can be conducted in an inert solvent. Preferred 3 solvents include the various hydrocarbons which are liquid at reaction 4 temperatures and in which the organometallic component is soluble.
Illustrative examples of useful solvents include the alkanes such as 6 pentane, i-pentane, hexane, heptane, octane, and nonane; and cycloalkanes 7 such as cyclopentane, and cyclohexane; aromatics such as benze~e, toluene, 3 ethylbenzene and diethylbenzene. The amount of solvent to be used is not 9 critical. Nevertheless, the amount should be employed so as to provide adequate heat transfer away from the catalyst components during the 11 reaction and to permit good mixing.
12 The organometallic composition is preferably added to the solvent in 13 the form of a solution. Preferred solvents for the organometallic 14 composition are the alkanes such as hexane, heptane, octane and the like.
However, the same solvent as employed for the reaction can be employed 16 for the organometallic composition. The concentration of the organo 17 metallic composition in the solvent is not criticaI and is limited only by 18 handling needs.
19 Ihe reaction between the transition n~ta1 corlpound and the orgar~tallic con~osition can be conducted at temperatures in the 21 range of from akout -50 to a~out 150C. r~e preferred t~T~rature 22 range is from about -30C to about 60C with -10 to 50 being most 23 preferred. The reaction time can range ~rc~ out 5 rll~nutes to about 24 24 hours. Ebwever, lesser or greater t~m3s ca~ be employed. Prefer-ab1y the reaction time will be from about 1/2 hour to about 8 hours.
26 Dur~ng ~he reaction constant agita~ion is desirable.
27 The order of addition of the organometallic composition and the 28 transition metal compound to the solvent in the absence of a support 29 material is not critical. The organometallic composition can be added first with the transition metal compound being added thereafter or the 31 transition metal compound can be added first with the organometallic 32 composition being added thereafter. Preferably, the organome1 allic 33 composition and the transition nnetal compound are added simultaneously to 34 the reaction solvent.
In one preferred aspect of this invention the reaction product of l:he 36 organometallic compound and the transition metal halide compound is 37 formed in the presence of a support material. Preferably the support 38 material is a Group IIA, IIIA, IVA or IVB metal oxide in finely divided L:~'7~
form. The metal o~ides generally contain acidic surface hydroxyl groups 2 which will react with the organometallic composition or transition metal 3 compound first added to the reaction solvent. Other suitable support 4 materials, however, can be employed. For exarnple, finely divided polyolefins such as finely divided polyethylene rnay be us~d.
6 Suitable inorganic oxide materials which are desirably employed in 7 accordance with this invention include silica, alumina and silica-alumina.
8 Other inorganic oxides that may be employed either alone or in 9 combination with the silica, alumina or silica-alumina are magnesia, titania, zirconia, and the like.
11 Prior to use, the inorganic oxide support is preactivated, i.e., 12 subjected to a thermal treatment in order to remove water and reduce the 13 concentration of the surface hydroxl groups. The treatment is carried out14 while purging with a dry inert gas such as nitrogen at a temperature of about ~00 to 1000C, and preferably from about 300 to 800C. Pressure 16 considerations are not critical. The duration of the thermal treatment can 17 be from about 1 to about 24 hours. However, shorter or longer times can 18 be employed.
19 In order to insure that the reactions between the organometallic composition and the transition metal compound occurs within the pores of 21 tlle inorganic oxide support, sequential addition of the reactants is 22 desirable. The order of sequential addition of the reactants to the 23 reactant solvent containing the inorganic oxide support material is not 24 critical; however, the catalyst composition may be different depending onthe order of addition. For example, one can make multiple additions of 2G one or more organometallic compositions and one or more transition metal 27 compounds in any order so long ~ as they are added to the support ~8 sequentially and sufficient time is allowed for complete reaction 29 to occur between additions.
The ratio of the transition metal compound with respect to the 31 support material may vary over a wide range. However, for best results 32 the transition metal content can be between about 0.02 to about 3 mmols 33 of transition metal compound per gram of support materiaL
3D~ Halogenation of the reaction product of the organometallic composi-tion with the transition metal compound in the absence of or with a 36 support can be conducted in the reaction solvent or the reaction product 37 can be recovered and washed and dried prior to halogenation treatmentO
.
7~
~ 9 _ Conditions for the halogenation treatrnent of the reaction product can be 2 carried out under a wide range of conditions. Good results can be obtained 3 by halogcnation treatment at ambient conditions for flbout 5 minutes to 4 about 24 hours. Halogen treatment at higher or lower temperatures and 5 lower or higher pressures can be performed while still obtaining the 6 excellent results in accordance with this invention.
7 Prior to the halogenation treatment the r eaetion product can be 8 contacted with other halogenating materials such as, for example, other 9 halogen-containing compourlds such as ethylaluminum dichloride, boron 10 trihalides, hydrogen halides such as HCl and HBr; Si tetrahalide and 11 halogenated hydrocarbons such as CCl4 and C2Cl6. As shown in the 12 Examples such treatment with a halogen-containing compound such as 13 hydrogen chloride followed by the treatment with a halogen or interhalogen 14 compound obtains significantly increased activity over the identical 15 cata1~rst treated with halc~en cbnta~n~ng cornpounds alone.
16 The halogens which can be suitably employed in accordance with this 17 invention are Cl2, Br2, I2 and mixtures thereof. Illustrative interhalogen 18 compounds are (: lF, ClF3, BrF, BrF3, BrFs, ICl, ICl3 and IBr. The 19 preferred halogens are Clz and Br2, the preferred interhalogens contain Br 20 or Cl. In a preferred aspect of the invention the reaction product is 21 reacted completely with the halogen; however, good results are obtained 22 with less than complete reaction.
23 The catalysts prepared in accordance with this invention and 24 described above are usefully employed with the co-catalyst known in the 25 art of ~iegler catalysis for the polymeri~ation of olefins. The co-catalysts 26 desirably used are the alkylaluminum co-catalysts. ~he alkylaluminum 27 compounds are represented by the formula AlR"nX"3_n wherein R" is 28 hydrogen, hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 29 carbon atoms, X is halogen and n is from 1 to 3 with at least one R" being a hydrocarbyl or substitu~ed hydrocarbyl group. Preferably R" is an alkyl 31 group having from 2 to 3 carbon atoms. Illustrative examples of the c~
32 catalyst material are ethylaluminum dichloride, ethylsesquialuminum 33 chloride, diethylaluminum chloride, triethylaluminum, tributylaluminum 34 andl the like. Trialkylaluminum compounds are most preferred with triisobutylaluminum being highly desirable.
36 The catalyst syste~ comprising the aluminum alkyl co-catalyst and 37 the halogen treated or interhalogen compound treated organometallic -- 10 ~
composition - transition metal compound reaction product is usefully 2 employed for the polymerization of ethylene, other alpha-olefins having 3 from 3 to 20 c~rbon atoms, such as, for example, propylene, butene-1, 4 pentene-1, hexene-1, 4-methyl-pentene-1, and the like and ethylene 5 copolymers with other alpha-olefins or diolefins such as 1,4-pentadiene, 6 1,5-hexadiene, butadiene, 2-methyl-1,3-butadiene and the like. The 7 polymerizable monomer of preference is ethylene. The catalyst mav be 8 usefully employed to produce polyethylene or copolym~rs o~ ethylene 9 by copolymerizin~ with other alpha-olefins or diolefins, Earticul æ ly propylene, butene-l anrl pentene-l, hexene-l, octene-l 11 The polymerization reaction employing catalytic amounts of the 12 above-described catalyst can be carried out under conditions well known in 3 the art of ~iegler polymerization, for example, in an inert diluent at a 14 temperature in the range of 50C to 100C and a pressure of 2 to 40 15 atms, in the gas phase at a temperature range of 70 to 100C at about 16 5 atms and upward.
17 In the processes according to this invention it has been discovered 18 that the catalyst system is highly responsive to hydrogen for the control 19 of molecular weight. Other well known molecular weight controlling 20 agents and modifying agents, however, may be usefully employed.
21 The polyolefins prepared in accordance with this invention can be 22 extruded, mechanically melted, cast or molded as desired. They can be 23 ~Ised for plates, sheets, films and a variety of other objects.
24 While the invention is described in connection with the specific 25 examples below, it is understood that these are only for illustrative 26 purposes. Many alternatives, modifications and variations will be apparent 27 to those skilled in the art in light of the below examples and such 28 alternatives, modifications and variations fall within the general scope of 29 the claims.
In the following examples the silica support was prepared by placing 31 Davison Chemical Company G-~52 silica gel in a vertical column and 32 fluidizing with an upward flow of N2. The column was heated slowly to 33 800C and held at that temperature for 12 hours after which the silica was 34 cooled to ambient temperature.
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Exarnple l .
2 Catalyst Preparation 3 A 3 g portion of the dried dehydrated silica gel was weighed under 4 ultra anhydrous conditions into a dry glass vessel equipped with a stirrer 5 and 75 ml of a purified mineral oil was added and stirred to mix well. 6.5 6 ml of a solution of butylethylmagnesium (BEM) comprising 0.69 mmol BEM
7 and 0.01 mmol triethylaluminum (TEAL) in n-heptane was added dropwise 8 at ambient temperature to the silica slurry while stirring vigorously. After 9 stirring for l0 minutes, the slurry was allowed to stand for 20 minutes.
A 2 ml portion of a solution of TiC14 in n-hexane containing 1.5 mmol 11 TiC14 per ml of solution was slowly added to the slurry of silica supported 12 BEM at ambient temperature while stirring vigorously. The particles of 13 silica gel turned dark brown and no color was detected in the supernatent 14 mineral oil. This reaction product is hereinafter referred to as precursor 15 catalyst. Titanium constituted 3.7% by weight of the total precursor 16 catalyst.
17 One-half of the precursor catalyst slurry was transferred to a 18 pressure tight glass vessel, equipped with a stirrer, which was connected to 19 a source of dry chlorine gas. The vessel was purged with the Cl2 gas to 20 remove the N2 blanket over the precursor slurry and thereafter the vessel 21 was pressured to 7.5 psig with C12. The slurry was stirred vigorously for 22 3 hours after which the unreacted Cl2 was removed by connecting the 23 vessel to a vacuum source. The vessel was then pressured up with dry N2.
24 Polymerizations using the precursor catalyst and the halogenated 25 catalyst were performed in a 1.5 liter stainless steel stirred reactor. 875 26 ml of hexane was added to the reactor and the reactor was thereafter 27 heated to 85C. 2.3 mmol of triisobutylaluminum (TIBAL~ cocatalyst was 28 added as a solution in n-heptane to the reactor. A weighed ~ortion ~f 29 catalyst was then added to the reactor~ 45 psig of H2 pressure was 30 introduced to the reactor. Polymerization was initiated by introduction of 31 ethylene at a pressure of 75 psi and constant total pressure was maintained 32 by flow of ethylene into the reactor on demand. The polymerizations ~ere 33 terminated after one hour. The results of the polymerizations are 34 summarized in Table I.
'7~
ABLE I_ 2 Chlorinated Precursor 3 Precursor _talyst 4 gms of catalyst 0.056 0.192 gms of resin 159 192 6 Productivity 7 gms of resin/gm ofcatalyst/hour 2,840 530 8 Resin 9 Melt Index 1.32 0.34 10 Bullc Density (gms/cc) 0.31 0.18 11 The results demonstrnte that the catalyst of this invention h~s about 12 five times the activity, a significantly improved response to H2 for melt 13 index control and produces a resin having a higher bulk density as 14 compared with the results of the precursor catalyst.
5 Examples 2 A, B and C ~nd Comparative E~amples 2A, B and C
16 The objective of these examples is to show that various alkyl 17 magnesium/aluminum complexes are highly effective for the preparation of 18 catalysts in accordance with the invention.
19 The precursor catalysts A, B and C were prepared in the manner as 20 described in Example 1 except the alkyl metal components were reacted 21 with the silica g~l support for one hour before adding TiCl4. Precursor A
22 comprised BEM/TEAL (Butyl Ethyl Magnesium/TriEthyl Pluminum) in a 23 ratio of 1:0.014, precursor s com~rised di-n-butylmagnesium DN~M/T~AL
24 in a ratio of 1:0.13 and precursor C comprised DNBM/TE~L in a ratio 25 of 1:1.75. Ihe chlorinated catalysts A, B and C were prepared by 26 treatment of the precursor catalysts with C12 gas in the manner as 27 described in Example 1. Employing the a~ount of catalyst as summar-28 ized in Table II, polymeriza~ions were conducted under the conditions 29 as described in Example 1. Ihe results are summarized in Table II.
~he results demonstrate that the three catalysts were substantially 31 improved by chlorinating with C12 gas with ~le lower aluminum content 32 catalysts be.ing the preferred comFositions.
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Examples 3A, B and C and Comparative Examples 3~, B and C
This Example demonstrates that various transition metal compounds 3 can be usefully employed for the preparation of catalysts of this invention.
4 Three different transition metal compounds, listed in Table III were used to prepare the catalysts. Employing (BEM) (TEAL)0.014 the precursor 6 catalysts were prepared as in Example 1. The mole ratio of BEM to 7 transition metal component was 1.5 in each case. Portions of the supported 8 catalyst were treated with chlorine gas for l hour at 7.5 psig to produce 9 catalyst components in accordance with the invention. The precursor catalysts A, B and C and the catalysts A, B and C prepared in accordance 11 with the invention were evaluated by polymeri7ation of ethylene. Em-12 ploying the amount of catalyst as listed in Table III ethylene polymeriza-13 tions were carried out under the conditions as in Example 1. I~e results of14 the polymeri~ations are summarized in Table III. Productivities were greatly increased in each case where the chlorine treatment was employed.
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1 Example 4 2 miS example demonstrates the superiority of halogens over hydro-3 gen halides for preparing the catalysts of this invention.
4 One portion of the precursor catalyst prepared as in Example 1 was treated with HCl gas for 18 hours at 7.5 psig. Another portion of 6 the precursor catalyst was treated with C12 gas for 1 hour at 7.5 7 psig to produce a catalyst component in accordance with the invention.
8 The precursor catalyst, the HCI treated precursor catalyst and the 9 catalyst prepared in accordance with the invention were compared by 10 polymerizing ethylene as described in Example l. The results of the 11 polymerizations are summarized in Table IV. Treatment with C12 gas 12 increased productivity, H2 response as indicated by melt index and 13 improved bulk to a much greater extent than does treatment of the 14 precursor catalyst with HCl.
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Example 5 2 The objective of this example is to show that even after treating a 3 precursor catalyst exhaustively with HCl, a very large improvement in 4 catalyst performance can be achieved by subsequent treatment with C12 gas.
6 A portion of the precursor catalyst prepared as in Example 1, was 7 treated with HCI gas for 24 hours at 7.5 psig HCl to produce a HCl treated 8 precursor catalyst. This catalyst was used to polymerize ethylene under 9 conditions as in Example 1 with the results shown in Table V as Comparative Example 5.
11 The remaining HCI treated precursor catalyst was treated with C12 12 gas for 3 hours at 7.5 psig C12 to produce a catalyst in accordance with 13 the invention. Ethylene was polymerized under conditions as in Examp]e 14 1. The results are summarized in Table V as invention Example 5.
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Example 6 2 The purpose of this example is to SIlOW that different orders of 3 addition of alkylma~nesium compound and transition metal compound to 4 the silica gel support can be employed in preparing the catalysts of this 5 invention. The example further demonstrates that lower Ti concentrations 6 on the silica supFort o~ta~n rluch 1arger ~crease in productivity 7 ~ased on 1~.
A precursor catalyst was prepared using the procedure of Example l g by treating a 3.0 g portion of silica gel with 4.S mmol of BEM and allowing 10 the material to react for 30 minutes at ambient temperature. 1.5 mmol 11 of TiC14 was then added and stirring was continued for 5 minutes. This 12 catalyst is labeled Precur~or A.
13 A second precursor catalyst was prepared except l.5 mmol of TiC14 14 was added first to 3.0 gms of silica support and reacted for 30 minutes 15 after which 4.5 mmol of BEM were added and stirred for S minutes. This 16 catalyst is labeled Precursor B.
17 Portions of Precursors A and B were subsequently chlorinated using 18 Cl2 gas at 7.5 psig for 3 hours at ambient temperature and labeled 19 Catalyst A flnd B respectively.
Ethylene was polymerized in the manner and under conditions as 21 described in Example 1 using Precursors A und B and Invention Catalysts 22 A and B. The polymerization results are summarized in Table Vl.
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a) -- .. o o 0 ~ ' o Example 7 2 The objective is to show that unsupported catalysts are greatly 3 improved by tha halogen treatment in accordance with this invention.
4 A stirred glass vessel containing 90 ml of hexane was cooled to -5C
5 under a blanket of dry M2., Dilute solutions containing 3 mmols of TiCl4 6 in hexane and 3 m~.ols of (BEM)(TEAL)~ 17 complex were added droF,wise 7 and simultaneously to the cold hexane ovér a time period of 80 minutes.
8 A clark brown catalyst precipitated as the addition proceeded. The 9 resulting catalyst slurry was allowed to warm to room temperature and 10 then to age for 24 hours at ambient temperature under a blanket of dry 11 N2. This unsupported comparative catalyst is identified as Precursor A.
12 A portion of Precursor A was subsequently treated with Cl2 gas for 13 l hour at atmospheric pressure. Precursor A and the Cl2 treated catalyst 14 of this invention were employed to polymerize ethylene in the manner of 15 Example l. The results of polymerization are summarized in Table VII.
16 Each catalyst contained approximately 18% by weight of titanium.
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A precursor catalyst was prepared exactly as in Example l and was 6 treated with C12 gas for l hour at atmospheric pressure. The resulting 7 catalyst was used to copolymerize ethylene and butene-l.
8 The polymerization was conducted as in Example I except that, after 9 addition of the triisobutylaluminum cocatalyst, 50 g of butene-l were addedto the reac~or. The reactor WAS pressured with 45 psi H2 after which 45 l1 psi of ethylene pressure was introduced, a constant total pressure was 12 maintained for 60 minutes and the temperature controlled to 85C. The 13 results are presented in Table VIII.
15 Grams of catalyst 0.038 16 Grams of resin 112 17 Productivity (wtlwt/hr) 2,947 18 Resin density (gms/cc) 0.935 l9 Melt index 9.9
involves, for example, the addition of an appropriate aluminum alkyl to a 2 solid dialkyl magnesium in the presence of an inert hydrocarbon solvent.
3 The organomagnesium-organoaluminum complex will form at a reasonable 4 rate under ambient conditions. However, lower temperatures or higher 5 temperatures can be suitably employed. A method for preparing 6 organomagnesium-organoaluminum complexes is described in U.S. Patent 7 No. 3,737,393. ~ ~ever, any other suitable method for preparation 8 of organometallic compounds can be suitably employed.
9 Transition metal compounds which can be employed ln accordance 10 with this invention are represented by the formula TrX'4_q(OR')q, 11 TrX'4 qR~q~ VOX'~ and VO(OR')3. Tr is a Group IVB, VB, VIB, VIIB and VIII
12 rnetal prefexably Group IVB and VB metals and most pxeferably ~ nium, 13 vanadium and zirconium, q is 0 or a numker equal to or less than 4, 14 X' is halogerl and R' is a hydrocaxbyl or substituted hydrocarbyl group, for example, alkyl, axyl or cycloalkyl having from 1 to 20 carbon 16 aboms and R" is an aryl group, aralkyl group, substituted araIkyl, 17 1,3-cyclopentadienyls and the like. The aryl, aralkyls and substituted 18 aralkyls contain from 1 to 20 carbon atoms and preferably 1 to 10 19 carbon atcms. Mixtures of the transition metal oompounds can be em-ployed if desired.
21 Illustrative examples of the well known transition metal cornpounds 22 include TiC14, TiBr4, Ti(OCH3)3Cl, Ti(OC2H5)C13, Ti(OC4H933Cl, 23 Ti(OC3H7)2C12- Ti(C6H13)2Cl~ Ti(O C~17)2Br2 and Ti(ocl2H25~cl3.
2~i Other well known transition metal compounds are VCL~, VOC13, ZrC14, zirconium tetrabenzyl and ~/O(OC2Hs)3.
26 As indicated above, mixtures of the transition metal compounds may 27 be us~fully employed, no restriction being imposed on the number of 2~ transition metal compounds which may be reacted with the organometallic 2? composition. Any halogenide, R" and alkoxide transition metal compound 30 or mixtures thereof can be usefully employed. The titanium tetrahalides 31 are especially preferred with titanium tetrachloride being most preferred.
32 In the preparation of the reaction product of an organometallic 33 composition and the transition metal compound the organometallic com-34 position is employed in amounts such that the atomic ratio of the metals 35 in the organometallic composition to the transition me~al in the 36 transition metal co~ound is in the range of about 0.2:1 to about 37 100:1, preferably about 0.5:1 to about 20:1.
~'78fi%
The reaction between the organometallic composition and the transi-2 tion metal compound can be conducted in an inert solvent. Preferred 3 solvents include the various hydrocarbons which are liquid at reaction 4 temperatures and in which the organometallic component is soluble.
Illustrative examples of useful solvents include the alkanes such as 6 pentane, i-pentane, hexane, heptane, octane, and nonane; and cycloalkanes 7 such as cyclopentane, and cyclohexane; aromatics such as benze~e, toluene, 3 ethylbenzene and diethylbenzene. The amount of solvent to be used is not 9 critical. Nevertheless, the amount should be employed so as to provide adequate heat transfer away from the catalyst components during the 11 reaction and to permit good mixing.
12 The organometallic composition is preferably added to the solvent in 13 the form of a solution. Preferred solvents for the organometallic 14 composition are the alkanes such as hexane, heptane, octane and the like.
However, the same solvent as employed for the reaction can be employed 16 for the organometallic composition. The concentration of the organo 17 metallic composition in the solvent is not criticaI and is limited only by 18 handling needs.
19 Ihe reaction between the transition n~ta1 corlpound and the orgar~tallic con~osition can be conducted at temperatures in the 21 range of from akout -50 to a~out 150C. r~e preferred t~T~rature 22 range is from about -30C to about 60C with -10 to 50 being most 23 preferred. The reaction time can range ~rc~ out 5 rll~nutes to about 24 24 hours. Ebwever, lesser or greater t~m3s ca~ be employed. Prefer-ab1y the reaction time will be from about 1/2 hour to about 8 hours.
26 Dur~ng ~he reaction constant agita~ion is desirable.
27 The order of addition of the organometallic composition and the 28 transition metal compound to the solvent in the absence of a support 29 material is not critical. The organometallic composition can be added first with the transition metal compound being added thereafter or the 31 transition metal compound can be added first with the organometallic 32 composition being added thereafter. Preferably, the organome1 allic 33 composition and the transition nnetal compound are added simultaneously to 34 the reaction solvent.
In one preferred aspect of this invention the reaction product of l:he 36 organometallic compound and the transition metal halide compound is 37 formed in the presence of a support material. Preferably the support 38 material is a Group IIA, IIIA, IVA or IVB metal oxide in finely divided L:~'7~
form. The metal o~ides generally contain acidic surface hydroxyl groups 2 which will react with the organometallic composition or transition metal 3 compound first added to the reaction solvent. Other suitable support 4 materials, however, can be employed. For exarnple, finely divided polyolefins such as finely divided polyethylene rnay be us~d.
6 Suitable inorganic oxide materials which are desirably employed in 7 accordance with this invention include silica, alumina and silica-alumina.
8 Other inorganic oxides that may be employed either alone or in 9 combination with the silica, alumina or silica-alumina are magnesia, titania, zirconia, and the like.
11 Prior to use, the inorganic oxide support is preactivated, i.e., 12 subjected to a thermal treatment in order to remove water and reduce the 13 concentration of the surface hydroxl groups. The treatment is carried out14 while purging with a dry inert gas such as nitrogen at a temperature of about ~00 to 1000C, and preferably from about 300 to 800C. Pressure 16 considerations are not critical. The duration of the thermal treatment can 17 be from about 1 to about 24 hours. However, shorter or longer times can 18 be employed.
19 In order to insure that the reactions between the organometallic composition and the transition metal compound occurs within the pores of 21 tlle inorganic oxide support, sequential addition of the reactants is 22 desirable. The order of sequential addition of the reactants to the 23 reactant solvent containing the inorganic oxide support material is not 24 critical; however, the catalyst composition may be different depending onthe order of addition. For example, one can make multiple additions of 2G one or more organometallic compositions and one or more transition metal 27 compounds in any order so long ~ as they are added to the support ~8 sequentially and sufficient time is allowed for complete reaction 29 to occur between additions.
The ratio of the transition metal compound with respect to the 31 support material may vary over a wide range. However, for best results 32 the transition metal content can be between about 0.02 to about 3 mmols 33 of transition metal compound per gram of support materiaL
3D~ Halogenation of the reaction product of the organometallic composi-tion with the transition metal compound in the absence of or with a 36 support can be conducted in the reaction solvent or the reaction product 37 can be recovered and washed and dried prior to halogenation treatmentO
.
7~
~ 9 _ Conditions for the halogenation treatrnent of the reaction product can be 2 carried out under a wide range of conditions. Good results can be obtained 3 by halogcnation treatment at ambient conditions for flbout 5 minutes to 4 about 24 hours. Halogen treatment at higher or lower temperatures and 5 lower or higher pressures can be performed while still obtaining the 6 excellent results in accordance with this invention.
7 Prior to the halogenation treatment the r eaetion product can be 8 contacted with other halogenating materials such as, for example, other 9 halogen-containing compourlds such as ethylaluminum dichloride, boron 10 trihalides, hydrogen halides such as HCl and HBr; Si tetrahalide and 11 halogenated hydrocarbons such as CCl4 and C2Cl6. As shown in the 12 Examples such treatment with a halogen-containing compound such as 13 hydrogen chloride followed by the treatment with a halogen or interhalogen 14 compound obtains significantly increased activity over the identical 15 cata1~rst treated with halc~en cbnta~n~ng cornpounds alone.
16 The halogens which can be suitably employed in accordance with this 17 invention are Cl2, Br2, I2 and mixtures thereof. Illustrative interhalogen 18 compounds are (: lF, ClF3, BrF, BrF3, BrFs, ICl, ICl3 and IBr. The 19 preferred halogens are Clz and Br2, the preferred interhalogens contain Br 20 or Cl. In a preferred aspect of the invention the reaction product is 21 reacted completely with the halogen; however, good results are obtained 22 with less than complete reaction.
23 The catalysts prepared in accordance with this invention and 24 described above are usefully employed with the co-catalyst known in the 25 art of ~iegler catalysis for the polymeri~ation of olefins. The co-catalysts 26 desirably used are the alkylaluminum co-catalysts. ~he alkylaluminum 27 compounds are represented by the formula AlR"nX"3_n wherein R" is 28 hydrogen, hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 29 carbon atoms, X is halogen and n is from 1 to 3 with at least one R" being a hydrocarbyl or substitu~ed hydrocarbyl group. Preferably R" is an alkyl 31 group having from 2 to 3 carbon atoms. Illustrative examples of the c~
32 catalyst material are ethylaluminum dichloride, ethylsesquialuminum 33 chloride, diethylaluminum chloride, triethylaluminum, tributylaluminum 34 andl the like. Trialkylaluminum compounds are most preferred with triisobutylaluminum being highly desirable.
36 The catalyst syste~ comprising the aluminum alkyl co-catalyst and 37 the halogen treated or interhalogen compound treated organometallic -- 10 ~
composition - transition metal compound reaction product is usefully 2 employed for the polymerization of ethylene, other alpha-olefins having 3 from 3 to 20 c~rbon atoms, such as, for example, propylene, butene-1, 4 pentene-1, hexene-1, 4-methyl-pentene-1, and the like and ethylene 5 copolymers with other alpha-olefins or diolefins such as 1,4-pentadiene, 6 1,5-hexadiene, butadiene, 2-methyl-1,3-butadiene and the like. The 7 polymerizable monomer of preference is ethylene. The catalyst mav be 8 usefully employed to produce polyethylene or copolym~rs o~ ethylene 9 by copolymerizin~ with other alpha-olefins or diolefins, Earticul æ ly propylene, butene-l anrl pentene-l, hexene-l, octene-l 11 The polymerization reaction employing catalytic amounts of the 12 above-described catalyst can be carried out under conditions well known in 3 the art of ~iegler polymerization, for example, in an inert diluent at a 14 temperature in the range of 50C to 100C and a pressure of 2 to 40 15 atms, in the gas phase at a temperature range of 70 to 100C at about 16 5 atms and upward.
17 In the processes according to this invention it has been discovered 18 that the catalyst system is highly responsive to hydrogen for the control 19 of molecular weight. Other well known molecular weight controlling 20 agents and modifying agents, however, may be usefully employed.
21 The polyolefins prepared in accordance with this invention can be 22 extruded, mechanically melted, cast or molded as desired. They can be 23 ~Ised for plates, sheets, films and a variety of other objects.
24 While the invention is described in connection with the specific 25 examples below, it is understood that these are only for illustrative 26 purposes. Many alternatives, modifications and variations will be apparent 27 to those skilled in the art in light of the below examples and such 28 alternatives, modifications and variations fall within the general scope of 29 the claims.
In the following examples the silica support was prepared by placing 31 Davison Chemical Company G-~52 silica gel in a vertical column and 32 fluidizing with an upward flow of N2. The column was heated slowly to 33 800C and held at that temperature for 12 hours after which the silica was 34 cooled to ambient temperature.
j raol~ ~l a r l~
, 7~
Exarnple l .
2 Catalyst Preparation 3 A 3 g portion of the dried dehydrated silica gel was weighed under 4 ultra anhydrous conditions into a dry glass vessel equipped with a stirrer 5 and 75 ml of a purified mineral oil was added and stirred to mix well. 6.5 6 ml of a solution of butylethylmagnesium (BEM) comprising 0.69 mmol BEM
7 and 0.01 mmol triethylaluminum (TEAL) in n-heptane was added dropwise 8 at ambient temperature to the silica slurry while stirring vigorously. After 9 stirring for l0 minutes, the slurry was allowed to stand for 20 minutes.
A 2 ml portion of a solution of TiC14 in n-hexane containing 1.5 mmol 11 TiC14 per ml of solution was slowly added to the slurry of silica supported 12 BEM at ambient temperature while stirring vigorously. The particles of 13 silica gel turned dark brown and no color was detected in the supernatent 14 mineral oil. This reaction product is hereinafter referred to as precursor 15 catalyst. Titanium constituted 3.7% by weight of the total precursor 16 catalyst.
17 One-half of the precursor catalyst slurry was transferred to a 18 pressure tight glass vessel, equipped with a stirrer, which was connected to 19 a source of dry chlorine gas. The vessel was purged with the Cl2 gas to 20 remove the N2 blanket over the precursor slurry and thereafter the vessel 21 was pressured to 7.5 psig with C12. The slurry was stirred vigorously for 22 3 hours after which the unreacted Cl2 was removed by connecting the 23 vessel to a vacuum source. The vessel was then pressured up with dry N2.
24 Polymerizations using the precursor catalyst and the halogenated 25 catalyst were performed in a 1.5 liter stainless steel stirred reactor. 875 26 ml of hexane was added to the reactor and the reactor was thereafter 27 heated to 85C. 2.3 mmol of triisobutylaluminum (TIBAL~ cocatalyst was 28 added as a solution in n-heptane to the reactor. A weighed ~ortion ~f 29 catalyst was then added to the reactor~ 45 psig of H2 pressure was 30 introduced to the reactor. Polymerization was initiated by introduction of 31 ethylene at a pressure of 75 psi and constant total pressure was maintained 32 by flow of ethylene into the reactor on demand. The polymerizations ~ere 33 terminated after one hour. The results of the polymerizations are 34 summarized in Table I.
'7~
ABLE I_ 2 Chlorinated Precursor 3 Precursor _talyst 4 gms of catalyst 0.056 0.192 gms of resin 159 192 6 Productivity 7 gms of resin/gm ofcatalyst/hour 2,840 530 8 Resin 9 Melt Index 1.32 0.34 10 Bullc Density (gms/cc) 0.31 0.18 11 The results demonstrnte that the catalyst of this invention h~s about 12 five times the activity, a significantly improved response to H2 for melt 13 index control and produces a resin having a higher bulk density as 14 compared with the results of the precursor catalyst.
5 Examples 2 A, B and C ~nd Comparative E~amples 2A, B and C
16 The objective of these examples is to show that various alkyl 17 magnesium/aluminum complexes are highly effective for the preparation of 18 catalysts in accordance with the invention.
19 The precursor catalysts A, B and C were prepared in the manner as 20 described in Example 1 except the alkyl metal components were reacted 21 with the silica g~l support for one hour before adding TiCl4. Precursor A
22 comprised BEM/TEAL (Butyl Ethyl Magnesium/TriEthyl Pluminum) in a 23 ratio of 1:0.014, precursor s com~rised di-n-butylmagnesium DN~M/T~AL
24 in a ratio of 1:0.13 and precursor C comprised DNBM/TE~L in a ratio 25 of 1:1.75. Ihe chlorinated catalysts A, B and C were prepared by 26 treatment of the precursor catalysts with C12 gas in the manner as 27 described in Example 1. Employing the a~ount of catalyst as summar-28 ized in Table II, polymeriza~ions were conducted under the conditions 29 as described in Example 1. Ihe results are summarized in Table II.
~he results demonstrate that the three catalysts were substantially 31 improved by chlorinating with C12 gas with ~le lower aluminum content 32 catalysts be.ing the preferred comFositions.
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Examples 3A, B and C and Comparative Examples 3~, B and C
This Example demonstrates that various transition metal compounds 3 can be usefully employed for the preparation of catalysts of this invention.
4 Three different transition metal compounds, listed in Table III were used to prepare the catalysts. Employing (BEM) (TEAL)0.014 the precursor 6 catalysts were prepared as in Example 1. The mole ratio of BEM to 7 transition metal component was 1.5 in each case. Portions of the supported 8 catalyst were treated with chlorine gas for l hour at 7.5 psig to produce 9 catalyst components in accordance with the invention. The precursor catalysts A, B and C and the catalysts A, B and C prepared in accordance 11 with the invention were evaluated by polymeri7ation of ethylene. Em-12 ploying the amount of catalyst as listed in Table III ethylene polymeriza-13 tions were carried out under the conditions as in Example 1. I~e results of14 the polymeri~ations are summarized in Table III. Productivities were greatly increased in each case where the chlorine treatment was employed.
'~
m C~
~ O C~ I
~a O O O O
~ ~ CD O U~ ~
~ C C~ O ~
U~
o ~ .
~ C) 3 ~ o ~ o o ~ ~
~ :4 o ~ o - ~ .5 D~ o ~ o ¢
o~
cn ~ ~) o o o o o C~
,.
o o~ o Cr~ C- ~ U--a~ o Z. Z ~ ~, .. o ¢ O ~ ~0 ~. mo o c~
~ C`~~ ~ ~
E ~ ,, c~ E
.
.
1 Example 4 2 miS example demonstrates the superiority of halogens over hydro-3 gen halides for preparing the catalysts of this invention.
4 One portion of the precursor catalyst prepared as in Example 1 was treated with HCl gas for 18 hours at 7.5 psig. Another portion of 6 the precursor catalyst was treated with C12 gas for 1 hour at 7.5 7 psig to produce a catalyst component in accordance with the invention.
8 The precursor catalyst, the HCI treated precursor catalyst and the 9 catalyst prepared in accordance with the invention were compared by 10 polymerizing ethylene as described in Example l. The results of the 11 polymerizations are summarized in Table IV. Treatment with C12 gas 12 increased productivity, H2 response as indicated by melt index and 13 improved bulk to a much greater extent than does treatment of the 14 precursor catalyst with HCl.
~L:lB'7~
a:
E~ d O C U~ ~ 00 QL~ ~ O O O
C~
_. _ O O
>~
.~
~ O O
O '~O O C~
~1 C~
~0 U~
.~
0 _ CD
~~
O ~J
O~ ;"
C~ O O ~
O C~ O O
, ~
p E~
O ~
~e 0 ~ C.~ C':\ C'~ O
~: ~ ,C
o ~ '~ ' '~
0 (~
~bf S ~ ~ O
_ ~ :Z; 0 r 6,V,~
Example 5 2 The objective of this example is to show that even after treating a 3 precursor catalyst exhaustively with HCl, a very large improvement in 4 catalyst performance can be achieved by subsequent treatment with C12 gas.
6 A portion of the precursor catalyst prepared as in Example 1, was 7 treated with HCI gas for 24 hours at 7.5 psig HCl to produce a HCl treated 8 precursor catalyst. This catalyst was used to polymerize ethylene under 9 conditions as in Example 1 with the results shown in Table V as Comparative Example 5.
11 The remaining HCI treated precursor catalyst was treated with C12 12 gas for 3 hours at 7.5 psig C12 to produce a catalyst in accordance with 13 the invention. Ethylene was polymerized under conditions as in Examp]e 14 1. The results are summarized in Table V as invention Example 5.
:~ N C.~
O O
~ ~1 o Z ~
~ _ ~ ~ O O
a ~ O O
E.5 0 J 1~ a~
o~l 0 ~1 ~
-,o 6~
Cl ~.~D 4,e~ , o 0 ~ ~ 'tClD
V ~ O
.. E ~
~ r-l '7~
Example 6 2 The purpose of this example is to SIlOW that different orders of 3 addition of alkylma~nesium compound and transition metal compound to 4 the silica gel support can be employed in preparing the catalysts of this 5 invention. The example further demonstrates that lower Ti concentrations 6 on the silica supFort o~ta~n rluch 1arger ~crease in productivity 7 ~ased on 1~.
A precursor catalyst was prepared using the procedure of Example l g by treating a 3.0 g portion of silica gel with 4.S mmol of BEM and allowing 10 the material to react for 30 minutes at ambient temperature. 1.5 mmol 11 of TiC14 was then added and stirring was continued for 5 minutes. This 12 catalyst is labeled Precur~or A.
13 A second precursor catalyst was prepared except l.5 mmol of TiC14 14 was added first to 3.0 gms of silica support and reacted for 30 minutes 15 after which 4.5 mmol of BEM were added and stirred for S minutes. This 16 catalyst is labeled Precursor B.
17 Portions of Precursors A and B were subsequently chlorinated using 18 Cl2 gas at 7.5 psig for 3 hours at ambient temperature and labeled 19 Catalyst A flnd B respectively.
Ethylene was polymerized in the manner and under conditions as 21 described in Example 1 using Precursors A und B and Invention Catalysts 22 A and B. The polymerization results are summarized in Table Vl.
7~6;~
N ~ I
:~, ~ o o oo CL. NC'~
E._ ~ ~ ~
o _ E ~ 0 ~
5 ~ ~ o c~ o o ~S
C 6!~
:C Cq O ~
o o ~ E
~: ~ .-i U~
O. O. O. O. ,t:
a) -- .. o o 0 ~ ' o Example 7 2 The objective is to show that unsupported catalysts are greatly 3 improved by tha halogen treatment in accordance with this invention.
4 A stirred glass vessel containing 90 ml of hexane was cooled to -5C
5 under a blanket of dry M2., Dilute solutions containing 3 mmols of TiCl4 6 in hexane and 3 m~.ols of (BEM)(TEAL)~ 17 complex were added droF,wise 7 and simultaneously to the cold hexane ovér a time period of 80 minutes.
8 A clark brown catalyst precipitated as the addition proceeded. The 9 resulting catalyst slurry was allowed to warm to room temperature and 10 then to age for 24 hours at ambient temperature under a blanket of dry 11 N2. This unsupported comparative catalyst is identified as Precursor A.
12 A portion of Precursor A was subsequently treated with Cl2 gas for 13 l hour at atmospheric pressure. Precursor A and the Cl2 treated catalyst 14 of this invention were employed to polymerize ethylene in the manner of 15 Example l. The results of polymerization are summarized in Table VII.
16 Each catalyst contained approximately 18% by weight of titanium.
'7~6~
x 1 Z
¢"1 N
j;~ a ~0 E._ x ~Ul E~ N C"
O. O, C~
E~~ o S E ~c ~,, o _ E
'7~ J2 -- 2~ --E~ample 8 2 The objective of this example is to demonstrate that the halogenated 3 precursor catalysts of this invention are well suited for the preparation of 4 low density polyethylene copolymers.
A precursor catalyst was prepared exactly as in Example l and was 6 treated with C12 gas for l hour at atmospheric pressure. The resulting 7 catalyst was used to copolymerize ethylene and butene-l.
8 The polymerization was conducted as in Example I except that, after 9 addition of the triisobutylaluminum cocatalyst, 50 g of butene-l were addedto the reac~or. The reactor WAS pressured with 45 psi H2 after which 45 l1 psi of ethylene pressure was introduced, a constant total pressure was 12 maintained for 60 minutes and the temperature controlled to 85C. The 13 results are presented in Table VIII.
15 Grams of catalyst 0.038 16 Grams of resin 112 17 Productivity (wtlwt/hr) 2,947 18 Resin density (gms/cc) 0.935 l9 Melt index 9.9
Claims (139)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. A catalyst component for the polymerization of alpha-olefins comprising the product of (1) reacting in an inert solvent (a) an organometallic composition represented by the formula MeIIxMeIIIyRzX2x+3y-z wherein MeII is a Group IIA or IIB metal or mixtures thereof and MeIII is a Group IIIA metal or mixtures thereof, R is a hydrocarbyl or substituted hydrocarbyl group having from 1 to about 20 carbon atoms, X is a halogen or alkoxide or mixtures thereof, the ratio of y/x+y is from 0 to 1, z has a value within the range of 1 to 2x+3y and (b) a transition metal compound or combination of transition metal compounds represented by the formula TrX'4-q(OR')q, TrX'4-qR"q, VOX'3 or VO(OR')3 wherein Tr is a transition metal, R' is a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms, R" is an aryl group, aralyl group, substituted aralkyl group having from 1 to 20 carbon atoms and 1,3 cyclopentadienyls, X' is halogen and q is 0 or a number equal to or less than 4, (2) treating the reaction product of (1) with ahalogen or an interhalogen compound, and (3) recovering the halogen or interhalogen treated reaction product. - 2. The catalyst component of claim 1 wherein MeIII can be aluminum and boron and MeII can be Mg and Zn.
- 3. The catalyst component of claim 1 wherein the organometallic composition is represented by the formula (R2Mg)x(RnAlX3-n)y wherein n is a number from 1 to 3 and x is greater than zero.
- 4. The catalyst component of claim 1 wherein y/x+y is from 0 to about 0.7.
- 5. The catalyst component of claim 4 wherein y/x+y is 0 to about 0.3.
- 6. The catalyst component of claim 1 wherein the transition metal compound is one of TiCl4, TiBr4, VCl4, VOCl3, ZrCl4, Ti(OR')C13, Ti(OR')2Cl2, Ti(OR''')3Cl, VO(OC2H5)3 and Zr(CH2C6H5)4.
- 7. The catalyst component of claim 6 wherein the transition metal compound is TiCl4.
- 8. The catalyst component of claim 1 wherein the halogen is C12.
- 9. The catalyst component of claim 1 wherein the halogen (interhalogen) treatment is at ambient conditions for about 5 minutes to about 24 hours.
- 10. The catalyst component of claim 1 wherein the halogen treatment is conducted in an inert solvent.
- 11. The catalyst component of claim 1 wherein the halogen treatment is conducted on the dry catalyst component.
- 12. The catalyst component of claim 1 wherein the mole ratio of the organometallic composition to the transition metal compound in the reaction product is about 0.2:1 to about 100:1.
- 13. The catalyst component of claim 1 wherein R and R' each independently have between 1 and 8 carbon atoms.
- 14. The catalyst component of claim 13 wherein R is ethyl or butyl and R' is ethyl.
- 15. The catalyst component of claim 14 wherein X and X' are chlorine.
- 16. The catalyst component of claim 1 wherein the transition metal compound is added to the organometallic compound.
- 17. The catalyst component of claim 1 wherein the organometallic composition is added to the transition metal compound.
- 18. The catalyst component of claim 1 wherein the organometallic composition and the transition metal compound are added to the inert solvent simultaneously.
- 19. The catalyst component of claim 1 wherein the organometallic compound and the transition metal compound are sequentially added to the inert solvent containing a support material of a Group IIA, IIIA, IVA and IVB metal oxide or a finely divided polyolefin.
- 20. The catalyst component of claim 19 wherein the support material is selected from the group consisting of silica, alumina and silica-alumina.
- 21. The catalyst component of claim 19 wherein the organometallic compound is added to the support material prior to the addition of the transition metal compound.
- 22. The catalyst component of claim 19 wherein the transition metal compound is added to the support material prior to the addition of the organometallic compound.
- 23. The catalyst component of claim 19 wherein two or more organometallic compounds are added sequentially to the support material.
- 24. The catalyst component of claim 19 wherein between about 0.02 to about 3 mmol of transition metal compound is present per g of support material.
- 25. The catalyst component of claim 19 wherein the organometallic compound is represented by the formula (R2Mg)X(RnAlX3-n)y wherein n is a number from 1 to 3 and x is greater than zero.
- 26. The catalyst component of claim 19 wherein y/x+y is from about 0 to about 0.7.
- 27. The catalyst component of claim 19 wherein the transition metal compound is one of TiCl4, TiBr4, VCl49,VOC13, ZrCl4, Ti(OR''')Cl3, Ti(OR''')2Cl2, Ti(OR''')3Cl, VO(OC2H5)3 and Zr(CH2C6H5)4.
- 28. The catalyst component of claim 27 wherein the transition metal compound is TiCl4.
- 29. The catalyst component of claim 19 wherein the halogen compound is C12.
- 30. The catalyst component of claim 25 wherein y/x+y is about 0 to about 0.3.
- 31. The catalyst component of claim 19 wherein the halogen (interhalogen) treatment is at ambient conditions for about 5 minutes to about 24 hours.
- 32. The catalyst component of claim 19 wherein the mole ratio of the organometallic compound to the transition metal compound is about 0.2:1 to about 100:1.
- 33. The catalyst component of claim 19 wherein R and R' each independently have between 1 and 8 carbon atoms.
- 34. The catalyst component of claim 33 wherein R is ethyl or butyl and R' is ethyl.
- 35. The catalyst component of claim 34 wherein X and X' are chlorine.
- 36. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 1 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 37. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 2 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 38. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 3 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 39. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 4 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 40. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 5 and an organoaluminum compound of the formula AlR"nX"3-n wherein R is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 41. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 6 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 42. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 7 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 43. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 8 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 44. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 9 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 45. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 10 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 46. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 11 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 47. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 12 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 48. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 13 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 49. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 14 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 50. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 15 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 51. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 16 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 52. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 17 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 53. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 18 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 54. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 19 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 55. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 20 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 56. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 21 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 57. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 22 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 58. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 23 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 59. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 24 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 60. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 25 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 61. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 26 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 62. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 27 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 63. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 28 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 64. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 29 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 65. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 30 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 66. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 31 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 67. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 32 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 68. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 33 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 69. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 34 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 70. A catalyst system for the polymerization of alpha-monoolefins comprising the catalyst component of claim 35 and an organoaluminum compound of the formula AlR"nX"3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3.
- 71. A process for polymerizing ethylene and other alpha-olefins or mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylen and other alpha-olefins and diolefins in the presence of the catalyst system of claim 70.
- 72. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene, other alpha-olefins and a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 36.
- 73. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 37.
- 74. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 38.
- 75. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 39.
- 76. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 40.
- 77. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ehtylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 41.
- 78. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 42.
- 79. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 43.
- 80. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 44.
- 81. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 45.
- 82. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 46.
- 83. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 47.
- 84. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 48.
- 85. A process for polymerizing ehtylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 49.
- 86. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catlayst system of claim 50.
- 87. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 51.
- 88. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene find other alpha-olefins and diolefins in the presence of the catalyst system of claim 52.
- 89. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 53.
- 90. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 54.
- 91. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 55.
- 92. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 56.
- 93. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 57.
- 94. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 58.
- 95. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 59.
- 96. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprise polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 60.
- 97. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprise polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 61.
- 98. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 62.
- 99. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 63.
- 100. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 64.
- 101. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 65.
- 102. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 66.
- 103. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 67.
- 104. A process for polymerizing ethylene, othee alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha olefins and diolefins in the presence of the catalyst system of claim 68.
- 105. A process for polymerizing ethylene, other alpha-olefins and mixtures of ethylene and other alpha-olefins and diolefins which comprises polymerizing ethylene or a mixture of ethylene and other alpha-olefins and diolefins in the presence of the catalyst system of claim 69.
- 106. A process for the production of a catalyst component for the polymerization of alpha-monoolefins comprising (1) reacting under suitable conditions and constant agitation in an inert solvent by contacting (a) an organometallic composition r represented by the formula MeIIxMeIIIyRzX2x+3y-z wherein MeII is a Group IIA or IIB metal or mixtures thereof and MeIII is a Group IIIA metal or mixtures thereof, R is a hydrocarbyl or substituted hydrocarbyl group having from 1 to about 20 carbon atoms, X is a halogen or alkoxide or mixtures thereof, the ratio of y/x+y is from 0 to 1, z has a value within the range of 1 to 2x+3y and (b) a transition metal compound or combination of transition metal compounds represented by the formula TrX'4-q(OR')q, TrX'4-qR''q, VOX'3 or VO(OR')3 wherein Tr is a transition metal, R' is a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms, R" is an aryl group, aralkyl group, substituted aralkyl group having from 1 to 20 carbon atoms and 1,3-cyclopentadienyls X' is halogen and q is 0 or a number equal to or less than 4, (2) treating the reaction product of (l) with a molecular halogen or an interhalogen compound, and (3) recovering the halogen or interhalogen treated reaction product.
- 107. The process of claim 106 wherein MeIII can be aluminum and boron and MeII can be Mg or Zn.
- 108. The process of claim 106 wherein the organometallic composi-tion is represented by the formula (R2Mg)x(RnAIXX3-n)y wherein n is a number from 1 to 3 and x is greater than zero.
- 109. The process of claim 106 wherein y/x+y is from 0 to about 0.7.
- 110. The process of claim 109 wherein y/x+y is 0 to about 0.3
- 111. The process of claim 106 wherein the transition metal com-pound is one of TiCl4, TiBr4, VCl4, VOCl3, ZrCl4, Ti(OR''')Cl3, Ti(OR''')2Cl2 and Ti(OR''')3Cl, VO(OC2H5)3 and Zr(CH2C6H5)4.
- 112. The process of claim 111 wherein the transition metal com-pound is TiCl4.
- 113. The process of claim 106 wherein the halogen is Cl2.
- 114. The process of claim 106 wherein the halogen (interhalogen) treatment is at ambient conditions for about 0.5 hours to about 24 hours.
- 115. The process of claim 106 wherein the halogen treatment is conducted in an inert solvent.
- 116. The process of claim 106 wherein the halogen treatment is conducted on the dry catalyst component.
- 117. The process of claim 106 wherein the mole ratio of the organometallic compound to the transition metal compound in the reaction product is about 0.2:1 to about 100:1.
- 118. The process of claim 106 wherein R and R' each independently have between 1 and 8 carbon atoms.
- 119. The process of claim 118 wherein R is ethyl or butyl and R' is ethyl.
- 120. The process of claim 119 wherein X and X' are chlorine.
- 121. The process of claim 106 wherein the transition metal com-pound is added to the organometallic compound.
- 122. The process of claim 106 wherein the organometallic compound is added to the transition metal compound.
- 123. The process of claim 106 wherein the organometallic compound and the transition metal compound are added to the inert solvent simultaneously.
- 124. The process of claim 106 wherein the organometallic compound and the transition metal compound are sequentially added to the inert solvent containing a support material of a Group IIA, IIIA, IVA and IVB
metal oxide or a firmly divided polyolefin. - 125. The process of claim 124 wherein the support material is selected from the group consisting of silica, alumina and silica-alumina.
- 126. The process of claim 124 wherein the organometallic compound is added to the support material prior to the addition of the transition metal compound.
- 127. The process of claim 124 wherein the tarnsition metal com-pound is added to the support material prior to the addition of the organometallic compound.
- 128. The process of claim 124 wherein two or more organometallic compounds are added sequentially to the support material.
- 129. The process of claim 124 wherein between about 0.02 to about 3 mmol of transition metal compound is present per g of support material.
- 130. The process of claim 124 wherein y/x+y is from about 0 to about 0.7.
- 131. The process of claim 124 wherein the transition metal com-pound is one of TiCl4, TiBr4, VCl4, VOCl3, ZrCl4, Ti(OR''')Cl3, Ti(OR''')2Cl2 and Ti(OR''')3Cl, VO(OC2H5)3 and Zr(CH2C6H5)4.
- 132. The process of claim 131 wherein the transition metal com-pound is TiCl4.
- 133. The process of claim 124 wherein the halogen compound is Cl2.
- 134. The process of claim 130 wherein y/x+y is about 0 to about 0.3.
- 135. The process of claim 124 wherein the halogen (interhalogen) treatment is at ambient conditions for about 5 minutes to about 24 hours.
- 136. The process of claim 124 wherein the mole ratio of the organometallic compound to the transition metal compound is about 0.2:1 to about 100:1.
- 137. The process of claim 124 wherein R and R' each independently have between 1 and 8 carbon atoms.
- 138. The process of claim 137 wherein R is ethyl or butyl and R' is ethyl.
- 139. The process of claim 138 wherein X and X' are chlorine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US30713481A | 1981-09-30 | 1981-09-30 | |
| US307,134 | 1994-09-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1187862A true CA1187862A (en) | 1985-05-28 |
Family
ID=23188386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000412442A Expired CA1187862A (en) | 1981-09-30 | 1982-09-29 | Polymerization catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1187862A (en) |
-
1982
- 1982-09-29 CA CA000412442A patent/CA1187862A/en not_active Expired
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