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