Mono-olefin/polyene interpolymers, method of preparation, compositions containing the same, and articles made thereof

Interpolymer of a) a mono-olefin selected from the group consisting of .alpha.-olefins and cyclic olefins, and b) a non-conjugated polyene having at least 7 carbon atoms and having two readily polymerizable double bonds, having an improved melt tension, improved processability, or a combination of both, a process of preparing such interpolymers, composition comprising such interpolymers and one or more further natural or synthetic polymers or one or more additives or adjuvants, as well as articles obtained by subjecting such interpolymers to melt processing conditions.

The present invention relates to interpolymers of a mono-olefin and a 
polyene having two readily polymerizable bonds, to a process for preparing 
these, to compositions containing these, as well as to articles obtained 
by subjecting such interpolymers to melt processing conditions. 
BACKGROUND OF THE INVENTION 
Olefin-based polymers, especially ethylene polymers and copolymers have 
been well known for many years. Olefin-based polymers prepared by free 
radical initiated polymerization processes generally have good processing 
properties, yet have mechanical properties which are not sufficient for a 
large number of applications. On the other hand, polymers prepared by 
transition metal coordination catalysts have many desirable physical 
properties, yet have rheological characteristics which limit their use in 
melt processing. Many attempts have been made to modify the properties of 
olefin-based polymers made by transition metal coordination catalysts 
using specific comonomers, such as polyenes. 
U.S. Pat. No. 3,291,780 mentions polymers prepared from ethylene, an 
.alpha.-olefin, and a non-conjugated hydrocarbon diene, such as 
dicyclopentadiene, aliphatic .alpha.-internal dienes, 
5-alkenyl-substututed-2-norbornenes, 5-methylene-2-norbornene, and 
2-alkyl-2,5-norbornadienes using coordination catalysts, especially of the 
vanadium halide, oxyhalide, or OR type wherein the R is an organic 
radical, cocatalyzed by organoaluminum compounds. 
U.S. Pat. No. 3,819,591 discloses sulphur-vulcanizable, chain saturated 
elastomeric .alpha.-olefin copolymers having improved cold flow. These 
copolymers consist of ethylene, propylene, a non-conjugated diolefin 
containing only one polymerizable double bond, and a polyolefin containing 
two polymerizable double bonds. It is mentioned that the latter 
polyolefins can introduce chain branching into the polymer. The polymers 
were prepared by using a soluble compound of vanadium in conjunction with 
an organoaluminum compound. 
U.S. Pat. No. 3,984,610 relates to partially crystalline thermoplastic 
polymers of ethylene, optionally an .alpha.-olefin, and a diene selected 
from the group of alpha, omega dienes of at least 8 carbon atoms and 
endomethylenic cyclic dienes where each of the two double bonds is readily 
polymerizable. These polymers were said to have a higher activation energy 
of viscous flow and a low residual carbon-carbon double bond unsaturation. 
The activation energy of viscous flow (E.sub.A) was said to have a 
rheological property which is to provide an indication of the change in 
melt viscosity of the polymer over a certain temperature range. The higher 
the change, the higher the activation energy. The catalyst used was 
preferably a compound of vanadium in conjunction with an organoaluminum 
compound. The process disclosed herein has a relatively low catalyst 
efficiency. 
EP-A-219,166 describes polymers of ethylene, optionally one or more 
.alpha.-olefins, and one or more polyunsaturated compounds with at least 7 
carbon atoms and at least two non-conjugated double bonds. The 
polyunsaturated compound is used in such an amount that the activation 
energy of the viscous flow is not significantly influenced by it. The 
amounts of polyunsaturated compounds used were to improve the optical 
properties without affecting the other properties, such as rheological 
polymer properties, for example, melt flow index ratio and the viscosity 
ratio. The catalyst system used was a titanium tetrabutoxide/-sesquiethyl 
aluminumchloride/ethylbutylmagnesium/-isopropylchloride system. 
EP-A-273,655 discloses uncrosslinked polymers of ethylene, optionally an 
.alpha.-olefin, and 1,5-hexadiene of narrow molecular weight distribution 
and a narrow compositional distribution of comonomer. The polymer is 
preferably substantially devoid of long chain branching/intermolecular 
coupling and has substantially all of the 1,5-hexadiene incorporated in 
the polymer as a cyclopentane structure. The catalyst system used is a 
metallocene complex in conjunction with an alumoxane cocatalyst. 
EP-A-667,359 discloses olefin copolymers comprising units derived from 
olefin and units derived from a diolefin having a weight average molecular 
weight of 200 to 800,000 and a relation between the content of the unit 
derived from the diolefin in mole percent(DOU) and the total content of 
the unsaturated group in mole percent (TUS) in a molecular chain is in the 
range of 0.001 to 200. 
EP-416,815 discloses constrained geometry complexes and catalyst systems 
comprising such a constrained geometry complex and an activating 
cocatalyst. Conjugated and non-conjugated dienes and polyenes are among 
the group of addition polymerizable monomers. It also discloses 
pseudo-random polymers comprising an interpolymer of an olefin and a 
vinylidene aromatic monomer or of an olefin and a hindered aliphatic 
vinylidene compound. Divinylbenzene is mentioned as suitable vinylidene 
aromatic monomer and vinylcyclohexenes are mentioned as suitable hindered 
aliphatic vinylidene compound. 
U.S. Pat. Nos. 5,272,236 and 5,278,272 disclose substantially linear 
polymers which may be interpolymers of ethylene with at least one 
C.sub.3-20 .alpha.-olefin and/or C.sub.2-20 acetylenically unsaturated 
monomer and/or C.sub.4-18 diolefins. The substantially linear polymers 
have processing properties remarkably improved with respect to the 
traditional linear olefin-based polymers. 
U.S. Pat. No. 5,470,993 and WO-9500526 disclose Ti(II) and Zr(II) complexes 
and addition polymerization catalysts comprising the same. The catalyst 
may be used to polymerize ethylenically and/or acetylenically unsaturated 
monomers of 2 to 100 carbon atoms either alone or in combination. 
Despite the existing products and processes, there is a desire to provide 
olefin-based polymers having improved processability or improved melt 
tension properties, and preferably a combination of both, and further 
having mechanical and optical properties similar to those of linear 
olefin-based polymers produced by coordination catalysts. Highly 
desirably, such olefin-based polymers contain very small amounts of 
catalyst residues or, in other words, are produced at high catalytic 
activities or productivities so that catalyst residues do not have to be 
removed, such as by washing the polymer. Further, it is desired to provide 
such polymers of improved properties using only very small amounts of the 
relatively expensive polyene. It would also be desirable to provide such 
improved polymers over a wide range of densities and especially at 
relatively lower densities, such as in the range of 0.85 g/cm.sup.3 to 
0.930 g/cm.sup.3. 
SUMMARY OF THE INVENTION 
The present invention provides an interpolymer of a) a mono-olefin selected 
from the group consisting of .alpha.-olefins and cyclic olefins, and b) a 
non-conjugated polyene having at least 7 carbon atoms and having two 
readily polymerizable double bonds, comprising constituent units derived 
from a) and b); 
said interpolymer having a density, d, of from 0.85 to 0.97 g/cm.sup.3 as 
measured in accordance with ASTM D-792; 
a melt flow rate, I.sub.2, from 0.001 to 50 g/10 min as measured in 
accordance with ASTM D-1238, Condition 190.degree. C./2.16 kg; and 
the melt tension of the interpolymer satisfying the following relationship: 
EQU MT&gt;1.328-0.7879log(I.sub.2)+22.5(d-0.85) -40.56{log(I.sub.2)}.times.(d-0.85 
) 
wherein MT represents the melt tension in g. 
In a further aspect, there is provided an interpolymer of a) a mono-olefin 
selected from the group consisting of .alpha.-olefins and cyclic olefins, 
and b) a non-conjugated polyene having at least 7 carbon atoms and having 
two readily polymerizable double bonds, comprising constituent units 
derived from a) and b); 
said interpolymer having a density, d, of from 0.85 to 0.97 g/cm.sup.3 as 
measured in accordance with ASTM D-792; and 
a melt flow rate, I.sub.2, from 0.001 to 50 g/10 min as measured in 
accordance with ASTM D-1238, Condition 190.degree. C./2.16 kg; 
the interpolymer having a DRI index satisfying the following relationship 
(i) or (ii): 
for interpolymers having an I.sub.2 &lt;8: 
(i) DRI&gt;7-0.75*I.sub.2, or 
for interpolymers having an I.sub.2 .gtoreq.8: 
(ii) DRI&gt;1; 
wherein DRI represents the Dow Rheology Index. 
According to yet a further aspect, the invention provides a process of 
preparing an interpolymer of a) a mono-olefin selected from the group 
consisting of .alpha.-olefins and cyclic olefins, and b) a non-conjugated 
polyene having at least 7 carbon atoms and having two readily 
polymerizable double bonds, by interpolymerizing in a polymerization 
reactor the mono-olefin and the polyene in the presence of a transition 
metal catalyst comprising a transition metal compound containing at least 
one .pi.-bonded anionic ligand group, wherein the feed to a polymerization 
reactor comprises the polyene and olefin in a mole ratio of from 0.00005 
to 0.3 mole of polyene per mole of olefin. 
DETAILED DESCRIPTION OF THE INVENTION 
All references herein to elements or metals belonging to a certain Group 
refer to the Periodic Table of the Elements published and copyrighted by 
CRC Press, Inc., 1989. Also any reference to the Group or Groups shall be 
to the Group or Groups as reflected in this Periodic Table of the Elements 
using the IU system for numbering groups. 
The interpolymers according to the present invention have been found to 
possess surprisingly high melt tension properties and good processability 
properties and, furthermore, mechanical and optical properties comparable 
to those of olefin-based linear polymers or interpolymers of the same 
density and melt flow rate lacking the polyene. 
Melt tension is measured by a specially designed pulley transducer in 
conjunction with a melt indexer. Melt tension is the load that the 
extrudate or filament exerts while passing over the pulley at the speed of 
50 rpm. The melt indexer is operated at 190.degree. C. and the polymer is 
extruded under a weight of 2160 g through a vertical die with a diameter 
of 2.1 mm and a length/diameter ratio of 3.82. The molten strand crosses 
an air gap of 45 cm until it is stretched by a take-up roll gyrating at 50 
rpm. The tensile force, or melt tension, required for this stretching is 
measured by a force cell and expressed in grams. The melt tension 
measurement is similar to the "Melt Tension Tester" made by Toyoseiki and 
is described by John Dealy in Rheometers for Molten Plastics, published by 
Van Nostrand Reinhold Co. (1982) on pp. 250-251. 
The Dow Rheology Index (DRI) is a processability parameter which 
characterizes the Theological behavior of the present interpolymers. The 
DRI has been described earlier as expressing a polymer's "normalized 
relaxation time as the result of long chain branching". (See, S. Lai and 
G. W. Knight ANTEC '93 Proceedings, INSITE.TM. Technology Polyolefins 
(ITP)--New Rules in the Structure/Rheology Relationship of Ethylene 
.alpha.-Olefin Interpolymers, New Orleans, La., May 1993, the disclosure 
of which is incorporated herein by reference). Before, it was found that 
DRI values range from 0 for polymers which do not have any measurable long 
chain branching (e.g. Tafmer.TM. products available from Mitsui 
Petrochemical Industries and Exact.TM. products available from Exxon 
Chemical Company, Tafmer and Exact polymers being examples of prior art 
linear low density ethylene interpolymers wherein the .alpha.-olefin is 
homogeneously distributed over the interpolymer) to about 15. In general, 
for low- to medium-pressure ethylene polymers (particularly at lower 
densities), DRI provides improved correlations to melt elasticity and high 
shear flowability relative to correlations of the same attempted with melt 
flow ratios. 
DRI can be calculated from the equation: 
EQU DRI=(3652879*.tau..sub.o 1.00649/.eta..sub.o -1)/10 
where .tau..sub.o is the characteristic relaxation time of the material and 
.eta..sub.o is the zero shear viscosity of the material. Both .tau..sub.o 
and .eta..sub.o are the "best fit" values to the Cross equation, i.e., 
EQU .eta./.eta..sub.o =1/(1+(.gamma.*.tau..sub.o)n) 
where n is the power law index of the material, and .eta. and .gamma. are 
the measured viscosity and shear rate, respectively, which best fit values 
are obtained by a non-linear Gauss-Newton fitting procedure. Baseline 
determination of viscosity and shear rate data are obtained using a 
Rheometric Mechanical Spectrometer (RMS-800) under dynamic sweep mode from 
0.1 to 100 radians/second at 190.degree. C. and a Gas Extrusion Rheometer 
(GER) at extrusion pressures from 1000 psi to 5000 psi (6.89 to 34.5 MPa), 
which corresponds to shear stress from 0.086 to 0.43 MPa, using a 0.0754 
mm diameter, 20:1 L/D die at 190.degree. C. Specific material 
determinations can be performed from 140.degree. C. to 190.degree. C. as 
required to accommodate melt index variations. 
The mono-olefins incorporated in the present interpolymers are 
.alpha.-olefins having from 2 to 20 carbon atoms (including ethylene) and 
cyclic olefins. Examples of the .alpha.-olefins having 3 to 20 carbon 
atoms include propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 
3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 
4,4-dimethyl-1-pentene, 3-ethyl-1-pentene, 1-octene, 1-nonene, 1-decene, 
1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. 
Furthermore, the cyclic olefins preferably have 3 to 20 carbon atoms, and 
typical examples of the cyclic olefins include cyclopentene, cyclohexene, 
norbornene, 1-methylnorbornene, 5-methylnorbornene, 7-methylnorbornene, 
5,6-dimethylnorbornene, 5,5,6-trimethylnorbornene, 5-ethylnorbornene, 
5-propylnorbornene, 5-phenylnorbornene, and 5-benzylnorbornene. 
Preferably, the .alpha.-olefin comprises ethylene and optionally a further 
.alpha.-olefin containing from 3 to 18 carbon atoms. More preferably, the 
.alpha.-olefin comprises ethylene and a further .alpha.-olefin containing 
from 3 to 12 carbon atoms. Especially preferred further .alpha.-olefins 
contain from 4 to 8 carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 
4-methyl-1-pentene, and 1-octene. 
The term readily polymerizable double bond as used in the present invention 
in connection with the term polyene means a double carbon-carbon bond 
which is a terminal carbon-carbon double bond or a carbon-carbon double 
bond in a strained ring structure. The polyene used in the present 
invention is a non-conjugated polyene. Preferably, the two readily 
polymerizable bonds are of about the same or equal reactivity under the 
polymerization conditions specified herein later. 
Preferred non-conjugated polyenes of at least 7 carbon atoms having two 
readily polymerizable double bonds include straight-chain or branched 
acyclic diene compounds. Preferably, the polyenes have up to 35 carbon 
atoms. 
Examples of the straight-chain or branched acyclic diene compounds include 
1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 
1,11-dodecadiene, 1,13-tetradecadiene, and lower alkyl substituted 
derivatives thereof; examples of the monocyclic alicyclic diene compounds 
include 1,3-divinylcyclopentane, 1,2-divinylcyclohexane, 
1,3-divinylcyclohexane, 1,4-divinylcyclohexane, 1,5-divinylcyclooctane, 
1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 
1-allyl-5-vinyl-cyclooctane, 1,5-diallylcyclooctane, and lower alkyl 
substituted derivatives thereof. Other suitable polyenes include 
bicyclo-(2,2,1)-hepta-2,5-diene (norbornadiene), the dimer of 
norbornadiene, and diolefins having two strained ring double bonds, such 
as the reaction product obtained by reacting 2,5-norbornadiene with 
cyclopentadienyl-1,4,4a,5,8,8a-hexahydro-1,4,5,8-dimethano-naphthalene. 
Compounds similar but resulting from the addition of more bridged ring 
units by further condensation with cyclopentadiene can also be used. 
The polyenes are used singly or in combination in the polymerization with 
the monoolefin. 
Preferably, the polyene is a diene, advantageously an aliphatic diene, 
having an olefinic double bond at both terminals, in other words an 
.alpha.-omega diene, containing from 8 to 18 carbon atoms. More 
preferably, the polyene is an aliphatic .alpha.-omega diene containing 
from 10 to 18 carbon atoms. Interpolymers containing units derived from 
1,9-decadiene are highly preferred. Highly preferred are interpolymers 
comprising units derived from ethylene, from an .alpha.-olefin with from 3 
to 12 carbon atoms, preferably from 4 to 8 carbon atoms, and from 
1,9-decadiene. 
Generally, the interpolymers of the present invention have a density of 
from 0.85 to 0.97 g/cm.sup.3, preferably up to 0.96 g/cm.sup.3. For 
interpolymers containing units derived from ethylene and an .alpha.-olefin 
of at least three carbon atoms, the density of the interpolymer is mainly 
determined by the amount of .alpha.-olefin incorporated in the 
interpolymer. The higher the .alpha.-olefin content, the lower the 
density. Interpolymers wherein the .alpha.-olefin comprises ethylene and a 
further .alpha.-olefin containing 3 to 18 carbon atoms preferably have a 
density of from 0.85 to 0.92 g/cm.sup.3, more preferably of from 0.85 to 
0.91 g/cm.sup.3, most preferably of from 0.86 to 0.89 g/cm.sup.3. The 
amounts of .alpha.-olefin other than ethylene included in the 
interpolymers generally range from 0 mole percent for the interpolymers of 
about 0.96 g/cm.sup.3 to about 17 mole percent for interpolymers of a 
density of 0.85 g/cm.sup.3. For the highly preferred density range of 0.86 
to 0.89 g/cm.sup.3 the amount of .alpha.-olefin is between about 15 and 
about 5 mole percent. Interpolymers in this highly preferred density range 
show, besides the melt tension and processability improvements, further 
improved flexibility, transparancy, and, in general, behave as elastomers. 
The polyene in the amounts incorporated in the present interpolymer has a 
slight effect on the density of the interpolymer in a sense that the 
density is slightly decreased, typically with 0.001 to 0.02 g/cm.sup.3 
units. The polyene content is typically not used to adjust the density, 
but is primarily used to adjust the product properties such as melt 
tension and processability. It has been found that the incorporation of 
surprisingly low amounts of polyenes in the present interpolymers is 
capable of improving greatly the desired properties. Typical polyene 
contents in the interpolymer range from 0.005 to 0.7 mole percent, 
preferred polyene content is from 0.02 to 0.2 mole percent. If the polyene 
content becomes too high, Dart impact strenth and tear strength will 
deteriorate, and there crosslinking or gel formation may occur. For the 
highly preferred interpolymers containing 1,9-decadiene units, the 
preferred polyene content is from 0.02 to 0.19 mole percent, most 
preferably from 0.02 to 0.1 mole percent. The polyene content can be 
determined by solution .sup.13 C NMR for those interpolymers not 
containing other monomers that may interfere with the determination. Such 
other monomers are monomers that give pendant side chains of more than 5 
carbon atoms, such as 1-octene, which gives a hexyl side chain having 6 
carbon atoms. For interpolymers of ethylene and polyene and for 
interpolymers of ethylene, an .alpha.-olefin of 3 to 7 carbon atoms, and a 
polyene, this technique can be used to determine the polyene content. 
Alternatively and for other interpolymers, the polyene content of the 
interpolymer can be determined by measuring the amounts or concentration 
of monomers used (mono-olefin or mono-olefins and polyene) introduced to 
the reactor and the amounts or concentrations of the same when leaving the 
reactor. From these data, the composition of the interpolymer can be 
easily calculated and thus the polyene content determined. The amounts or 
concentrations of the monomers can be determined by any suitable 
technique, such as, for example, Fourier Transform Infrared Spectroscopy, 
Fourier Transform Near Infrared Spectroscopy, or Gas Chromatography. 
Alpha, omega aliphatic dienes of lower carbon numbers have been found to 
have a tendency to be incorporated into the interpolymer as intramolecular 
rings, i.e., both ends of the diene are reacted into the same polymer 
backbone. For the improvements in melt tension and processing properties, 
such intramolecular rings do not contribute significantly, and are 
therefore not desirable. For example, 1,5-hexadiene is incorporated for a 
major proportion in the form of intramolecular rings (EP-A-273,655). 
Intramolecular rings, for example those comprising 6 to 8 ring carbon 
atoms as may be formed by copolymerizing 1,7-octadiene and ethylene, can 
be detected by .sup.13 C-NMR spectroscopy, provided that other comonomers 
are not present in such high quantities that their signals interfere with 
or obscure the signals of the respective rings. In the preferred 
interpolymers of the present invention, not more than 15 percent of the 
polyene is incorporated in the interpolymer as an intramolecular ring, and 
preferably not more than 5 percent. 
It has been found that, under the polymerization conditions described later 
herein, with increasing polyene carbon number interpolymers are formed 
containing less intramolecular rings and having remarkably improved 
properties. Significant proportions of such dienes having higher carbon 
numbers are not incorporated in ring form but are reacted into different 
growing polymer backbones and thus form a linkage between two different 
polymer backbones. This type of linkage may be referred to as "H"-type 
branching. In case of, for example 1,7-octadiene or 1,9-decadiene, the 
linking groups between the two polymer chains will be 1,4-butanediyl and 
1,6-hexanediyl. In interpolymers of ethylene, optionally a mono-olefin 
comonomer having not more than 7 carbon atoms and polyenes, the existence 
of such "H"-type branching can be detected by solution .sup.13 C-NMR 
spectroscopy. This technique, as described in J. L. Koenig, Spectroscopy 
of Polymers, ACS, Washington, D.C., 1992, can quantify the mole percent 
content of branches with six or more carbon atoms within the interpolymer 
(C6+content). The "H"-type branches are not distinguishable, by this 
technique, from long chain branches originated by the interpolymerization 
of vinyl-terminated polymer chains into another growing polymer chain. 
Such type of long chain branching is described in U.S. Pat. No. 5,272,236 
and in U.S. Pat. No. 5,278,272 (and the corresponding WO-93/08221), the 
disclosures of which are herein incorporated by reference. In case the 
interpolymers contain both H-type branching and long chain branching, the 
NMR technique provides information on the total number of branching, 
whether H-type or long chain branching. 
The present interpolymers derived from an olefin and a polyene having two 
readily polymerizable double bonds do not contain substantial amounts of 
unsaturation. Typically, the amount of residual terminal vinyls is less 
than 1 terminal vinyl per 1000 carbon atoms in the main chain, preferably 
less than 0.5 terminal vinyls, as determined with Infrared spectroscopy 
from the 909 cm.sup.-1 absorption band. The amount of vinylidene 
unsaturation in the present interpolymers is typically in the range of 
0.01 to 0.5 vinylidenes per 1000 carbon atoms in the main chain. The 
amount of transvinyl unsaturation in the present interpolymers is 
typically in the range of 0.01 to 0.3 transvinyls per 1000 carbon atoms in 
the main chain. The amounts of vinylidene and transvinyl unsaturations are 
about the same as for similar interpolymers not containing polyenes; the 
amount of terminal vinyl unsaturation is about the same or slightly higher 
than that of similar interpolymers not containing polyenes, showing that 
indeed most of the polyene incorporated in the interpolymer has completely 
reacted and thus does not leave appreciable amounts of unreacted double 
bonds. 
The interpolymers generally have an I.sub.2 generally in the range from 
0.001 to 50 g/10 min, preferably from 0.05 to 15 g/10 min, and most 
preferably from 0.2 to 5 g/10 min. Especially in a solution polymerization 
process, interpolymers having melt indices of less than 0.05 g/10 min may 
give highly viscous solutions which limit the rate of production of such 
polymer and are therefore less desirable. At too high melt indices, the 
improvements, especially in melt tension, are less pronounced, yet still 
significantly higher than for polymers having the same melt index yet 
containing no polyene. 
Where melt flow rate values are specified in the present application 
without giving measurement conditions, the melt index as defined in ASTM 
D-1238, Condition 190.degree. C./2.16 kg (formerly known as "Condition 
(E)") is meant. The term melt flow rate may also be referred to as melt 
index and is inversely proportional to the molecular weight of the 
polymer. Thus, the higher the molecular weight, the lower the melt index, 
although the relationship is not linear. 
The interpolymers of the present invention generally have a molecular 
weight distribution, M.sub.w /M.sub.n, as determined by gel permeation 
chromatography from 1.8 to 5. The term molecular weight distribution as 
used herein, also referred to as "polydispersity", is the weight average 
molecular weight, M.sub.w, divided by the number average molecular weight, 
M.sub.n, and is determined as follows. 
The polymer or composition samples are analyzed by gel permeation 
chromatography (GPC) on a Waters 150C high temperature chromatographic 
unit equipped with three mixed porosity columns (Polymer Laboratories 
10.sup.3, 10.sup.4, 10.sup.5, and 10.sup.6) operating at a system 
temperature of 140.degree. C. The solvent is 1,2,4-trichlorobenzene, from 
which 0.3 percent by weight solution of the samples are prepared for 
injection. The flow rate is 1.0 milliliters/minute and the injection size 
is 200 microliters. 
The molecular weight determination is deduced by using narrow molecular 
weight distribution polystyrene standards (from Polymer Laboratories) in 
conjunction with their elution volumes. The equivalent polymer molecular 
weights are determined by using appropriate Mark-Houwink coefficients for 
polyethylene and polystyrene (as described by Williams and Ward in Journal 
of Polymer Science, Polymer Letters, Vol. 6, (621) 1968, incorporated 
herein by reference) to derive the following equation: 
EQU M.sub.polyethylene =a * (M.sub.polystyrene).sup.b. 
In this equation, a=0.4316 and b=1.0. Weight average molecular weight, 
M.sub.w, is calculated in the usual manner according to the following 
formula: M.sub.w =.SIGMA..sub.i w.sub.i * M.sub.i, where w.sub.i and 
M.sub.i are the weight fraction and molecular weight, respectively, of the 
i.sup.th fraction eluting from the GPC column. The highly preferred 
interpolymers comprising units derived from ethylene, from an 
.alpha.-olefin with from 3 to 12 carbon atoms, preferably from 4 to 8 
carbon atoms, and from 1,9-decadiene, preferably have a molecular weight 
distribution, M.sub.w /M.sub.n, from 2.0 to 4.0. 
The present interpolymers are different from the prior art linear 
olefin-based polymers and copolymers and from the prior art substantially 
linear olefin-based polymers and copolymers in a sense that, at about the 
same melt index (MI.sub.2) and density, the number average molecular 
weight of the present interpolymer is lower than that of the substantially 
linear olefin-based polymers and interpolymers which, again, is lower than 
that of the prior art linear olefin-based polymers and interpolymers. 
For the present interpolymers as well as for some prior art substantially 
linear olefin polymers, the activation energy of viscous flow (E.sub.A) 
has been measured according to the procedure described in U.S. Pat. No. 
3,984,610. The values for the prior art polymers were typically between 8 
and 12 and for the present interpolymers typically also between 8 and 12. 
E.sub.A was found to be substantially independent from the melt index for 
both the prior art and inventive polymers, whereas it was also found to be 
substantially independent from the polyene content of the present 
interpolymers. Furthermore, no correlation was found between the improved 
properties of the present interpolymers and the E.sub.A. 
Preferably, the present interpolymers have melt tension properties 
satisfying the following relationship: 
EQU MT&gt;1.7705-1.0504 log(I.sub.2)+30.00(d-0.85) 
-54.09{log(I.sub.2)}.times.(d-0.85) 
wherein MT, I.sub.2, and d have the definitions given above. 
The present interpolymers advantageously have melt tension properties which 
are at least 35 percent higher, and preferably at least 50 percent higher 
than the melt tension of a similar polymer of substantially the same 
density and melt index yet containing no polyene. Interpolymers containing 
.alpha.-omega dienes of at least 10 carbon atoms, such as 1,9-decadiene, 
can have the same melt tension properties as those containing, for 
example, alpha-omega dienes of 8 carbon atoms or less, such as, for 
example, 1,7-octadiene, yet at significantly lower diene contents. In very 
preferred embodiments, the MT of the present interpolymers approaches or 
improves that of high pressure, free radical polymerized low density 
polyethylene (LDPE) having the same melt index. 
The present interpolymers alternatively can be characterized by their 
DRI/melt index relationship. The present interpolymers preferably have DRI 
values which are at least 0.5 times, more preferably at least 2 times, and 
most preferably at least 3 times higher than the DRI values of a similar 
polymer of substantially the same density and melt index yet containing no 
polyene. Preferably, the DRI of the present interpolymers is at least 2.5, 
more preferably at least 5.0. As is the case with the melt tension 
properties, similar improvements in DRI can be obtained by interpolymers 
containing .alpha.-omega dienes of at least 10 carbon atoms, such as 
1,9-decadiene, compared to those containing, for example, alpha-omega 
dienes of 8 carbon atoms or less, yet at significantly lower diene 
contents. Preferably, the present interpolymers possess both improved melt 
tension and improved processability properties or, in other words, the 
present interpolymers preferably satisfy both the melt tension and DRI 
relationships given above. 
An alternative characteristic for the ease with which the present 
interpolymers can be processed is the viscosity at a shear rate of 316 
s.sup.-1. This is determined as follows. The shear rate versus viscosity 
curve for the polymer is obtained employing a Rheometrics Mechanical 
Spectrometer (RMS-80) under dynamic sweep mode from 0.1 to 100 
radians/second at a temperature of 190.degree. C. The resulting data are 
fitted using the least squares criteria with a polynomial equation of the 
formula 
##EQU1## 
wherein .tau. is the viscosity in Pa.s, .gamma. is the shear rate in 
s.sup.-1, and a.sub.i are coefficients which follow from the fitting 
procedure. The viscosity at a shear rate of 316 s.sup.-1 (log .gamma.=2.5) 
is then calculated from this equation. Preferably, the interpolymers of 
the present invention have a viscosity at 316 s.sup.-1 (.tau..sup.316) 
which meets the following relationship: 
EQU log .eta..sup.316 .rect-ver-solid.2.80-0.2861.times.log(I.sub.2), 
and most preferably meets 
EQU log .eta..sup.316 .rect-ver-solid.2.61-0.2298.times.log(I.sub.2). 
The interpolymers of the present invention, when derived from a diene which 
contains only two unsaturated carbon-carbon double bonds which both are 
readily polymerizable double bonds, do not contain substantial amounts of 
unsaturation and are generally non-vulcanizable. It will be clear that the 
benefits of the present invention also apply and can be obtained when it 
is desired to provide an interpolymer which is vulcanizable. 
According to a further aspect of the present invention, such a vulcanizable 
interpolymer can be provided by either introducing a further polyene in 
the interpolymer, which further polyene has only one double bond which 
under the polymerization conditions is readily polymerizable, or by 
introducing a polyene which, in addition to having two readily 
polymerizable carbon-carbon double bonds, has an additional double bond 
which does not readily polymerize. The resulting interpolymer will contain 
residual unsaturated bonds that can be used for crosslinking or 
vulcanization purposes, for example by using crosslinking agents such as 
sulfur, phenolic crosslinkers, and the like. Examplary of such further 
dienes containing only one readily polymerizable bond include 
non-conjugated dienes having a) one double bond of the type selected from 
terminal olefinic bond and a double bond in a strained ring system, and b) 
one double bond selected from the group consisting of internal, 
non-terminal double bonds and double bonds in unstrained systems. Examples 
of such further dienes are 1,4-hexadiene, 5-ethylidene-2-norbornene, 
5-vinylidene-2-norbornene, 5-methylene-2-norbornene, and 
dicyclopentadiene. Examples of a polyene which, in addition to having two 
readily polymerizable carbon-carbon double bonds, has an additional double 
bond which does not readily polymerize are 1,4,9-decatriene and 
1,4,11-dodecatriene. 
The interpolymers of the invention are typically characterized by one DSC 
melting peak, typically in the range of 60.degree. C. to 130.degree. C., 
using a differential scanning calorimeter standardized with indium and 
deionized water. The method involves 5-7 mg samples sizes, a "first heat" 
to about 150.degree. C. which is held for 4 minutes, a cool down at 
10.degree. C./minute to 30.degree. C. which is held for 3 minutes, and 
heat up at 10.degree. C./minute to 150.degree. C. for the "second heat." 
The melting peak(s) is taken from the "second heat" heat flow versus 
temperature curve. 
Interpolymers prepared using non-unitary polymerization conditions, i.e., 
using more than one reaction zone with different polymerization conditions 
in each zone, or using two different catalytic systems with different 
polymerization behaviour, or a combination of both, may have more than one 
DSC melting peak. 
The interpolymers of the present invention can be prepared according to a 
process comprising interpolymerizing in a polymerization reactor the 
olefin and the polyene in the presence of a transition metal catalyst 
comprising a transition metal compound containing at least one .pi.-bonded 
anionic ligand group, wherein the feed to a polymerization reactor 
comprises the polyene and olefin in a mole ratio of from 0.00005 to 0.3 
mole of polyene per mole of olefin. If desired, more than one polyene may 
be incorporated simultaneously. 
Depending on the desired density of the interpolymer, the relative amounts 
of olefins can be adjusted. For example, for ethylene-based polymers, 
density can conveniently be adjusted using a further olefin, particularly 
a further .alpha.-olefin. The amount of such other olefin to be used in 
the polymerization process depends on the amount of olefin to be 
incorporated into the interpolymer and on the relative reactivities of the 
ethylene and such other olefin. These relative reactivities can easily be 
determined and depend on the catalyst system and polymerization conditions 
used. The amount of .alpha.-olefin to be fed to the polymerization reactor 
varies from 0 mole for a density of about 0.97 g/cm.sup.3 to about 0.3 
mole of .alpha.-olefin per mole of ethylene for a density of 0.85 
g/cm.sup.3. The catalysts described herein and especially the so-called 
constrained geometry catalysts are capable of incorporating high amounts 
of .alpha.-olefin into an interpolymer. When producing ethylene-based 
interpolymers, the ethylene conversion is preferably between 50 and 95 
percent, preferbly from 65 to 95 percent, and most preferably from 75 to 
92 percent. At too low conversions, the process is not very economic, and 
at too high conversions, it may be difficult to control the process, as 
slight variations in monomer concentrations or ratios may have a great 
influence on the ultimate product. The conversion of the additional 
.alpha.-olefin is typically in the range of 20 to 60 percent. 
The amount of polyene used is small compared to the large improvement in 
product properties. The catalysts decribed herein and especially the 
constrained geometry type catalyst is very effective in incorporating the 
polyene into the interpolymer. In order to provide the de sired 
improvements in melt tension or processing properties, the amount of 
polyene to be used depends, among other things, on the length of the 
carbon chain in the polyene. Typically, the mole ratio of 1,7-octadiene to 
ethylene in the feed to the polymerization reactor is from 0.001 to 0.3 
mole of 1,7-octadiene per mole of ethylene, preferably from 0.001 to 0.02, 
and most preferably from 0.003 to 0.007. Surprisingly, polyenes having at 
least 10 carbon atoms, for example, 1,9-decadiene, have been found to be 
much more effective with respect to final polymer properties than lower 
carbon number polyenes. Typically, the mole ratio of 1,9-decadiene to 
ethylene in the feed to the polymerization reactor is from 0.00005 to 0.03 
mole of 1,9-decadiene per mole of ethylene, preferably from 0.0001 to 
0.005, and most preferably from 0.0003 to 0.002. At too high amounts of 
polyene, gel formation may occur which will lead to less desirable 
properties. In addition, in a solution polymerization process, too high 
amounts of polyene lead to increased viscosity of the polymer solution, 
which is less desirable. 
It has been found that only about one-fifth of the molar equivalents of 
1,9-decadiene are required to achieve the same level of improvements in 
melt tension or processing properties than for 1,7-octadiene for 
ethylene-based interpolymers of a density up to about 0.89 g/cm.sup.3. For 
ethylene-based interpolymers of a density higher than about 0.89 
g/cm.sup.3, only about one-fifteenth of the molar equivalents of 
1,9-decadiene is required for the same properties than with 1,7-octadiene. 
It has further been found that less unreacted 1,9-decadiene remains with 
the interpolymer than 1,7-octadiene. 
The catalyst system to be used in the present process comprises a 
transition metal compound containing at least one .pi.-bonded anionic 
ligand group. Suitable transition metal compounds include derivatives of 
any transition metal including Lanthanides, but preferably of the Group 3 
or 4 transition metals or the Lanthanides which are in the +2, +3, or +4 
formal oxidation state and which cary at least one .pi.-bonded anionic 
ligand group. Preferred compounds include metal complexes containing from 
1 to 3 .pi.-bonded anionic ligand groups, which may be cyclic or 
non-cyclic delocalized .pi.-bonded anionic ligand groups. Exemplary of 
such .pi.-bonded anionic ligand groups are conjugated or non-conjugated, 
cyclic or non-cyclic dienyl groups, allyl groups, and arene groups. By the 
term ".pi.-bonded" is meant that the ligand group is bonded to the 
transition metal by means of a .pi.-bond. 
Each atom in the delocalized .pi.-bonded group may independently be 
substituted with a radical selected from the group consisting of halogen, 
hydrocarbyl, halohydrocarbyl, and hydrocarbyl-substituted metalloid 
radicals wherein the metalloid is selected from Group 14 of the Periodic 
Table of the Elements. Included within the term "hydrocarbyl" are 
C.sub.1-20 straight, branched and cyclic alkyl radicals, C.sub.6-20 
aromatic radicals, C.sub.7-20 alkyl-substituted aromatic radicals, and 
C.sub.7-20 aryl-substituted alkyl radicals. In addition two or more such 
radicals may together form a fused ring system or a hydrogenated fused 
ring system. Suitable hydrocarbyl-substituted organometalloid radicals 
include mono-, di-and trisubstituted organometalloid radicals of Group 14 
elements wherein each of the hydrocarbyl groups contains from 1 to 20 
carbon atoms. Examples of suitable hydrocarbyl-substituted organometalloid 
radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, 
methyldiethylsilyl, triphenylgermyl, and trimethylgermyl groups. 
Examples of suitable anionic, delocalized .pi.-bonded groups include 
cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, 
tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, 
dihydroanthracenyl, hexahydroanthracenyl, and decahydroanthracenyl groups, 
as well as C.sub.1-10 hydrocarbyl-substituted derivatives thereof. 
Preferred anionic delocalized .pi.-bonded groups are cyclopentadienyl, 
pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl, 
2,3-dimethylindenyl, fluorenyl, 2-methylindenyl and 
2-methyl-4-phenylindenyl. 
Suitable transition metal compounds may be any derivative of any transition 
metal including Lanthanides, but preferably of the Group 3, 4, or 
Lanthanide transition metals. More preferred are metal complexes 
corresponding to the formula: 
L.sub.1 MX.sub.m X'.sub.n X".sub.p, or a dimer thereof 
wherein: 
L is an anionic, delocalized, .pi.-bonded group that is bound to M, 
containing up to 50 non-hydrogen atoms, optionally two L groups may be 
joined together forming a bridged structure, and further optionally one L 
may be bound to X; 
M is a metal of Group 4 of the Periodic Table of the Elements in the +2, +3 
or +4 formal oxidation state; 
X is an optional divalent substituent of up to 50 non-hydrogen atoms that, 
together with L, forms a metallocycle with M; 
X' is an optional neutral Lewis base having up to 20 non-hydrogen atoms; 
X" each occurrence is a monovalent, anionic moiety having up to 40 
non-hydrogen atoms, optionally, two X" groups may be covalently bound 
together forming a divalent dianionic moiety having both valences bound to 
M, or form a neutral, conjugated or non-conjugated diene that is 
.pi.-bonded to M (whereupon M is in the +2 oxidation state), or further 
optionally, one or more X" and one or more X' groups may be bonded 
together, thereby forming a moiety that is both covalently bound to M and 
coordinated thereto by means of Lewis base functionality; 
l is 1 or 2 or 3; 
m is 0 or 1; 
n is a number from 0 to 3; 
p is an integer from 0 to 3; and 
the sum, l+m+p, is equal to the formal oxidation state of M. 
Preferred complexes include those containing either one or two L groups. 
The latter complexes include those containing a bridging group linking the 
two L groups. Preferred bridging groups are those corresponding to the 
formula (ER*.sub.2).sub.x, wherein E is silicon or carbon, R* 
independently each occurrence is hydrogen or a group selected from silyl, 
hydrocarbyl, hydrocarbyloxy and combinations thereof, said R* having up to 
30 carbon or silicon atoms, and x is 1 to 8. Preferably, R* independently 
each occurrence is methyl, benzyl, tert-butyl, ethoxy, propoxy, 2-butoxy 
or phenyl. 
Examples of the foregoing bis(L)-containing complexes are compounds 
corresponding to the formula (A) or (B): 
##STR1## 
wherein: M is titanium, zirconium or hafnium, preferably zirconium or 
hafnium, in the +2 or +4 formal oxidation state; 
R' and R" in each occurrence independently are selected from the group 
consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and 
combinations thereof, said R' or R" having up to 20 non-hydrogen atoms, or 
adjacent R' or R" groups together form a divalent derivative (i.e., a 
hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring 
system; 
X* independently each occurrence is an anionic ligand group of up to 40 
non-hydrogen atoms, or two X* groups together form a divalent anionic 
ligand group of up to 40 non-hydrogen atoms or together are a conjugated 
diene having from 4 to 30 non-hydrogen atoms forming a .pi.-complex with 
M, whereupon M is in the +2 formal oxidation state; and 
R*, E and x are as previously defined. 
The foregoing metal complexes are especially suited for the preparation of 
polymers having stereoregular molecular structure. In such capacity, it is 
preferred that the complex possess Cs symmetry or possess a chiral, 
stereorigid structure. Examples of the first type are compounds possessing 
different delocalized p-bonded systems, such as one cyclopentadienyl group 
and one fluorenyl group. Similar systems based on Ti(IV) or Zr(IV) were 
disclosed for preparation of syndiotactic olefin polymers in Ewen et al., 
J. Am. Chem. Soc., 110, 6255-6256 (1980). Examples of chiral structures 
include bis-indenyl complexes. Similar systems based on Ti(IV) or Zr(IV) 
were disclosed for preparation of isotactic olefin polymers in Wild et 
al., J. Organomet. Chem., 232, 233-47, (1982). 
Exemplary bridged ligands containing two .pi.-bonded groups are: 
(dimethylsilyl-bis-cyclopentadienyl), 
(dimethylsilyl-bis-methylcyclopentadienyl), 
(dimethylsilyl-bis-ethylcyclopentadienyl), 
(dimethylsilyl-bis-t-butylcyclopentadienyl), 
(dimethylsilyl-bis-tetramethylcyclopentadienyl), 
(dimethylsilyl-bis-indenyl), (dimethylsilyl-bis-tetrahydroindenyl), 
(dimethylsilyl-bis-fluorenyl), (dimethylsilyl-bis-tetrahydrofluorenyl), 
(dimethylsilyl-bis-2-methyl-4-phenylindenyl), 
(dimethylsilyl-bis-2-methylindenyl), 
(dimethylsilyl-cyclopentadienyl-fluorenyl), 
(1,1,2,2-tetramethyl-1,2-disilyl-bis-cyclopentadienyl), 
(1,2-bis(cyclopentadienyl)ethane, and 
(isopropylidene-cyclopentadienyl-fluorenyl). 
Preferred X* groups are selected from hydride, hydrocarbyl, silyl, germyl, 
halohydrocarbyl, halosilyl, silylhydrocarbyl and aminohydrocarbyl groups, 
or two X* groups together form a divalent derivative of a conjugated diene 
or else together they form a neutral, .pi.-bonded, conjugated diene. Most 
preferred X* groups are C.sub.1-20 hydrocarbyl groups. 
Suitable divalent X* substituents preferably include groups containing up 
to 30 non-hydrogen atoms comprising at least one atom that is oxygen, 
sulfur, boron or a member of Group 14 of the Periodic Table of the 
Elements directly attached to the delocalized .pi.-bonded group, and a 
different atom, selected from the group consisting of nitrogen, 
phosphorus, oxygen or sulfur, that is covalently bonded to M. 
A further class of metal complexes utilized in the present invention 
correspond to the formula: 
L.sub.l MX.sub.m X'.sub.n X".sub.p, or a dimer thereof 
wherein: 
L is an anionic, delocalized, .pi.-bonded group that is bound to M, 
containing up to 50 non-hydrogen atoms; 
M is a metal of Group 4 of the Periodic Table of the Elements in the +2, +3 
or +4 formal oxidation state; 
X is a divalent substituent of up to 50 non-hydrogen atoms that, together 
with L, forms a metallocycle with M; 
X' is an optional neutral Lewis base ligand having up to 20 non-hydrogen 
atoms; 
X" each occurrence is a monovalent, anionic moiety having up to 20 
non-hydrogen atoms, optionally two X" groups together may form a divalent 
anionic moiety having both valences bound to M or a neutral C.sub.5-30 
conjugated diene, and further optionally, X' and X" may be bonded 
together, thereby forming a moiety that is both covalently bound to M and 
coordinated thereto by means of Lewis base functionality; 
l is 1 or 2; 
m is 1; 
n is a number from 0 to 3; 
p is an integer from 1 to 2; and 
the sum, l+m+p, is equal to the formal oxidation state of M. 
A preferred class of such Group 4 metal coordination complexes used 
according to the present invention correspond to the formula: 
##STR2## 
wherein: M is titanium or zirconium in the +2 or +4 formal oxidation 
state; 
R.sub.3 in each occurrence independently is selected from the group 
consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and 
combinations thereof, said R.sub.3 having up to 20 non-hydrogen atoms, or 
adjacent R.sub.3 groups together form a divalent derivative (i.e., a 
hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring 
system; 
each X" is a halo, hydrocarbyl, hydrocarbyloxy or silyl group, said group 
having up to 20 non-hydrogen atoms, or two X" groups together form a 
C.sub.5-30 conjugated diene; 
Y is --O--, --S--, --NR*--, --PR*--; and 
Z is SiR*.sub.2, CR*.sub.2, SiR*.sub.2 SiR*.sub.2, CR*.sub.2 CR*.sub.2, 
CR*.dbd.CR*, CR*.sub.2 SiR*.sub.2, or GeR*.sub.2, wherein: R* is as 
previously defined. 
Illustrative Group 4 metal complexes that may be employed in the practice 
of the present invention include: cyclopentadienyltitaniumtrimethyl, 
cyclopenta-dienyltitaniumtriethyl, dienyltitaniumtriethyl, 
cyclopentadienyltitaniumtriisopropyl, cyclopentadienyltitaniumtribenzyl, 
cyclopentadienyltitanium-2,4-pentadienyl, 
cyclopentadienyltitaniumdimethylmethoxide, 
cyclopentaienyltitaniumdimethylchloride, 
pentamethylcyclopentadienyltitaniumtrimethyl, indenyltitaniumtrimethyl, 
indenyltitaniumtriethyl, indenyltitaniumtripropyl, 
indenyltitaniumtriphenyl, tetrahydroindenyltitaniumtribenzyl, 
pentamethylcyclopentadienyltitaniumtriisopropyl, 
pentamethylcyclopentadienyltitaniumtribenzyl, 
pentamethylcyclopentadienyltitaniumdimethylmethoxide, 
pentamethylcyclopentadienyltitaniumdimethylchloride, (.eta..sup.5 
-2,4-dimethyl-1,3-pentadienyl)titaniumtrimethyl, 
octahydrofluorenyltitaniumtrimethyl, tetrahydroindenyltitaniumtrimethyl, 
tetrahydrofluorenyltitaniumtrimethyl, 
(1,1-dimethyl-2,3,4,9,9,10-.eta.-1,4,5,6, 
7,8-hexahydronaphthalenyl)titaniumtrimethyl, (1,1,2,3-tetramethyl-2,3,4, 
9,10-.eta.-1,4,5,6,7,8-hexahydronaphthalenyl)titaniumtrimethyl, 
(tert-butylamido)(tetramethyl-.eta..sup.5 
-cyclopentadienyl)dimethylsilanetitanium dichloride, (tert-butylamido) 
(tetramethyl-.eta..sup.5 -cyclopentadienyl)-dimethylsilanetitanium 
dimethyl, (tert-butylamido) (tetramethyl-.eta..sup.5 
-cyclopentadienyl)-1,2-ethanediyltitanium dimethyl, 
(tert-butylamido)(tetramethyl-.eta..sup.5 -indenyl) dimethylsilanetitanium 
dimethyl, (tert-butylamido)(tetramethyl-.eta..sup.5 -cyclopentadienyl) 
dimethylsilane titanium (III) 2-(dimethylamino)benzyl, (tert-butylamido) 
(tetramethyl-.eta..sup.5 -cyclopentadienyl) dimethylsilanetitanium (III) 
allyl, (tert-butylamido)(tetramethyl-.eta..sup.5 
-cyclopentadienyl)-dimethylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene, 
(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II) 
1,4-diphenyl-1,3-butadiene, 
(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) 
1,3-butadiene, 
(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II) 
1,4-diphenyl-1,3-butadiene, 
(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) 
1,3-butadiene, 
(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II) 
1,3-pentadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium 
(II) 1,3-pentadiene, 
(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) dimethyl, 
(tert-butylamido) (2-methyl-4-phenylindenyl)dimethylsilanetitanium (II) 
1,4-diphenyl-1,3-butadiene, (tert-butylamido)(tetramethyl-.eta..sup.5 
-cyclopentadienyl)-dimethylsilanetitanium (IV) 1,3-butadiene, 
(tert-butylamido) (tetramethyl-.eta..sup.5 
-cyclopentadienyl)-dimethylsilanetitanium (II) 1,4-dibenzyl-1,3-butadiene, 
(tert-butylamido)(tetramethyl-.eta..sup.5 -cyclopentadienyl) 
dimethylsilanetitanium (II) 2,4-hexadiene, 
(tert-butylamido)(tetramethyl-.eta..sup.5 -cyclopentadienyl) 
dimethylsilanetitanium (II) 3-methyl-1,3-pentadiene, 
(tert-butylamido)(2,4-dimethyl-1,3-pentadien-2-yl) 
dimethylsilanetitaniumdimethyl, 
(tert-butylamido)(1,1-dimethyl-2,3,4,9,10-.eta.-1,4,5,6, 
7,8-hexahydronaphthalen-4-yl) dimethylsilanetitaniumdimethyl, and 
(tert-butylamido) (1,1,2,3-tetramethyl-2,3,4,9,10-.eta.-1,4,5,6, 
7,8-hexahydronaphthalen-4-yl)dimethylsilanetitanium dimethyl. 
Bis(L)-containing complexes including bridged complexes suitable for use in 
the present invention include: biscyclopentadienylzirconiumdimethyl, 
biscyclopentadienyltitaniumdiethyl, 
biscyclopentadienyltitaniumdiisopropyl, biscyclopentadienyltitaniumdipheny 
l, biscyclopentadienylzirconiumdibenzyl, 
biscyclopentadienyltitanium-2,4-pentadienyl, 
biscyclopentadienyltitaniummethylmethoxide, 
biscyclopentadienyltitaniummethylchloride, 
bispentamethylcyclopentadienyltitaniumdimethyl, 
bisindenyltitaniumdimethyl, indenylfluorenyltitaniumdiethyl, 
bisindenyltitaniummethyl(2-(dimethylamino)benzyl), 
bisindenyltitaniummethyltrimethylsilyl, 
bistetrahydroindenyltitaniummethyltrimethylsilyl, 
bispentamethylcyclopentadienyltitaniumdiisopropyl, 
bispentamethylcyclopentadienyltitaniumdibenzyl, 
bispentamethylcyclopentadienyltitaniummethylmethoxide, 
bispentamethylcyclopentadienyltitaniummethylchloride, 
(dimethylsilyl-bis-cyclopentadienyl)zirconiumdimethyl, 
(dimethylsilyl-bis-pentamethylcyclopentadienyl) titanium-2,4-pentadienyl, 
(dimethylsilyl-bis-t-butylcyclopentadienyl)zirconium dichloride, 
(methylene-bis-pentamethylcyclopentadienyl)titanium(III) 
2-(dimethylamino)benzyl, (dimethylsilyl-bis-indenyl)zirconiumdichloride, 
(dimethylsilyl-bis-2-methylindenyl)zirconiumdimethyl, 
(dimethylsilyl-bis-2-methyl-4-phenylindenyl)zirconium dimethyl, 
(dimethylsilyl-bis-2-methylindenyl) zirconium-1,4-diphenyl-1,3-butadiene, 
(dimethylsilyl-bis-2-methyl-4-phenylindenyl) zirconium (II) 
1,4-diphenyl-1,3-butadiene, 
(dimethylsilyl-bistetrahydroindenyl)zirconium(II) 
1,4-diphenyl-1,3-butadiene, 
(dimethylsilyl-bis-fluorenyl)zirconiumdichloride, 
(dimethylsilyl-bis-tetrahydrofluorenyl)zirconium di(trimethylsilyl), 
(isopropylidene)(cyclopentadienyl)(fluorenyl)zirconium dibenzyl, and 
(dimethylsilylpentamethylcyclopentadienylfluorenyl)-zirconium dimethyl. 
Other compounds which are useful in the catalyst systems, especially 
compounds containing other Group 4 metals, will, of course, be apparent to 
those skilled in the art. 
The complexes are rendered catalytically active by combination with an 
activating cocatalyst or by use of an activating technique. Suitable 
activating cocatalysts for use herein include polymeric or oligomeric 
alumoxanes, especially methylalumoxane, triisobutyl aluminum modified 
methylalumoxane, or isobutylalumoxane; neutral Lewis acids, such as 
C.sub.1-30 hydrocarbyl substituted Group 13 compounds, especially 
tri(hydrocarbyl)aluminum or tri(hydrocarbyl)boron compounds and 
halogenated (including perhalogenated) derivatives thereof, having from 1 
to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more 
especially perfluorinated tri(aryl)boron compounds, and most especially 
tris(pentafluorophenyl)borane; non-polymeric, compatible, 
non-coordinating, ion-forming compounds (including the use of such 
compounds under oxidizing conditions), especially the use of ammonium, 
phosphonium, oxonium, carbonium, silylium or sulfonium salts of 
compatible, non-coordinating anions, or ferrocenium salts of compatible, 
non-coordinating anions; bulk electrolysis (explained in more detail 
hereinafter); and combinations of the foregoing activating cocatalysts and 
techniques. The foregoing activating cocatalysts and activating techniques 
have been previously taught with respect to different metal complexes in 
the following references: EP-A-277,003, U.S. Pat. No. 5,153,157, U.S. Pat. 
No. 5,064,802, EP-A-468,651 (equivalent to U.S. application Ser. No. 
07/547,718), EP-A-520,732 (equivalent to U.S. application Ser. No. 
07/876,268), EP-A-520,732 (equivalent to U.S. application Ser. No. 
07/884,966 filed May 1, 1992), and U.S. Pat. No. 5,470,993, the teachings 
of which are hereby incorporated by reference. 
Combinations of neutral Lewis acids, especially the combination of a 
trialkyl aluminum compound having from 1 to 4 carbons in each alkyl group 
and a halogenated tri(hydrocarbyl)boron compound having from 1 to 20 
carbons in each hydrocarbyl group, especially 
tris(pentafluorophenyl)borane, further combinations of such neutral Lewis 
acid mixtures with a polymeric or oligomeric alumoxane, and combinations 
of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane 
with a polymeric or oligomeric alumoxane, are especially desirable 
activating cocatalysts. 
Suitable ion-forming compounds useful as cocatalysts comprise a cation 
which is a Bronsted acid capable of donating a proton, and a compatible, 
non-coordinating anion, A-. As used herein, the term "non-coordinating" 
means an anion or substance which either does not coordinate to the Group 
4 metal containing precursor complex and the catalytic derivative derived 
therefrom, or which is only weakly coordinated to such complexes, thereby 
remaining sufficiently labile to be displaced by a neutral Lewis base. A 
non-coordinating anion specifically refers to an anion which, when 
functioning as a charge balancing anion in a cationic metal complex, does 
not transfer an anionic substituent or fragment thereof to said cation, 
thereby forming neutral complexes. "Compatible anions" are anions which 
are not degraded to neutrality when the initially formed complex 
decomposes and are non-interfering with desired subsequent polymerization 
or other uses of the complex. 
Preferred anions are those containing a single coordination complex 
comprising a charge-bearing metal or metalloid core, which anion is 
capable of balancing the charge of the active catalyst species (the metal 
cation) which may be formed when the two components are combined. Also, 
said anion should be sufficiently labile to be displaced by olefinic, 
diolefinic and acetylenically unsaturated compounds or other neutral Lewis 
bases such as ethers or nitrites. Suitable metals include, but are not 
limited to, aluminum, gold and platinum. Suitable metalloids include, but 
are not limited to, boron, phosphorus, and silicon. Compounds containing 
anions which comprise coordination complexes containing a single metal or 
metalloid atom are, of course, well known and many, particularly such 
compounds containing a single boron atom in the anion portion, are 
available commercially. 
Preferably, such cocatalysts may be represented by the following general 
formula: 
EQU (L*-H)d.sup.+ (A).sup. d- 
wherein: 
L* is a neutral Lewis base; 
(L*-H).sup.+ is a Bronsted acid; 
A.sup.d- is a non-coordinating, compatible anion having a charge of d-, 
and 
d is an integer from 1 to 3. 
More preferably, A.sup.d- corresponds to the formula: 
M'Q.sub.4 !.sup.- ; 
wherein: 
M' is boron or aluminum in the +3 formal oxidation state; and 
Q independently each occurrence is selected from hydride, dialkylamido, 
halide, hydrocarbyl, hydrocarbyloxide, halosubstituted hydrocarbyl, 
halosubstituted hydrocarbyloxy, and halosubstituted silylhydrocarbyl 
radicals (including perhalogenated hydrocarbyl perhalogenated 
hydrocarbyloxy and perhalogenated silylhydrocarbyl radicals), said Q 
having up to 20 carbons with the proviso that in not more than one 
occurrence is Q halide. Examples of suitable hydrocarbyloxide Q groups are 
disclosed in U.S. Pat. No. 5,296,433, the teachings of which are herein 
incorporated by reference. 
In a more preferred embodiment, d is one, that is, the counterion has a 
single negative charge and is A-. Activating cocatalysts comprising boron 
which are particularly useful in the preparation of catalysts of this 
invention may be represented by the following general formula: 
(L*-H).sup.+ (BQ.sub.4).sup.- ; 
wherein: 
L* is as previously defined; 
B is boron in a formal oxidation state of 3; and 
Q is a hydrocarbyl, hydrocarbyloxy, fluorinated hydrocarbyl, fluorinated 
hydrocarbyloxy, or fluorinated silylhydrocarbyl group of up to 20 
non-hydrogen atoms, with the proviso that in not more than one occasion is 
Q hydrocarbyl. 
Most preferably, Q is each occurrence a fluorinated aryl group, especially 
a pentafluorophenyl group. 
Illustrative, but not limiting, examples of boron compounds which may be 
used as an activating cocatalyst in the preparation of the catalysts are 
tri-substituted ammonium salts such as: trimethylammonium 
tetrakis(pentafluorophenyl) borate, triethylammonium 
tetrakis(pentafluorophenyl) borate, tripropylammonium 
tetrakis(pentafluorophenyl) borate, tri(n-butyl)ammonium 
tetrakis(pentafluorophenyl) borate, tri(sec-butyl)ammonium 
tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium 
tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium 
n-butyltris(pentafluorophenyl) borate, N,N-dimethylanilinium 
benzyltris(pentafluorophenyl) borate, N,N-dimethylanilinium 
tetrakis(4-(t-butyldimethylsilyl)-2,3, 5,6-tetrafluorophenyl) borate, 
N,N-dimethylanilinium tetrakis(4-(tri-isopropylsilyl)-2,3, 
5,6-tetrafluorophenyl) borate, N,N-dimethylanilinium 
pentafluorophenoxytris(penta-fluorophenyl) borate, N,N-diethylanilinium 
tetrakis(pentafluorophenyl) borate, N,N-dimethyl-2,4,6-trimethylanilinium 
tetrakis(pentafluorophenyl) borate, trimethylammonium tetrakis(2,3, 
4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3, 
4,6-tetrafluorophenyl) borate, tripropylammonium 
tetrakis-(2,3,4,6-tetrafluorophenyl) borate, tri(n-butyl)ammonium 
tetrakis(2,3,4,6-tetrafluorophenyl) borate, dimethyl(t-butyl)ammonium 
tetrakis(2,3, 4,6-tetrafluorophenyl) borate, N,N-dimethylanilinium 
tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-diethylanilinium 
tetrakis(2,3,4,6-tetrafluorophenyl) borate, and 
N,N-dimethyl-2,4,6-trimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl) 
borate; dialkyl ammonium salts such as: di-(i-propyl)ammonium 
tetrakis(pentafluorophenyl) borate, and dicyclohexylammonium 
tetrakis(pentafluorophenyl) borate; tri-substituted phosphonium salts such 
as: triphenylphosphonium tetrakis(pentafluorophenyl) borate, 
tri(o-tolyl)-phosphonium tetrakis(pentafluorophenyl) borate, and 
tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate; 
di-substituted oxonium salts such as: diphenyloxonium 
tetrakis(pentafluorophenyl) borate, di(o-tolyl)oxonium 
tetrakis(pentafluorophenyl) borate, and di(2,6-dimethylphenyl)oxonium 
tetrakis(pentafluorophenyl) borate; di-substituted sulfonium salts such 
as: diphenylsulfonium tetrakis(pentafluorophenyl) borate, 
di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and 
bis(2,6-dimethylphenyl)sulfonium tetrakis(pentafluorophenyl) borate. 
Preferred (L*-H).sup.+ cations are N,N-dimethylanilinium and 
tributylammonium. 
Another suitable ion-forming, activating cocatalyst comprises a salt of a 
cationic oxidizing agent and a non-coordinating, compatible anion 
represented by the formula: (Ox.sup.e+).sub.d (A.sup.d-).sub.e wherein: 
Ox.sup.e+ is a cationic oxidizing agent having a charge of e.sup.+ ; e is 
an integer from 1 to 3; and A.sup.d- and d are as previously defined. 
Examples of cationic oxidizing agents include: ferrocenium, 
hydrocarbyl-substituted ferrocenium, Ag.sup.+, or Pb.sup.+2. Preferred 
embodiments of A.sup.d- are those anions previously defined with respect 
to the Bronsted acid containing activating cocatalysts, especially 
tetrakis(pentafluorophenyl)borate. 
Another suitable ion-forming, activating cocatalyst comprises a compound 
which is a salt of a carbenium ion and a non-coordinating, compatible 
anion represented by the formula: .COPYRGT..sup.+ A.sup.- wherein: 
.COPYRGT..sup.+ is a C.sub.1-20 carbenium ion and A.sup.- is as 
previously defined. A preferred carbenium ion is the trityl cation, i.e., 
triphenylmethylium. 
A further suitable ion-forming, activating cocatalyst comprises a compound 
which is a salt of a silylium ion and a non-coordinating, compatible anion 
represented by the formula: R.sub.3 Si(X').sub.q.sup.+ A.sup.-, wherein: R 
is C.sub.1-10 hydrocarbyl, and X', q and A.sup.- are as previously 
defined. 
Preferred silylium salt activating cocatalysts are trimethylsilylium 
tetrakis(pentafluorophenyl) borate, triethylsilylium 
tetrakis(pentafluorophenyl) borate and ether-substituted adducts thereof. 
Silylium salts have been previously generically disclosed in J. Chem Soc., 
Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al., 
Organometallics, 1994, 13, 2430-2443. The use of the above silylium salts 
as activating cocatalysts for addition polymerization catalysts is claimed 
in U.S. application Ser. No. 08/304,315, filed Sep. 12, 1994, issued as 
U.S. Pat. No. 5,495,036, incorporated herein by reference. 
Certain complexes of alcohols, mercaptans, silanols, and oximes with 
tris(pentafluorophenyl)borane are also effective catalyst activators and 
may be used according to the present invention. Such cocatalysts are 
disclosed in U.S. Pat. No. 5,296,433, the teachings of which are herein 
incorporated by reference. 
The technique of bulk electrolysis involves the electrochemical oxidation 
of the metal complex under electrolysis conditions in the presence of a 
supporting electrolyte comprising a non-coordinating, inert anion. In the 
technique, solvents, supporting electrolytes and electrolytic potentials 
for the electrolysis are used such that electrolysis by-products that 
would render the metal complex catalytically inactive are not 
substantially formed during the reaction. More particularly, suitable 
solvents are materials that are: liquids under the conditions of the 
electrolysis (generally temperatures from 0.degree. C. to 100.degree. C.), 
capable of dissolving the supporting electrolyte, and inert. "Inert 
solvents" are those that are not reduced or oxidized under the reaction 
conditions employed for the electrolysis. It is generally possible, in 
view of the desired electrolysis reaction, to choose a solvent and a 
supporting electrolyte that are unaffected by the electrical potential 
used for the desired electrolysis. Preferred solvents include 
difluorobenzene (all isomers), dimethoxyethane (DME), and mixtures 
thereof. 
The electrolysis may be conducted in a standard electrolytic cell 
containing an anode and cathode (also referred to as the working electrode 
and counter-electrode, respectively). Suitable materials of construction 
for the cell are glass, plastic, ceramic and glass-coated metal. The 
electrodes are prepared from inert conductive materials, by which are 
meant conductive materials that are unaffected by the reaction mixture or 
reaction conditions. Platinum or palladium are preferred inert conductive 
materials. Normally an ion-permeable membrane such as a fine glass frit 
separates the cell into separate compartments, the working electrode 
compartment and counterelectrode compartment. The working electrode is 
immersed in a reaction medium comprising the metal complex to be 
activated, solvent, supporting electrolyte, and any other materials 
desired for moderating the electrolysis or stabilizing the resulting 
complex. The counter-electrode is immersed in a mixture of the solvent and 
supporting electrolyte. The desired voltage may be determined by 
theoretical calculations or experimentally by sweeping the cell using a 
reference electrode such as a silver electrode immersed in the cell 
electrolyte. The background cell current, the current draw in the absence 
of the desired electrolysis, is also determined. The electrolysis is 
completed when the current drops from the desired level to the background 
level. In this manner, complete conversion of the initial metal complex 
can be easily detected. 
Suitable supporting electrolytes are salts comprising a cation and a 
compatible, non-coordinating anion, A.sup.-. Preferred supporting 
electrolytes are salts corresponding to the formula G.sup.+ A.sup.- ; 
wherein: 
G.sup.+ is a cation which is non-reactive towards the starting and 
resulting complex, and A.sup.- is as previously defined. 
Examples of cations, G.sup.+, include tetrahydrocarbyl-substituted ammonium 
or phosphonium cations having up to 40 non-hydrogen atoms. Preferred 
cations are the tetra(n-butylammonium) and tetraethylammonium cations. 
During activation of the complexes of the present invention by bulk 
electrolysis, the cation of the supporting electrolyte passes to the 
counter-electrode and A.sup.- migrates to the working electrode to become 
the anion of the resulting oxidized product. Either the solvent or the 
cation of the supporting electrolyte is reduced at the counterelectrode in 
equal molar quantity with the amount of oxidized metal complex formed at 
the working electrode. Preferred supporting electrolytes are 
tetrahydrocarbylammonium salts of tetrakis(perfluoroaryl) borates having 
from 1 to 10 carbons in each hydrocarbyl or perfluoroaryl group, 
especially tetra(n-butylammonium) tetrakis(pentafluorophenyl) borate. 
A further recently discovered electrochemical technique for generation of 
activating cocatalysts is the electrolysis of a disilane compound in the 
presence of a source of a non-coordinating compatible anion. This 
technique is more fully disclosed and claimed in the previously mentioned 
U.S. Application Ser. No. 08/304,315, filed on Sep. 12, 1994. 
The foregoing electrochemical activating technique and activating 
cocatalysts may also be used in combination. An especially preferred 
combination is a mixture of a tri(hydrocarbyl)aluminum or 
tri(hydrocarbyl)borane compound having from 1 to 4 carbons in each 
hydrocarbyl group with an oligomeric or polymeric alumoxane compound. 
The molar ratio of catalyst/cocatalyst employed preferably ranges from 
1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferably 
from 1:1000 to 1:1. Alumoxane, when used by itself as an activating 
cocatalyst, is employed in large quantity, generally at least 100 times 
the quantity of metal complex on a molar basis. Tris(pentafluorophenyl) 
borane, where used as an activating cocatalyst is employed in a molar 
ratio to the metal complex of from 0.5:1 to 10:1, more preferably from 1:1 
to 6:1, most preferably from 1:1 to 5:1. The remaining activating 
cocatalysts are generally employed in approximately equimolar quantity 
with the metal complex. A most preferred activating cocatalyst comprises 
both a strong Lewis acid and an alumoxane, especially 
tris(pentafluorophenyl)borane and methylalumoxane, modified 
methylalumoxane, or diisobutylalumoxane. Preferred molar ratios of 
transition metal complex:tris(pentafluorophenyl)borane:alumoxane are from 
1:1:1 to 1:5:20, more preferably from 1:1:1.5 to 1:5:15. The use of lower 
levels of alumoxane for the production of olefin polymers with high 
catalytic efficiencies requires less of the expensive alumoxane and 
provides polymers with lower levels of aluminum residue and, hence, 
greater clarity. 
In a particularly preferred embodiment of the invention, the cocatalyst can 
be used in combination with a tri(hydrocarbyl)aluminum compound having 
from 1 to 10 carbons in each hydrocarbyl group or an oligomeric or 
polymeric alumoxane. It is possible to employ these aluminum compounds for 
their beneficial ability to scavenge impurities such as oxygen, water, and 
aldehydes from the polymerization mixture. Preferred aluminum compounds 
include trialkyl aluminum compounds having from 2 to 6 carbons in each 
alkyl group, especially those wherein the alkyl groups are ethyl, propyl, 
isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl, and 
methylalumoxane, modified methylalumoxane (that is, methylalumoxane 
modified by reaction with triisobutyl aluminum) (MMAO) and 
diisobutylalumoxane. The molar ratio of aluminum compound to metal complex 
is preferably from 1:10,000 to 1000:1, more preferably from 1:5000 to 
100:1, most preferably from 1:100 to 100:1. 
The catalyst system may be prepared as a homogeneous catalyst by addition 
of the requisite components to a solvent. The catalyst system may also be 
prepared and employed as a heterogeneous catalyst by depositing the 
requisite components on a catalyst support material. A support, especially 
silica, modified silica (silica modified by calcining, treatment with a 
trialkylaluminum compound having from 1 to 10 carbons in each alkyl group, 
or treatment with an alkylalumoxane), alumina, or a polymer (especially 
polytetrafluoroethylene or a polyolefin) or other suitable inorganic or 
organic support material, may be employed, and desirably is employed when 
the catalysts are used in a slurry or gas phase polymerization process. 
The support is preferably employed in an amount to provide a weight ratio 
of catalyst (based on metal) to support from 1:100,000 to 1:10, more 
preferably from 1:50,000 to 1:20, and most preferably from 1:10,000 to 
1:30. When prepared in heterogeneous or supported form, it is preferred to 
use silica as the support material. 
In general, the polymerization may be accomplished at conditions well known 
in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization 
reactions, i.e., temperatures from 0.degree. C. to 250.degree. C. and 
pressures from atmospheric to 2000 atmospheres (0.1 to 100 MPa) and above. 
Suspension, solution, slurry, gas phase or other process conditions may be 
employed if desired. Preferred are the solution, gas phase, or slurry 
polymerization processes. Most preferred is the solution process. 
Depending on the type of polymerization process, suitable solvents or 
diluents to be used are non-coordinating, inert liquids. In solution 
polymerization conditions, a solvent is used for the respective components 
of the reaction, particularly the interpolymer produced. Preferred 
solvents include mineral oils and the various hydrocarbons which are 
liquid at reaction temperatures. Illustrative examples of useful solvents 
include straight- and branched-chain hydrocarbons such as alkanes, e.g., 
isobutane, butane, pentane, isopentane, hexane, heptane, octane and 
nonane, as well as mixtures of alkanes including kerosene and Isopar 
E.TM., available from Exxon Chemicals Inc.; cyclic and alicyclic 
hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, 
methylcyclohexane, methylcycloheptane, and mixtures thereof; and aromatics 
and alkyl-substituted aromatic compounds such as benzere, toluene, 
xylenes, ethylbenzene, diethylbenzene, and the like; and perfluorinated 
hydrocarbons such as perfluorinated C.sub.4-10 alkanes. Suitable solvents 
also include liquid olefins which may act as monomers or comonomers. 
Mixtures of the foregoing are also suitable. 
Slurry polymerization takes place in liquid diluents and under conditions 
in which the polymer product is substantially insoluble in the diluent. 
Preferably, the diluent for slurry polymerization is a hydrocarbon, 
preferably a saturated aliphatic or cycloaliphatic hydrocarbon of at least 
3, more preferably at least 4 carbon atoms. Likewise, the .alpha.-olefin 
monomer or a mixture of different .alpha.-olefin monomers may be used in 
whole or part as the diluent. Typical operating conditions for slurry 
polymerizations are from 0.degree. C. to 120.degree. C., more preferably 
from 30.degree. C. to 100.degree. C. The pressure is typically from 
subatmospheric to 50 bar. 
Typical operating conditions for gas phase polymerizations are from 
20.degree. C. to 100.degree. C., more preferably from 40.degree. to 
80.degree. C. In gas phase processes, the pressure is typically from 
subatmospheric to 100 bar. Preferred gas phase polymerization processes 
are disclosed in U.S. Pat. Nos. 4,588,790, 4,543,399, 5,352,749, and 
5,405,922, and U.S. application Ser. No. 122,582, filed Sep. 17, 1993 
(corresponding to WO 9507942), which are hereby incorporated by reference. 
In most polymerization reactions, the molar ratio of catalyst:polymerizable 
compounds employed is from 10.sup.-12 :1 to 10.sup.-1 :1, more preferably 
from 10.sup.-9 :1 to 10.sup.-5 :1. 
At all times, the individual ingredients as well as the recovered catalyst 
components must be protected from oxygen and moisture. Therefore, the 
catalyst components and catalysts must be prepared and recovered in an 
oxygen- and moisture-free atmosphere. Preferably, therefore, the reactions 
are performed in the presence of a dry, inert gas such as, for example, 
nitrogen. 
Advantageously, the polymerization process is carried out with a 
differential pressure of ethylene of from about 10 to about 1000 psi (70 
to 7000 kPa), most preferably from about 40 to about 400 psi (30 to 300 
kPa). The polymerization is generally conducted at a temperature of from 
0.degree. C. to 150.degree. C., preferably from 70.degree. C. to 
150.degree.C. 
The polymerization may be carried out as a batchwise or a continuous 
polymerization process. A continuous process is preferred, in which event 
catalyst, olefin, polyene and, optionally, solvent are continuously 
supplied to the reaction zone and polymer product continuously removed 
therefrom. Preferably, the interpolymers are produced in a solution 
process, most preferably a continuous solution process. 
Without limiting in any way the scope of the invention, one means for 
carrying out such a polymerization process is as follows: In a 
stirred-tank reactor, olefin monomer is introduced continuously together 
with solvent and polyene monomer. The reactor contains a liquid phase 
composed substantially of monomers together with any solvent or additional 
diluent. Catalyst and cocatalyst are continuously introduced in the 
reactor liquid phase. The reactor temperature and pressure may be 
controlled by adjusting the solvent/monomer ratio, the catalyst addition 
rate, as well as by cooling or heating coils, jackets or both. The 
polymerization rate is controlled by the rate of catalyst addition. The 
polymer product molecular weight is controlled, optionally, by controlling 
other polymerization variables such as the temperature, monomer 
concentration, or by a stream of hydrogen introduced to the reactor, as is 
well known in the art. The reactor effluent is contacted with a catalyst 
kill agent such as water or an alcohol. The polymer solution is optionally 
heated, and the polymer product is recovered by flashing off gaseous 
monomers as well as residual solvent or diluent at reduced pressure, and, 
if necessary, conducting further devolatilization in equipment such as a 
devolatilizing extruder. In a continuous process, the mean residence time 
of the catalyst and polymer in the reactor generally is from about 5 
minutes to 8 hours, and preferably from 10 minutes to 6 hours. 
In a preferred manner of operation, the polymerization is conducted in a 
continuous solution polymerization system comprising at least two reactors 
connected in series or parallel. In one reactor, a relatively high weight 
average molecular weight (M.sub.w) product (M.sub.w from 100,000 to 
600,000) is formed, while in the second reactor, a product of a relatively 
low molecular weight (M.sub.w 10,000 to 200,000) is formed. The polyene is 
preferably introduced in the reactor producing the higher molecular weight 
interpolymer fraction using the catalysts system and relative feeding 
rates of polyene to olefin as described above. The catalyst used in the 
second reactor may be the same as or different from that in the first 
reactor. In particular, it could be a Ziegler-type catalyst, preferably a 
heterogeneous Ziegler catalyst containing a solid catalyst component 
comprising magnesium, titanium, halogen, and aluminum, optionally on a 
support material. When employing a Ziegler-type catalyst, reaction 
conditions typical for such catalyst are used in the relevant part of the 
process. The final product is a blend of the two reactor effluents which 
are combined prior to devolatilization to result in a uniform blend of the 
two polymer products. When incorporating the polyene in the higher 
molecular weight fraction, the desired properties can be achieved using 
less of the polyene. Such a dual reactor process further allows for the 
preparation of products having properties which may be improved 
selectively by varying certain reaction parameters and, thus, product 
properties independently. In a preferred embodiment, the reactors are 
connected in series, that is, effluent from the first reactor is charged 
to the second reactor and fresh monomers, solvent and hydrogen is added to 
the second reactor. Reactor conditions are adjusted such that the weight 
ratio of polymer produced in the first reactor to that produced in the 
second reactor is from 5:95 to 95:5. In addition, the temperature of the 
second reactor can be controlled to produce the lower molecular weight 
product. This system beneficially allows for the production of 
interpolymer products having a large range of mechanical, optical, and 
processing properties. 
The interpolymer of the present invention may further comprise additives or 
adjuvants which are typically added to olefin-based polymers, such as 
fillers, antioxidants, colorants, UV stabilizers, flame retardants, etc. 
The interpolymer of the present invention may be blended with other 
components such as natural or synthetic polymers, both thermoplastic and 
thermosetting. Typical polymers are styrenic polymers and styrenic block 
copolymers, olefinic polymers, ethylene vinyl alcohol copolymers, 
ethylene(meth)acrylic acid copolymers, polyesters, polyethers, and natural 
and synthetic rubbers. 
Blending can be carried out by any conventional compounding operation, such 
as, for example, single- and twin-screw extruders, Banbury mixers, 
Brabender mixers, Farrel continuous mixers, and two-roll mixers. The order 
of mixing and the form of the blend components to be mixed is not 
critical. The mixing temperatures are preferably such that an intimate 
blend is obtained of the components. Typical temperatures are above the 
softening or melting points of at least one of the components, and more 
preferably above the softening or melting points of all the components. 
The interpolymers of the present invention or their blend compositions may 
be used to fabricate articles, such as films, sheet, moldings, and other 
shaped articles by conventional processes, preferably under melt 
processing conditions. Suitable processes include injection molding, 
compression molding, blow-molding, extruding, rotational molding, and 
thermoforming. The present interpolymers can also be functionalized or 
grafted according to methods and techniques well known in the art. 
It has been found that the present interpolymers having melt indices in the 
range of 0.05 to 1 g/10 min are suitable for processing according to blown 
film extrusion techniques to make very wide films, for example, 
agricultural films which may require bubble diameters of 3 m, or thick 
membranes such as used for landfills. This was not very well possible with 
prior art olefin-based polymers produced by coordination catalysts. 
Because of the advantageous properties, the present interpolymers can also 
be used in blow-molding applications, for example, to make bottles or 
containers having relatively larger dimensions. Interpolymers in the 
elastomeric range having a density of less than about 0.89 g/cm.sup.3 are 
especially suitable for wire and cable applications, profile extrusion, 
and injection molded articles. 
The present interpolymers can further be used to make foams or expandable 
products by combining them with an expanding agent and optionally 
subjecting the composition to expanding conditions. With the term 
"expanding agent" is meant an agent or compound which, while subjected to 
expanding conditions, such as, for example, heating, change of pressure, 
or application of mechanical force, undergoes a change in its physical or 
chemical condition, such as to occupy a greater volume. Preferred 
expanding agents are conventional blowing agents used to produce foams.

The invention will be further illustrated by the following examples, 
without limiting the invention thereto. 
EXAMPLES 
General Polymerization Method 
The polymers described in the examples were produced in the following way. 
A continuous stirred tank reactor with a volume of five liters was used. 
Hydrogen, if added for control of melt index, was combined into one stream 
with the ethylene before being introduced into the diluent mixture. 
Typically, this diluent mixture comprises a mixture of C.sub.8 -C.sub.10 
saturated hydrocarbons (e.g., Isopar.TM. E, trademark of Exxon) and the 
optional .alpha.-olefin(s) and the diene. In the case of the examples 
described, 1-octene is used as .alpha.-olefin. The dienes 1,7-octadiene or 
1,9-decadiene, if used, and the 1-octene were previously purified by 
passing them through silica and/or alumina molecular sieves. The reactor 
feed mixture is continuously introduced into the reactor. The transition 
metal complex and the cocatalyst, dissolved in the same solvent, were 
combined into a single stream and were also continuously injected into the 
reactor. The reactor pressure was held constant at about 30 bar. 
Temperature was controlled by the catalyst flow and by the use of a 
cooling jacket. The outlet stream of the reactor was taken to a heat 
exchanger where its temperature was raised to 270.degree. C. and then to a 
devolatilizing unit where the solvent was separated from the polymer. The 
molten polymer was then carried to a pelletizer, where additives (e.g., 
antioxidants, pigments, etc.), if desired, were incorporated. 
The catalyst/cocatalyst system used was {(tert-butylamido)dimethyl 
(tetramethyl-.eta..sup.5 -cyclopentadienyl)silane} dimethyl titanium (IV) 
with tris(pentafluorophenyl) borane and isobutyl-modified methylalumoxane 
commercially available from Akzo Nobel under the designation MMAO, in the 
molar ratios 1:3:5 to 1:3:10, except for Example 14 where the transition 
metal compound was {(tert-butylamido)dimethyl(tetramethyl-.eta..sup.5 
-cyclopentadienyl)silane} titanium (II) 1,3-pentadiene, the titanium being 
in the formal +2 oxidation state. 
Typically, the following additives were employed in the examples and 
comparative examples: 50 to 2000 parts per million of Irganox.TM. B-900 
and 100 to 2200 parts per million of calcium stearate. Irganox.TM. B-900 
is available from Ciba-Geigy and is a mixture of 1 part of a phenolic-type 
antioxidant and 4 parts of a phosphite-type antioxidant. 
The specific process conditions are incorporated in Table 1 and the product 
properties in Table 2. In the tables, the following abbreviations are 
used: OD for 1,7-octadiene; DD for 1,9-decadiene; Et for ethylene; H2 for 
hydrogen; and OCT for 1-octene. Examples 1-4 use OD and Examples 5-16 use 
DD. Comparative examples are indicted with "C-Ex". 
The ethylene (Et) conversion in Table 1 is defined as the ratio (ethylene 
feed to reactor--ethylene out of the reactor)/(ethylene feed to reactor). 
The process of Example 15 was carried out in two steps, the conditions of 
both steps being given in Table 1. 
Table 2 provides both the values for the melt tension as measured and for 
the minimum melt tension as calculated according to formula: 
EQU MT min.=1.328-0.787910 log(I.sub.2) 
+22.5(d-0.85)-40.56{log(I.sub.2)}.times.(d-0.85). 
Table 2 provides both the values for the DRI as measured and for the 
minimum DRI as calculated according to formula: 
EQU DRI min.=7-0.75*I.sub.2. 
Table 2 provides both the logarithmic value for the viscosity at a shear 
rate of 316 s.sup.-1 and the logarithmic value for the maximum viscosity 
at that shear rate as calculated according to formula: 
EQU log .eta..sup.316 max.=2.80-0.2861.times.log(I.sub.2). 
TABLE 1 
__________________________________________________________________________ 
Process Conditions of Examples and Comparative Examples 
OCT/ Diene/ 
Et Cat. 
Diluent/ Et (OCT + 
H2/Et 
Et Conver- 
Tempe- 
Eff. 
Et Feed 
ET) mole 
mole/ 
sion 
rature 
kg pol/ 
kg/kg! kg/hr! 
wt %! 
%! mole! 
%! .degree.C.! 
g Ti! 
__________________________________________________________________________ 
Ex. 1 
9.5 2.50 
52 -- 0.0049 
75.2 
105 970 
(OD) 
Ex. 2 
9.5 2.50 
52 -- 0.0051 
73.1 
111 1098 
(OD) 
Ex. 3 
8.8 2.50 
0.0 0.122 
0.0075 
92.0 
136 160 
(OD) 
Ex. 4 
8.4 2.50 
-- 0.127 
0.0087 
89.0 
130 82 
(OD) 
Ex. 5 
10.3 
2.0 44 -- 0.0013 
85 100 -- 
(DD) 
Ex. 6 
10.1 
2.0 35 -- 0.0014 
84 100 -- 
(DD) 
Ex. 7 
9.8 2.0 20 -- 0.0013 
84 100 -- 
(DD) 
Ex. 8 
7.9 3.0 15 -- 0.0014 
87 130 -- 
(DD) 
Ex. 9 
7.2 2.50 
-- -- 0.0017 
85 130 -- 
(DD) 
Ex. 10 
9.5 2.50 
52 -- 0.0024 
73.7 
112 532 
(DD) 
Ex. 11 
9.5 2.50 
52 -- 0.0020 
80.5 
108 698 
(DD) 
Ex. 12 
9.5 2.50 
52 -- 0.0024 
76.0 
112 678 
(DD) 
Ex. 13 
7.3 3.00 
-- 0.076 
0.0005 
89.0 
130 366 
(DD) 
Ex. 14 
8.8 4.0 -- -- 0.0007 
85.5 
130 -- 
(DD) 
Ex15 9.3 1.8 11 0.084 
0.001 
85.4 
130 -- 
1st rect. (DD) 
Ex15 6.4 2.6 12 0.060 
-- 86.0 
128 165 
2nd rect. 
Ex. 16 
6.0 4.0 17.5 
0.072 
0.0004 
82.3 
133 -- 
(DD) 
C-Ex. 1 
9.3 2.50 
55 -- -- 75.0 
95 692 
C-Ex. 2 
9.6 2.40 
47 -- -- 82.5 
92 622 
C-Ex. 3 
6.7 3.50 
0.0 0.057 
-- 95.5 
136 414 
C-Ex. 4 
9.8 2.50 
45 -- -- 85.0 
87 5323 
C-Ex. 5 
9.4 2.50 
51 -- -- 78.4 
94 3463 
__________________________________________________________________________ 
TABLE 2 
__________________________________________________________________________ 
Product Properties of Examples and Comparative Examples 
l2 Viny- 
Trans- Melt 
MT log 
Density dg/ 
l10/l2 
Vinyls/ 
lidenes/ 
vinyls/ 
Diene 
Tension 
min. DRI 
log (.eta..sup.316) 
g/cc! min! 
Ratio 
1000 C 
1000C 
1000C 
mole %! 
(g) (g) 
DRI 
min. 
(.eta..sup.316) 
max. 
__________________________________________________________________________ 
Ex. 1 
0.867 
4.0 
11.1 
0.29 
0.44 
0.22 
0.3 2.7 0.8 
5.2 
4.0 
2.44 
2.63 
Ex. 2 
0.877 
2.1 
11.4 
0.30 
0.41 
0.23 
0.34 4.3 1.3 
7.8 
5.5 
2.61 
2.71 
Ex. 3 
0.951 
1.9 
12.3 
0.31 
0.05 
0.05 
0.62 4.3 2.2 
9.5 
5.6 
2.67 
2.72 
Ex. 4 
0.944 
1.7 
14.6 
0.18 
-- -- 0.67 3.5 2.4 
-- -- 2.53 
2.73 
Ex. 5 
0.876 
0.4 
19.0 
0.15 0.11 &gt;10 2.7 
7.8 
6.7 
-- -- 
Ex. 6 
0.885 
1.2 
13.4 
0.21 0.12 3.6 1.9 
11.9 
6.1 
-- -- 
Ex. 7 
0.909 
1.1 
14.3 
0.20 0.11 4.0 2.6 
10.5 
6.2 
-- -- 
Ex. 8 
0.920 
1.1 
16.6 
0.33 0.11 11.4 
2.7 
-- -- 2.51 
2.79 
Ex. 9 
0.952 
0.1 
31.2 
-- 0.12 &gt;12 8.6 
4.8 
6.9 
2.80 
3.09 
Ex.10 
0.871 
1.2 
14.4 
0.43 
-- -- 0.18 2.8 1.7 
10.0 
6.1 
2.53 
2.78 
Ex.11 
0.867 
4.6 
10.7 
0.45 
-- -- 0.16 4.4 0.7 
5.3 
3.6 
2.41 
2.61 
Ex.12 
0.869 
6.9 
8.4 
0.43 
-- -- 0.18 3.7 0.4 
5.3 
1.8 
2.44 
2.56 
Ex.13 
0.956 
1.7 
14.3 
0.14 
-- -- 0.04 3.4 2.5 
6.7 
5.7 
2.53 
2.73 
Ex.14 
0.954 
1.6 
12.7 
0.13 
0.02 
0.01 
0.05 3.2 2.7 
5.9 
5.8 
2.55 
2.74 
Ex.15 
0.924 
2.1 
10.8 
0.18 
-- -- 0.03 2.6 1.8 
-- -- 2.64 
2.71 
Ex.16 
0.923 
1.9 
10.3 
0.11 
-- -- 0.03 2.0 1.9 
-- -- 2.70 
2.72 
C-Ex. 1 
0.862 
4.3 
7.9 
0.19 
0.43 
0.22 
-- 0.2 0.8 
0.4 
3.8 
-- -- 
C-Ex. 2 
0.880 
2.2 
8.6 
0.16 
0.38 
0.18 
-- 1.0 1.3 
0.7 
5.4 
-- -- 
C-Ex. 3 
0.956 
1.7 
13.0 
0.12 
0.03 
0.04 
-- 2.0 2.5 
2.9 
5.7 
-- -- 
C-Ex. 4 
0.870 
4.5 
8.0 
0.16 
0.40 
0.17 
-- 0.5 0.7 
0.8 
3.6 
-- -- 
C-Ex. 5 
0.870 
1.0 
7.3 
-- -- 1.3 1.8 
1.0 
6.3 
-- -- 
__________________________________________________________________________ 
The significant improvement in the melt strength and DRI index in the 
interpolymers of the present invention follows from a comparison with 
comparative examples. With respect to Example 2, it is noted that even at 
an ethylene conversion which is significantly lower than the one used for 
Comparative Example 2, still the improvements in melt tension and DRI are 
significant. 
The M.sub.w /M.sub.n values for the interpolymers of Examples 13, and 4 
were 2.7, and 2.7 respectively; for Comparative Examples 2, 3, and 4, 
respectively, 1.8, 2.4, and 2.0. 
No ring structures were detected in Example 13, which is a polymer of 
ethylene and DD, or in any other equivalent copolymer or terpolymer of the 
same two monomers plus 1-octene by solution .sup.13 C-NMR. A comparison of 
Example 13 with 4 shows that to achieve about the same properties, the 
ethylene/1,7-octadiene copolymer with approximately equal melt index, melt 
tension and DRI requires about 23 times as much diene as the interpolymer 
of Example 13. Solution .sup.13 C-NMR shows the presence of 3.1 rings (C7 
and C6) per thousand carbons in Example 4, while these or other rings are 
undetectable in Example 13. 
A comparison between Examples 15 and 16 shows that using the same overall 
amount of polyene, in this case 1,9-decadiene, in either a process using 
two reactors in series (Example 15) or only one reactor, illustrates that 
an even more efficient use of the polyene can be obtained in the two-step 
polymerization process by introducing the polyene in the reactor making 
the higher molecular weight interpolymer fraction. At the same overall 
polyene/ethylene molar ratio, the interpolymer of Example 15 has a higher 
melt tension, even though its melt index is slightly higher. 
The interpolymers of Examples 8, 15, and 16 were blown film extruded in a 
45 mm screw extruder. The processability expressed as the torque applied 
to the extruder to keep the extruder running at a constant value of 40 rpm 
was, for the interpolymers of Examples 15 and 16, only 29 percent and 41 
percent higher than for a standard LDPE of about the same melt index and 
density. The head pressure for the interpolymers of Examples 15 and 16 was 
the same and 21 percent higher, respectively, than that for the LDPE. 
Typical prior art linear low density polyethylenes (LLDPE) have torques 
which are about 80 to 90 percent higher than that of the standard LDPE. 
For typical LLDPE's, the head pressure is about 200 to 300 percent higher 
than for LLDPE. For a standard blown film blend of 70 weight percent of 
LLDPE and 30 weight percent of LDPE, the torque and head pressure are 
typically 60 percent and 80 to 90 percent higher, respectively, than for 
standard LDPE. 
The interpolymer of Example 8 was extruded into a blown film using an 
extruder having a screw of 70 mm, a die diameter of 350 mm, and a die gap 
of 2.3 mm. The blow-up ratio (diameter of bubble to diameter of die) used 
was 2.5. Compared to a LDPE and a LLDPE of similar melt index and density, 
the interpolymer of Example 8 required: practically the same melt 
temperature as LDPE (192.degree. C. to 195.degree. C.) and a lower 
temperature than LLDPE (239.degree. C.); a head pressure of 194 bar versus 
209 bar for LDPE and 308 bar for LLDPE; and an amperage of 93 A versus 80 
A for LDPE and 148 A for LLDPE.