Progress in Olefin Polymerization Catalysts and Polyolefin

Polyolefin Materials 271

T. Shiono, K. Nomura and M. Terano (Editors)
© 2006 Elsevier B.V. All rights reserved.

45
Effect of a-Olefins on Copolymerization of
Ethylene and a-Olefin with [*-BuNSiMe2Flu]TiMe2
Catalyst
Nawaporn mtaragamjona, Takeshi Shionob*, Bunjerd Jongsomjif**
Piyasan Praserthdam8*

"Center of Excellence on Catalysis and Catalytic Reaction Engineering

Department of Chemical Engineering, Faculty of Engineering
Chulalomgkam University, Bangkok 10330 Thailand

^Department of Applied Chemistry, Graduate School of Engineering, Hiroshima

University, 1-4-1 Kagamiyama, Higashi-Hiroshima, 739-8527, JAPAN.

Abstract

The effect of a-olefm was observed in ethylene/a-olefin copolymerization

toward [?-BuNSiMeaFlu]TiMe2 catalyst with MMAO. Three kinds of a-olefm
monomers were chosen for the present study. Activity, polymer microstrueture,
thermal properties, molecular weight and molecular weight distribution of
polymers were investigated. Our results revealed that the activity of
polymerization was strongly dependent on the a-olefins employed. Thus, the
polymerization behavior can be altered with the a-olefins used during
polymerization. It indicated that the crystallinity of polyethylene was broken by
the large amounts of a-olefin insertion on ethylene and a-olefin copolymer.

1. INTRODUCTION

From the industrial point of view, linear low-density polyethylene (LLDPE) is

produced in gas, solution and high pressure processes. The density of
polyethylene is an important variable that we use to control polymer properties.
Density of polyethylene can be controlled in many ways, especially, the level
and distribution of branching. The catalytic polymerization of ethylene with «-
olefins is a typical way of introducing short-chain branching in polyethylene
272 JV. Intaragamjan et al,

backbone. Nowadays, new generation of polymerization catalysts i.e.

metallocene and late transition metal catalysts, can control the amount of a-
olefin insertion into polyethylene with uniform and homogeneous sequence and
composition distributions. With the difference of comonomer composition and
its distribution, it can cause significant changes in polymer properties. These
included differences in glass transition, melting temperatures, melt viscosity,
the mechanical and optical properties [1-7]. As a matter of fact, we can use the
ethylene/a-olefm in the wide range of applications.
In the present paper, we are communicating the results of polymerization
regarding to the a-olefin monomer in ethylene/oc-olefin polymerization
behaviors. Polymerization proceeded with [t-BuNSiMe2Flu]TiMe2 and
modified-methylaluminoxane (MMAO) system using heptane as the solvent
medium. Polymer properties and polymer microstructure were also investigated
to suggest the interpretation of comonomer effect on the copolymer
composition and comonomer distribution.

2. EXPERIMENTAL

Materials; All manipulations were carried out under an argon atmosphere using
standard Schlenk techniques. All solvents were refluxed with
sodium/benzophenone or calcium hydride and distilled before use. The complex
was prepared according to the method reported previously [8].
Polymerization Procedure; Ethylene/a-olefm copolymerizations were carried
out in a 100-ml semi-batch stainless steel autoclave reactor equipped with a
magnetic stirrer. Heptane was introduced to reactor followed by the addition of
the desired amount of MMAO. The catalyst was added to the reactor in a glove
box. The reactor was then immersed in liquid nitrogen to freeze the solution and
evacuated to remove argon. The a-olefin was added to the freezed reactor
equipped with Schlenk line to keep system in argon atmosphere. After that, the
reactor was heated to the desired polymerization temperature. Feeding ethylene
started the reaction. The pressure in the reactor was kept at 50 psi by a
continuous ethylene feed. Polymerizations were conducted on the certain time
and terminated with acidic methanol. The polymer obtained was precipitated in
acidic methanol, filtered, adequately washed with methanol, and finally dried in
the atmospheric pressure for 3 days to ensure for solvent evaporation.
Analytical Procedures; Molecular weights and molecular weight distributions
of polyethylene obtained were determined by gel permeation chromatography
(GPC) with a Waters 150CV at 135 °C using 1,,2,4-trichlorobenzene as a solvent.
The 13C NMR spectra of the polyethylene were measured at 70 "C on a JEOL
GX 500 spectrometer operated at 125.65 MHz in the pulse Fourier-transform
mode. The pulse angle was 90° and about 5000 scans were accumulated in pulse
45. Effect ofa-Olefin on Copolymerization with [t-BuNSiMe3Flu]TiMe2 Catalyst 273

repetition of 4.0 s. Sample solutions were prepared in ehloroform-a?i up to 10

wt-%. Differential scanning calorimetry (DSC) curves of the samples were
recorded on a Perkin-Elmer DSC P7 under nitrogen with a heating rate of 10
"C/min.

3. RESULTS AND DISCUSSION

Ethylene/a-olefin copolymerization was conducted at 70 °C with various a-

olefin types, of which results are summarized in Table 1. The copolymerization
of ethylene/a-olefin gave the highest activity when 1-octene was employed.
From this evident, it should be noted that the active species of ion pair can be
affected from the second monomer in polymerization. In this case the proper
geometry and steric of 1-octene can generate the highest activity in ethylene/a-
olefin polymerization. Again, from Table 1, we found that the molecular weight
of polymer was reduced when the copolymerization was conducted. This was
because the chain transfer of polymer occurred after the a-olefin insertion unit
during copolymerization. Moreover, with the higher a-olefin monomer, we
obtained the higher molecular weight of copolymer.

Table 1 Results of ethylene/a-olefin copolymerization3

Polymer Yield (g) Activity" M n (10 4 ) 6 MWff 7?

E° 0.75 1000 4.2 3.9 134

EH 3,08 2460 2.6 2,2
EO 3.52 2g20 3.6 2.0
ED 2.31 1840 3.6 2.1 99

'Polymerization conditions: Ti = 5 (xmol, Al/Ti = 1000, 50 psi of ethylene pressure,

polymerization temperature = 70 °C, bActivity = kg(polymer) mor'fTi) hr"1. cNumber of average
molecular weight and molecular weight distributions were measured by GPC analysis using poly
styrene as reference.
d
Measured by DSC (°C) "Using Ti = 3 junol.

A quantitative analysis of triad distribution for all copolymer samples was

performed by 13C NMR. The assignments of the spectra their analysis were
based on those of ethylene/1-hexene copolymer [9]. The triad distribution and
product reactivity ratio of monomer are shown in Table 2.
It should be noted that the a-olefin incorporation in the main chain of
copolymer apparently decreased with the larger a-olefin monomer applied. The
next focus was on the copolymer structure. The product of monomer reactivity
ratios increased from 1.1 with 1-hexene to 2.4 with 1-decene according to the
size of a-olefin, which indicates that the comonomer distribution in the
274 N. Intaragamjon et al.

copolymer was changed from random to blocky by the size of a-olefin

comonamer.
Table 2 Microstrueture and comonomer content of the copolymers
Polymer ccc ECC ECE EEE CEC EEC %E %C We
EH 0.097 0.243 0.124 0.203 0.137 0.196 54 46 1.14
EO 0.064 0.136 0.119 0.362 0.086 0.233 68 32 1.67
ED 0.025 0.106 0.096 0.558 0.064 0.150 77 23 2.36

E and C denote ethylene and comonomer (H = hexene, O = octene and D = decene), respectively.

4. CONCLUSIONS

Comonomer effects were investigated in the copolymerization of ethylene and

a-olefin with the [/-BuNSiMe2Flu]TiMe2MMAO catalyst. The size of the a-
olefin used as a comonomer was found to affect the copolymerization ability of
the catalytic system, which was probably caused by the a-olefin inserted at the
propagation chain end.

Acknowledgments

We give the grateful thanks to the Thailand Research Fund (TRF), The
Thailand Japan Technology Transfer Project (TJTTP), and the Royal Golden
Jubilee program scholarship.

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