CATALYSIS AND THE UNIPOL PROCESS

FREDERICK J. KAROL and FELIX I. JACOBSON

_.

Union Carbide Corporation, UNIPOL Systems Department, P.O. Box 670,

Bound Brook, NJ 08805, USA

ABSTRACT
Production of low-density polyethylene (LDPE) is undergoing the
kind of revolution not seen in the field since the discoveries by
Ziegler and Natta. Union Carbide has developed a unique and versa-
tile low-pressure, fluid-bed process (UNIPOL) that yields vastly
improved polyethylene resins, linear low-density polyethylenes
(LLDPE), at greatly reduced costs. Proprietary catalysts are key to
success of the UNIPOL process. Catalysts have an important effect
on productivity, polymer molecular weight, polymer molecular weight
distribution, copolymerization kinetics, and degree of stereoregu-
larity. Moreover the size, shape, and porosity (morphology) of the
catalyst particle play an important role in regulating the morphol-
ogy of the resultant polymer.
Today, Union Carbide and its more than twenty-five licensees are
operating or constructing polyethylene plants based on the UNIPOL
process in fifteen countries. By 1986 the combined capacity of UNI-
POL reactors will be sufficient to supply 25% of the world's total
demand for polyethylene. A recent development has been the produc-
tion of polypropylene by the UNIPOL process. This is a result of a
cooperative undertaking between Union Carbide and Shell Chemical,
USA, and combines for the first time a high activity catalyst with
simplicity and improved economics of gas-phase, fluidized-bed tech-
nology. A new polypropylene plant of 80,000 tons per year based on
the UNIPOL process is starting production in 1985 at Seadrift, Texas.

UNION CARBIDE--WORLD LEADER IN POLYETHYLENE TECHNOLOGY

The polyethylene industry and scientific community recently cel-
ebrated its golden jubilee in London.l) Since its discovery in
the 1930s polyethylene has grown to be the world's largest thermo-

32 3
324 F.J. Karol a n d F.I. J a c o b s o n

plastic. Indeed, world plant-capacities for. polyolefins are very

l a r g e (Table I ) .2)
By 1986 t h e c o m b i n e d c a p a c i t y o f UNIPOL r e a c t o r s i n o p e r a t i o n o r
uncjer c o n s t r u c t i o n a r o u n d t h e w o r l d w i l l be s u f f i c i e n t t o s u p p l y 25%
of the world's t o t a l demand f o r p o l y e t h y l e n e . Fifty-three reactors
will be i n p l a c e i n 15 c o u n t r i e s on six continents. Linear low-
density polyethylene (LLDPE) has already revolutionized the poly-
ethylene industry, and w i l l c o n t i n u e t o i m p a c t s i g n i f i c a n t l y on t h e
future of the e n t i r e polyolefins business. T h e UNIPOL process is
recognized as a significant technological accomplishment. Union
Carbide received the prestigious Kirkpatrick Award for UNIPOL in
1979. 3, Changes in polyethylene process and product technologies
i n t h e last decade , brought about through p o l y m e r i z a t i o n c a t a l y s i s ,
are so s i g n i f i c a n t t h a t t h i s p e r i o d w i l l no doubt b e c a l l e d "Cataly-
sis a n d The P o l y e t h y l e n e R e v o l u t i o n . " Key t o t h e s u c c e s s of t h e
UNIPOL p r o c e s s i s t h e p r o p r i e t a r y c a t a l y s t s t h a t o p e r a t e a t l o w
p r e s s u r e s and l o w temperatures, and which are s u i t a b l e for u s e i n a
gas-phase, fluid-bed reactor. I t i s p r i m a r i l y b y m e a n s of c a t a l y s t
c o m p o s i t i o n t h a t r e s i n p r o p e r t i e s a r e c o n t r o l l e d i n t h e UNIPOL pro-
cess. High-pressure technology, dominated by concerns for reactor
engineering and reactor control of polymer properties is rapidly
g i v i n g way t o a new t e c h n o l o g y i n w h i c h c a t a l y s i s a n d c h e m i c a l c o n -
t r o l o f p r o d u c t p r o p e r t i e s are k e y f a c t o r s .

PROCESS DESCRIPTION AND BENEFITS OF UNIPOL PROCESS

I n t h e UNIPOL p r o c e s s ( F i g u r e 1, 21, g a s e o u s e t h y l e n e , a comono-
m e r a n d a c a t a l y s t a r e r e a c t e d i n t h e p r e s e n c e of a c h a i n t r a n s f e r
a g e n t a t t e m p e r a t u r e s of a b o u t 1 0 0 ° C o r l e s s a n d p r e s s u r e s of 2 . 1
MPa (300 p s i ) o r l e s s t o p r o d u c e a p o l y e t h y l e n e p r o d u c t t h a t i s re-
moved d i r e c t l y from t h e r e a c t o r a s a g r a n u l a r , s o l i d m a t e r i a l . Gas-
e o u s e t h y l e n e , comonomer a n d c h a i n t r a n s f e r a g e n t a r e f e d c o n t i n u -
ously i n t o a f l u i d i z e d bed reactor. C a t a l y s t is added s e p a r a t e l y .
C i r c u l a t e d by a s m a l l c o m p r e s s o r , t h e gas stream f l u i d i z e s t h e p o l y -
m e r bed, p r o v i d e s r e a c t a n t s for p o l y m e r i z a t i o n , and removes e x o t h e r -
m i c h e a t of r e a c t i o n . T h e c i r c u l a t i n g gas s t r e a m p a s s e s t h r o u g h a
cooler before b e i n g r e t u r n e d t o t h e r e a c t o r .
G r a n u l a r p o l y e t h y l e n e is removed t h r o u g h a g a s - l o c k chamber.
O n l y a s m a l l a m o u n t of r e s i d u a l monomer a c c o m p a n i e s t h e p r o d u c t i n t o
t h i s chamber, and t h i s is purged s a f e l y from t h e r e s i n . Overall,
 Catalysis and the U n i p o l Process 325

the combined conversion rate of ethylene and comonomer is approxi-

mately 97% to 99%. The average catalyst residence time is three to
five hours during which the polymer particles grow to an average
size of 500-1000 microns. The granular product, with o r without
conventional additives, is ready for packaging and shipping to the
customer without any further processing. The size and the shape of
the polymer granules are such that their bulk density and solid flow
characteristics are suitable for subsequent materials handling and
processing operations by the customer. For pelleted product, the
granular material may be fed to conventional pelleting equipment o r
to proprietary Union Carbide pelleting systems.

PROCESS OPTIONS
The UNIPOL Process is available in three versions, i.e., Grass
Roots Plant, Waterborne Option, and Facility Modernization System
(FMS) (Figures 3 - 4 ) . The Waterborne Option involves construction of
UNIPOL LLDPE plants on ocean-going barges and delivered as turnkey
operations anywhere in the world accessible by deep water. The FMS
Option offers high-pressure LDPE producers a highly efficient way to
enter the LLDPE market immediately and minimizes investment costs by
making maximum use of existing plant facilities.
Waterborne ODtion
Union Carbide has completed the first "Waterborne" plant f o r
Ipako S.A., Argentina (Figure 5). The plant was constructed in the
shipbuilding facilities of Ishikawajima-Harima Heavy Industries near
Nagoya, Japan. It has a design capacity of 135,000 metric tons-per-
year of LLDPE. The plant was delivered to Ipako's waterside site in
Bahia Blanca, Argentina in late 1981. Construction of the plant
from keel-laying to shipyard commissioning was completed in just
eight months. The plant was in full commercial operation by Decem-
ber 1981--just 22 months from signing of the sales agreement. This
represents a reduction in construction time of at least a year from
that required for land-based construction of a traditional polyeth-
ylene plant.
FMS Ostion
UNIPOL FMS offers process and product technology equal to that
formerly possible only with a "grass roots" UNIPOL facility. North-
ern Petrochemical Company in Illinois chose FMS to upgrade its ex-
isting high-pressure facility to produce LLDPE. With this approach
326 F.J. K a r o l and F . I . Jacobson

a cost-efficient, l o w - p r e s s u r e UNIPOL r e a c t o r s y s t e m c a n b e " d r o p p e d

in" t o a n outmoded h i g h - p r e s s u r e polyethylene plant and tied into
e x i s t i n g process and s u p p o r t facilities. The old reactor is t h e n
s h u t d o w n , a n d t h e "new" p l a n t s t a r t e d u p , c a p a b l e of producing not
o n l y LLDPE, b u t a f u l l r a n g e of p o l y e t h y l e n e s .

T a b l e 1. World-Plant Capacities f o r Polyolefins2)

MM T o n s / Y r .
LDPE LLDPE HDPE pp
1980 16.10 8.48 6.86

1981 16.10 0.44 9.27 7.04

1982 14.48 1.78 8.70 7.27

1983 13.92 2.91 9.40 7.93

1984 14.22 3.92 9.80 8.19

1985 14.62 4.65 10.07 8.81

T o t a l 1984 C a p a c i t y nd36 MM T o n s ( 7 9 MMM l b s )

F i g u r e 1:
Fluid-Bed P l a n t at Seadrift, T e x a s for P o l y e t h y l e n e P r o d u c t i o n
 32 7

reactor

Purge

Catalyst
Product
discharge

Comonomer J Granular polyethylene

Figure 2: Schematic of Low-Pressure,

Fluid-Bed Process for Polyethylene Production

I UNIPOL F Y I

---
Figure 3: UNIPOL Facilities Modernization System (FMS)

I
UNIPOL Proceao

Low/Controiled
Investment Coat Investment Coat

Figure 4: UNIPOL Process Options

328 F.J. K a r o l and F . 1 . Jacobson

Figure 5 :
Ipako Barge-Mounted Plant

POLYETHYLENE PRODUCTS FROM UNIPOL PROCESS

The UNIPOL process commercially produces ethylene homopolymers,
and copolymers with several alpha olefins including butene-1 and
hexene-1. The process can produce products over the entire density
range of polyethylene. Catalyst and process technology know-how
permit control of polymer molecular weight o r melt index from less
than 0.1 g/10 min to melt indexes well above 100. Likewise, polymer
molecular weight distribution may be adjusted from Mw/Mn as nar-
row as 3 to as broad as 30.
The development and commercialization in the United States of
LLDPE products from the UNIPOL process have occurred at a rapid rate
(Table 11-111). 4, By contrast it took traditional LDPE twenty
years to reach a billion pounds annual consumption--HDPE over a
decade. The pace was set with introduction of general purpose LLDPE
products in 1978. Shortly thereafter film producers, using retrofit
technology, were able to modify LDPE fabrication equipment to handle
LLDPE products at competitive rates. Use of higher alpha-olefins
such as hexene-1 as a comonomer, led to a line of new, high-strength
LLDPE products. Through the use of specially-designed air rings
with specially-formulated UNIPOL LLDPE products, a series of clar-
ity-grade products was introduced in 1983. A new family of easy-flow
 C a t a l y s i s and the U n i p o l Process 329

LLIIPE products has recently been developed and introduced to the

marketplace. Shortly a line of IlhlW-LLDPE resins will also be seen
in the marketplace. 5)
T h e fi lm industry represents two-thirds of the U . S . polyethylene
market. Film made Prom LLDPE resin offers high tensile strength,
improvcd puncture resistance, and higher elongation, as well. as
better toughness and improved properties at both low and high tempe-
ratures.
In jection molding is the second largest market for polyethylene
accounting for 10% of consumption. LLDPE has virtually replaced
conventional LDPE in all major injection molding applications due to
its exceptional toughness and high environmental stress-crack resis-
tance (ESCR).
F o r blow molders, LLDPE resins provide superior ESCR and higher
modulus/lower gas permeability. These improved properties allow
blow molders to go after new small-bottle and food-container mar-
kets. Blow-molded LLDPE drum liners either meet o r exceed industry
standards for low temperature toughness and ESCR.
Rotational molders have turned to LLDPE because its high im-
pact strength and improved ESCR provide a competitive alternative to
more expensive resins. In addition, using a high melt index LLDPE
resin, a rotomolder can reduce cycle time by more than 25% and still
maintain maximum toughness.
Pipe and tubing extruders have moved up to LLDPE because of its
outstanding physical properties. Exceptional burst strength, high
modulus values, excellent ESCR, low temperature toughness, and over-
all thermal stability are some reasons LLDPE is finding widespread
use in the extrusion market.
LLDPE is rapidly penetrating such specialty markets as power and
communications cable insulation and jacketing systems. These resins
offer improved high and low temperature toughness, excellent ESCR
and good dielectric properties. LLDPE is already the U.S. "stan-
dard" for communications cable jacketing.
330 F.J. K a r o l a n d F . I . Jacobson
Table 11. LDPE and LLDPE Markets in USA (1980-1985)4)
MM Tons/Yr
__
YEAR LDPE LLDPE % LDPE % LLDPE
19130 2.59 0.28 90 10

1982 2.32 0.66 78 22

19133 2.40 0.85 74 26

1984 2.35 1.10 68 32

( 1985) (2.30) (1.41) (62) (38)

Table 111. Introduction of UNIPOL Process LLDPE Products5)

1978 General Purpose LLDPE
1979 Retrofit Film-Fabrication Technology
1982 High-Strength LLDPE
1983 Clarity Technology for LLDPE
1984 Easy-Flow LLDPE
1985 Ultra-Strength HMW-LLDPE

UNIPOL PROCESS FOR POLYPROPYLENE

Polypropylene by the UNIPOL process is the result of a coopera-
tive undertaking between Union Carbide Corporation and Shell Chemi-
cal (a Division of Shell Oil Company) and combines for the first
time a high-activity catalyst with the simplicity and improved eco-
nomics of gas-phase, fluid-bed technology. Polypropylene made by
this process contains such low catalyst ash and atactic polymer le-
vels that no removal steps are required (Figures 6-7). Therefore,
investment and operating costs associated with conventional extrac-
tion, purification, and drying steps are eliminated as well. 6 )
The UNIPOL process offers the lowest investment and operating
costs of any available polypropylene process. Featured are 10-1578
lower investment and operating costs than that of any other "new
generation" process being licensed. A new polypropylene plant (Fig-
ure 6 ) of 80 thousand tons per year based on the UNIPOL process
started production recently in our Seadrift, Texas plant. This
plant, based on the FMS concept, was constructed in only nine months.
 Catalysis and the U n i p o l Process 331

In the production of polypropylene by the UNIPOL process, cata-

lyst, propylene, and othcr reactants, such as hydrogen, cocatalysts,
and comonomers, are continuously fed to a reaction system. This
system consists of a reactor, a blower, and a heat exchanger. The
reactor is a vertical fluid-bed reactor containing granular polypro-
pylene about 0.025 inches, and a small amount of active catalyst.
Usually polymerization conditions are 1.7-4.1 MPa (250-600 psi)
pressure and 5 0 - 8 8 ' C . Typically, high-activity catalysts yield o n
the order of 20,000 lb of polypropylene/lb of catalyst.
The gaseous reactants pass through the reactor, providing fluid-
ization and absorbing the heat of reaction. After passing through
the fluidized bed of polypropylene, the gas enters an expanded sec-
tion where fine particles are disengaged. The gas then passes
through a heat exchanger where it is cooled. The cooled gas is then
recirculated to the reactor. Polypropylene is removed directly from
the reactor through a discharge system where unreacted monomer is
separated and recycled. The resin is then purged of any residual
hydrocarbons and conveyed out of the system.
Homopolymers and random copolymers are made using a single
fluid-bed reactor. For production of in-situ impact copolymers, the
polypropylene containing active catalyst is transferred from the
homopolymer reactor to a second, smaller reactor, where the ethy-
lene-propylene rubber phase is produced. Product recovery is simi-
lar to the system used for homopolymers. Only two reactors in
series are required to make the full range of medium- to super-high
impact products.
The UNIPOL process for polypropylene produces a full line of
products consisting of homopolymers, and random and block copolymers
(Table IV). 7 , The process produces impact copolymers directly in
the reactor thereby eliminating post-reaction blending. Because Of
independent control of (a) stereoregularity and molecular weight for
homopolymers, (b) molecular weight, comonomer type/content for ran-
dom copolymers, and (c) stereoregularity, molecular weight and ethy-
lene content for impact (in-situ) copolymers, the process will allow
the development of optimized products to satisfy demanding end-use
requirements in the marketplace.
332 F.J- K a r o l a n d F . I . Jacobson

The UNIPOL process has gained worldwide recognition as the pre-

eminent process for producing polyethylene. And the same simpli-
city, minimal equipment requirements and reduced space needs which
UNIPOL brought to polyethylene, it has now brought to polypropylene.

Figure 6:
Union Carbide/Shell Chemical UNIPOL PP Plant at Seadrift, Texas

6Product
DIasharge

Purging/

Figure 7:
Schematic of Union Carbide/Shell Chemical UNIPOL PP Plant
 C a t a l y s i s a n d the U n i p o l Process 333

Table IV: UNIPOL PP Product Capabilities7 )

IIomopo1vmer
High, Controllable Stereoregularity (I1 93-98%)
Broad Mi4 Range ((0.1 to >lo0 MF)

Random Copolvmers
Broad Range of Comonomer Content ((7%)
Not Limited to Ethylene
Broad hlW Range ((0.1 to > l o 0 MF)

Impact (In-Situ) Copolvmers

Excellent Impact/Stiffness Balance
Competitive to World Leaders Using Complex Technology
Broad Range of Total Ethylene Content ((25%)
Not Limited to Ethylene
Broad MW Range ((0.1 to > 5 0 MF)

CATALYSTS MAKE IT ALL POSSIBLE

Without suitable catalysts, the giant step in reducing the
operating pressure for production of low density polyethylenes would
not have been possible.8-9)
Polymerization catalysts must show attractive behavior in a
number of areas, particularly catalyst productivity, polymer molecu-
lar weight and molecular weight distribution, comonomer incorpora-
tion, and polymer morphology (Table V ) . In propylene polymeriza-
tion, control of polymer isotactic index is also important. Produc-
tion of catalysts should be made as simple as possible in order to
provide the basis for reproducible production of polyolefins.
Catalvst Productivity
Catalyst productivities based on the transition metal should
be sufficiently high (2105-106 kg polymer/kg transition metal)
so that catalyst residues need not be removed from the polymer.
Catalyst supports such as silica o r magnesium chloride to improve
polymerization activity by increasing the concentration of active
sites are particularly effective. With chromium catalysts, chemical
anchoring to silica supports to form new surface compositions has
proven highly effective for providing catalysts showing very high
ethylene polymerization activity. High-activity titanium catalysts
334 F.J. K a r o l a n d F.I. J a c o b s o n

can be based on c a t a l y s t precursors prepared from b i m e t a 1 l . i ~ eom-

plexes (Mg, Ti), through insertion into defects of a hlgCI2 sub-
s t r a t e , by f o r m a t i o n o f h i g h s u r f a c e a r e a s p o n g e s , a n d b y f o r m a t i o n
of solid solutjons of TiC13 and hlgC12 by cocrystallization.
T y p i c a l examples of high a c t i v i t y c a t a l y s t s d e s c r i b e d i n t h e p a t e n t
1 0 , 11)
and s c i e n t i f i c l i t e r a t u r e are l i s t e d i n T a b l e V I .
M o l e c u l a r Weight and M o l e c u l a r Weight D i s t r i b u t i o n
Molecular weight of the polyethylenes can be c o n t r o l l e d by
the reaction temperature and the concentration of chajn transfer
agent i n t h e system. Hydrogen is a n e f f e c t i v e c h a i n t r a n s f e r a g e n t
w i t h many c a t a l y s t s . The s p e c i f i c c a t a l y s t type significantly af-
f e c t s molecular weight distribution. Many c h r o m i u m - b a s e d catalysts
p r o v i d e p o l y e t h y l e n e s o f i n t e r m e d i a t e o r b r o a d m o l e c u l a r w e i g h t 431s-
tribution while use of titanium-based catalysts lead t o polyethy-
l e n e s of r e l a t i v e l y narrow molecular weight d i s t r i b u t i o n . Consider-
a b l e experimental d a t a s u p p o r t t h e view t h a t a d i v e r s i t y o f chemi-
c a l l y d i s t i n c t a c t i v e s p e c i e s is p r i m a r i l y r e s p o n s i b l e f o r t h e r a n g e
o f molecular weight d i s t r i b u t i o n s measured i n e t h y l e n e and propylene
polymerizations. Among t h e f a c t o r s t h a t c o u l d a f f e c t t h e d i v e r s i t y
of a c t i v e s p e c i e s a r e t h e s p e c i f i c t r a n s i t i o n metal compound i n c l u d -
i n g l i g a n d e n v i r o n m e n t a n d o x i d a t i o n s t a t e , t h e t y p e of cocatalyst
and e l e c t r o n donor used t o generate t h e c a t a l y t i c a l l y a c t i v e spe-
c i e s , t h e p h y s i c a l s t a t e of t h e c a t a l y s t , a n d t h e n a t u r e of t h e c a t -
alyst substrate.
C o m p r e h e n s i v e s t u d i e s h a v e e v a l u a t e d t h e e f f e c t of n-bonded
o r g a n i c l i g a n d s a t t a c h e d t o chromium on p o l y m e r i z a t i o n p a r a m e t e r s o f
chromium catalysts. In these studies differences in hydrogen
response, comonomer incorporation, and polymerization activity with
these c a t a l y s t s suggested that t h e n a t u r e of the active sites was
different due, at least in part, to changes i n l i g a n d environment
(eq. 1):
 Catalysis and t h e U n i p o l Process 335

Table V: Catalyst Requirements in UNIPOL Process

High Catalyst Productivities
Control of Polymer Molecular Weight
Control of Polymer Molecular Weight Distribution
Good Comonomer Incorporation
Good Polymer Morphology
Simple, Reproducible Catalyst Preparation
High Polymer Isotactic Index

Table VI: Examples of High Activity Catalysts for Olefin

Polymerization

Titanium/Magnesium Composition Metal Alkyl Po1vmer

TiC14/MgC12 (Activated) PE
TiCl /MgC12/Electron Donor It

4
TiCl4/Mg(OC2H5l2 11

TiCl4/MgCl2/Ethy1-p-Toluate PP

Chromium Composition
Cr03/Si02 + Modifiers PE
(C5H5I2Cr/SiO2 PE

Comonomer Incorporation
Comonomer incorporation rates are highly dependent on the nature
of the specific catalyst used to produce the copolymers. Improve-
ments in comonomer incorporation lead to higher comonomer effi-
ciency, and less dilution of the more reactive ethylene monomer.
Generally heterogeneous catalysts, based on titanium or chromium,
produce copolymers of broad compositional heterogeneity.
Morphology
Heterogeneous olefin polymerization catalysts can replicate
their morphology into the morphology of the polymer particles. The
catalyst particles act as a template for growth of the polymer par-
ticles. For high activity catalysts in olefin polymerization, the
average particle size of the polymer is about 15-20 times larger
than the size of the catalyst particle. Polymer particle growth can
be influenced by the specific catalyst activity, the nature of the
support matrix, the kinetic profile of the polymerization, and the
nascent polymer viscosity.
336 F.J. Karol and F.I. Jacobson

Isotactic Index
Addition of electron donors to high activity catalysts for poly-
propylene production raises the isotactic index of the polymer.
With many high activity catalysts, electron donors added to both the
titanium precursor and the aluminum alkyl cocatalyst provide a route
to polypropylene of very high isotactic content. In addition to
raising the isotactic index of polypropylene, the addition of elec-
tron donors to high activity catalysts provides a means of stabiliz-
ing catalyst crystallites and a route to accelerating the rate of
reaction of the magnesium/titanium compounds.

OUTLOOK FOR THE FUTURE

The UNIPOL gas-phase process has evolved, first to IIDPE, then to
low- and medium-density ethylene-propylene and ethylene-butene co-
polymers, and more recently, to LLDPE containing higher n-olefins.
The capability of the UNIPOL process is being extended outside of
the density and melt index limits normally associated with polyethy-
3
lene. In particular, products with densities lower than 900 kg/m
offer significant new product opportunities where toughness and
flexibility are special requirements. In addition, the process is
now capable of producing a new line of easy-flow LLDPE resins that
combine the excellent strength and drawdown characteristics of gen-
eral-purpose LLDPE with the easy processability of a broad molecu-
lar-weight-distribution product.
Polypropylene by the UNIPOL process represents an extension of
recent polypropylene technology trends to their most advanced level
yet. Polypropylene technology using the UNIPOL process is capable
of producing a full range of competitive homopolymer and copolymer
products to serve all significant market segments. This technology
offers considerable potential for new and improved products to meet
future market demands.
Olefin polymerization catalysis continues to be a fertile area
of research, with worldwide participation in both industrial and
academic laboratories. The intensity of research, documented in
patents and publications, has shed light on important features in
catalysis. The polyethylene revolution has instilled great vitality
to studies in olefin polymerization catalysis. This renewed vitali-
ty should provide an important stimulus for catalyst research in the
1980s and beyond. The combination of polymerization catalysis
 Catalysis and the Unipol Process 337

and the UNIPOL process will provide worldwide focus for future new
developments in the polyolefin arena.

REFERENCES
1. Abstracts of Papers Presented at Golden Jubilee Conference for
Polyethylene, 1933-1983, London, June 8-10, 1983.
2. Digest of Polymer Developments, Springborn Laboratories, Inc.,
N. Platzer, Ed., Confidential Publ., October 1984, by permission
o f Editor.
3 . Chem. Eng., 1979, @ (Dec. 3 1 , 80-85 (1979 Kirkpatrick Chemical
Engineering Achievement Award [Union Carbide Corp.].
4. Plastics Industry Europe, V o l . 8, No. 1 8 , End-September 1984.
5 . D. E. James, Paper Presented at 11th CDC International Business
Conference, Brussels, Belgium, April 17-18, 1985.
6. S. P. Sawin and C. J. Baas, Chem. Eng., 1985 (May 2 7 ) 42-43.
7. G. S . Cieloszyk and B. J. Garner, Paper Presented at Achema
1985, June 1 4 , 1985 in Frankfurt, W . Germany.
8. F. J. Karol, Chemtech, pp. 222-228 (April 1 9 8 3 ) .
9. F . J . Karol, Paper Presented at 189th National Meeting of Ameri-
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