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History of Polyolefins
a a
H. R. Sailors & J. P. Hogan
a
Research and Development Phillips Petroleum
Company, Bartlesville, Oklahoma, 74004
Published online: 05 Dec 2006.

To cite this article: H. R. Sailors & J. P. Hogan (1981) History of Polyolefins,

Journal of Macromolecular Science: Part A - Chemistry: Pure and Applied
Chemistry, 15:7, 1377-1402

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 J. MACROMOL. SC1.-CHEM., A15(7), pp. 1377- 1402 ( 1981)

History of Polyolefins
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H. R. SAILORS and J. P. HOGAN

Research and Development

Phillips Petroleum Company
Bartlesville, Oklahoma 74004

ABSTRACT

The history of polyolefins actually began in the 1890s with the

synthesis of polymethylene from diazomethane. In the 1930s
researchers in England discovered that ethylene at high pressure
and in the presence of oxygen polymerized to a high molecular
weight resin. Further research there and in the United States
at still higher pressures yielded essentially straight chain,
higher density polyethylenes. Early in the 1950s, groups in the
United States and Europe independently discovered that linear,
high-density polyethylenes could be made at low pressure over
heterogeneous catalysts. Concurrently, groups catalytically pro-
duced polyolefin plastics from propylene and higher a-olefins.
The inventorship of crystalline polypropylene was awarded to
Phillips Petroleum Co. by United States courts in early 1980
(subject to final appeal). Commercial production of low-density
polyethylene began in England (ICI) in 1939. High-pressure plants
appeared in the United States (DuPont and Union Carbide) and in
Germany during World W a r 11. Production of linear polyethylene
started in late 1956 in the United States (Phillips). A semiworks
Koppers plant began polyethylene production for commercial use
earlier in 1956. Other plants quickly followed suit, using Phillips
and Ziegler processes. Polypropylene production began in Europe
and in the United States in 1957-1958. Two other polyolefin
plastics have been produced in small commercial quantities,
starting about 1965: poly(4-methyl-1-pentene) and poly-1-butene.

1377
Copyright 0 1981 by Marcel Dekker, Inc.
 1378 SAILORS AND HOGAN
INTRODUCTION

The history of polyolefins is of particular interest because it en-

compasses the largest volume synthetic resin (polyethylene) manu-
factured today. As a basis for delineating the scope of resins to be
considered in this history of polyolefins, composition and structure
have been chosen as the controlling features. The term "polyolefin"
implies the polymerization of olefins to high polymers, but to base
the subject matter on this alone would leave out a historically im-
portant resin-polymethylene. This basis is not new and has previ-
ously been employed, e.g., by Raff [ 11 and by Bawn and Ledwith [ 21.
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Empirically, polyethylene has been represented as (-CH2-)x and

(-CzH4-)x, end groups being neglected in each case. One can postu-
late that the first formula fits polyethylene only if x is an even integer,
but from the practical standpoint, a perfectly linear ethylene polymer
could not be distinguished from a perfectly linear methylene polymer
simply on this basis. Consequently, the t e r m s "polyethylene" and
"polymethylene" are used here as a matter of convenience to differ-
entiate between methods of synthesis without implying that they are
two separate products.

POLYMETHYLENE

In the period of 1897 through 1938, production of polymethylene by

diazomethane decomposition appeared in the literature numerous
times. Such publications were by Hinderman [ 31, von Pechman [ 41,
and Bamberger and Tschirner [ 51 in 1897-1900; by Hertzig and
Schonbach [ 61 in 1912; by Meerwein and Burneleit [ 71 in 1928, and
by Werle [ 81, a student of Meerwein's, in 1938. Catalysts such as
unglazed china, amophous boron, and boric acid esters were used.
From work on the products, the melting points were found to be 126.5
and 128°C and the empirical formula to be CHZ by carbon-hydrogen
analysis. The product was called polymethylene and the formula ex-
pressed as (-CH2-)x. Analysis showed the polymer to be free of
nitrogen. Solubility in common organic solvents was reported as
very slight.
The data reported in these publications were not as complete as
more recently desired on high polymers, and Phillips Petroleum Co.
repeated the work of Werle [ 81 and Bamberger and Tschirner [ 51.
Results [ 91 of analysis and testing were: carbon, 85.5-85.8 wt%;
hydrogen, 14.3-14.7 wt% (calculation for CH2 is 85.6 wt% C and 14.4
wt% H); crystallinity (x-ray), 90-92%; side chains, 5 0.4 per 200
carbons; 134-137°C melting point; 3720-4140 psi tensile strength;
1.13-1.22 relative viscosity (0.125 wt% polymer in xylene at 85°C);
0.964-0.970 g/cc annealed density. Very similar data were obtained
by Hoberg and Ziegler [ 101.
 POLYOLEFINS 1379
In 1938 and 1940 Pichler [ 111 and Pichler and Buffleb [ 121 pub-
lished work on separation (by sequential extraction with boiling sol-
vents) of hydrocarbons produced by hydrogenation of carbon monoxide
over ruthenium and cobalt catalysts. The ruthenium catalyzed (1000
a h ) product was extracted with a series of five hydrocarbon solvents
(pentane through octane). A saturated fraction of 1 2 to 15% of the
original product was isolated which had a melting point of 132-134" C,
a density of 0.980 g/cc, and a number-average molecular weight of
23,000 (weight-avera e molecular weight would be significantly higher).
Raff and Lyle [ 13f stated that the high-density polymer was dis-
covered before low-density polyethylene, and they refer to Hoberg
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and Ziegler's publication [ 101 in which those authors recognized that

the Ziegler product and the polymethylenes of Meerwein and Burneleit
[ 71 and Werle [ 81 were the same.

DISCOVERY O F POLYETHYLENE-
HIGH- P R E S S U R E P R O C E S S E S

As related by Swallow [ 141, Imperial Chemical Industries (ICI)

started a high-pressure research program in 1932. In 1933, a mix-
ture of ethylene and benzaldehyde at 170°C and 1400 atm produced
a reaction which coated the walls of the reactor with a thin layer of
a white waxy solid, recognized at the time as being a polymer of
ethylene. On repeating the experiment with ethylene alone, a violent
reaction occurred which caused rupturing of the apparatus and pro-
duced hydrogen, methane, and amorphous carbon. With more suitable
apparatus available in 1935, ethylene was polymerized a t high pres-
sure and a t 180"C, with 8 g of polyethylene being recovered. After
much work it was found that following a leak, the ethylene used in
repressuring happened to have the right amount of oxygen to cause the
polymerization to take place.
The polyethylene produced at this time had a melting point of about
115"C, density of 0.91-0.92, could be drawn into filaments, and ex-
hibited "cold drawing." Based on earlier observations by Carothers,
these properties were believed to indicate polyethylene to be a reason-
ably straight-chain, high molecular weight polymer. A s indicated by
Swallow [ 141, qolyethylene had been considered up to 1940 as a purely
linear long-cham hydrocarbon, with the partially crystalline nature
noted by Bunn [ 151 fitting well with the fringed micelle theory to
explain the morphology of the olymers.
P
In an ICI British patent [ 16 based on three provisional applica-
tions filed in 1936, there were disclosed pressures of 500 to 3000 atm,
temperatures of 100 to 300"C, the necessity of removing heat to con-
trol temperature, and the necessity of controlling the oxygen content
of the ethylene used. Molecular weights (Staudinger) of 2,000 to 24,000
were said to have been obtained. In these applications the product
was described as both (-CH2-)x and (-C2Hp)x.
 1380 SAILORS AND HOGAN
POLYETHYLENE STRUCTURE STUDIES

In 1940 Fox and Martin [ 171 found by infrared that there were more
methyl groups in high-pressure polyethylene than could be accounted
for by the end groups. From then on, the presence of chain branching
in the molecule was recognized, and the resulting studies of branch-
ing led to better understanding of mechanical properties, morphology,
and the effect of synthesis conditions, The understanding of poly-
ethylene gained in the 1940s was the result of many workers' efforts.
In 1950 and 1952 Buckley, Cross, and Ray [ 181 and Buckley and Ray
[ 191 prepared polymethylene from diazomethane and additionally in-
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troduced methyl and higher branches by including controlled amounts

of diazoethane or higher alkyl- substituted diazomethane com22unds.
For polymethylene they found a melting point of 132°C and d4 of
0.965, higher than the then-known low-density polyethylene. They
further found that with the introduction of methyl branching, poly-
ethylene-like polymers of lower density were produced. Rubbery
polymers were produced when, e.g., 15 or more methyl branches
were introduced for each 100 carbon atoms. This, along with other
investigations too voluminous to review, provided a much improved
understanding of the role of branching in polyethylene and its effect
on crystallinity and other properties.

DEVELOPMENT O F HIGH-DENSITY
ETHYLENE POLYMERS

In this same general period the operating range of pressure for

ethylene polymerization w a s extended above the 3000 atm of the origi-
nal British patent, Krase [ 201 showing an upper pressure of 4000 atm
and Larcher and Pease [ 211 disclosing 5,000 to 20,000 atm, each
patent showing free radical initiators. Larcher and Pease disclosed
that their pressure range produced polyethylene with densities of
0.95-0.97 g/cc, tensile strengths between 2,900 and 11,800 psi,
relative viscosities of 1.0 to 1.5 (0.125% in xylene at 85"C), branching
to the extent of less than one side chain per 200 carbon atoms, and
melting points above 127°C. The Larcher and Pease patent has
claims to polyethylene including the above properties.
Low-pressure processes for high-density polyethylene were dis-
covered in the early 1950s. Patent ap lications were filed by Zletz
[ 221 in 1951, by Hogan and Banks [ 23fin early 1953, and by Ziegler,
Breil, Martin, and Holzkamp [ 241in late 1953. The term "low-
pressure'' is to be taken relative to the pressures of the high-pressure,
free radical processes. Operating pressures of 100-200 psig up to
about 1500 psig are usually employed, although more or less pressure
can be used. All of these processes a r e catalytic.
The Zletz (Standard Oil of Indiana) patent [ 221 describes a sup-
ported reduced molybdenum oxide or cobalt molybdate catalyst on
 POLYOLEFINS 1381

alumina, with the ethylene preferably contacting the catalyst in an

aromatic solvent to effect the polymerization. The patent examples
show operating temperatures from 100 to 270°C. Depending on con-
ditions, products vary from greases to high molecular weight, tough
resins.
Hogan and Banks (Phillips Petroleum Co.) patents [ 231 describe
the starting catalyst as being hexavalent chromium oxide on silica,
alumina, or silica-alumina, activation usually being with air or other
oxygen-containing gas at elevated temperature. The process was
primarily conducted as a liquid-phase operation employing paraffins
o r cycloparaffins as preferred reaction media. Preferred reaction
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temperatures a r e in the range of about 60 to about 190°C. Polymer

characteristics, particularly molecular weight, can be varied by
changes in the activation and operating conditions.
The process of Ziegler and co-workers described in the German
patent [ 241 employs an organometal catalyst using an aluminum tri-
alkyl with a transition metal compound of Groups IVa through VIa (Ti
preferred), temperature of at least 50"C, and pressure of at least
10 atm. The later U.S. patent [ 241 indicates aromatic, paraffin, and
cycloparaffin reaction media to be suitable.
Each of the catalytic processes summarized above in terms of the
initial patents has been the subject of much further research and
development. It is beyond the scope of this discussion to get into the
literally thousands of patents and publications describing this subse-
quent widespread work. Table 1 provides information on the early
work for these three processes.
As of today, polyethylenes of densities from about 0.90 to about
0.98 g/cc have been produced. The differences a r e mainly those
caused by variation of branching, though molecular weight enters
importantly into the picture. Polyethylenes branched from five or six
methyl groups per 100 carbon atoms to essentially unbranched poly-
mers have been produced as commercial products. With decreased
branching, the polymer increases in melting point, density, stiffness,
tensile strength, crystallinity, and modulus of elasticity, thus providing
a wide choice of properties to the users.

CRYSTALLINE POLYPROPYLENE-
A NEW C O M P O S I T I O N

In the case of crystalline polypropylene, the polymer itself has

been a commercial product for many years, but the question of who
first invented the product has been the subject of intense argument in
the U.S. Patent and Trademark Office and the Federal District Court
(Delaware) for more than 20 years. Although scientific publications
and available patents provide a considerable amount of information
on the discovery of polypropylene, the Patent Office and court records
provide a bonanza of additional scientific and historic information
unavailable elsewhere.
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TABLE 1. Early Dates of F i r s t Low-Pressure Polyethylenes

Approximate date Filing date of Polymer

of f i r s t laboratory first density
Process development patent application k/CC 1
Standard (Jndiana) Last half 1950 [ 261 April 28, 1951 0.96 [ 26)
Phillips Last half 1951 January 27, 1953 0.95-0.97
Ziegler November, 1953 [ 271 November 17, 1953 0.94 [ 14, 281"

aLater developments provided densities to 0.965.

 POLYOLEFINS 1383

The Patent Office declared an interference [ 291 in 1958 involving

five patent applications. (An interference is a proceeding in which
evidence is presented to the Patent Office from which a decision is
reached as to whom it believes first invented the subject matter and
is entitled to a patent thereon.) The subject matter, or "count," of
the interference was as follows:

Normally solid polypropylene, consisting essentially of recurring

propylene units, having a substantial crystalline polypropylene
content.
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The interference was declared with the following five parties:

E. H. Vandenberg (Hercules, Inc.); J. P. Hogan and R. L. Banks
(Phillips Petroleum); A. Zletz (Standard Oil Co., Indiana); W. N.
Baxter, N. G. Merkling, I. M. Robinson, and G. S. Stamatoff (DuPont);
and G. Natta, P. Pino, and G. Mazzanti (Montecatini, now Montedison
S.P.A.). Vandenberg was dropped from the activities because he
could not show sufficiently early dates for his work.
The catalysts used by DuPont and Montecatini were organometallic.
The catalysts used by Standard and by Phillips were supported metal
oxides as described for polyethylene.
As background for what follows, it should be understood that
two bases for a completed invention exist in patent law; these
a r e termed an actual reduction to practice and a constructive
reduction to practice. In an actual reduction to practice of a
polymer (here polypropylene), the inventor must make the product
of the count, recognize the polymer, and recognize a specific
practical use for the polymer, each of these being provable. A
constructive reduction to practice consists of filing a patent
application telling how to make the polymer, adequately describ-
ing that polymer, and giving a practical use for it. Such a
patent application must meet all other requirements of the Patent
Office.
In the Patent Office the Montecatini applicants were judged to be
the first inventors [ 291, and U.S. Patent 3,715,344 was issued to them
on February 6, 1973.
The Patent Office decision was appealed to the Federal District
Court (Delaware) by each of the three losing parties in 1972, these
appeals being consolidated into a civil action in 1975 [ 261. After a
trial lasting 7 months, beginning September 19, 1977, and generating
about 15,000 pages of testimony and hundreds upon hundreds of ex-
hibits, the Court reversed the Patent Office decision and concluded
(January 11, 1980) that the Phillips applicants, Hogan and Banks, were
the first inventors of crystalline polypropylene. The Court concluded
that Phillips had proven making the crystalline polypropylene four
times in the period of October 9, 1951, to April 16, 1952, and had met
the other requirement for actual reduction to practice. Additionally,
the Court concluded that the Phillips U.S. patent application filed
 1384 SAILORS AND HOGAN

January 27, 1953 [ 231 was a constructive reduction to practice, meet-

ing all the necessary legal requirements.
The Montecatini applicants made crystalline polypro ylene in
Italy in the period between March and June 1954 [ 30, 315, but they
were limited in the interference to the date of the first filed Italian
patent application [ 311, June 8, 1954. Any date in this range is about
2 years later than the dates of Hogan and Banks.
The DuPont claims to making crystalline polypropylene on May 17,
1954 [ 261, and to filing an adequate patent application [ 321 on
August 19, 1954, were upheld by the Court. However, the Court said
DuPont failed to satisfy the product recognition and showing of utility
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requirements of an actual reduction to practice. Thus, while DuPont

did make crystalline polypropylene by May 17, 1954, for patent pur-
poses they were limited to the date of filing of the patent application,
again about 2 ye a r s later than the Hogan and Banks' dates.
Standard conducted work on propylene polymerization in the last
half of 1950 and in late April throu h about July 1953, two products
being made in the latter period [ 267. A patent application was filed
on October 15, 1954 [ 331. The Court agreed with the opposing wit-
nesses that the 1950 products were not the polypropylene of the count
but were copolymers. Concerning the products of the 1953 period,
the Court agreed with Standard that those two products were the
crystalline product of the count and that one was recognized as being
that product. The Court said the actual laboratory work failed to show
that these later polymers had a practical use, and Standard was
awarded the date of the filing of the patent application, October 15,
1954, as the best date for the interference.
The decision handed down by the Court, which is 200 typewritten
pages, contains a large amount of information on each party's work,
but in more condensed form than in the massive transcript of the
court proceedings. The Court's decision can be appealed to a higher
court by any or all of the lo sers (in appeal, December 1980). In sum-
mary of the Court's findings, the Phillips inventors were first actually
to make crystalline polypropylene, the Standard inventors were second,
and the DuPont and Montecatini inventors almost a tie for third and
fourth places. But as decided by the Court on legal grounds, the order
was Phillips first, Montecatini second, DuPont third, and Standard
fourth. These initial separate successes were apparently completely
independent, each without any knowledge of the others' work, and all
taking place in a period of 3 years.

HIGHER 1 - O L E F I N POLYMERS

By mid-1952, Hogan, Banks, and co-workers had produced poly-

m e r s of 1-butene, 1-pentene, 1-hexene, and 4-methyl-1-pentene.
They had fractionated the products and by infrared analysis shown the
structure of each of these polymers as well as polypropylene to be
 POLYOLEFINS 1385
head-to-tail [ 34a]. In particular, the poly-4-methyl-1-pentene was
described as a tough, solid polymer with a melting point in the range
of 210°C (410-420" F) [ 34bl. These polymers were produced with
supported chromium oxide catalysts [ 231.
In the period between March 1954 and late July 1954, Natta and
co-workers produced polymers of 1-butene and 1-hexene in addition
to polypropylene [ 30, 311. In one of the patent applications it was
stated that polymers from a-olefins higher than 1-butene were more
interesting as elastomers. In a (June 8, 1955) U.S. patent application
[ 351, poly-1-pentene had been added, with first-order transitions
given for all but poly-1-hexene, which was indicated to be amorphous
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at 20°C. In late 1955 and 1956, Natta and co-workers announced

[ 36-38] their syntheses and descriptions of polymers of branched
chain a-olefins including 3-methyl- 1-butene, 4-methyl- 1-pentene,
-
5-methyl- 1 hexene, and 5-m ethyl- 1-hexene.
From a patent to Haven filed June 23, 1955 [ 391, it is evident that
DuPont also soon followed its polypropylene work with polymeriza-
tion of higher 1-olefins. Examples in this patent include high poly-
mers made from 3-methyl-l-butene, 4-methyl-l-pentene, 4,4-
dimethyl- 1-pentene, 4-methyl- 1-hexene, 4,4-dimethyl- 1-hexene,
3-cyclopentyl-l-propene, and 3-cyclohexyl- 1-propene. A polymer
of 4-methyl-1-hexene is shown with a crystalline melting point of
160°C, all others being from 225 to over 350°C, the temperature limit
of the melting point apparatus used.

STRUCTURE-CRYSTALLINITY RELATIONSHIPS

The structural studies spawned by the discovery of crystalline

polymers of propylene and higher a-olefins discussed above led to
the findings that the crystallinity was related to the steric regularity
of the alkyl branches on the alternate carbons along the main chain
of the head-to-tail polymers. For an accurate historical perspec-
tive of the discovery and structural studies of these crystalline poly-
mers, it is necessary that the earlier contributions of other scientists
be considered.
In 1943, Alfrey, Bartovics, and Mark [ 401 proposed that different
amounts of branching along the polymer chains of several polystyrenes
were responsible for the differences in properties. But in 1944,
Huggins [ 411 proposed an explanation of these differences based on
steric regularity of the phenyl side groups along the chain, saying,
In a polymer produced at low temperature one would expect a
tendency toward some regular sequence of disposition of H and Ft,
such as one in which all the R groups would be on the same side
of the plane of the zig-zag carbon chain i f the molecule were
stretched out, or one in which the R groups alternated from one
side to the other. In a polymer produced at a high temperature, a
more random sequence would be expected. (Emphasis in original.)
 1386 SAILORS AND HOGAN

Huggins extended the explanation to other high polymers of the gen-

eral formula (-CH2CHR-)x, noting that randomness of H and R dis-
positions was probably responsible for the poor crystallinity of
stretched polymers of this general formula.
Though not working with a-olefins, Schildknecht and co-workers
[ 421 were probably first (1949) to make rubbery and nonrubbery
vinyl high polymers (vinyl butyl ether polymers), to show a differ-
ence between the two through the use of x-ray, and to correctly
attribute this difference to the placement of the side groups. They
also recognized that the main chain might not be zig-zag but deter-
mined by the d and 1 placements of the side groups, such placements
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possibly being all on one side, alternating, or completely random.

Crystallinity of the nonrubbery polymers was attributed to regularity
of the side chains. Natta, Bassi, and Corradini [ 431 a few years later
confirmed this, making poly(viny1 isobutyl ether) by the same method
and finding complete structural analogy between this polymer and
isotac tic poly(5- m ethyl- 1 -hexene).
After Natta and co-workers had made polypropylene in 1954,
followed closely by other poly- 1-olefins, they studied intensively the
structure and morphology of these polymers and published prolifically
on their findings in the period 1954-1960 [ 441. They found the poly-
mers to be head-to-tail in chemical structure and, with the exception
of poly(1-hexene), to have partially crystalline fractions separable
by solvent extraction, melting points for fractions being determined.
Principally by x-ray study of the crystalline fractions, it was estab-
lished that the crystallinity of the polymers resulted from a steric
structure of long sequences, with all of the alkyl groups lying on one
side where the main chain was rolled out in a plane as described by
Huggins [ 411. They further established that in the polymer crystals
the chains had a spiral conformation with alternating right- and left-
hand spirals in adjacent chains. They also found that in a relatively
small number of polymers they could identify sequences in which the
alkyl groups lay alternately on opposite sides of the plane. Natta
termed those sequences with alkyl groups on one side of the plane
to be isotactic, those alternating to opposite sides of the plane to be
syndiotactic, and those with random positions to be atactic. This
terminology is well accepted at this time.
As is true of any major field, continuing work by a large number
of scientists has greatly amplified the information initially available
on poly- 1-olefin structure and morphology, including additional crys-
tal forms and further details of chain conformations throughout the
partially crystalline polymer mass.
While the history of polyolefins so far has been discussed with
respect to homopolymers, olefin copolymers were also made by the
catalytic processes and by mixed diazo compounds. Using small
amounts of comonomer along with the principal monomer, polymers
of modified physical properties were made. Tailoring of products
was possible to fit specific uses a bit better than homopolymers.
 POLYOLEFINS 1387

(Major property changes were also found possible, such as making

ethylene-propylene copolymers with properties similar to rubber. )

COMMERCIAL PRODUCTION O F P O L Y O L E F I N S

P o l y e t h y l e n e - H i gh - P r e s s u r e Pr o c e s s e s

The first plastic polymer from olefins to be discovered and the

first to be produced commercially was polyethylene. ICI started up
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a small plant in England in September of 1939. The plant had appar-

ently been sized to meet the estimated requirements for coating
telephone and telegraph cable to be laid on the ocean floor. The poly-
mer appeared to have properties which were ideal for this applica-
tion: high dielectric constant, low dielectric loss at high frequencies,
high moisture resistance, and excellent flexibility and toughness
[ 141.
The ethylene monomer used for this new venture at first had to
be made by the catalytic dehydration of ethyl alcohol [ 141. This was
a sobering situation. However, in a few years, all ethylene monomer
was being made by the thermal cracking of petroleum fractions
ranging from ethane to gas oil.
The start of World War I1 quickly changed both the use and the
demand for polyethylene. Polyethylene arrived on the scene just
in time to make airborne radar feasible for the British early in the
war, giving Britain enough of an edge in antisubmarine and naval
warfare to survive until the United States entered the war. Because
of this new demand for polyethylene, ICI quickly built larger units
for its production. In 1941, both information on the manufacture of
polyethylene and its use in radar was transmitted to the United ’
States, and DuPont built a plant to produce polyethylene under an ICI
license [ 141.
Union Carbide independently developed a polyethylene process
which was commercialized in 1943. The Union Carbide process used
tubular reactors, while the early ICI design utilized stirred autoclave
reactors. During the war, Germany developed polyethylene tech-
nology, based apparently on the ICI patents but using tubular reactors
[ 141.
As late as 1943, the significance of polyethylene as a viable plastic
was apparently not fully appreciated in technical circles. In the book
Synthetic Resins and Rubber by P. 0. Powers, published by Wiley in
1943, a table listed 42 of the significant synthetic polymer develop-
ments from 1831 through 1942. Polyethylene was not included, al-
though a short paragraph in the book described the production and
properties of high-pressure polyethylene. However, postwar develop-
ments quickly changed the stature of the first polyolefin plastic.
Following World War 11, only DuPont and Union Carbide had poly-
ethylene plants in the United States. That situation changed abruptly
 1388 SAILORS AND HOGAN

when an antitrust suit resulted in a court decision in 1952 that ICI

must license to all comers in the United States. Companies obtaining
licenses within the next year were Dow Chemical, Eastman Kodak,
and National Petrochemical. Spencer Chemical, Monsanto, and
Koppers, with licenses from BASF in West Germany, also built high-
pressure polyethylene plants which started up in 1954 and 1955.
Meanwhile, Union Carbide and DuPont greatly expanded production
facilities.
It was realized very early that the Union Carbide polyethylene
differed in physical properties from the early ICI product, and Union
Carbide polyethylene was preferred for certain critical applications
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during the war. It has since been learned that operating pressure
and other conditions affect short-chain branching and density, and
the type of reactor affects long-chain branching. Tubular reactors
with plug flow apparently tend to produce less long-chain branching
and so-called super molecules than autoclave reactors with back-
mixing, Regardless of reactor type, operating pressure was gener-
ally 15,000-40,000 psig, and temperature was 150-250°C. A very
small amount of oxygen or a peroxide was used as a free radical
initiator to initiate and promote chain growth. Various chain trans-
fer agents were used to modify molecular weight. Figure 1 depicts
high-pressure polyethylene manufacture.
The density of early commercial polyethylenes was in the range
of 0.910-0.925, and the crystalline melting point was about 115°C.
The polymer was at first called polythene in England and simply
polyethylene in the United States. However, the discovery and com-
mercial development of low-pressure, catalytic processes in the

MOL. WT. 0 2 OR
REGULATOR PEROXIDE RECYCLE PURIFICATION

YI
I

m
L.P. H.P.
COMPRESSORS
i
OR: J A I I
A U l'OCLAVE REACTOR 2
/
/
.;
-
+

MELT MIXING,
U PELLETIZING

FIG. 1. High-pressure ethylene polymerization to LDPE.

 POLYOLEFINS 1389
1950s called for new nomenclature, since the new polyethylenes were
quite different, having densities up to 0.97 and a crystalline melting
point up to 135°C. Thus the "old" polyethylene began to be called
high-pressure polyethylene (HPPE) or low-density polyethylene
(LDPE), while the new type was called low-pressure polyethylene
(LPPE) or high-density polyethylene (HDPE). Because of the essen-
tial absence of long-chain branching, it also began to be called linear
polyethylene.

Polyethylene-Low Pressure Processes

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Phillips Petroleum Company Process

Of the first low-pressure processes for polymerizing ethylene
discovered in the early 1950s, the authors are, of course, able to
give the most details on the Phillips commercial development. The
Phillips polyethylene process, which in 1979 accounted for 1 billion
pounds of polyethylene produced by Phillips Petroleum Co. alone at
Pasadena, Texas, grew out of the discovery made in the Phillips
laboratories in 1951 [ 23, 451. By 1954, pilot plant studies had pro-
gressed f a r enough to permit commercial process design of a con-
tinuous process. By 1955, a 1000-lb per day semiworks plant was
on stream. Being a scale-down of the commercial design, it was
invaluable in the successful start-ups of the first commercial plants.
In April of 1955, Phillips management approved building a com-
mercial complex, including an initial 75 million pounds per year HDPE
plant and a 180 million pounds per year high-purity ethylene plant,
However, it was concluded that no one manufacturer could develop the
full market potential of the Phillips HDPE, and Phillips decided to
license the process. In 1955 and 1956, nine companies in seven
countries became licensees [ 461. Each company was supplied with
complete technical information and ground-up plant designs, and was
furnished HDPE for evaluation and market development from the
semiworks plant in Oklahoma.
Public disclosure (other than foreign patents) of details of the new
Phillips process, information on structure of the polymer, and a sur-
vey of properties and expected applications came at the National ACS
Meeting in April, 1956 [ 47-49].
The Phillips plant first produced polyethylene on December 31,
1956. Licensee plants were not f a r behind. The first commercial
grades of HDPE produced by the Phillips process were homopolymers
of less than 1 melt index. Ethylene-1-butene copolymers were intro-
duced in 1958 [ 501, and soon other polymer parameters were utilized
to extend the choice of polymer types. Production was entirely by
the solution version of the process for the first 4 years [ 511. The
commercial plant process is depicted in Fig. 2. A liquid hydrocarbon
stream containing cyclohexane is fed continuously with powdered
catalyst, ethylene, and 1-butene comonomer as needed, to large
 1390 SAILORS AND HOGAN

ETHYLENE AND
COMONOYER
RECYCLE

SOLVENT
RECYCLE
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CATALYST
DISCARD BLENDING

FINISHED
RESIN
4
BAGGING

FIG. 2. Phillips original solution process (HDPE homopolymer

and copolymer).

stirred reactors where polymerization takes place at temperatures

of 125-175°C and pressures of 400-500 psig. Polymer solution is
continuously withdrawn, flashed to remove ethylene, filtered or
centrifuged to remove catalyst, steam stripped to remove solvent,
dried, and pelletized. (A more recent system has no catalyst re-
moval, and removes the solvent by flashing in devolatizing extruders.)
Laboratory discoveries at Phillips in the early 1950s led to a
slurry version of the process called the particle-form process [ 52, 531.
This system was commercialized in early 1961 and was quickly adopted
also by licensees. It soon overtook the solution process in production
capacity worldwide. The commercial particle-form process is de-
picted in Fig. 3. A low-boiling liquid isopardfin is passed together
with powdered catalyst, ethylene, and a- olefin comonomer to a loop
reactor, which operates at an internal temperature of 70-100" C or
higher and enough pressure to maintain liquid phase. A slurry of
polymer and liquid hydrocarbon is discharged from a settling zone
in the reactor to a flash tank, where hydrocarbon diluent and ethylene
a r e recovered for recycle, The polymer crumb is freed of hydro-
carbon and pelletized. Since catalyst yield is high, no catalyst re-
moval step is used.
New copolymers containing 1-hexene comonomer and having new
long-term porperties were introduced in 1968. Although since 1958
we had been introducing short-chain branching with a-olefins and
 POLYOLEFINS 1391

CATALYST FEEDING 'HAPOR RECYCLE

n
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v v v v v
RESIN
PELLETS

EXTRUDING

FIG. 3. Phillips particle-form process (HDPE and LDPE).

producing copolymers in the medium- and high-density ranges, we

were not yet producing low-density polyethylene. But in 1969,
Phillips announced to the press a new low-density process for pro-
ducing polyethylene [ 54, 551. Beginning in 1969, Phillips produced
polymers with densities as low as 0.925 in a modified particle-form
process .
Ziegler Process
Following discoveries by Karl Ziegler and co-workers in Germany
in 1953 that polyethylene could be produced with titanium halides plus
aluminum alkyls, Ziegler quickly began to license his patent. Start-
ing in 1954, licenses were sold to Hoechst, Huels, and Ruhrchemie in
Germany, Montecatini in Italy, Petrocarbon (later Shell) in Great
Britain, Mitsui in Japan, and Dow, DuPont, ESSO, Goodrich-Gulf,
Hercules, Koppers, Monsanto, and Union Carbide in the United States.
The license included use of Ziegler's patent and a 100-page manual
describing a laboratory process. Each licensee had to develop a
viable process from this meager information, which apparently did
not include information on how to adequately control the molecular
weight of the polyethylene.
The first commercial production of polyethylene in a Ziegler-type
plant apparently occurred in the Hoechst plant in late 1956. A semi-
works Koppers plant began polyethylene production for commercial
use earlier in 1956. In the United States, Hercules went on stream
first (1957), thus obtaining an early lead in Ziegler polyethylene, but
later dropped out of polyethylene production in favor of polypropylene.
 1392 SAILORS AND HOGAN
By 1960, production of polyethylene by Ziegler catalysts had
reached about 70 million pounds in the United States. (Production of
HDPE by Phillips and licensees in the United States in 1960 was nearly
200 million pounds.) Both slurry and solution processes, apparently
involving both batch and continuous operation, were developed for the
Ziegler catalysts. A problem with early continuous slurry processes
was the build-up of "ivory" in the stirred autoclaves (slow polymer
growth to large lumps in various poorly mixed zones in the reactors,
requiring shut-down and cleaning). Polymerization is done at tem-
peratures ranging from 50-120°C and pressures of 10-20 atm in the
presence of paraffin diluents and hydrogen to control molecular
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weight [ 56, 571. Catalyst deactivation in the reactor effluent, and

catalyst decomposition and/or solution by methanol or various other
polar compounds, is used to stop the reaction and purify the poly-
ethylene product. Of particular concern is the removal of halides.
Steam treatment of the polymer to remove catalyst components and
solvents is sometimes practiced.
New supported Ziegler-type catalysts came into use in the early
1970s, increasing the catalyst efficiency and simplifying or eliminat-
ing the removal of catalyst. Several companies led by Solvay et cie
[ 581, Montedison [ 591, and Mitsubishi [ 601, have announced the use
of such catalysts. In general these catalysts involve a titanium com-
pound supported on a magnesium salt or orride and used with metal
alkyl cocatalysts such as alkyl aluminum halides.

Standard Oil (Indiana) Process

Although the initial discovery of the synthesis of high polymers of
ethylene over molybdena-promoted catalysts at the Standard Oil
(Indiana) laboratories was a year earlier than the Phillips discovery,
commercialization was much slower. A decision was made in 1958
to build polyethylene plants [ 611, and a plant built by Furukawa in
Japan of about 22,000,000 pounds annual capacity, went on stream in
1961 1621. Later in the 1960s a plant utilizing the Standard process
went on stream on the island of Sardinia.
These plants utilized a solution process a t temperatures up to
300°C, requiring operating pressures up to 1000 psig. Molybdena-
alumina catalysts were used [ 62, 631. A plant built by Amoco in
Texas went on stream in 1971, and probably used a chlorided
molybdena-alumina catalyst [ 641. However, because of economics,
this plant was shut down in about 1973 and scrapped, apparently
ending that Standard Oil (Indiana) process in the United States.
(Amoco quickly built a new plant, having licensed Solvay-US1 tech-
nology. )
Other, More Recent Low Pressure Processes
Modified Ziegler processes were announced in the 1960s and early
1970s that utilized modified Ziegler catalysts. Snam Progetti, Solvay,
 POLYOLEFINS 1393

Montedison, Mitsubishi, and Mitsui Petrochemicals announced slurry

processes, and Stamicarbon announced a concentrated solution
process.
Gas phase was studied at Phillips in the 1950s [65, 661, but the
first gas-phase process was developed by Phillips licensee BASF in
West Germany [ 671, where a small plant using Phillips catalysts was
built in about 1964. Later in the 1960s Union Carbide, which had
access to the BASF developments, developed a gas-phase process
which was announced in the early 1970s. The Carbide gas-phase
process using chromium-promoted catalysts was widely licensed in
the 1970s, and a low-density gas-phase process was being licensed
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in the late 1970s [ 681.

Amoco recently started up a gas-phase process, based on Amoco
technology, in Texas. Dow Chemical has recently announced com-
mercialization of new low-density polyethylenes made in a low-
pressure process which may be a solution process.
To sum up the status of LDPE and HDPE production in the United
States up to 1980, Table 2 is presented. Shown a r e all current pro-
ducers, with approximate production capacities and an indication of
type of process being listed. Not shown a r e plants under construction.
It is worth noting that polyethylene is by f a r the largest volume of all
synthetic resins manufactured today. Polyethylene plants a r e now
found in about 45 countries of the world.

Polypropylene

The first commercial production of polypropylene began in December

1957 by Hercules. Hoechst in West Germany and Montecatini (later
Montedison) in Italy ap arently started up polypropylene plants very
soon thereafter [ 57, 69’. Thus polypropylene became a viable thermo-
plastic (and fiber) in 1958.
The earliest polypropylene plants used a slurry process in which
a liquid diluent such as h e m e or heptane was used, together With
propylene, catalyst, and a small amount of hydrogen, The traditional
catalyst has been a crystalline, violet colored form of TiCh plus di-
ethyl aluminum chloride as cocatalyst. The TiCL has usually been
made by the reduction of Tic14 with powdered aluminum, the final
product being ball milled to generate the proper crystalline form to
give high selectivity for the production of crystalline polypropylene.
Another method of roduction is by the reduction of Tic14 with an
aluminum alkyl [ 57’.
The slurry processes involve polymerization in a stirred autoclave
at temperatures below about 90°C and at a pressure sufficient to
maintain liquid phase With a l0-20% propylene corkcentration. The
polymer forms as particles and is removed as a 20-40% solids slurry,
which is flashed to remove propylene. The catalyst is deactivated
and dissolved by means of an alcohol plus HC1 or other polar organic
compounds. Aqueous (or steam) extraction may also be used for
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TABLE 2. United States Manufacturers of LDPE and HDPE, 1979

Billions of lb, Billions of lb

Manufacturer LDPE capacity Processa HDPE capacity Process a

Allied Chemical 0.6 Phillips, Solvay

Amoco - - 0.35b Solvay- US1
Arc0 0.4 IC I 0.35 Ziegler
Chemplex 0.3 USI, DuPont 0.3 Phillips
rn
Cities Service 0.35 us I 0.2 Ziegler z
W
Dart Industries 0.55 OWn -
Dow Chemical l.oc OWn 0.6 OWn
DuPont 0.7 ICI, own 0.45 OWn
Eastman 0.25 IC I -
Exxon 0.7 Dart (To build Union Carbide
Gas Phase) k
 Downloaded by [Monash University Library] at 01:43 10 July 2013

Gulf Oil 0.85 Own (Spencer) 0.45 Phillips, Union Carbide 8

- - 0.02d Ziegler !?
Hercules
-
Mobil 0.3 BASF -
;rco
M
NPCC (USI) 0.7 Own 0.5 Phillips, Solvay- US1
Northern Petrochemical 0.65 BASF - - ?i
m

Phillips Petroleum (See HDPE) 1.0e Own

Soltex - - 0.6 Phillips, Solvay
Union Carbide 1.5
- OWn 0.45
- Phillips, Own
Total 8.25 5.85
Actual production, 7.11 4.20
1978

'Process information based on early licensing arrangements plus later announcements.

bhcludes gas-phase process plant developed by Amoco.
CIncludes new low-pressure plant.
dThe only ultrahigh molecular weight (UHMW) plant in the United States-now shut down.
ehcludes capacity for up to 0.3 LDPE.
 1396 SAILORS AND HOGAN

C3Hg RECYCLE

A ORGANIC
SOLVENTS

H2
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LOOP CATALI
REACTOR
FLASH
C3H6-SOLUBLE POLYMER

FIG. 4. Phillips bulk-slurry polypropylene process.

catalyst removal. Amorphous polypropylene, amounting to only a

few percent, is removed as a solution in the liquid hydrocarbon which
may be separated from the polymer by centrifuging or filtering [ 571.
Solution polymerization has been used commercially, including
Texas- Eastman in the United States.
The first bulk polymerization system was commercialized by
Phillips Petroleum Co. As shown in Fig. 4, a loop reactor is used in
a slurry process in which liquid propylene is the only hydrocarbon
diluent [ 70, 711. In this process, catalyst is removed by solubiliza-
tion with polar organic compounds which a r e washed from the granu-
lar polymer by a countercurrent stream of liquid propylene. The
polymer is then separated from the propylene by flashing.
Dart Industries developed a bulk polymerization system in which
liquid propylene is permitted to boil to remove the heat of reaction
in a stirred vessel having vapor space in the top [ 571.
BASF put on stream a new gas-phase polypropylene plant in the
mid-1960s in which mechanical stirring was relied on to prevent
lumping in the reactor. High activity titanium catalysts reportedly
avoided the need for catalyst removal, other than de-chloridin
the products are higher than normal in amorphous content [ 577: but
Northern Petrochemical licensed this process and began operations
in the United States in the mid-1970s. Very recently, Amoco has
apparently put on stream a large new gas-phase plant in Texas,
based on technology developed by Amoco.
Before the 1970s, catalyst activity in commercial processes was
fairly low. Solvay developed a higher activity TiCls catalyst in which
Tic14 is converted to a highly specific TiCla through a four-step
 Downloaded by [Monash University Library] at 01:43 10 July 2013

'd
TABLE 3. United States Manufacturers of Polypropylene, 1979 0
I?
Ic
Plant capacities
Manufacturer (millions of lb/yr) Process, catalyst information
PB
Amoco 830 Slurry and Amoco gas-phase processes 1%1

Arc0 Polymers 400 Bulk (Phillips) process

(Mitsui P. - Montedison catalyst license )
Dart Industries 300 Bulk-boiling process
Exxon 550 Slurry
Gulf Oil 400 Slurry
Hercules 1,150 Slurry (Solvay catalyst license)
Northern Petrochemical 200 Gas-phase process (BASF)
Novamont 430 Slurry process (Mitsui-Montedison)
Phillips 200 Bulk slurry (Phillips)
Shell Chemical 600 Slurry
Soltex 200 Slurry (Solvay process)
Texas Eastman 140 Solution process
Total 3,700
Production in U.S. in 1978 3,074
 1398 SAILORS AND HOGAN

ANNUAL
PRODUCTION,
BILLIONS OF LBS.
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YEAR

FIG. 5. United States production of low- and high-density poly-

ethylene and polypropylene (U.S. Trade Commission).

process [ 721. This catalyst decreases the amount of catalyst residues

to be removed but does not eliminate the need for catalyst removal
entirely. More recently, Montedison [ 731 and perhaps others have
developed supported titanium catalysts which decrease and may soon
eliminate the need for catalyst removal. These catalysts generally
have some form of magnesium halide as an ingredient.
The brittleness temperature of crystalline polypropylene is about
15OC, with the result that the low-temperature impact resistance of
the thermoplastic is poor. Impact resistance grades of polypropylene
were developed in the 1950s a t Phillips [ 741 through the introduction
of ethylene polymer blocks. The addition of elastomers and poly-
ethylene by melt blending also improves the low-temperature prop-
erties. Random copolymers containing 2-3% ethylene a r e also made
to lower the modulus.
Table 3 summarizes the status up to 1980 of production of poly-
propylene in the United States, showing manufacturers, an estimate
of capacity, and information on the process.
Figure 5 shows the growth of the major polyolefins, LDPE, HDPE,
and polypropylene (PP) in the United States since start-up of the first
plants. What the 1980s will bring is anybody's guess, but predictions
of about 8% annual growth in the near future a r e common.

OTHER POLYOLEFIN PLASTICS

Poly- 1-butene
The commercialization of poly-1-butene plastic has been fraught
with uncertainty, to say the least. Petrotex Corp. began commercial
development of poly-1-butene in about 1963 with a 2000 lb/day semi-
works plant, which was operated until about 1966 before it was
 POLYOLEFINS 1399
abandoned as unpromising [ 751. Mobil Chemical Co. started up a 4
million pound per year poly-l-butene plant in Texas in 1967. How-
ever, Mobil later decided not to proceed and licensed the Mobil tech-
nology to Witco Chemical Corp. in 1972 [ 75, 761. Witco built a 50-
million lb/yr plant in Louisiana, which began start-up operations in
1975, with difficulties. The plant was sold to Shell in late 1977 [ 771,
and Shell has been working to bring the plant toward rated capacity.
Apparently, about 25 million pounds were produced in 1978.
The Shell plant uses a bulk polymerization process and a "Ziegler-
Natta" catalyst at 40-90°C and enough pressure to maintain liquid
phase. Hydrogen is added to the stirred reactor to control molecular
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weight. Catalyst removal is required, but there is no removal of

amorphous polymer.
Huels AG, West Germany, began operation of a poly-l-butene plant
in 1971. This plant had a rated capacity of 26 million lb/yr by 1973.
The Huels process uses a hydrocarbon solvent, and some amorphous
polymer is separated from the product [ 781.
Poly-l-butene is a unique polyolefin because of its slow (4-8 day)
transition from one crystalline form to another harder one. It is of
particular interest in pipe applications and in heat-resistant film.
Both the polymerization problems (it forms neither a true slurry nor
a trouble-free solution) and the slow crystalline change problem has
slowed its commercial growth up to 1980.

P o l y ( 4 - m e t h y l - 1- p e n t e n e )

The high melting point and extreme clarity of crystalline poly(4-

methyl-l-pentene) made it of interest for commercial development.
ICI started commercial development in 1965 and began production of
polymeth 1 pentene (PMP) in a 4.5 million lb/yr plant in England in
1968 [ 79f The ICI version of PMP is principally made of 4-methyl-l-
pentene but contains minor amounts of a-olefin. The comonomer en-
hances clarity and other physical properties. Ziegler- type catalysts
similar to those used for propylene polymerization are used. Polym-
erization is at temperatures and pressure near ambient and can be
done in the bulk or with added inert hydrocarbons.
Since 1975, P M P has been manufactured (on a fairly small scale)
solely by Mitsui Petrochemical Industries, Japan, by license from
ICI [ 801. Some of the applications a r e laboratory and medical ware
such as throw-away syringes and cook-in-bag food packaging.
Though compounds of the nature of polyolefins can be said to have
been known for more than 80 years and the subject of quite intensive
work for nearly 50 years, more information on products, processes,
and catalyst continues to be developed. Nimble minds will no doubt
continue to produce new and useful information on this broad subject
for many years to come.
 1400 SAILORS AND HOGAN

REFERENCES

[ 11 R. A. V. Raff, in Encyclopedia of Polymer Science and Tech-

nology, Vol. 6 (N. M. Bikales, ed.), Wiley-Interscience, New
York, 1967, p. 276.
[ 21 C. E. H. Bawn and A. Ledwith, in Encyclopedia of Polymer Sci-
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science, New York, 1969, p. 344.

t 31
41
[ 51
E. Hinderman, Dissertation, Zurich, 1897.
H. von Pechman, Er., 3 l , 2643 (1898).
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f[ 71
81
91
H. Meerwein and W. Burneleit, Ber. 618, 1840 (1928).
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101 H. Hoberg and K. Ziegler, Brennst.-Chem.,z, 302 (1958).
111 H. Pichler, Ibid 19 226 (1938).
121 H. Pichler a n d . & f f l e b , E, 2 ( 2 4 ) , 285 (1940).
131 R. A. V. Raff and E.
(R. A. V. Raff and K. W.
York, 1965, p. 8.
[ 141 J. C. Swallow, in Polythene, 2nd ed. (A. Renfrew and P. Morgan,
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C. W. Wmn, Trans. Faraday SOC.,3 482 (1939).
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A. W. Larcher and D. C. Pease (to DuPont), U.S. Patent 2,816,883
(Issued 1957; Filed 1951).
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(Issued 1954; Filed April 28, 1951).
J. P. Hogan and R. L. Banks (to Phillips Petroleum Co.),
Belgian Patent 530,617 [Filed January 24, 1955 (Filed in United
States January 27, 1953, Serial Number 333,576)] ; Australian
Patent Application 864/54 (Filed August 6, 1954).
K. Ziegler, H. Breil, H. Martin, and E. Holzkamp (to K. Ziegler),
German Patent 973,626 (Issued April 14, 1960; Filed November
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K. W. Doak and A. Schrage, in H i h Pol ers Vol. 20, Part 1
(R. A. V. Raff and K. W. Doak,-terscience, New
York, 1965, p. 351.
 POLYOLEFINS 1401
Consolidated Civil Action No. 4319, Federal District Court
(Delaware) (consolidation of civil actions filed in 1972).
Karl Ziegler testimony, Civil Action 3-2225, Federal District
Court (Northern District of Texas, Dallas), May 10, 1971.
C. W. Bunn, in Polythene, 2nd ed. (A. Renfrew and P. Morgan,
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Interference No. 89,634, initiated by the U.S. Patent and Trade-
mark Office, September 9, 1958.
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Patent Application 25,109 (Filed July 27, 1954).

W. N. Baxter, N. G. Merckling, L M. Robinson, and C. S. Stam-
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August 19, 1954).
A. Zletz [ t o Standard Oil (Indiana)], U.S. Patent Application S.N.
462,480 (Filed October 15, 1954).
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Application S.N. 514,099 (Filed June 8, 1955).
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Rend, Accad. Naz. Lincei, 1 3 397 (1955).
G. Natta, P. Corradini, and I. W. Bassi, Ibid., 19, 404 (1955).
G. Natta, An ew Chem 68 393 (1956).
A. C. H a v m $ o x ) , U.S. Patent 3,257,367 (Issued
June 21, 1966; Filed June 23, 1955).
T. Alfrey, A. Bartovics, and H. Mark, J. Am. Chem. SOC., 65,
2319 (1943).
M. L. Huggins, Ibid., 66, 1991 (1944).
C. E. Schildknecht, S. T. Gross, H. R. Davidson, J. M. Lambert,
and A. 0. Zoss, Ind. Eng. Chem., 40, 2104 (1949).
G. Natta, I. W. Bassi, and P. Corradini, Makromol. Chem.,
*-
18-19. 455 (1955).
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Stereospecific Polymerizations, Pergamon, New York, 1967,
two volumes.
J. P. Hogan, Chemist, 50(2), 46 (1973).
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Interscience, New York, 1964, p. 111.
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-.,
Chem 3 48 1152 (1956).
R. V. Jones and P. J. Ebeke, Ibid. 1155 (1956).
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*Plast , 237 132 (1959).
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P. Morgan, eds.), Interscience, New York, 1960, p. 29.
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(1965).
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