Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Nickel organophosphorus compounds have been used
alone and with cocatalysts for the controlled polymerization of
olefins as shown, for example, in United States Patent Nos.
3,432,518; 3,655,810 and 3,660,445.
The object of this invention is to provide new
catalyst combinations for controlled oligomerization both alone
and during high polymerization of olefins with other catalysts.
This invention employs novel compounds of the general
formula
Ni[OP(O) (R)2]2
in which each R is a non-aromatic hydrocarbon group free of
aliphatic unsaturation, i.e. an alkyl or cycloalkyl group, con-
taining one to eight, preferably two to four, carbon atoms or a
non-aromatic hydrocarbon ether group free of aliphatic unsatur-
ation, i.e. an alkoxyalkyl group, containing three to six
carbon atoms or a chlorinated or brominated derivative of any
of such groups. These compounds are disclosed in the parent
application, Canadian Patent Application 213,706, filed Decemb-
er 18, 1974.
This invention also comprises a combination catalyst
for controlled olefin oligomerization consisting essentially of
the reaction product of (A) a nickel bis-diorgano-ortho-
phosphate of the general formula Ni[OP tO) (OR)2]2 in which
each R is as defined above and (B) an alkyl aluminum halide of
the general formula R'cAl Xd in which each R' is an alkyl group
of one to six carbon atoms, each X is a halogen atom, preferably
chlorine or bromine, each of c and d is 1 or 2 and the total of
c and d is 3. The mol ratio of (A) to (B) can range from 1:1 to
1:20 but is preferably in the range of 1:8 to 1:12.
This invention comprises a combination catalyst for
olefin polymerization consisting essentially of components (A)
and (B) as described above in the ratio range described togeth-
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er with ~C) a vanadium bis-diorganoorthophosphate of the gener-
- al formula V(O)[OP (0) (OR)2~2 in which each R is as defined
above, mol ratio of (C) to (B) ranging from 1:4 to 1:10.
This invention further comprises the use of the
above-described catalyst combinations in a method for olefin
aligomerization or polymerization consisting essentially of (1)
mixing the appropriate catalyst combination described above
with (D) a mono- or di-olefin which can be any aliphatic,
cycloaliphatic or aromatic hydrocarbon containing no more than
about 8 carbon atoms, preferably an aliphatic hydrocarbon con-
taining no more than about 4 carbon atoms and/or a styrene,
either alone or with (E) a hydrocarbon solvent free of aliphat-
ic unsaturation, i.e., an alkyl, cycloalkyl or aromatic
; hydrocarbon containing up to 14 carbon atoms, any aromatic
hydrocarbon being optionally substituted with up to about four
lower alkyl groups or other non-interfering substituents such
as, for example, amines, oxygen-free anions of non-metallic in-
organic acids such as chlorine atoms and bromine atoms and
nitrile groups, at a temperature and pressure and for a time
sufficient to cause reaction of (D) and (2) separating the
resulting products. The total amount of catalyst combination
is present in an amount of from about 0.0001 to 0.01 total mol
per mol of (D)~ This system operates spontaneously as an
exothermic reaction as soon as the components are mixed.
Generally, the system temperature can range from 0 to 250C.,
preferably 50 to 150C., and the system pressure can range
from 1 to 500 psig., preferably 10 to 100 psig. The desired
reaction can take up to 24 hours, but for the aliphatic olefins
; the reaction is generally almost instantaneous and is maintain-
ed by a continuous addition of monomer or monomers with or
without additional catalyst.
Examples of desired products employed in the present
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invention include:
Nickel bis (dipropyl orthophosphate), nickel bis (di-
n-octyl orthophosphate), nickel bis (di-4,4-dimethylhexyl
orthophosphate), nickel bis (di-2-ethylhexyl orthophosphate),
nickel bis (diethyl orthophosphate), nickel bis (diisobutyl or-
thophosphate), nickel bis (monobutyl mono-tert-butyl ortho-
phosphate), nickel bis (monopentyl mono-2-methylpentyl ortho-
phosphate), nickel bis (di-3-methylhexyl orthophosphate),
nickel bis (mono-2-ethyl-hexyl mono-3-methylhexyl orthophos-
phate), nickel bis (di-2,3-dimethylhexyl orthophosphate), .-
nickel bis (dicyclohexyl orthophosphate), nickel bis (dibutyl
orthophosphate), nickel mono(diethyl orthophosphate) mono (di-
isohexyl orthophosphate), nickel bis (di-3,3-dimethylpentyl
orthophosphate), nickel mono (monoheptyl monohexyl orthophos-
phate) mono(monoheptyl monooctyl orthophosphate), nickel bis -
. (di-2,2,4-trimethylpentyl orthophosphate), nickel bis (di-2-
-` ethosyethyl orthophosphate), nickel bis (dicyclopentyl
orthophosphate), nickel bis (di-2,2-dimethylbutyl
orthophosphate), nickel mono(monopropyl monobutyl
orthophosphate) mono(monoamyl monohexyl orthophosphate), nick-
el bis (dicyclohexyl orthophosphate), nickel bis (dicyclobutyl
orthophosphate), nickel bis (di-3-chloropropyl
orthophosphate), nickel bis (bis-2,3-dibromopropyl
- orthophosphate) and nickel bis (di-2-chloroethyl
orthophosphate).
The alkyl aluminum halides employed are primarily the
compounds R' Al X2, R'2 Al X and mixtures thereof including the
mixtures of the formula R'3A12X3 usually referred to as the
sesquihalides. Each R' can be, for example, a methyl, ethyl,
propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, pentyl or
hexyl group. Each X can be fluorine, chlorine, bromine or
iodine. Examples of suitable alkyl aluminum halides include
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diethylaluminum chloride, n-butylaluminum dibromide, ethyl
aluminum sesquichloride, methyl aluminum sesquichloride, ethyl
aluminum sesquibromide, ethyl aluminum sesquifluoride and the
like.
The catalyst combination of (A) and (B) is further
augmented with an additional cocatalyst (C) one or more vana-
dium bis-diorgano-orthophosphates of the formula V(0) OP (0)
(OR)2 2 as described above. Examples of such compounds (C)
correspond directly to the examples of the corresponding nickel
compounds set forth above except that a vanadium atom with an
oxygen atom is substituted for the nickel atom in each
compound. Such catalyst combinations of (A), (B) and (C)
combine the oligomerizing properties of the novel nickel
compounds with the known high polymerization properties of the
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vanadium compound. When component (C) is included, it should
be present in a mol ratio to component (B) in the range of 1:4
to 1:10.
The catalyst composition of (A), (B) and (C) are sim-
ply prepared by mixing the components. The components can be
mixed prior to addition to the polymerization reaction system
or can be added simultaneously or separately to such reaction
system. The desired reaction generally takes place
immediately, but in any case it is known that the desired reac-
tion takes place in no more than two hours.
The combination catalyst system is used in the method
comprising (1) mixing the appropriate combination catalyst des-
cribed above with (D) one or more mono- or di-olefins which can
be any aliphatic, cycloaliphatic or aromatic hydrocarbons
containing no more than about 8 carbon atoms, preferably
styrene, and/or one or more aliphatic hydrocarbons containing
; no more than about 4 carbon atoms, alone or with (E) a hydrocar-
bon solvent free of aliphatic unsaturation selected from the
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class aromatic hydrocarbon being optionally substituted with up
to about four lower alkyl groups or other non-interfering
substituents such as amines, anions of non-metallic inorganic
acids and nitrile groups, at a temperature and pressure and for
a time sufficient to cause the reaction of (D) and (2) separat-
ing the resulting product.
Examples of suitable olefins (D) include ethylene,
propylene, isobutylene, butene-l, cis-butene-2, trans-butene-
2, pentene-l, hexene-l, cyclopentene, cyclohexene, cyclo-
heptene, 4-methylcyclooctene, 2-methylbutene-1, styrene, buta-
diene, isoprene, 3-vinylcyclohexene and the acyclic and cyclic
terpenes. Substitution or inclusion of non-interfering groups
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as in acrylonitrile, methyl vinyl ether, vinyl chloride and
chloroprene is not intended to put such olefins outside the
scope of suitable olefins (D). The preferred olefins are
styrene and aliphatic olefins of 2 to 4 carbon atoms.
For these polymerization reactions the reacting mono-
mer or monomers may act as a solvent for the system.
Alternatively, an inert solvent (E) can be employed. While
` 20 simple paraffin oils, cycloaliphatic hydrocarbons and aromatic
- hydrocarbons can be used, the halogeno-alkanes are preferred,
particularly methylene chloride, chloroform, carbon tetrachlo-
ride and ethylene chloride.
The mol ratio of total catalysts to (D) can be as
little as 0.0001:1 as taught in the prior art but preferably
` ranges from 0.001:1 to 0.01 to 1.
For the polymerization of olefins (D) no solvent com-
ponent (E) need be present, but a small amount of component (E)
may accelerate the polymerization reaction. In such cases the
mol ratio of (E) to (D) should be less than 0.01:1, preferably
no more than about 0.001:1.
The temperatures required for polymerization reac-
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tions with the catalyst combinations of this invention are not
particularly critical with the catalyst combinations of this
invention. Some heat may be necessary to initiate reaction
such as heating to at least 30C. The maximum temperature
which can be employed is dependent on the melting points, boil-
ing points and decomposition points of the catalytic
components, the reaction component (D) and the products as well
- as the desired control over rate of reaction. For practical
purposes, the maximum temperature is about 200C. and the pre-
ferred temperature range is 40C to 100C.
Ambient pressures are satisfactory generally ranging
from atmospheric pressure to no more than about 50 atmospheres,
preferably no more than 100 psig.
Under these conditions of temperature and pressure
the polymerization reactions can be operated batchwise for from
five minutes to four hours or more or these reactions can be run
continually. The separation of the desired product is well
within the skill of the art being primarily a problem of
fractional distillation.
Typically, for polymerization a reaction vessel is
purged with some monomer (D) if gaseous or an inert gas such as
nitrogen. Then enough of the alkyl aluminum halide (B) is
added to dry the vessel. An inert solvent such as heptane may
be added. The desired amount of components (A) and (B) and (C),
if any, are added, preferably in (A) to (B) mol ratios of 1:8 to
1:12 and (B) to (C) mol ratios of 4:1 to 10:1, with monomer (D)
at ambient pressure at a sufficient rate to allow continuous
reaction but not at such an excessive rate as to kill the
reaction. The product is then distilled off if oligomer or
extracted if high polymer. Although prior addition of
cocatalyst (B) favors rapid initiation and more rapid reaction
of monomer (D) in the presence of the initial excess of this
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component (B), concurrent addition of (B) with (A), with or
without (C), favors formation of higher molecular weight oligo-
mer products. Generally, this latter method is preferred for
the catalyst combination of (A), (B) and (C).
The following example is illustrative of the best
presently-known methods of practising this invention and are
- not intended to limit this invention the scope of which is
delineated in the appended claims. Unless otherwise stated,
all quantitative measurements are by weight.
Example
Gopolymerization of Ethylene and Propyl-e-ne
A stirred two liter autoclave with controlled cooling
coils was purged and then pressurized to 30 psig with ethylene
gas. Hydrogen gas was then ~dded until the pressure rose to 34
psig. Subsequently, 1300 ml. of dry, pure n-heptane was added
- followed by 320 ml. of liquid propylene. A reservoir
containing an equimolar mixture of ethylene and propylene was
coupled to the autoclave, and the mixture was introduced at a
rate sufficient to maintain a pressure of 60 psig throughout
- 20 the copolymerization reaction to give a total of 3.5 moles of
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: monomer.
A combination catalyst was prepared by dissolving
0.31 gram of vanadium bis-diethylorthophosphate (0.00083 mole)
and 0.19 gram of nickel bis-dibutylorthophosphate (0.00040
- mole) in 30 ml. of benzene. The cocatalyst was 2.4 grams of
ethyl aluminum sesquichloride (0.020 mole as calculated above)
dissolved in 30 ml. of n-heptane.
The combination catalyst and cocatalyst solutions
were added concurrently and continuously to the reaction
mixture for a period of 80 minutes after initiation, the
temperatures being maintained in the range of 20 to 30C. Upon
completion of the reaction and removal of solvent 123 grams of
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clear polymer gum product was isolated.
The above preparation was then repeated omitting the
nickel bis-dibutylorthophosphate to produce another polymer gum
product. -
Both products were examined and found to be ethylene-
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propylene copolymers. However, the proton magnetic resonance
(60 Mhz NMR) spectra of the products showed that the first
product contained olefinic bond structures which were absent in
the second polymer product. This finding was verified by the
- 10 infrared spectra of cast films of the products, the first
product having significant absorption around 900 cm. -1. Vap-
or bromination of the film of nickel-catalyzed polymer appreci-
, ably increased absorption around 1600 cm. 1, indicating
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bromine replacement of the olefinic hydrogens without anysignificant saturation of the olefinic bond structures.
Oxidation of the films on glass in air at 200F. for
several hours resulted in curing of the nickel-catalyzed film
; to less gummy texture than the other polymer. Adhesion of the
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nickel catalyzed polymer to glass was appreciably greater than
the other polymer.
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