Note: Descriptions are shown in the official language in which they were submitted.
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POLYMERIZATION PROCESS TO PREPARE A POLYOLEFIN FROM
STERICALLY HINDERED, METHYL BRANcHED~ ALPHA-oLEFINS
?
BACKGROUND OF THE INVENTION
~ This invention relates to polymeri2ing alpha-olefins which have a
?` methyl branch at the 3-position.
Thousands of processes are known for polymeriæing linear and
branched alpha-olefins. Branched alpha-olefins tend to be harder to
polymerize than linear alpha-oleEins. This is due, in part, to the steric
hindrances to the polymerization process. It is generally accepted -that as
the branching substituent is positloned nearer to the double bond, tha ability
,~ to polymerize the branched alpha-olefin correspondingly decreases. However,
these branched alpha-olefins upon polymeri~ation yield polymers which tand to
have higher melting points and be-tter chemical resistance than their linear
cousln3 while retaining good elsctrical propertieS.
;~ An example of a polymerizable branched alpha-olefln~ ls
~ 3-methyl-1-butene. Various processes in the art have produce~
:::
~ poly(3-methyl-1-butane) in characteristically low yialds. This ~s due to the
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steric hindrance imposed by the branched methyl group of the monomer which
inhibits polymerization. It has long been recognized that long residence
times and high polymerization temperatu]res were necessary in order to overcome
this steric hiDdranca effect. Typically, polymerlza-tion of 3-methyl-1-butene
has been reported as anywhere from about 2 grams of polymer produced pex gram
of catalyst, to about 400 grams of polymer produced per gram of catalys-t.
Therefore, a process which produced poly(3-methyl-1-butene) in better yields
would make the commercial production of poly(3-methyl-1-butene) more
economical. Furthermore, a process which polymerized thesa sterically
hindered~ methyl branched at the 3-position, alpha-olefins would be of great
scientific and economic value. Additionally, it would be of great value if a
sterically hindered, methyl branched at the 3-position, alpha-olefin could be
produced at a high productivity rate and wi-th as high of a molcular weight as
possible.
.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a high productlvity
process to produce a high molecular weight copolymer of an alpha olefin having
a methyl branch at the 3 position.
It is an object of this invention to provide an improved
copolymerization process for preparing a polyolefin from a sterically
hindered, methyl branched a-t the 3-position, alpha-olefin and at least one
comonomer.
It is another object of this invention to provide an improved
copolymerization process for 3-methyl-1-butene and at least one comonomer.
It is still another object of this invention to provide an improved
copolymerization process for 3-methyl-pentene and at least one comonomer.
In accordance with this invention a process is provided comprising
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contacting under polymeriæation conditions: at least one
trialkylaluminum cocatalyst; at least one alpha-olafin which has a methyl
branch at the 3-position and which has at least five carbon atoms, and at
leas-t one comonomer;
with a catalyst prepared by the process comprising comminuting at
least one aluminum halide; at least one electron donor; at least one metal
compound wherein the metal is selected from the group consisting of chromium,
hafnium, molybdenum, niobium, tantalum, titanium, tungsten, vanadium,
zirconium, and mixtures thereof; and a salt compound wherein at least one
component of said salt compound is selected from the group COnSiStiDg o~
barium, beryllium, calcium, magnesium, strontium, zinc, and mixtures ther~of,
to produce a comminuted solid then subjecting said comminuted solid to a
double activation-extraction step;
to produce a copolymer at a productivity level of at least 700 grams
of copolymer per gram of catalyst utllized.
DETAILED DESCRIPTION OF T~IE INVENTION
CATALYST SYSTEM
` :'
Aluminum Halide Component
The term aluminum halide is used to refer to aluminum compounds~
having at least one halogen bonded directly to the aluminum. Included are
aluminum halids compounds of the formula:
R AlX
y z
wherein R is an alkyl, aryl, or cycloalkyl group; X is fluorine, chlorine,
bromine, or iodine; z is 1, 2, or 3 and z ~ y = 3.
Examples include~
AlCl3;
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~l-dichloro-phenoxy;
Al-mono-chloro-diphenoxy;
Al-dichloro-xylenoxy;
Al-mono-chloro-dixylenoxy;
Al-dichloro-2,6-t-butyl-p-cresoxy;
Al-dichloro-octoxy; and
Al-monoethyl-dichloride.
Presently the most preferred is ~lCl3.
Electron Donor Component
Examples of electron donors include organic compounds having a-t
least one atom of oxygen, sulfur, nitrog~n, or phosphorus which can function
as the electron donor. More specifically, the term electron donor is used to
include ethars, esters, ketones, aldehydes, alcohols, carboxyllc acids,
phenols, thioethers, thioesters, thioketones, amines, amides, nitriles,
isocyanates, phosphites, phosphoryl compounds, and phosphines. Typically it
is preferred to ~Ise compounds having no more than 16 carbon atoms per
molecula. It is currently believed that aromatic ethers and the esters of
aromatic acids ar~ the most useful electron donors.
In an especially preferred embodiment both an aromatic ester and an
aromatic ether are employed. The more common esters are those derived from
carboxylic acids having 1 to 12 carbon atoms and alcohols having 1 to 12
carbon atoms. The more common ethers are those containing 2 to 12 carbon
atoms and 1 to 10 ether oxygen atoms. Typical examples of the aromatic esters
include the alkyl and aryl esters of aromatic carboxylic acids such as
ben7oic, toluic, p-methoxybenzoic, and phthalic acid. Some specific examples
include ethyl benzoate, methyl benzoate, methyl p-tolua-te, ethyl p-toluate,
and methyl anisate. The term aromatic ethers is intended to include those
ethers having two aromatic groups as well as those having one aromatic group
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and one alkyl group. Some specific examples include methoxybenzene,
phenetole, diphenyl ethar, phenylallyl ether, and benzofuran. The currently
most preferred combination is ethyl benzoate and methoxybenzene.
M~tal Compound Component
The metal compound component includes tri, tetra, and pentavalent
metal compounds. Examples include compounds of the formula MOp(OR)m-X(n 2p m
wherein M is a metal selected from the group consisting of chromium, hafnium,
molybdenum, niobium, tantalum, titanium, tungsten, vanadium and zirconium,
with a valency of n=3, 4, or 5, 0 is oxygen, p is O or 1, R is an alkyl, aryl,
cycloalkyl group or substituted derivative thereof, X is a halid~ and n~m>O.
In practice the metal is generally selected from the group consisting of
chromium, titanium, vanadium, and 7-irconium. In a preferred embodiment, tha
metal is titanium. The choice of a particular metal compound within the above
formula will depend upon the reactlon conditions and other constituents
present in the catalyst. Some examples of metal compounds having
polymerization actlvity are TiCl~, Ti(OCH3)Cl3, Ti(OCHzC~13)Cll, VCl3, VOCl2,
VOCl3 and VO(OCH3)C12- In a preferred embodiment liquid titanium
tetrachloride is used as the metal compo~nd.
Salt Component
Included within the scope of salts referred to above are the halogen
containing compounds of barium, beryllium, calcium, magnesium, strontium, and
zinc. Specific examples of such compounds include magnesium chloride,
magnesium bromide, calcium chloride, ~inc chloride and magnesium
hydroxychloride. It is currently believed that the best salt components are
the salts of magnesium. Typical examples of such salts includa magnesium
dihalides, alkyloxides, aryloxides, and combinations thereof. The pre~erred
salt components are M(OR)nX(2 n) where M is magnesium, R is an ~lkyl or aryl
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radical, X i3 a halide and n is 0, 1, or 2. Some typical examples of salts
having such a formula are MgC12, MgBr2, MgF2, Mg(OCH3)2, Mg(OCH2CH3)2,
Mg(OC6Hs)2. It is within the scope of the invention to employ mixtures of
such salts. The currently most preferred embodiment employs magnesium
halides, especially magnesium chloride. The molar proportions of the
components are illustrated by the table below.
Table of the molar proportlons of the catalyst components
based on one mole of metal compound component
Component Broad Range Preferred Range Most Preferred
Salt Compound 82S.C.280 102S.C.280 142S.C.216
Aluminum Halide
Compound 12AHC25 1.25>AHC23.0 1.52AHC22.5
Electron Donor
Compound l>EDC>lO 1.52EDC28 22EDC_7
_
An example of a preferred catalyst and the molar propor-tions of its
components is:
tl) l mole of TiCl4 (metal compound component)
(2~ 15 moles of MgCl2 (salt compound component)
(3) 2 moles of AlCl3 ~aluminum halide component)
(4) 3 moles of C6HsCO~C2Hs and
2 moles of C6HsOCH3; for a total of 5 moles of (electron donor
compound components)
Preparation of the Catalyst
The term comminuting is used herein to refer to grinding or
pulverization of the components. This term ls used to distinguish over simple
mixing which does not result in any substantial alteration of the particle
size of the components of the catalyst. One method to attain such comminuting
is by using a ball~ pebble, or rod mill. Basically, these mills are used for
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tha size reduction of materials prior to processing. They are generslly made
up ~f a ro-t~ting drum which operates on a horizontal axis and which is filled
partially with a free-moving grinding medium which is harder and tou~her than
the material to be ground. The tumblin~ act:ion of the grinding medium (balls~
pebbles, or rods) crushes and grinds the material by a combination of
attrition and impact. Grinding generally requires several hours to assure the
necessary fineness within particle size limits.
A method of producing the above catalyst system comprises the
comminution of the components preferably under an inert atmosphere in a ball
or vibration type mill. The salt component is initially charged in-to the
mill. If the salt component contains water which must be removed, a
sufficient quantity of dehydrating agent ls initially added to the salt
component and the resulting mixture is comminuted at temperatures between
about 0C and about 90C for about 15 minutes to about 48 hours. Preferably
this comminuting is from about 6 hours to about 24 hours, optimally for about
15 hours, at temperatures between 35C and about 50C so that the salt
component becomcs substan-tially anhydrous. It is preferred that the catalyst
components be substantially anhydrous because the catalyst system is
susceptible to water and air degradation. It is important that -the wa-ter
content of the catalyst be sufficiently low so as not to substantially
interfere with the catalytic activity. Usually it is only the salt component
which carries a possibility of a significant amount of water within its
composition. Therefore, drying the salt component prior -to use is generally
preferred. Further examples of various methods to dehydrate the components of
the catalyst are disclosed in U.S. patent 4,680,351 which is hereby
incorporated by reference.
Although comminution may take place at temperatures between about
0C and 90C the preferred comminuting temperature is from about 20C to about
40C with a range of 30C to 34C being most preferred. Comminution time
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varies but may range from about 15 minutes to abou-t 48 hours. Prsferred
commlnution times are from about 12 hours to about 20 hours and most
prefsrably are from about 14 hours to about 18 hours. Insufflcisnt
comminution will no-t yield a homogeneous composition, while over comminuting
may cause agglomerization or may significantly decrease particle size of the
catalyst composition causing a possible reduction in the particle size of the
polymers produced from the catalyst system. The comminution of the components
can be carried out in any order. Ths componsnts can be added one at a time
with additional comminution with each newly added component or several of the
components can be combined first and comminuted simultaneously. It is also
possible to combine some of the components before combining with a comminuted
product. Currsntly -the most preferred technique involves co~minuting the salt
component and the aluminum halide component, then comminu-ting -that product
- with one or more ~lectron donors and then comminuting that product with ths
metal compound component. Further examplss of various msthods to comminute
ths components are disclosed in U.S. Patent 4,680,351.
The solid obtained as describsd above is then contacted with a
liquid undsr conditions sufficient -to extract aluminum from ths solid and to
Eurthsr increase ths activity of the catalyst. The amount of ths
extrac-tion/activation liquid employed can vary but, typically, it would be
~mployed in such an amount that the resulting slurry would contain about 10 to
about 40 weight percent solids based on the total weight of the liquid and
solids, more prsferably about 20 to about 30 weight percent solids. The
actual temperature and time for the extraction/activation can vary depending
on the results dssired. Typically the extraction/ac-tivation would be
conducted at a temperature in the range of about 40C to about 120C.
Gsnerally, however) the temperature should be kept below the boiling point of
ths liquid having the lowest boiling point. It is currently prsfsrred -to use
a temperature in ths range of about 60C to about 110C, ~ore prsf~rably 85C
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to about 105C. It is currently preferred to contact the cstalyst w:Lth the
llquid for about 0.5 to about 5 hours, most preferably from about 1 to abou-t 3
hours.
Any suitable organic compounds in combination with t:ttanium
tetrachloride can be employed as the extraction/activation liquid. The
currently preferred organic compounds are hydrocarbons. Some typical examples
include heptane, pentane, 2,3-dimethylpentane, hexane, ben7ene, toluene,
xylene, and ethyl benzene. It is currently preferred to use a combination of
aromatic and paraffinic hydrocarbons, for example, heptane and toluene. The
results obtained will vary depending on the specific extraction/activation
liquid employed. For the preferred heptane/toluene/titanium tetrachloride
~- mixture, the heptane would generally account for about 50 to 70 weight percent
:! of the liquid, more preferably, the heptane would account for about 54 -to
about 62 weight percent of the liquid, ths toluene would generally account for
about 30 to 50 weight percent of the liquid, more preferably -the toluene would
account for about 3~ to 42 weight percent of the llquid, and the titanium
tetrachloride would account for about 1 to about 20 weight percent of the
liquid, more preferably about 1 to 10 weight percen-t.
It is currently preferred that after the ex-traction/activation is
conducted that the solid component be separated from the liquid component.
This subsequently a-ttained solid componen-t should then again be subjected to
an extraction/activation step similar to the previous extraction/activation
step. Further examples of various methods to extract/activate the components
are disclosed in U.S. patent 4,680,351. A preferred method of preparing the
catalyst is disclosed in Example I of this specification.
':
~' COCATAL~STS
The catalyst system produced by the foregoing methods disclosed
above and in the references cited, and as illustrated in Example I, are
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330~30CA
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preferably used in conjunction with a cocatalyst of an organometallic
compound. The organometallic compound cocatalys-t is selected from the gro~lp
consisting of trialkylaluminums. For example, preferred cocatalysts are
triethylaluminum, trimethylaluminum, and triisobutylaluminum. The molar ratio
of organometallic cocatalyst to titanium-con-taining catalyst component
employed can vary but may range up to about 400 to 1. However, close
attention should be paid to the aluminum/titanium mole ratios, in the final
total catalyst/cocatalyst package~ because certain mole ratios of these
components are preferred over other mole ratios when considering productivity
and the weight percent of solubles in the reactor. The term "solubles" is
defined in this specification as the amount of soluble polymer left in the
monomer, comonomer and/or diluent. The weight percent of solubles is based on
the total polymer weigh-t both soluble and insoluble ~See Example VIII).
POLYMERIZATION CONDITIONS
The olefins which can be polymeriæed using this procass are those
olefins which ha~e a methyl branch at the 3-position. Fur-thermore, these
alpha-olefins should have between about 5 and 21 carbon atoms in the molecule
inclusive. Examples of such olefins are 3-methyl-1-butene,
3-methyl-1-pentene, 3-methyl-1-hexene, 3-methyl-1-heptene, 3-methyl-1-octene,
3-methyl-1-nonene and 3-methyl-1-decene. Additionally, it is within the scope
of this invention that these monomars can be copolymerized with other
slpha-olefins (fllso called comonomers) such as, for example, etnylene,
-- propylene, l-hexene, 4-methyl-1-pentene, 3-ethyl-l-hexene3 l-octene, l-decene,
and l-hexadecene. When adding the comonomer to reaction it is preferred that
the comonomer be added incrementally or continuously through the
polymerization reaction. Incremental or continuous addition of the comonomer
is pre~erred because a higher molecular weight copolymer resin is obtained and
less reaction solubles are produced. Incremental addition means that the
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amount of comonomer to be added to the reactor, is divided up into discre-te
individual releases in the reactor. For example, if ten mole percent of co-
monomer (based on total moles oE monomer and comonomer) is to be added to a
reac-tor during the next hour, one mole percen-t of comonomer could be added
every 6 minutes, instead of dumping all o the comonomer in at the start of
the copolymerization. Continuous addition means that monomer is added through
all, or essentially all, of the polymer:Læation period. This addition can be
uniform through the addition or its rate can be increased or decreased during
the polymerization.
The preferred reactor temperature for polymerizing these monomers i9
in the range of 60C to lZ0C. Preferably it is in the range of 85C to 115C
and most preferably from about 90C to 110C. Temp~ratures high~r than 120C
usually result in catalyst degradation to the point that polymerization
results in significantly reduced yield and temperatures below 60~C tend to
result in productivlties which are not commercially viabla for these types of
monomers. The reactor residence time of the catalyst varies. ~sually,
however, lt is in the range of abou-t 0.1 hours to about 4 hours. Nost
preferably it i9 In the range of about 0.25 hours to about 2 hours and most
preferably it is in the range of about 0.5 hours to about 1.5 hours.
Additionally, hydrogen can be charged to -the reactor in order to facili-tate
the polymeriæation. However, it should be noted that higher levels of
hydrogen after a certain point tend not to significantly effect the
productivity oE the polymeriæation reaction. I-t should also be noted, however,
that this hydrogen effect seems related to the particular type of monomer used
in the polymerization. Therefore, some leeway ~nd experimenta-tion should be
done in order to determine the optimum hydrogen concentration when considering
the various production variables (see Example YI). The production of
poly(3-methyl-1-butene) sugges-ts that the aluminum/titanium mole ratio should
also be regulatcd. The data indicate that an aluminum/titanium mole ratio
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between about 10 to abou-t 60 is best. Preferably, however, this ratio is
between about 15 to about 55 and most preferably it is between 25 to 50, for
the polymeriza-tion of 3-methyl-1-butene.
Examples
These examples are provided to further flSSiSt a person skilled in
the art with understanding this inven-tion. The particular reactants,
conditions, and the like, are intended to be ~enerally illustrative of this
invention and are not meant to be construed as unduly limiting the reasonabla
scope of this invention. Examples I-IX illustrate the polymerization process
and the variety of different settings. Example X describes the b~nefit of
copolymerization in a variety of ways.
Example I: Preparation of a Tvpical Catalyst Used in This Invention
This example illustrates a preferred method of making the catalyst.
This method is similar to those methods disclosed in U.S. Patents 4,555,496
and 4,680,351 which are hereby incorporated by reference.
The components of the catalys-t were comminuted in a nitrogen purged
250 liter ball mill. To this ball mill was added:
[1] 130.0 pounds of anhydrous magnesium chloride (MgCl2);
[2] 24.5 pounds of aluminum chloride (AlCl3).
The temperature of the ball mill was then brought to a temperature
in the range of 30C to 34C. The contents of the ball mill were -then ball
milled for 16 hours. During this ball milling and in all subsequent ball
millings the temperature was maintained between 30C and 34C. To the ball
mill was then added:
[3] 41.4 pounds of ethyl benæoate (C6HsC02C2Hs).
The ethyl benæoate was slowly added over a period of 1 hour while
the ball mill was milling. After the addition of ethyl benzoate was completed
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the ball mill was allowed -to mill an addi-tional 2 hours. To the ball mill was
then added:
[4] 24.8 pounds of methoxybenæene (C6HsOCH3).
The methoxybenzene was slowly added over a period of 0.5 hours while
the ball mill was milling. ~fter the addition of the me-thoxybenzene was
completed the ball mill was allowed to mill an additional 2.5 hours. To the
ball mill was then added:
[5] 17.7 pounds of titanium tetrachloride (TiCl~).
The titanium tetrachloride was slowly added over a period of 0.5
hours while the ball mill was milling. After the addition of the titanium
tstrachloride was completed the ball mill was allowed to mill an additional 16
hours. The resulting solid was then recovered from the ball mlll and screened
to remove ~20 mesh course material. A portion of the finer resulting matarial
obtained af-tex the screening was subjected to -the following double
activation/extraction process. To a 20 gallon glass ~acketed stainlass steel
reactor equipped with a 200 rpm agitator the following was added:
[1] 26.0 pounds of the screened material;
[2] 46.8 pounds of hep-tane (C~13(CH7)sCH3);
[3] 31.2 pounds of toluane (C6H5CH3);
[4] 4.2 pounds of tltanium tetrachloride.
The reactor was then heated to a temperature between 95C and lOO~C.
This temperature was maintained for 2 hours. During these heating steps the
reac-tor was constantly agitated. The resulting mixture was then immediately
filtered to recover the solid material. To the reactor was then added:
[5] the filtered solid material;
[6] 46.8 pounds of heptane;
[7] 31.2 pounds of toluene;
[8] 4.2 pounds of titanium tetrachloride.
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The reactor was then heated to a tempera-ture between 95C and 100C.
This temperature was maintained for 2 hours. During these heating steps -the
reactor was cons-tantly agitated. The rasulting mixture was then immediately
filtered to recover the solid material. To the reactor was then added:
[9] the solid material;
~ 10] 26.0 pounds of heptane.
The reactor was then agitated for 0.25 hours. After thc agitation
was complete the resulting mixture was filtered to recover the solid material.
To this solid material was added:
[11] 26.0 pounds of heptane.
The resulting slurry was then collected as the catalyst used in th~
following inventive examples.
Example II: Initial Catalyst Survey
In this example a variety of transition metal catalysts were
evaluated at reac-tion temperatures between 60C and 120C in a series of 4
hour runs. A total of 8 different catalysts were used in this initial survey.
These catalysts are described in Table IIA.
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Table IIA
Welght Percent of
Metal Components ! b
Catalyst Ti Mg Al Comments
_ _ _ _ _ _ _ _, _
2.2~0.9 .68 Catalyst used in this invention
B 1.718.3
.
C 15.5 - - Titanium trichloride with 50 wt%
polypropylene prepolymer
D 21.8 - - Ti-tanium Chloride with 30 w-t%
stereoregulator
E 31.1 - - Titanium trichlorido
F 0.4 3.9 - Catalyst with 80 wt% polypropylene
prepolymer
G 2.019.5 - Same catalyst as F without -the
prepolymer
H 24.1 - 4.5
.. _ . ... ~
- b"-" indicates zero or a trace amount.
Catalysts B through H are catalysts known for their polymerization ability
with propylene.
CThe weight percents were determined by Plasma analysis.
A reactor residence time oE 4 hours was used in all runs. This time
was selected on the basis of early work which suggested tha-t longer residsnce
times are necessary in order to optimize polymer yield. It has since been
discovered that shorter rosidence times are adequate for some of the ca-talysts
surveyed. Triethylaluminum was used as the cocatalyst for this study.
Regardless of catalyst charge, the samo amount of triethylaluminum (TEA)
(4.63mmol, 5.0 mL of a 15 wt% solution in heptane) was used in each run. This -
lead to the broad disparity in the aluminum/titanium ratios shown in Table IIB
below.
All of the polymerizations were performed in a one gallon, stainl~ss
~` steel Autoclave Eng:Lneers reactor. Under a purge of nitrogen, the reac-tor was
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16
charged with the selected catalystJ 5.0 m:illiliters of trie-thylflluminum
solution, and then sealed. 3-Nethyl-l~butene was drained into the reactor
from a 2.0 liter reservoir followad by a press~lre drop of 25 psig from a 300
milliliter cylinder of hydrogen. The reactor was then heated -to the desired
temperature and held there for 4 hours. After this time, a mixture of
acetylacetone and propylene oxide were added to deactivate the catalyst.
Unreacted monomer was then drained from the bo-ttom of the reactor into fl
grounded aluminum pan. The polymer was -then washed with 2 liters of n-heptane
at 80C for 30 minutes, then removed from the reactor, and dried in an
aluminum pan at 75C for 2 hours.
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19 ~ Q 3 33080CA
It is apparent from Table IIB that inventive catalys-t ~ is by far
the best catalyst of those screened for this type of polymerization. Although
this productivity is much less than the cata]yst productivity reported for
such commercial production operations as polyethylene and polypropylene, it is
still at least 2 to 4 times higher than what has previously been reportsd in
the llterature for the polymerization of 3-methyl-1-butene~ Furthermore, the
yield of poly(3-methyl-1-butene) with catalyst A is high enough to produce
this specialty polymer in a commercially viable process.
xample III: Polymerization of 3-methyl-1-butene~ 3-methYl-l-Pentene
and 3-ethYl-l-hexene
A further study was done to compare the productivity of various
catalysts for polymerizing the above-mentioned monomers. All of the runs were
performed using a procedure similar to the procedure in Example II.
.
~ ~ ~ 1 3 ~ ~ 33080C~
Table III
Catalyst Catalyst Yield Reactor-Solubl~s Prod~lctivity
Run Type ~onomer (g) (g) (g) (wt.%) (g/g)
3 A 3MB1 0.1593201.70 17.39 7.9 1375
11 Cl 3MB1 0.625866.04 5.74 8.0 229
19 E 3NB1 0.5092175.97 8.68 4.7 363
33 Al 3NB1 0.149326.70 30.47 53.3 383
. _ _ _ _
34 Al 3MP1 0.164115.09 45.46 75.0 369
A2 3MP1 0.1712114.06 23.65 17.1 804
36 A 3MP1 0.1763375.23 23.34 5.6 2261
37 C' 3MP1 0.994763.17 31.39 33.1 190
38 D2 3MP1 0.508189.88 23.10 20.4 31
39 A 3EH1 0.30494.53 12.04 72.6 5
lSee footnota 1 in Table IIB.
- 2See footnote 2 in Table IIB
3Catalyst Al is made the same way as Catalyst A except no electron donors
are added and Catalyst Al was not subjected to a double activation/extraction.
Catalyst A2 is mada the same way as Catalyst A except Catalyst A2 was not
-~ subjected to a double activation/extraction. Runs 3, 11, 19, and 33polymerized 3-methyl-1-butsne (3MBl) a-t 100C and 4 hour reactor residence
- time with 25 psig of hydrogen. Runs 34-38 polymerized 3-methyl-1-pentene
(3MPl) at 100C for 2 hour reactor residence time and 50 psig of hydrogen.
Runs 39 polymerized 3-ethyl-1-hexene (3EHl) at lOO~C for a 2 hour reactor
residence time with 50 psig of hydrogen.
The data clearly show that catalys-t A performed better than any of
the other catalysts in ~he series. However, it is interesting -to note that
the polymerization of 3-ethyl-1-hexene did not perform as well. For example,
comparing runs 36 with 39, it is apparent that 3-methyl-1-pentene polymerized
to yield about 4200 percent more polymer than 3-ethyl-1-hexene. Upon closer
inspection it is also apparent that -the polymerization of 3-ethyl-1-hexene
generated about 1200 percent more solubles than did the 3-methyl-1-pentene.
Therefore, it can clearly be seen that while catalyst A is not particularly
effective in the polymerization of 3-ethyl-1-hexene it is the catalyst of
choice for polymerizing alpha-olefins which havs a methyl branch at the
- 3-position.
.' ~:. . :
- -:-
~-. - - - :~
330~0C~
21 ~ 3~3
Example IV: Reactor Temperature EfEect on the Polymerization of 3MBl
and 3MPl with Catalyst A
~ serles of runs was conducted to determine the optimum temperature
at which maximum productivity i5 obtained. The procedure utilized to attain
.
the data below was similar to the procedure used in Example II. The specified
temperature was used for 2 houls with 50 psig of hydrogen and 5.0 milliliters
of TEA solution. The data are summarized below.
Table IV
Amo~mt of
Reactor Catalyst Polymer Reactor-Solubles Productivity
Run Monomer Temp (C) (g) Yield (g) (wt%) (g/g)
3MBl 50 0.262992.46 13.3212.6 402
41 3MB1 60 0.2792162.92 17.319.6 646
42 3MB1 70 0.2844199.11 20.379.3 772
43 3MB1 80 0.3506279.43 27.909.1 877
44 3MB1 90 0.3531310.29 25.797.7 952
3MB1 100 0.3388338.61 28.907.9 1085
46 3MB1 110 0.2920257.75 28.029.8 979
47 3MB1 120 0.3031228.57 25.139.9 837
48 3MP1 60 0.2312241.80 32.7311.9 1187
49 3MP1 80 0.1856286.71 27.258.7 1692
3MP1 90 0.1536297.07 22.457.0 2080
51 3MP1 95 0.1766377.40 19.494.9 2247
52 3MP1 100 0.1763375.23 23.345.9 2261
53 3MP1 110 0.1818296.62 25.207.8 1770
54 3MP1 120 0.1562204.00 26.6511.6 1477
____
The data in Table IV show the effect of the reactor temperature on
3MBl and 3MPl polymerization. To maximize productivity, the data indicate
that the reactor temperature range between 60C and 120C is preferred.
Operating within this temperature range also minimizes the total level of
solubles generated. Consequently, it it preferred to operate within these
- : . : :
:
~ 33080CA
22
temperature ranges listed in Table IV in order to generate maximum
productivity whil~ minimizing the amoun-t of reactor solubles.
.
Example V: Reactor Residence Time Effect on th~ Polymerization
of 3MBl and 3MPl with Catal~lst A
~ series of runs was conducted to show -the effect of reactor
residence time on the polymerization of 3MBl and 3MPl. The procedure utilized
in this run was slmilar to the procedure utilized in Exampl~ II. A reactor
temperature of 100C for the specified residence time was used along with 50
pslg of hydrogen for runs 63-68 and 25 psig o~ hydrogen ~or runs 55-62. The
data are summarizsd below.
Table V
Amount of
Residence Catalyst Polymer Reactor-Solubles Productivity
Run Monomer Time thr) (g) Yield (g) (wt%) (g/g
3MB1 0.25 0.144772.15 9.09 11.2 561
56 3MB1 0.50 0.1636126.73 13.80 9.8 859
57 3MB1 0.75 0.1445122.80 12.81 9.5 938
58 3MBl 1.00 0.1558148.63 15.77 9.6 1055
59 3MB1 2.00 0.1512148.28 14.84 9.1 1079
3MB1 3.00 0.1683176.98 16.22 8.4 1148
61 3MBl 4.00 0.1593201.70 17.39 7.9 1375
62 3MB1 5.00 0.1703204.53 14.90 6.8 1288
63 3MP1 0.25 0.2398215.88 24.02 10.0 1000
64 3MP1 0.50 0.1597259.63 27.65 9.6 1799
3MPl 1.00 0.1784316.15 21.85 6.5 1895
66 3MP1 1.50 0.1654282.78 20.62 6.8 1834
67 3MP1 2.00 0.1838335.26 21.80 6.1 1943
68 3MP1 3.00 0.1811380.57 21.43 5.3 2220
:
The data in Table V above illustrate that the productivity increases
from a residence -time of 0 hours (time a-t which the reactor reaches the
-~ desired operating temperature) to about 1 hour, after which little gain in
.,,~
;: : -
.
33080C~
~ 23 ~ 3 ~ 3
productivity is reallzed. While not wanting to be bound by theory, it is
believed that after about 1 hour the catalyst begins to decay which leads to
only modest gains in productivity at longer residence timss. Additionally, it
~hould be noted that the amount of react:or solubles generatsd in thiæ reaction
tends to decrease with residence time. Therefore, it is apparent that there
are competing considerations between lowering the amoun-t of reactor solubles
by increasing the reactor residence time and generating maximum economical
productivity with a lower reactor residence time.
Example VI: Hydro~en Concentration Effect on the Polymerization
of 3MBl and 3MPl with Catalvst A
A series of runs was done to illustrate the effect of the hydrogen
concentration on the polymerization of 3MBl and 3MPl. These runs were
conducted using procedures similar -to the procedures used in Example II. A
reactor temperature of 100C was used for a 2 hour residence time with the
specified amount of hydrogen. The data are summarized below.
: : . . ...................................... . ~ -
. . . - .
., ': " . : . . '.
33080CA
24 ~ l 3 ~ ~
Table VI
~-~ Amount of
, Hydrogen Catalys-t Polymer Re.actor-Solublas Productivity
Run Monom~r (psig) (g)Yi~ld (g) (wt%) (g/g
; 69 3MB1 0 0.3828113.52 6.40 5.3 313
3MB1 25 0.4119309.98 14.92 4.6 789
71 3MB1 50 0.4278397.64 18.30 4.4 972
72 3MB1 75 0.4399471.65 20.32 4.1 111~
73 3MB1 100 0.4217491.10 21.77 4.2 1216
74 3MB1 150 0.4244526.05 17.44 3.2 1281
3MB1 200 0.4214539.97 17.54 3.2 1323
76 3MB1 300 0.3996513.23 24.01 4.5 1344
77 3MBl 400 0.3938509.27 31.02 5.7 1372
78 3MP1 0 0.16496.40 12.36 65.9 114
79 3MP1 25 0.2077203.50 12.33 5.7 1039
3MP1 50 0.1833307.82 24.94 7.5 1815
81 3MP1 100 0.1694336.91 26.50 7.3 2145
82 3MP1 150 0.2048413.88 25.64 5.8 2146
83 3MP1 200 O.lR09449.58 26.96 5.7 2634
84 3MP1 400 0.1805497.79 28.74 5.5 2917
.
.~
The data above illustrates that the productivity starts to level off
aftor a charge of 100 psig of hydrogen. Since, in general, increased hydrogen
levels resul-t tn hlgher flow rates, it is usually desirable to keap the
hydrogen level at an amount lower -than what would optimlze productivity. That
1SJ productivity is sacrificed at the expense of processing characteris-tics
and properties.
,:
Example VII: Cocatalyst Survey with Catalyst A
In the previous catalyst screening study (see Example II},
triethylaluminum was used exclusively as the cocatalyst for polymerizing 3MBl.
To determine if some other cocatalyst provided a better result with the
catalyst used in this invention, a series of runs was performed varying the
cocatalyst from run to run. To insure the comparisons would be meaningful,
:
. . - - , - . . , . ~ , .
~ 3 ~ 3 33080CA
the aluminum to titanium mole ratio (Al/Tl) and all of the reactor conditions
were held constant. The procedure u-tili~ed in this example was similar to the
procedure utilized in Example II. A reactor temperature of 100C and a
reactor residence tlme oE 2 hours was used. Additionally, 50 psig of hydrogen
was used and -the Al/Ti mole ratio was equal to about 40. The data are
summarized below.
Table VII
ProductivitySolubles (wt%)
RunCocatalyst(g/g) Reactor Flow Rate
... .
TMA 940 7.5 95
86 TEA 1199 8.4 48
87 TIBA 983 5.8 35
88 DEAC 521 10.9 255
89 EASC 40 38.8 > 1000
90 EADC 10 100.0
(1) TMA = Trimethylaluminum
(2) TEA = Triethylalumlnum
(3) TIBA = Triisobutylaluminum
(4) DEAC = Diethylaluminum chloride
(5) EASC = Ethylaluminum sesquichloride
(6) EADC = Ethylalumlnum dichloride
(7) The flow rate was measured using the procedure similar to ASTM
D1238-82. This flow rate was measured a-t 320C under a 5 kilogram load after
a 5 minute hold period. During the hold the resin was weighted with a 360
gram load.
None of the other cocatalysts screened were any more effective than
TEA for optimizing the productivity of 3MBl. All of the trialkylaluminums
(runs 85-87) were effective cocatalysts. Substituting alkyl groups with
chlorides (as in runs 88-90~, however, resulted in progressively lower
productivities and higher reactor solubles.
:
33080CA
26 ~ 3 ~ 3
Example VIII._ The Aluminum/Titanium Mole Ratio Effect on
the Polymerization of 3MBl
A series of runs with increasing amount of TEA was used to determine
the effect of the Al/Ti mole ratio on the polymerization of 3MBl. The
procedure utilized was similar to the procedure utilized in E~ample II. A
reactor temperature of 100C for 2 hours was used. Additionally, a 50 psig
hydrogen charge was utilized along with TEA as a cocatalyst.
.
Table VIII
Al/Ti ProductivitySolubles (wt%)
RunNole Ratio (g/g) Reactor Flow Rate
-, 91 1 0
` 92 2.5 10 50.0 ---
933.75 25 31.7 ---
94 5 199 17.6 959
564 8.8 97
96 15 945 6.8 71
97 20 963 5.7 59
98 30 1022 4.9 47
99 40 1061 6.2 48
100 50 1076 6.9 83
101 60 1124 6.6 80
The data above show that a Al/Ti mole ratio of 15 results in near
optimum results. Increasing levels of TEA do not afford significant increases
ln productivity, but increasing the Al/Ti mole ratio to almost 50 tended to
minimize the polymer flow rate. Furthermore, an Al/Ti mole ratio of 30
- appears to be optimum for minimizing the amount of reactor solubles.
~ Consequently, it is clear to see that tha Al/Ti mole ratio should preferably
;~ be between about 10 to about 60.
.' '
.
.~ :
:: :
,.: .~, .... . .
-
330~0CA
27 ~.L3~
Example IX: The Effect of a TEA/DEAC_Cocatalys Mixture
_n the Polymerization oE 3MBl
In the polymerization of propylene with certain Ziegler type
catalysts, a mixture of TEA and DEAC as a cocatalyst system has been shown to
result in enhanced productivity at a specific compositioll of the cocatalyst
mixture. To determine if such an effect might occur in the polymerization of
3MBl with the catalyst used in this invention, a series of runs was performed
in which the composition of the TEA/DEAC cocatalyst mixture was constantly
changed. The procedure utilized in this example was similar to the procedure
utilized in Example II. A reactor temperature of 100C for 2 hours was
utilized. Additionally, 50 psig of hydrogen was included and the Al/Ti mole
ratio was held constant at about 40. Tha data are summarized below.
Table IX
Productivity Solubles (wt70)
Run% DEAC ~g/g) Reactor Flow Rate
102 0 1199 8.4 73
103 10 1175 8.7 74
104 20 1076 7.8 109
105 30 1054 8.4 137
106 40 1036 8.3 133
107 50 973 8.3 182
108 60 9~4 7.4 13~
109 70 884 7.5 1~6
110 80 751 9.O 177
111 90 536 7.4 233
112 100 521 10.9 300
:
As shown in the data above, enhanced produc-tivity was not observed.
Productivity dropped as the percent composition of DEAC in the cocatalyst
mixture was increased. An opposite effect was observed in the flow rate.
- : :
, ~
.
33080C~
28 ~ 3
Therefore, the effect observed in propylene type polymerizations was not
observed in the polymerization of 3-methyl-1-butene.
Example X: Gopolymerization with 3-methyl-1-butene
A series of runs were conducted to determine the productivity of
this catalyst with 3-methyl-1-butene and a comonomer. The procedure utilized,
in this example, was similar to the procedure utilized in Example II. A
reactor tempera-ture of 100C for two hours was used. Additionally~ a 50 psig
hydrogen charge was utilized along with 5.0 milliliters of TEA as a
cocatalyst. The data are summarized helow.
Table X
Mol % Comonomer Productivity
Run Comonomer~ Char&ed Found2 ~g/g)
... _ ............ .... _ _ ... _ . . ...
113 None 0.00 0.00 969
114 l-Hexene 0.25 0.46 1064
115 l-llexene 0.50 0.96 990
116 l-Hexene 1.00 2.06 1020
117 l-Hcxene 2.50 4.36 1097
118 l-Hexene 5.00 7.82 1170
119 l-Decene 0.25 0.44 1007
120 l-Decene 0.50 0.46 1011
121 l~Decene 1.00 1.23 989
122 l-Decene 2.50 3.09 1026
123 l-Decene 5.00 4.17 1251
_ _ _
124 l-Hexadecene 0.25 0.22 1085
125 l-Hexadecene 0.50 0.45 1036
126 l-Hexadecene 1.00 0.79 967
127 l-Hexadecene 2.50 1.37 1314
128 l-Hexadecene 5.00 3.19 1560
lComonomer added in quarter additions at T= 0,30,60, and 90 minutes.
2Determined by infrared analysis.
As can be seen from the above data, various comonomers can be
: .;
- copolymerlzed with 3-methyl-1-butene at high productivities, (i.e., ~ 700
~:
.
: `
29 ~ 3~3
g/g). The above data was analyzed to determine if there was a correlation
between -the amo~nt of comonomer charged to the reactor and the amount of
comonomers incorporated in the resulting resln. The results are presented
below.
Table X-A: Analys:is of l-Hexene Data
RunComonomer Charge Comonomer Incorporation (Mole Percent)
Number(Mole Percent) Actual Calculated
113 o.oo o.oo 0 0O
114 0.25 0.46 0.51
115 0.50 0.96 1.01
116 1.00 2.06 2.02
_
Tha calculated mole percents come from the linear equation indicated
by the data. Using the mole percent charge as the x-coordinate and using the
actual mole percent as the y-coordinate, a linaar equation in the form of
y=mx+b was deduced. (m ts equal to the slope of the line and b is equal to
the y-intercept, which in all cases is ~ero because wi-thout a comonomer charge
no comonomer can be incorporated). This linear equation was y=2.02x. The
correlation of thls line was 0.9988, where a correlation of plus or minus 1.00
is considered a perfect correlation. Consequently, the amount of comonomer
charged -to the reactor is a good predictor of the amount of comonomer
incorporated for l-hexene.
A similar analysis was done on l-decene. The results are presented
below.
,
- : '
, - : . , :
,
' :
:. : : . , ~ ~
33080CA
~ 3
Table X-B: Analysis of l-Decene Data
Run Comonomer Charge Comonomer Incorporation ~Mole Percent)
Number (Mole Percent) Actual Calculated
113 o.oo 0 0O 0 0O
119 0.25 0.44 0.30
120 0.50 0.46 0.61
121 1.00 1.23 1.20
The eq~lation of the line that generated the calculated data was
y=1.20x. The correlation of this line was O.Y747. Consequently, the amount of
comonomer charged to the reactor is a good predictor of -tha amount of
comonGmer incorporated, for l-decene.
A similar analysis was done on l-hexadecene. The results are
presented below.
:
Table X-C: Analysis of l-Hexadecene Data
. . _ . . _ .
Run Comonomer Charge Comonomer Incorporation (Nole Percent)
Number(Nole Percent) Actual Calculated
-. --. -- _ . . . .. _ . _
113 o.oo o.oo 0 0O
124 0.25 0.22 0.20
125 0.50 0.45 0.41
126 1.00 0.79 0.82
The equation of the line that generated the calcula-ted data was
y=0.82x. The correlation of this line uas 0.9960. Consequently, the amount
of comonomer charged to the reactor is a good predictor of the amount of
comonomer incorporated, for l-hexadecene.
Using procedures simllar to those used to calculate the data in
Tables X-A through X-C, diflerent methods of comonomer addition were comp-red.
:: . . : : :
, ~ : . ~ - . :
.: , .
33080CA
31 ~ 3
. The polymerizations were conducted in a manner similar to the polymeriza-tion
- proceduro in Exanlple II. A reactor temperature of 100C Eor two hours WflS
used. Additionally, a 50 psig hydrogen charge was utilized along with 5.0
milliliters of TEA as a cocatalyst. The results are summarized below.
.,
Run Comonomer Amount Method Amount Weight of Flow Activity
Number Added Added Addedl incorporated2 Solubles Rate3 (g/g)
. . .
129 l-decene 0.40 A 0.88 9.1 114 817
130 l-decene 0.60 A 1.3212.0 90 831
131 l-decene 0.60 C 0.77 9.5 68 1026
132 l-decene 1.00 C 1.28 8.3 65 1019
133l-hexadecene 0.20 A 0.30 - 91 1191
134l-hexadecene 0.40 A 0.60 - 330 1168
135l-hexadecene 0.20 B 0.23 9.4 43 1089
136l-hexadecene 0.60 C 0.5210.8 39 992
_ _ __ . . .
lMethod A was adding all of the comonomer to the reactor before heat was
added to the system. Nethod B was quarter additions of the comonomcr at
Time=0,15,30, and 45 minutes. Method C was quarter additions at Time=0,30,60,
and 90 minu-tes.
Amount incorporated was calcul~tcd usin~ linear analysis -techniqucs
similar to those in Table X-A through X-C.
3See Note 7, Table VII
It is apparent that changing the method of comonomer addition from a
ba-tch method (method A) to a incremental method (methods B~C) lowers the flow
rate indicating an increased molecular weight. (Compare runs 131 vs. 129, 132
vs. 130~ 135 vs. 133, 136 vs. 134.) It is further suggested that as the
comonomer addition becomes more continuous a further lowering of the flow rate
, ~ can be expected. Furthermore, another benefit is the lowering of -the amount
i of solubles wbich can significantly affect the economics of a polymerization
. process.
,:;
`: :
