Note: Descriptions are shown in the official language in which they were submitted.
~2~
1 331 23q
This invention relates to thermoplastic olefin
polymers having elastic properties, and to a method for
preparing same. More particularly this invention relates
to thermoplastic olefin polymers which have an e~cellent
S balance of several properties, such as flexibility, tensile
strength, impact strength, tear strength and elongation.
Thermoplastic olefin polymers prepared by physically
blending or mixing monoolefin copolymer or terpolymer
rubbers and polyolefins are known (see, e.g. U.S.
3,03h,987, 3,835,201 and U.S. 4,748,206?. However, in
order to achieve a good dispersion of the rubber in the
polyolefin it is necessary to employ enargy intensive
mi~ing.
The formation of thermoplastic elastomers (TPE) from
such blends is also known. Although there are a number of
methods taught, the one generally practiced is dynamic
vulcanization of such bl~nds, such as by the method
described in U.S. 3,806,558.
In order to avoid the disadvantages iassociated with
physical blending while at the same time avoid the
necessity to dynamically vulcanize such blends, efforts
have been made to produce reactor or chemical blends of a
crystalline polypropylene and an amorphous ethylene-
;~ propylene copolymer rubber by sequential polymerization in
a reactor.
In U.S. 4,489,195, for e~ample, the preparation ofpolyolefin thermoplastic elastomers by a two-stage
~ ~ r
" 1331239
polymerization process using stereospecific catalysts
composed of an organoaluminum compound and a solid catalyst
component on a magnesium halide support is taught. In the
first stage 5-50 wt. % of a homopolymer of propylene is
S formed, and in the second, 50-95% of an ethylene-propylene
copolymer having a propylene content of 5-60% is prepared
by adding ethylene monomer which reacts with the unreacted
propylene monomer of the first stage. The polypropylene
produced in the first stage and the ethylene-propylene
rubber of the second stage are believed to be chemically
combined so as to form a block copolymer. One of the
disadvantages of this method is that the temperature in the
second stage must be kept relatively low, i.e. not more
than 50C, in order to prevent agglomeration of the
ethylene-copolymer rubber particles and reactor fouling.
This need to operate the second stage at relatively low
temperatures penalizes the process with respect to heat
e~change and diminishes catalyst mileage.
U.S. 4,491,652 also describes the preparation of
polypropylene thermoplastic elastomers in two stages. In
the first stage the propylene is polymerized to a
homopolymer polypropylene. In the second stage, ethylene
is added and ethylene and propylene are polymerized in the
presence of a solvent, preferably at temperatures of
60-77C, to form rubbery copolymers and block copolymers
of the polypropylene and ethylene/propylene rubbery
copolymer. The polymerizations conditions employed in the
second stage leads to the formation of a partially soluble
rubbery copolymer which tends to cause the resultant
product to lump or agglomerate. These lumps or
agglomerates must be broken up to provide a homogeneous
product. Typically this is done by grinding on a mill. As
a matter of fact, it is known that when over 20%, based on
the thermoplastic elastomer, of the rubbery ethylene/
propylene copolymer is produced during the preparation of
--2--
` 1 33 1 239
. ~
the thermoplastic elastomer, it is impossible to avoid
3 agglomeration of the particles even when the polymerization
takes place in the presenca of stereospecific catalysts
(see, e.~., European application 0029651 and U.S.
4,259,461).
Polymerization of such rubbery copolymers in a gas
processr even in small amounts of 20~ or more, likewise
leads to product agglomeration and fouling of the
¦ reactors. This reactor fouling effectively prevents one
10 from conducting such a polymerization process in gas phase.
rhere~ore~ it is necessary to be able to produce a
thermoplastic olefin polymer having the desired balance of
mechanical properties in a reactor or sequence of reactors,
including, where desirable, at least one gas phase reactor,
15 which avoids the disadvantages associated with the present
methods of producing this type of polymer.
The present invention provides a thermoplastic olefin
polymer comprising
a) greater than 60 to about 85 parts of a
crystalline polymer fraction selected from the group
consisting of (i) a copolymer of propylene and at
least one alpha-olefin having the formula H2C~CHR,
where R is H or a C2 6 straight or branched chain
alkyl, containing over 85% by weight of propylene and
having an isotacticity inde~ of greater than 75, (ii)
a polybutene-l having an isotacticity index of greater
than 75, (iii) an ethylene homopolymer having a
density of 0.95 g/cm3 or greater, or a copolymer of
. ethylene with a C3 8 alpha-olefin having a density
of 0.94 g/cm or greater, (iv) polymer fraction (i),
, (ii) or (iii) in combination with, or mixtures thereof
alone or in combination with, from 10 to 90 parts,
based on the thermoplastic olefin polymer, of a
homopolymer of propylene having an isotacticity index
of greater than 85~
-3-
1331239
b) from about 1 up to less than 15 parts of a
semi-crystalline, low density, essentially linear
copolymer fraction consisting substantially of units
of the alpha-olefin used to prepare c) or the
alpha-olefin used to prepare c) which is present in
the greatest amount when two alpha-olefins are used,
which polymer is insoluble in xylene a~ room
temperature; and
c) from about 10 to less than 39 parts of an
amorphous copolymer fraction of an alpha-olefin having ;
the above formula and propylene, with or without 1 to
10~ of a diene or 1 to 20~ of a different alpha-olefin
termonomer having the above formula, which copolymer
contains from about 30 to about 80 weight ~ alpha-
olefin, e~cluding the alpha-olefin present, if any, as
a termonomer, and is soluble in ~ylene at room
temperature,
having a fle~ural modulus lower than 1000 MPa to 150 MPa,
tensile strength greater than 7 MPa, impact strength such
20 that it breaks with a ductile impact failure at -18C and
an elongation at break over 200~i, wherein the total of
components a), b) and c) is 100 parts.
This invention further provides a method of producing
such thermoplastic olefin polymers by sequential
25 polymerization in at least two stages in a reactor or two -
or more reactors, one or more of which may be gas phase
reactor, using certain catalysts supported on an activated
m magnesium dichloride.
Unless otherwise indicated, all parts and percentages
30 set forth herein are by weight.
Component a) is preferably present in an amount from
65 to about 75 parts.
Component a) (i) is typically a copolymer of propylene
and at least one alpha-olefin having the formula set forth
_4_
133123q
herein above, such as propylene/ethylene, propylene/
butene-l and propylene/4-methyl-pentene-1, or a terpolymer
of propylene and two different alpha-o~efins, such as
propylene/ethylene/butene-l, propylene/butene-1~4-methyl-
pentene-l and propylene/ethylene/4-methylpentene-1.
The crystalline propylene copolymer of component a) ,
(i) preferably contains from 90 to 98 wt. % propylene, most
preferably from 95 to 98 wt. % propylene.
The preferred isotacticity inde~ of component a) (i)
and (ii) is greater than ~5 with the most preferred being
greater than 90.
Typically when component a) (iii) is a copolymer of
ethylene with a C3 8 alpha-olefin, the alpha-olefin is
present in an amount from about 1 to 10%. Suitable
ethylene copolymers useful as component a) (iii) include
ethylene/butene-l, ethylene/hexene-l and ethylene/4-
methyl-l-pentene.
Preferably component a) is a propylene/ethylene
copolymer, propylene/butene-l copolymer or propylene/
eth~lene/butene-l terpolymer.
When component a) (i), (ii) or (iii) or mixtures
thereof are combined witb a homopolymer of propylene, it is
preferably present in an amount from 30 to 70 parts, most
preferably 40 to 60 parts.
Component b) is preferably present in an amount from
about 3 to less than 15, most preferably from about 5 to
less than 10.
Component c) is preferably present in an amount from
about 10 to less than 30, most preferably from about 20 to
less than 30.
The alpha-olefin in the copolymer of component c) is
preferably present in an amount from about 40 to about 75
wt. ~. ~hen component c) is a terpolymer, the alpha-olefin
employed as a termonomer is preferably present in an amount
from about 3 to about 10 wt. %.
1 33 1 239
Typical dienes useful in the preparation of component
c) are 1,4-hexadiene, 1,5-hexadiene, dicyclopentadiene,
ethylidene norbornene, l,6-octadiene and vinyl norbornene.
Ethylidene norbornene is preferred.
Component c) is preferably an amorphous ethylene/pro-
pylene copolymer, ethylene/propylene~diene monomer
terpolymer or ethylene/propylene~butene-l terpolymer.
Suitable alpha-olefins useful in the preparation of
the various components of the thermoplastic olefin polymers
of this invention include ethylene, butene-l, pentene-1,
4-methylpentene-1, hexene-l and octene-l. Ethylene and
butene-l are preferred.
The resultant thermoplastic olefin polymer has a high
bulk density and is in the form of free flowing spherical
particles having an average diameter from 250 and 7000
microns, preferably from 500 to 7000 microns. Hence,
post-polymerization granulation or grinding is not required
before the polymer can be further processed, converted or
fabricated. The flowability of the polymer particles at
70C is lower than 30 seconds and the bulk density
(compacted) is greater than 0.4 g/cc, preferably greater
than 0.4 to about 0.6 g/cc.
The total content of the polymerized alpha-olefin in
the thermoplastic olefin polymer of this invention,
excluding the alpha-olefin present, if any, as a termonomer
when component c) is a terpolymer, is from 10 to 30,
preferably from 15 and 25% by weight.
The molecular weight of the various components
(determined by measuring intrinsic viscosity in
tetrahydronaphthalene at 135C) varies depending on the
nature of the components and the melt index of the final
product. Generally it is within the following preferred
limits: preferably from 0.5 to about 3 dl/g for component
a) and from 1 to about 3 dl/g for components b) and c).
-6-
1 33 1 239
The thermoplastic olefin polymers of the present
invention have one major melting peak determined by DSC at
higher than 115C, preferably higher than 135C, most
preferably higher than 140C; fla~ural modulus lower than
1000 MPa to 150 MPa, preferably from 150 to 700 MPa, most
preferably from 500 to 700 MPa; elongation at break over
200%, preferably over 500%; tensile at break greater than 7
MPa, preferably greater than 10 MPa, most preferably
greater than 13 MPa; and an impact strength such that it
preferably breaks with a ductile impact failure at -29~C.
The polymers of this invention can be used to
manufacture parts, components and materials useful in the
automotive industry, such as automotive interior trim and
bumpers, and in the industrial consumer market, including
the medical, furniture, appliance, building/construction
and recreational/sports industries.
The compositions are prepared by a polymerization
process includinq at least two stages. In the first stage
the relevant monomers or monomers are polymerized to form
component a), and in the following stages the relevant
monomers are polymerized to form components b) and c).
The polymerization reactions can be done in liquid or
gas phase processes, or in a combination of liquid and gas
phase processes using separate reactors, all of which can
be done either by batch or continuously.
The preferred method of preparing the thermoplastic
olefin polymer of this invention is a two stage process
comprising the polymerization of component a) in liquid
phase in the presence of a liquid monomer, and the
polymerization of component b) and c) in gas phase.
The polymerization reactions are carried out in an
inert atmosphere in the presence of an inert hydrocarbon
solvent or of a liquid or gaseous monomer.
Hydrogen can be added as needed as a chain transfer
agent for control of the molecular weight.
1 33 1 23~
The typical reàction temperature used in the
polymerization of component a) and in the polymerization of
components b) and c) ma~ be the same or diferent~
Generally the reaction temperature employed for the
polymeri~ation of component a) is from about 40C to about
90OC, preferably from about 50C to about 80C. Components
b) and c) are typically polymerized at a temperature from
about 50C to about 80C, preferably about 65C to 80OC.
The reactions can be conducted at a pressure from
about atmospheric to about 1000 psi, preferably from about
150 to 600 psi in liquid phase polymerization and from
atmospheric to 30 atmospheres, preerably from 5 to 30
atmospheres, in gas phase polymerization. Typical
residence times are from about 30 minutes to about 8 hours.
Suitable inert hydrocarbons solvents include saturated
hydrocarbons such as propane, butane, he~ane and heptane.
The catalyst system used in the polymerization
comprises the reaction product of 1) a solid catalyst
component containing a titanium compound and an
electron-donor compound supported on activated magnesium
dichloride, 2) a trialkylaluminum compound as activator and
3) an electron-donor compound.
Suitable titanium compound include those with at least
one Ti-halogen bond, such as halides and halogen
alcoholates of titanium.
In order to obtain the thermoplastic olefin polymers
of this invention in the form of flowable spherical
particles having a high bulk density, it is essential that
the solid catalyst component have a) a surface area smaller
than 100 m2/g, preferably between 50 and 80 m2/g, b) a
, porosity from 0.25 to 0.4 cc/g. and c) an X-ray spectrum,
where the magnesium chloride refections appear, by the
presence of a halo between the angles 2 ~5~of 33.5 and 35
and by the absence of the reflection at 2 ~ of 14.95.
The symbol ~ ~ Bragg angle.
--8--
.
1 33 1 23q
The solid catalyst component is prepared by orming an
adduct of magnesium dichloride and an alcohol, such as
ethanol, propanol, butanol and 2-ethylhexanol, containing
generally 3 moles of alcohol per mole of MgC12,
S emulsiEying the adduct, cooling the emulsion quickly to
cause the adduct to solidify into spherical particles, and
partially dealcoholating th~ particulate adduct by
gradually increasing the temperature from 50C to 100C for
a period of time sufficient to reduce the alcohol content
from 3 moles to 1-1.5 moles per mole of MgC12. The
partially dealcoholated adduct is then suspended TiC14 at
OoC, such that the concentration of adduct to TiC14 is
40-50 9~1 TiC14. The mixture is then heated to a
temperature of 80C to 135C for a period of about 1-2 hr.
lS When the temperature reaches 40C, sufficient electron
donor is added so that the molar ratio of Mg to electron
donor is 8. When the heat treatment period has ended, the
e~cess hot TiC14 is separated by filtration or
sedimentation, and the treatment with TiClq is repeated
one or more times. The solid is then washed with a
suitable inert hydrocarbon compound and dried.
The solid catalyst component typically has the
following characteristics:
surface area: less than 100 m2/g, preferably
between 50 and 80 m2/g
porosity: 0.25 - 0.4 cc/g
pore volume
distribution: 50% of the pores have a radius
greater than 100 angstroms.
X-ray spectrum: where the Mg chloride refections
appear, showing a halo with maximum
intensity between angles of 2 ~ of
33.5 and 3S, and where the
reflection at 2 1~'of 14.95 is
absent. I-
_g _
` ` 1 33 1 239
Suitable electron-donor compounds for use in preparing
the solid catalyst component include alkyl, cycloalkyl or
aryl phthalates, such as diisobutylphthalate,
di-n-butylphthalate and di-n-octylphthalate.
~le~ane and heptane are typical hydrocarbon compounds
used to wash the solid catalyst component.
The catalyst is obtained by mi~ing the solid catalyst
component with a trialkyl aluminum compound, preferably
triethyl aluminum and triisobutyl aluminum, and an
1~ electron-donor compound.
Various electron donor compunds are known in the art.
The preferred electron donor compounds are those silane
compounds having the formula R'R''Si~OR)z where R' and R"
may be the same or different and are alkyl, cycloalkyl, or
1-18 carbon aryl radicals, and R is a 1-4 carbon alkyl
radical.
Typical silane compounds which may be used include
diphenyldimetho~ysilane, dicyclohe~yldimetho2ysilane,
methyl-t-butyldimethoxysilane, diisopropyldimethoxysilane
and phenyltrimethoxysilane.
The Al/Ti ratio is typically between 10 and 200 and
the Al/silane ratio between 2 and 100, preferably 5 and 50.
The catalysts may be precontacted with small
quantities of olefin monomer (prepolymerization),
maintaining the catalyst in suspension in a hydrocarbon
solvent and polymerizing at a temperature from room
temperature to 60C for a time suf f icient to produce a
quantity of polymer from 0.5 to 3 times the weight of the
catalyst.
This prepolymerization also can be done in liquid or
gaseous monomer to produce, in this case, a quantity of
polymer up to 1000 times the catalyst weight.
The content and amount of catalyst residue in the
thermoplastic olefin polymers of this invention is
'
--10--
" I 33 1 23q
sufficiently small so as to make the removal of catalyst
residue, typically referred to as deashing, unnecessary.
Unless otherwise specified, the following analytical
methods were used to characterize the supported catalyst
component, the thermoplastic olefin polymer samples of this
invention and comparative samples.
Proeertie$ MethQd
Melt Flow Inde~, g/10 min. ASTM-D 1238
Ethylene, wt % Spectroscopy I.R.
10 Intrinsic viscosity Determined in tetrahydro-
- naphthalene at 135C
Xylene solubles, wt % See description below.
Fle~ural modulus ASTM-D 790
Notched IZOD impact ASTM-D 256
VICAT (1 ~g) softening pt. ASTM-D 1525
Tensile Strength ASTM-D 638
~ Elongation at break ASTM-D 633
; Surface area B. E. T.
Porosity B. E. T.
20 Bulk density DIN-53194
Fluidity The time that it takes 100 g of
polymer to f low through a
funnel with an output opening
of 1.27 cm and walls inclined
at an angle of 20~ with respect
to the vertical.
Granulometry ASTM-D 1921-63
The physical tests are conducted on pelletized samples ,---
of this invention, which were stabilized with 500 ppm of
30 calcium stearate, 500 ppm of paraffinic oil, 350 ppm of
tetrakis(2,4-di-t-butylphenyl) 9,4'-biphenylylenediphos-
phonite, 500 ppm tetrakis[methylene(3,5-di-t-butyl-4-
hydro~yhydrocinnamate~ methane and 250 ppm octadecyl
--11--
1 33 1 239
3,5-di-t-but~1-4-hydro~yhydrocinnamate. The samples were
molded using a Negri & ~ossi 90 injection press with a melt
~emperature of 190C, a mold temperature of 60C, an
injection time 20 seconds and a cooling time of 25 seconds.
S The percent by weight of components b) and c) is
calculated by determining the weight of the propylene and
alpha-olefin (and diene or different alpha-olefin termonomer
if used) misture used in the second stage and comparing it
to the weight of the final product.
The weight percent of component a) is determined by
subtracting the weight percents of component b) and c) from
100 .
The weight percent of component c) is determined by
subtracting.the weight fraction of component a) soluble in
xylene multiplied by the weight percent of component a) from
the weight percent of the final product soluble in xylene.
The weight percent of component b) is determined by
subtracting ~he weight percent of component a) and of
component c) from 100.
The percent by weight of the alpha-olefin contained in
the copolymer of component c) which is soluble in xylene is
calculated using the following formula:
CF ~ C . Q
Alpha-olefin wt. ~ in component c) ~
y
where CF is the wt. % of alpha-olefin in the soluble of
xylene in the final product; Cw is the wt. % alpha-olefin in
the soluble in xylene of component a); Q is the wt. %
soluble in ~ylene of component a) multiplied by the weight
, 30 fraction of component a) and divided by the wt. fraction of
the final product soluble in xylene; and Y is the wt. % of
component c) multiplied by the sum of the wt. % of component
b) and component c) and then divided by one hundred.
-12-
~`l `.~`
l~ ~
1 33 1 239
The weight percent of soluble in xylene at room
temperature is determined by dissolving 2.5 9 of the pol~mer
in 250 ml of xylene in a vessel equipped with a stirrer
which is heated at 135C with agitation for 20 minutes. The
solution is cooled to 25C while continuing the agitation,
and then let to stand without agitation for 30 minutes so
that the solids can settle. The solids are filtered with
~ilter paper, the remaining solution is evaporated by
treating it with a nitrogen stream, and the solid residue is
vacuum dried at 80OC until a constant weight is reached.
The percent by weight of polymer insoluble in xylene at room
temperature is the isotactic index of the polymer. The
value obtained in this manner corresponds substantially to
- the isotactic inde~ determined via extraction with boiling
n-heptane, which by definition constitutes the isotactic
inde~ of the polymer.
Examples illustrative of the thermoplastic olefin
polymer o this invention, the physical properties thereof
and the method of preparing same are set forth ~elow.
~; 20 A) Preparation of MgC12/Alcohol Adduct
Under an inert atmosphere, 28.4 g anhydrous MgC12,
49.5 9 of an anhydrous ethanol, 100 ml of ROL O~/30 vaseline
oil~ 100 ml of silicone oil having a viscosity of 350 cs are
introduced into a reaction vessel equipped with a stirrer
and heated at 120C with an oil bath and stirred until the
Mg~12 is dissolved. The hot reaction mi~ture was then
transferred under inert atmosphere to a 1500 ml vessel
equipped with an Ultra Turra ~ -45 N stirrer and a heating
jacket and containing 150 ml of vaseline oil and 150 ml of
silicone oil. The temperature was maintained at 120C with
stirring for 3 minutes at 3,000 rpm. The mixture was then
discharged into a 2 liter vessel equipped with a stirrer
containing 1,000 ml of anhydrous n-heptane cooled at 0C
with a dry ice/isopar bath and stirred at a rip speed of 6
r~ ~-n~k -13-
1331239
m~sec for about 20 minutes while maintaining the temperature
at 0C~ The adduct particles thus formed were recovered by
filtering, were washed 3 times at room temperature with 500
ml aliquots of anhydrous he~ane and gradually heated by
increasing the temperature from 50C to 100C under nitrogen
~or a period of time sufficient to reduce the alcohol
content from 3 moles to 1.5 moles per mole of MgC12. The
adduct had a surface area of 9.1 m /g and a bulk density
of 0.564 g/cc.
B) Solid Catalyst Component Preparation
The adduct (25 g) was transferred under nitrogen into a
reaction vessel aquipped with a stirrer and containing 625
ml of TiC14 at 0C under agitation. It was then heated to
100C in 1 hr. When the temperature reached 40C,
diisobutylphthalate was added in an amount such that the
molar ratio of Mg to diisobutylphthalate is 8. The contents
of the vessel were heated at 100C for 2 hours with
agitation, the agitation was stopped and the solids were
allowed to settle. The hot liquid was removed ~y siphon.
550 ml of TiC14 was added to the solids in the ~essel and
; the mi~ture heated at 120C for 1 hr. with agitation. The
- agitation was stopped and the solids were allowed to
settle. The hot liquid was then removed by siphon. The
- solids were washed 6 Limes at 60C with 200 ml aliquots of
anhydrous hexane, and then 3 times at room temperature. The
solids, after be~ng vacuum dried, had a porosity of 0.261
cc~g, a surface area of 66.5 m2/g and a bulk density of
0.44 g~cc.
E~amples 1-4
These examples illustrate the thermoplastic olefin
~' polymers of this invention and a method for preparing the
- polymers.
The preparations for polymerization and the
polymerization runs were conducted under nitrogen in a
-14-
1331239
series of reactors with a means for transferring the product
produced in the immediately preceding reactor to the next
reactor. A11 temperatures, pressures and concentrations of
olefin monomers and hydrogen, when present, were constant
S unless otherwise indicated. The hydrogen is analyzed
continuously in gas phase and fed in order to maintain
constant the desired concentration of hydrogen.
In the following e~amples a mi~ture of TEAL activator
and dicyclohexyldimetho~ysilane electron donor in an amount
such that the weight ratio of TEAL:silane was about 4.0 in
e~amples 1, 2 and 3 and about 4.8 in e~ample 4, was
contacted with an amount of the solid catalyst component, as
described above, such thàt the molar ratio of TEAL:Ti was
191, 132, l~q and 142 in e~amples 1, 2, 3 and 4,
respectively, in a reactor at 15C for about 15 minutes.
The catalyst was then transferred to another reactor
containing an e~cess of liquid propylene and polymerized for
3 minutes at 20OC.
In the first stage, the prepolymer was transferred to
20 another reactor for a liquid phase polymerization of the '~
relevant monomer(s) to form a component a). The component
~; a) thus formed was then transferred to another reactor in
e~amples 1, 3 and 4 for a liquid phase polymerization of the
relevant monomer(s) to increase the amount of component a)
formed in the first polymerization reactor or to prepare a
different component a), and to a second stage reactor in the
~ case of example 2 as described below.
; In the second stage, the component a) product of the
immediately preceding reactor was first transferred into a
flash pipe and any unreacted monomers were degassed at
essentially atmospheric pressure and then fed to another
reactor for a gas phase polymerization of the relevant
monomers to form components b) and c). The resultant
product was then transferred to another reactor for an
15-
1 33 1 239
additional gas phase polymerization of the relevant monomers
in order to increase the amount of components b) and c) in
the product.
At the end of the second staqe polymerization reaction
the powder is discharged into a steaming apparatus and the
unreacted monomers and volatiles are removed by treating
with steam at 105C at atmospheric pressure for about 10
minutes and then dried.
The ingredients and relative operating conditions are
set forth in Table lA and the tests results are set forth in
Table lB.
``` 1 3~ 1 239
Table lA
_____________________________________________________________
E~amples 1 2 3 4
_____________________________________________________________
FIRST PHASE
First reactor
S Temperature, C 65 65 60 60
Pressure, atm 33 33 33 33
Time, min. 56 52 50 71
H2 in gas phase, ppm 18002400 3100 1400
C2 in gas phase, g/hr ` 24003500 2066 3800
- 10 C3 in liquid phase, 490540 550 500
Kg/hr
Isotactic index, % wt. - 92
Ethylene, % wt - 1.9
Ethylene in sol.xyl., - 7.9
% wt
Second Reactor
: Temperature, C 54 - 60 70
. Pressure, atm 33 - 33 33
Time, min. 39 - 39 49
~:~ 20 H2 in gas phase, ppm 1850 - 2896 6500
C2 in gas phase, g~hr 750 - 633
C3 in liquid phase, 190 - 150 195
Kg/hr
Isotactic index, ~ wt. 91.5 - 91 92.5
: Z5 Ethylene, % wt2.2 - 2.0 1.6
Ethylene in sol.xyl., 8.4 - 8.1 7.5
~ wt
: -17-
1331239
Table lA (Cont'd)
_____________________________________________________________
E~amples 1 2 3 4
_____________________________________________________________
SECO~D PH~SE
Third Reactor
Temperature, C 75 75 75 75
Pressure, atm 19 14. 14 14
Time, min. 22 24 22 19
H2 in gas phase,6.3 7.2 6.2 8.0
% moles
C2 in gas phase,40.6 39.2 41 36
% moles
C3 in gas phase,46 45.5 g8.5 45
% moles
Fourth Reactor
Temperature, C 75 75 75 75
Pressure, atm 11 11 11 10.7
Time, min. 27 29 26 23
H2 in gas phase,6.2 7.3 6.2 7.0
% moles
C2 in gas phase,40 39.3 41 39.5
% moles
C3 in gas phase,48 46.2 .49 47
% moles
_ _ _ _
:::
,
: -18-
133123~
Table lB
_____________________________________________________________
E~amples 1 2 3
_____________________________________________________________
FINAL PRODUCT
~ield, Kg pol/g cat19.3 12.2 17.5 16.5
Component b~ & c),30.0 25.0 29.0 38.0
% wt
Ethylene, ~ wt 21.0 19.3 22.9 25.3
Intrinsic ~iscosity,1.86 - 1.60
dl~g
Melt flow inde~, 10~0 16.0 20.0 11.0
g/10 min
~ylene sol., % wt25.5 2q.2 25.6 28.2
Component b), % wt7.0 6.8 9.8 14.9
Component c), % wt23.0 18.2 19.2 23.6
C2 in sol.xyl., ss.o 53.7 50.7 4B.8
% wt
C2 in component c),64.9 68.8 64.8 57.0
~: % wt
Melting point (DSC), C 151 152 152 154
~: ` 20 Fle~ural modulus, MPa 560 640 570560
: IZOD impact,-20C, J/m115 80 75 129
Impact failure at -18C ductile ductile ductile ductile
Vicat (1 kg), C 118122 - 115
~; Elong. at break, %~500~500 ~500 >500
Tensile strength, MPa 19.0 17.3 15.5 16.5
_________________________
-19_
`
1 33 1 239
Physical blends of a) a propylene homopolymer with (i)
an ethylene-propylene rubber or (ii) an ethylene-propylene
d;ene monomer rubber and b) a propylene-ethylene copolymer
with (ii) were prepared by mixing the two materials in a
~anbury mixer at a temperature of approx. 205C until a
homogeneous blend was obtain. Such blends are commercially
available.
The formulations and the physical properties are set
forth in Table II below.
TABLE II
Comparative Examples
Ingredients 1 2 3
Propylene homopolymerl 60 60
Propylene-ethylene copolymer2 - - 60
15 Ethylene propylene rubber3 40
Ethylene propylene diene
monomer (EPDM)4 - 40 40
Octadecyl 3,5-di-t-butyl-4-
hydroxyhydrocinnamate 0.1 0.1 0.1
20 MFR, dg/min 7.3 3.0 3.2
Tensile strength, MPa 15.3 13.013.5
Elongation, % 429 443 618
Flexural modulus, MPa 670 700 445
1 MFR of 12 dg~min.
25 2 Random copolymer having a MFR of 12 dg/min and
approx. 2.5% ethylene.
3 77% ethylene, polydispersity 2.8, Mooney Viscosity,
54 (ML 1~4 at 125C).
4 51% ethylene, 2.2% ethylidene norbornene,
polydispersity 3.8, Mooney Viscosity, 46 (ML 1+4 at
125C).
-20-
`` 1 33 1 239
Given the lower melt flow of the commercially available
physical blends set forth in Table II, which typically
translates into better physical properties, one would not
have e~pected the thermoplastic olefin polymers of this
invention with their higher melt flow rates to have such
superior tensile strength, elongation and ductile impact
properties when compared on an essentially equivalent
stiffness (flexural modulus) basis.
Other features, advantages and embodiments of the
invantion disclosed herein will be readily apparent to those
e~ercising ordinary skill after reading the foregoing
disclosures. In this regard, while speci~ic embodiments of
the invention have been describied in considerable detail,
variations and modifications of these embodiments can be
e~fected without departing from the spirit and scope of the
invention as described and claimed.
