Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~5~'~3
1 This invention relates to a process for
producing a copolymer having a high degree of randomness
by random-copolymerizing ethylene with an ~-olefin or
with an a-olefin and a non-conjugated diene with a
highly active Ziegler catalyst.
Catalysts for polymeriza~ion o~ olefins have
been greatly advanced since 7,iegler catalysts were
discovered, and the finding of highly active cat~lysts
have enabled the indus~rialization of the production
processes of polyethylene or polypropylene requiring
no catalyst-removal step.
On the other hand, ethylene-~-olefin
copolymer rubber, in particular, ethylene-propylene
copolymer rubber is produced using a vanadium compound~
organic aluminum compound as a catalyst.
Said catalyst has a high random-polymeriz-
ability, but reduces in catalyst activity at high
temperatures, resulting in a ~reat reduction in produc-
tivity. Therefore, the polymerization should be
effected at a relatively low temperature, and a very
high energy is necessary ~or removing the polymerization
reaction haat. Furthermore, when metallic vanadium
remains în the rubber, the rubber becomes liable to be
deteriorated, and therefore, sufficient removal of the
catalyst is required.
~P$
: , . .
.
.
. `
~ . . .
. ., .-
l Under such technical circumstances, a patent
has been applied for on copolymerization of ethylene
and an ~-olefin at a relatively high temperature under
high activity using a ti-tanium compound (Japanese Patent
Application Kokai (Laid~Open) No. 104,6~7/78 and U.S.P.
4,302,565. The former patent application aims at
modifying a polypropylene resin, and the latter at
modifying a polyethylene resin, but none of them aim
at obtaining a rubber-like random copolymer.
The production of a copolymer having a high
degreee of randomness by copolymerizing ethylene with
an ~-olefin under a high activity by use of a titanium
compound as a catalyst is very dif~icult, and can by
no means be predicted from techniques for the produc-
tion of resins such as polyethylene, polypropylene and
the like.
The present inventors have conducted extensive
research on a process for pxoducing a rubber-like olefin
copolymer having a high degree of randomness using a
highly active solid catalyst. As a result, it has been
ound that by using catalyst comprising a finely
divided substance containing Ti, Mg and P and an
organic aluminum compound or an alcohol-modified
organic aluminum compound, there can be obtained an
ethylene-~-olefin copolymer rubber which has a high
activity and a very high degree of randomness.
According to this invention, there is provided
: a process for producing a rubber-like olefin copolymer
-- 2 --
~ . ,
25711-375
having a high degree of randomness, whlch comprises copolymerizing
ethylene with from 30 to 70% o~ an ~-olefin or with an ~-olefin
and a non-conjugated diene us:Lng a cataly~t comprising:
(A) a powder obkalned by con~aini.ny
(1) a homogeneous solution containing a chlorlne-
containing magnesium compound and a phosphate or a phosphorus
compound of the formula O~P(OH)j (OR3)k R4l wherein Rl, R2, R and
R are independently hydrocarbon groups having 1 to 20 carbon
atoms; ; is 1 or 2, k and l are independently 0, 1 or 2 where j
iO k ~ l = 3 with
(2) a titanium compound preferably a powder deposited
from a homogeneous solution obtained by con~acting (1) the above-
mentioned homogeneous solution with (Z) the above titanium
compound, and
(B3 an organlc aluminum compound or an alcohol-modified
organic aluminum compound.
First of all, the catalyst component ~A) used in ~his
invention is explained below.
The chlorine-containing magnesium compound includes
specifically MgC12 and Mg(OH)Cl. MgC'12 is preferably anhydrous,
and there may also be used those which have been subjected to
modifi~ation treatment such as grinding by means o~ the ball mill,
grinding by means of a vibration mill, aomplexation treatment or
the like. Mg(OH)Cl can be obtained by heating MgCl2.6H20 at a
high temperakure.
As the phosphate compound there may be used at least one
of the compounds represented by the general ~ormulas, o~P(OR2)3
- 3 -
- . ,:
.
. ~.. : .:
..
,~
.. . :
~ 25711-375
and o=P(oH)j(oR3)k ~he~ei.n R2 and ~3 are independently hydrocarbon
groups having 1 to 20 carbon atoms; and j is 1 or ~ and k is 1 or
2, where j ~ k is 3. Preferred are compounds represented by the
formula, o=P(oH)j(oR3)k, and more preferably are those compounds
~hat j is 1, namely monohydroxy compounds.
Specific examples of these compounds include trimekhyl
phosphate, triethyl phosphate, tri-n-propyl phosphate, tri-iso-
propyl phosphate, ~ri-n-butyl phosphate, tri-i-bu~yl phosphate,
tri-t-butyl phosphate, tri-n-hexyl phosphate, tri-n-octyl
phosphate, ~ri-2-ethylhexyl phosphate, trilauryl phosphate,
triacetyl phosphate, tristearyl phospha~e, trioleyl phosphate,
triphenyl phosphate, tritolyl phosphate, trixylyl phosphate,
octyldiphenyl phosphate, tolyldiphenyl phosphate, xylydiphenyl
phosphate, monohydroxydiethoxyphosphine oxide, monohydroxydipro-
poxyphosphine oxide, monohydroxydi-n-butoxyphosphine oxide, mono-
hydroxydi-sec-butoxyphosphine oxide, monohydroxydi-t-butoxy-
phosphine oxide, monohydroxydi-n-hexyloxyphosphine oxide, mono-
hydroxydi-n-octyloxyphosphine oxide, monohydroxydi-2-ethylhexyl-
oxyphosphine oxide, monohydroxydi-n-decyloxyphosphine oxide, mono-
hydroxydi-n-dodecylphosphine oxide, monohydroxy(n-butyl)-n-butoxy-
phosphine oxide, monohydroxy(n-hexyl)-n-hexyloxyphosphine oxide,
monohydroxy(n-octyl)-n-octyloxyphosphine oxide, monohydroxy(2-
ethylhexyl)-2-ethylhexyloxyphosphine oxide, monohydroxydib-ltyl
phosphine oxide monohydroxydi-2-ethylhexylphosphine oxide and the
like.
~, i
, ' '
, ;
~ss~ o~
25711-375
The homogeneous solution (1) containing a chlorine
containing magnesium compound and the phosphate or phosphorus
compound of compound (A) (hereinafter referred to a~ the
phosphorus compound) may be prepared either in a large amount of
the phosphorus compound or in the presence of a hydrocarbon or
halogenated hydrocarbon solvent. When the phosphorus compound is
solid or waxy, the preparation should be carried out in the
presence of such a solvent.
Specific examples of these solvents include n-pentane,
n-hexane, n-heptane, n-octane, isooctane, n-decane, petroleum
ether, ligroin, k~rosine, benzene, toluene, xylene, cyclohexane,
methylcyclohexane,
4a -
$i
.. . ...
. . . .
.
, .. .
:
~2S~ 3
l methylene chloride, ethyl chloride, ethyl bromide,
1,2-dichloroethane, l,l-dichloroethane, n-butyl
chloride, n-octyl chloride, monochlorocyclohexane,
monochlorobenzene, o-dichlorobenzene, and the like.
However, any other solvents may be used. These solvents
may be used alone or in admixture of two or more.
As to the chlorine-containing magnesium
compound, a homogeneous solution of the chlorine-
containing magnesium compound can be obtained by add-
ing to the chlorine-containing magnesium compound one
of the above-mentioned phosphorus compounds in an amount
of 1 to 30 moles, preferably 2 to 10 moles, per mole
of the chlorine-containing magnesium compound in the
presence or absence of the solvent mentioned above,
and stirring the resulting mixture at a temperature of
~30C to 120C, preferably 0C to 60C, for 2 minutes
to 20 hours, preferably 5 minutes to 5 hours.
In addition, titanium tetrachloride is added
to the aforesaid solution containing the chlorine-
containing magnesi~m compound and the phosphoruscompound, in such a proportion that the atomic ratio
Ti/Mg is prefera~ly from 0.2 to 2.0, more preferably
from 0.1 to 1.5.
The solution containing the chlorine-
cQntain;ng magnesium compound and the phosphoruscompoun~ may be prepared in a large amount of titanium
tetrachloride. That is to say, a homogeneous solution
` can ~e obtained by adding the chlorine-containing
_ S_
-,:
, .,
:, . ...
~55~
1 magnesium compound and the phosphorus compound to a
large excess of titanium tetrachloride. However, in
this case, the dissolution becomes difficult if a
hydrocarbon or a halogenated hydrocarbon coeY~iStS.
Therefore, it is desirable to prevent these solvents
from coexisting.
Although the method of preparing a liquid
containing a chlorine~containing magnesium compound,
a phosphorus compound, and titanium tetrachloride is
not critical, the following processes may be used:
(1) a process comprising adding 1 to 30 moles of
the phosphorus compound to 1 mole of the chlorine-
containiny magnesium compound in the presence or absence
of a hydrocarbon or a halogenated hydrocarbon to obtain
a solution, and adding thereto a 0.2 to 2 moles of
titanium tetrachloride,
(2) a process comprising grinding together 1 mole
of the chlorine-containing magnesium compound and 0.2
to 2 moles of titanium tetrachlc ide by means of a
vibration mill, a ball mill or the like to obtain a
ground mixture, adding thereto 1 to 3Q moles of the
phosphorus compound to obtain a solution, and if
necessary, diluting the solution with one of the abovve-
mentioned solvents,
~3~ a process comprising wet-grinding together
1 mole of the chlorine-containing magnesium compound,
Q~2 to 2 moles of titanium tetrachloride, 1 to 3Q moles
of the phosphorus compound, and if necessary, one of
i'G
. .
: ~ ' '' .
25711-37
1 the above-mentioned solvents by means of a vibration
mill, a ball mill or the like -to obtain a solution, and
(4) a process comprising adding 5 to 1, ooa moles
of titanium tetrachloride to 1 mole of the chlorine
s containin~ magnesium compound to obtain a suspension,
adding thereto 2 to 10 moles of the phosphorus compound
to dissolve them in the large amount of titanium
tetrachloride.
The titanium compound (2) in this invention
is represented by the general formula, Ti(OR)pX3 p or
Ti(OR)qX4 q, wherein R is a hydrocarbon group, X is a
halogen, p is 0, 1, 2 or 3, q is 0 or an integer of
1 to 4, and includes, for example, TiC14, TiBr4, TiI4,
Ti(OC2H5)C13, Ti(OC6H5~C13, Ti(OC2H5~2C12, Ti(OC6H5)C12,
Ti (OC2H5)3Cl, Ti(OC2H~)4, Ti(OC6H13)4, TiC13,
Ti(oC2H5)3~ Ti(On C4Hg)3, ( 6 5)4
Among them, titanium trichloride (TiC13) and
titanium tetrachloride (TiC14~ are particularly
preferred.
When titanium trichloride is used as the
titanium compound (2~, it is preferable to from a
homogeneous solution containing titanium trichloride.
In the preparation of such a solution, titanium
trichloride can be dissolved by use o~ an ether such
as diethyl ether, di-n-propyl ether, di-n-butyl ether,
bis(.l-octenyll ether, anisole, diphenyl ether or the
like or the above-mentioned phosphorus compound having
a P=o bond~ In this case, the amount of the ether
7 _
,
~ 3
1 or the phosphorus compound used is such that in ~erms of
the molar ratio to the titanium compound, the ether or
the phosphorus compound/Ti ranges f~om 1.5 to 20, preEera~ly
from 2.0 to 10.
As the titanium trichloride, there may be used
homogeneous solutions prepared by the processes described in
U.S.P. 4,377,671; 4,366,297; and 4,356,160.
The mixing amounts of the homogeneous solution
containing the titanium compound and the homogeneous solu-
tion containing the chlorine-containing magnesium compound
are such that the molar ratio of Mg to Ti is 0.1 - 10,000,
preferably 1 - 1,000.
The temperature at which the powder as the
catalyst component (A) is deposited is 0 to 200C,
preferably 20~ to 150~C.
As a depositing agent, there may be used organic
aluminum compounds or halogen-containing compounds of
titanium, vanadium, boron, sulfur, tin, germanium and the
like, such as TiCl~, TiC13(OC2H5), TiC13(On C4Hg),
(C2H5)C12~ A12(C2H5)3C13 and the like.
Preferably used are titanium halides and organic
aluminum compounds particularly preferably TiC14,
Al(C2H5)C12 and A12(C2H5)3 3
The amount of the depositing agent used is 1.0
to 200 moles, preferably 1.0 to 100 moles, per mole of the
ether and/or the phosphorus compound contained in the
homogeneous solution containing the titanium compound and
the chlorine-containing magnesium compound.
l The ~eposition treatment o~ the powder as the
catalyst component (A) may be carried out in the presence
of an inorganic solid carrier. The inoryanic solid carrier
is an inorganic solid having a surface area o 50 m2/g or
more, preferably 60 m2/g or more, an average particle
diameter of 200 ~ or less, preferably 150 ~ or less, and
an average pore diameter of 50 A or more, preferably 60 A
or more, and examples thereof are silica, alumina, zeolite,
magnesia, etc. The amount of said inorganic solid carrier
used is 0.5 to 200 g, preferably 1 to 100 g, per gram of
the chlorine-containing magnesium used.
The powder as the catalyst component (A) pre-
pared in the manner described above is preferably washed
sufficiently with pentane, hexane, heptane, benzene, toluene
or the like, and then used as a catalyst for polymerization
in suspension in such a solvent.
When the infrared absorption spectrum of the
aforesaid sufficiently washed powder was measured by the
KBr tablet method, the characteristic absorption due to
the phosphorus compound was observed.
The amount of the phosphorus compound present in
said powder can be determined by pouring a suspension of
said powder in any of the above-mentioned solvents into
water to decompose the catalyst, and then measuring the
gas chromatogram of the solvent layer. The titanium
content was determined by a colorimetric method, and the
magnesium content by an atomic absorption method.
.. The Mg/Ti ratio of said powder ranges from 0.5
~ q
~ - ~,0 --
1 to 100 (molar ratio), preferably from 0.5 to 50 (molar
ratio), and the phosphorus compound/Ti ratio ranges ~rom
0.01 to 2 (molar ratio), preferabl~ from 0.05 to 2 (molar
ratio).
Next, the catalyst component (B) is explained
below.
The catalyst component (B) is an organic aluminum
compound or an alcohol-modified organic aluminum compound.
As the catalyst component (B), preferred are organic
aluminum compounds represented by the general ~ormula,
AlRrX3 r' wherein R is a hydrocarbon residue having 1 to
12 carbon atoms, X is a halogen atom, and r is a ~7alue of
1 to 3, and alcohol-modified organic aluminum compounds
obtained by contacting ~lRrX3 r with an alcohol having 1
to 2 carbon atoms.
The organic aluminum compound includes, for
example, trialkylaluminums such as trimethylaluminum,
t~iethlaluminum, tri-n-butylaluminum, triisobutylaluminum,
tri-n-hexylaluminum, tri~n-octylaluminum, tri-n-dodecyl-
aluminum and the like; dialkylaluminum halides such asdiethylaluminum chloride, diethylaluminum bromide, di-n-
butylaluminum chloride, di-n-octylaluminum chloride, di-
n-octylaluminum bromide and the like; alkylaluminum
sesquihalides such as ethylaluminum sesquichloride,
isobutylaluminum sesquichloride and the like; and mono-
alkylaluminum dihalides such as ethylalurninum dichloride,
n-butylaluminum dichloride, ethylaluminum dibromide and
`::
~o
.
.
~55~3
1 the like. Among them, trialkylaluminums are ~referred.
The alcohol as a rnodifier used in the alcohol-
modified organic aluminum compound as -the ca~alyst
component (B) includes alcohols having 1 to 20 carbon
atoms such as methyl alcohol, ethyl alcohol, prop~l
alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol,
2-ethylhexyl alcohol, nonyl alcohol, dodecvl alcohol,
nonylphenyl alcohol, stearyl alcohol and the like.
The aleohol-modified organie aluminum eompound
as the eatalyst eomponent (B) ean be prepared by contaet-
ing an organoaluminum compound represented by the
formula, AlRrX3 r' with an aleohol.
In the preparation of the aleohol-modified
organie aluminum eompound, the same solvents as those
used for preparing the eatalyst eomponent (A) (described
above) may be used.
The modifieation of the organie aluminum
compound is generally carried out at a temperature
of -10C to 50C, preferably 0C to 30C. The modifi-
eation time is 0.1 to 2.0 hours, preferably 0.5 to1.0 hour.
The amount of the aleohol used as the
modifier is 0.05 to 0.5 mole, preferably 0.1 to a . 3
mole, per mole of the organie aluminum eompound. The
ratio between the eatalyst eomponent (A) and the
eatalyst eomponent (B) is sueh that the amount of the
organie aluminum eompound in the eatalyst eomponent (B)
~`
_ ~ _
~2S~'k3
1 is 1.5 to 200 moles, preferably 2 to 100 moles, per mole
of Ti in the catalyst component (A).
The monomers used in this inven-tion are
ethylene, ~-olefins and non-conjuyated dienes. As the
~-olefins, there may be used, for e~ample, propylene
butene-l, pentene-l, 4-methylpentene-1, hexene-l,
heptene~l, 4-methylhexene-1, octene-l, and the like.
The non-conjugated dienes may be any of the non-
conjugated dienes used for renderlng the copolymer
vulcanizable in this type of copolymerization, and
include, for example, l,4-hexadiene, dicyclopentadiene,
tricyclopentadiene, 5-methyl-2,5-norbornadiene, 5-
ethylidene-2-norbornene, 5-isopropylidene-2-norbornene,
S-isopropenyl-2-norbornene, tetrahydroindene, and the
like. These non-conjugated dienes are added to a
polymerization reactor in the amount necessary for the
iodine value in the copolymer being 2 to 50, preferably
3 to 40. In this case, two or more of the non-
conjugated dienes may be used as a mixture.
The polymerization temperature is usually
10 to 150C, preferably 30 to 120C. The polymeriz-
ation pressure ranges usually from atmospheric pressure
to 100 kg/cm2G.
The copolymerization may be either solution
polymerization or suspension polymerization. That is
to say, the polymerization can be effected by suspension
polymerization using propylene as a medium by suspension
polymerization using a solvent in ~hich the resulting
C _ ,ac~;~ _
5~3
l polymer is slightly soluble, or b~ solution pol~meriz-
ation using a solvent in which the resulting pol~mer
is well soluble.
Specific examples of the polymerization
solvent are as follows: hydrocarbon sol~ents such
as propylene, which is a monomer, hexane, heptane, octane,
kerosine, benzene, toluene, xylene, cyclohe~ane and
the likej and halogenated ~ydrocarbon solvents such as
methylene chloride, monochloroethane, l,l-dichloroethane,
1,2-dichloroethane, 1,2-dichloropropane, monochlorobutane,
monochlorobenzene, and the like.
These solvents may be used in admixture of
two or more in order to control the solubiliky parameter.
The molecular weight of the copolymer can,
if necessary, be controlled by use of hydrogen.
Next, this invention is further explained
below in more detail referring to Examples, which are
not by way of limitation but by way of illustration.
Among the physical properties of the copoly-
mers in the E~amples, Mooney viscosity was determinedby measure.ment under the conditions that the pre~eating
time was l minute, the measurement time was 4 minutes
and the measurement temperature was 100C; propylene
conte~t was determined from lnfrared absorption
spectrum; iodine value was determined b~ titration
method; and heat of fusion of crystal was determined
by means of a differential scanning calorimeter (DSC~.
- lOQ% ~odulus, tensile strength, elonga~ion at break
f~ ~
''
~5~
l and Shore A hardness were determined by measurement
methods according to JIS K6301. Ti-tanium content of
each catalyst was determined by colorimetry, Mg content
is determined by chelatometry, and phosphorus compound
content was determined by colorimetry.
The quantity of heat absorbed determined by
means of DSC indicates quantity of heat absrobed owing
to the melting of crystalline portion in each rubber-
like copolymer. Therefore, that the quantity of heat
absorbed is small indicates that the crystalline
portion content is low. In other words, the degree of
randomness of the copolymer is high.
Examples 1-1 to 1-4
(1) Preparation of catalyst component (Al (solid
complex)
A rotator and 1 g (10.5 mmoles) of anhydrous
magnesium chloride were placed in a 100-ml flask which
had sufficiently been dried and then purged with nitrogen.
Thereto were added the predetermined amount of the
solvent shown in Table 1 whic~ had been dried by use
of molecular sieves and the predetermined amount of the
phosphorus compound shown in Table 1. The resul~ing
mixture was stirred at room temperature for 20 minutes,
upon whîch the magnesium chloride was completely dis-
solved and a colorless, transparent, homogeneoussolution was obtained.
To the homogeneous solution was added 1.16 ml
!
:'
1 (10.5 mmoles) of titanium chloride, and the resulting
mixture was allowed to stand for 30 minutes to o~tain
a yellow, transparent, homogeneous solu-tion. When 12 ml
of titanium tetrachloride was gradually added to this
solution with stirring, yellow fine powder was produced.
After the stirring was continued for 2 hours, a yellow
finely divided solid complex was deposited from the
solution, and the supernatant was removed by iltration.
To the residue was added 80 ml of fresh dried n-
hexane, and the resulting mixture was stirred for 30minutes, whereby the residue was washed. This washing
procedure was repeated 6 times. A yellowish-white
finely divided solid complex was obtained. Normal
hexane was added to this complex to obtain a total volume
of 50 ml of a slurry.
(2) Copolymerization of ethylene and 5-ethylidene-
2-norbornene
A 3-liter separable flask was equipped with
a stirring blade, a three-way cock, a gas-blowing tube,
a thermometer and a dropping funnel for addition of 5-
ethylidene-2-norbornene, and then sufficiently purged
with nitrogen. In this flask was placed 2 liters of
n-~exane which had ~een dried ~y use of molecular
sieves and degassed. Into the flask whose tempera-
ture was controlled to 35C were in ~ oduced for 10minutes, through the gas-blowing tube, dried ethylene
at a rate of 4 liters/min, propylene at a rate of 6
liters/min, and hydrogen at a rate of 0.2 liter/min
;3
1 in the form of a mixed gas, immediately after which 2 ml
of a n-hexane solution of triisobutylaluminum having
a concentration of 1 mole/liter was added. Thereafter,
the slurry in n-hexane of the catalyst component (A)
prepared ln above (1~ was added in an amount or 0.05
mmole in terms of titanium atom, and polymerization was
initiated.
Simultaneously with the initiation of the
polymerization, a mixed solution of 10 ml of 5-ethyl-
idene-2-norbornene and 200 ml of n-hexane was added
dropwise at a rate of 7 ml/min, and polymerization was
effected for 30 minutes. During the polymerization, a
mixed gas of the monomers at the respective flow rates
described above was introduced into the flask. The
polymerization temperature was controlled to 35~C by
external cooling.
During the copolymerization, substantially no
gel was produced. After 30 minutes, the polymerization
was stopped by addition of 20 ml of methanol. A small
amount of an antioxidant was added, after which steam
stripping was carried out to o~tain solid rubber. The
yield, the Mooney viscosity, and the propylene content
of the copolymer were determined. The results are shown
in Table 1.
The raw rubber physical properties of the
copolymer obtained in Example 1 were as follows:
100% Modulus = 7 kg/cm
Tensile strength = 17 kg/cm
Elongation at break = 4,500
Shore A hardness = 32
1 Comparative Fxample 1-1
An attempt was made to prepare a solid
complex by repeating the same procedure as in Example
l 1, except that the tri-n-butyl phosphate [OP(OC4H9)3]
used in Example 1-1 was replaced by tri-n-butyl
S phosphite [P(OC4Hg)3]. However, no solid complex was
deposited. From this Comparative Example, it can be
seen that a O = P bond is needed in the form of a
phosphorus compound.
Comparative Example l-2
An attempt was made to prepare a solid complex
by repeating the same procedure as in Example 1 l, except
that the monochlorobenzene solvent used in Example 1 1
was replaced by n-hexane. ~owever, an oily precipitate
was formed and no solid complex was deposited. From
this Comparative Example, it can be seen that the solvent
to be used is important.
, .
.
'
__ _ _ __..,,...,..,., ~;
o ~,~, ~o, = o o = ~
~ . _ _ _
a~ ~ ~
~ o ~ s
X O U~ N O N
l ~ ~; o o ~ a)
h O Z 5:: U ~ s::
~ ~Q o a) c~ .~ o ~.
c~ a) ~ 'E~ ~ ~; ~ :C
~r ~ ~ :) Ln
'O S ~ o _ _ _ ~ _
~ ,~: ~ _
_l ~ ~ C~ ~1 _ = _ ~1 _
~a'1~ O ~! ~ N __ ~ ~I
~1 . ~
a~ ~ ~a~ ~a~ ~ ,
Q 1~ O ~ ~ ~ ~
(~ O E~ ~ ~ ,4~rl
E~ ~ Z ~ S~ . ~ ~ ~ C SR~ ~ ~
~1 0 ~ O ~rl O
E-l~ . E~L, E-~
_ _ _1 _ _ _
~' ~ ~ ~ ~ ~ ~ ~
~ O l l ~ l ~ ~ l
_. _ ~_1 _ ~ Ei,P~.I ~1 .
~ ' ~g
o~r ~--- O ~ _ __ X
r-J r~ ~ ~) ~) r~) r
. ___ _ ~O~
~: r~
~ O ~ Ct~ r~ O
~ _ _ _ O
~1 1: d~ ~ r~
C: -1 a) ~a~ o ~1--ra ra
O ~ ~ ~ ~n ~9 u~ u7 a)
~) O ~ `' r l ~1
N t Ll ~ _ O O
~ S~ rd 3
r-l ~D .~1 O O O O ~d a)
O ~3 E~ o o o o 3 ~
_ g' ~ l O ~ In ~ ~
~ ~ O Lt~U3 ~d' O ~
O O t~ ~1 ~ ~t~l O r
_ _ _ r~ r~
~_1 r--I _ O ~d~ CO r~ ~1 0
a~ dP ~D ~0 Ll~ 1/7 ~1 r~l
Q r-l ~ U~ O
E~ _ z ~ 3
~ O o = = =
,~ o
o --
_ _
CO o
o )~ a) ~r ~ ,~
U ~ o ~o l l
Ul ~ tU r l ~3 O O O O
r~ X t) IJ ~ ------ ----
O r~l O r~l ~ ~ In
r_l .,1 ~3-rl ~r ~ ~D a~
E~ 0~ o o o o
(a ~3 ~ ~ ~11 . . .,
C) O ~ ~ ~ 0 O O O
~1 rO _ _
r~ l rl rl O
~ o o ~ ~t) ~ ~r In l
. . ~ ~ 1 ~r co r-/ c~
/~
.
~ ,.: ,: ,. ....
,.
....~.., 1-:, , .: , .
:
, .
.. ,, , ,'
,~'' : '
~2~5~
1 Examples 2-1 to 2-5
(1~ Preparation of catalyst component (A) (solid
complex)
A rotator and 1 g ~10.5 mmoles) of anhydrous
magnesium chlo;-ide were placed in a 100-ml flask which
had sufficiently been dried and then purged with
nitrogen. Thereto were added the predetermined amount
of the solvent shown in Table 2 which had been dried
by use of molecular sieves and the predetermined amount
of the phosphorus compound shown in Table 2. When ~he
resulting mixture was stirred at room temperature for
20 minutes, the magnesium chloride was completely
dissolved and a colorless, transparent, homogeneous
solution was obtained.
To the homogeneous solution was added 1.16 ml
(10.5 mmoles) OL titanium tetrachloride, and the result-
ing mixture was deteriorated for 30 minutes to obtain
a yellow, transparent, homogeneous solution. When a
mixture of 40 ml of n-hexane and 12 ml of titanium
tetrachloride was gradually added to this solution with
stirring, yellow fine powder ~as produced. A yellow,
finely divided, solid complex was deposited by continu-
ing the stirring for 2 hours, and the supernatant was
removed by filtration. To the residue was added 80 ml
of fresh dried n-hexane, and the resulting mixture was
stirred for 30 minutes, whereby the residue was washed.
This washing procedure was repeated 6 times to obtain
~; a yellowish-white finely divided solid complex.
:
.: :; .
.
:' ' .
, .
. :
1 Normal hexane was added to this complex to o~tain a
total volume of 50 ml of a slurry.
(2) Copolymerization of ethylene, propylene and
5-ethylidene~2-norbornene
A 3-liter separable flask was equipped with
a stirring blade, a three-way cock, a gas blowing tube,
a thermometer and a dropping funnel for addition of 5-
ethylidene-2-nor~ornene, and then sufficiently purged
with nitrogen. In this flask was placed 2 liters of
n-hexane which had been dried by use of molecular
sieves and degassed. Into the flask whose temperature
was controlled to 35C were introduced for lO minutes
dried ethylene at a rate of 4 liters/min, propylene at
a rate of 6 liters/min, and hydrogene at a rate of 0.2
liter/min in the form of a mixed gas, through the gas
blowing tube, immediately after which 2 ml of a
triisobutylaluminum solution in n-hexane having a
concentration of l mole/liter was added. Therea~ter,
the n-hexane slurry of the catalyst component (A~
prepared in above (1~ was added thereto in an amount of
O ~ as mmole in terms of titanium atom, and polymeriz-
ation was initiated.
Simultaneously with the initiation o~ the
polymerization, a mixed solution of lO ml of 5-ethyl-
idene-2-norbornene and 200 ml of n-hexane was added
dropwise at a rate of 7 ml/min, and the polymerization
was effected for 30 minutes. During the polymerization,
- a mixed gas of the monomers at the respective flow rates
t ~ _ c~/ _
.. . . .
:
.
:
,,
. .
... .
. :
l described above was introduced int~ the flask. A-t this
time, the polymerization temperature was controlled to
35C by external cooliny.
During the polymerization, sugstantiall~ no
gel was produced. After 30 minutes, the polymerization
was stopped by addition of 20 ml of methanol. A small
amount of an antioxidant was added, after which steam
stripping was carried out to obtain a solid rubber.
The yield, the Mooney viscosity, and the prospylene
content of the copolymer were measured. The results
are shown in Table 2.
The raw rubber physical properties of the
copolymer obtained in Example 2-1 were as follows:
lO0~ Modulus - 7 kg/cm2
Tensile strength = 16 kg/cm2
Elongation at break = 4,600
Shore A hardness = 31
Example 2-6
(1) Preparation of the catalyst component (A~
A finely divided solid complex was prepared
by the process of Example 2-1 and washed with three
80-ml portions of water, after which 50 ml of n-hexane
and 12 ml of titanium tetrachloride were freshly added
2Q to the complex, and the resulting mixture was stirred
at 6QqC for 2 hours. The supernatant was removed by
filtration, after which 80 ml of n-hexane was added to
` the residue, and the resulting mixture was stirred for
_ ,;~ _
- ~.
. ~
~Z~4'~3
1 30 minutes, whereby the residue was washed. This wash-
ing procedure was repeated 6 times. ~ yellowish-white,
finely divided, solid complex was obtained. Mormal
hexane was added to this complex to obtain a total
volume of SO ml of a slurry.
(2) Copolymerization of ethylene, propylene and
5-ethylidene-2-norbornene
The copolymerization was effected by repeating
the same procedure as in Example 2-1. The results
are shown in Table 2.
C _ ~ _
....
. ..
'
~ -
., .
E-~ ~ -
,~ ~ ~u o ~ a
Z ~ ~ a~ u
~1
-o' x 8 ~ ~ x
u~ ~ o o ~ m
O ~ ~ E~ ,~
~ ~ _
~ o +
~ ~ r~ ~
~ ~ _ __ _ _
5~ ~ ~ ~ ~ ~
oI ,, x ,, I .,
UI Q~ ~\ ~ I Q~
U~ ~ ~3 0 U~ ~
::~~ ~ Q ~ 5
~ ~ ~ ~ O ~ ~ ~
~ X ~ .,1 ~ X
u~ a) a) ~ ~ a~ ~ a
O ~ ~ X _ ~ U ~ ~C
r~ ~ ~ a) ~-~1 o r~l a)
Z
~1-l 0 ~ ~ 1:~ 0
~1ra ~ U~ I ~:1
1~ ~ '~-J x ~ ~ 'x
~ ~ O ~ ~ E~ O ~ a) o
_ _ . _
a)
~0 ~ l l l l l
Z N t~l ~1 ~`1 N _
CJ~ .,, ~ ~ , _ _ ~ .
,~ ~ ~r ~,
_
a)
J~ H ~ ,~ O ) O ~ r-l
~1
~ ~_
~ ~ ~ dP
O ~ ~ ~ ~ ~ ~O ~ ~ L~
.~ O~ ~ u~ ~n u~ In n
S~ P~ U _ _ .
~ ~ .
~1 h .~;
o a) E~ o o o o o ~
o o o o o o
~ ~ l ~r In ~ ~ ~
O tJ~ ~ U~ I~ 1~ ~D O
~ ~ ~r el~ u~ ~r ~ ~D
~`l _ _
~1 ~1 _ ~ a~ 1~ ~ .~9 ~
R a~ o o ~ ~1 a) ~r
E~ . _ ,1 r-l -I 1-l ~1
_ _
~ 1 Lr)
~ o = _ _ =
_ O - _
I
U~
O ~ ~ ~ ~ ~1
o ~ o~o1 O o o o o o
U~ ~-1 a)-,l ~ o o o o o o
a) E~
X _ _ _ r ~ __ ~ _ .
a~ ~ ô ~D ~ L~ ~ er In
~1.,1~rl ~ O O O O
,~ ~E~ O ~ . . . . .
~ ~ e ~ o O ' O O O c)
~ O ~
~ O _ __
~0 E~ aJ rl t- ~r ~r o o o
~ u~ ~ ~0 ~ r~ co ~1
., _~
'~,
- ` . ' :
,;
1 Examples 3-1 to 3-5
(1~ Preparation of the catal~sk component (A~
Under a nltrogen steam, 100 g o magnesium
chloride hexahydrate was placed in a 300~ml flask, and
heated to 300C. It first forrned a homogeneous solu-
tion t and further heating resulted in a white solid.
The solid was ground under a nitrogen stream and then
heated at 300C for 10 hours under reduced pressure to
obtain a powder of Mg(OH)Cl.
A rotator was placed in a 100-ml flask which
had sufficiently been dried and then purged with nitrogen,
and 1 g (13 ~noles) of the Mg(OH)Cl powder was placed
therein. Thereto were added 36 mmoles of the phosphorus
compound shown in Table 3 whiah had been dried by use
of molecular sieves and then degassed and 30 ml of the
solvent shown in Table 3, and the resulting mixture was
heated to 130C. In this state r the Mg(OH)Cl powder
did not dissolve, but when 13 mmoles of titanium tetra-
chloride was placed in the flask, the Mg(OH~Cl powder
dissolved to give a brown homogeneous solution. The
homogeneous solution was further heated at 130C for 2
hours, thereafter cooled to room temperature, and then
made up to a total volume of 130 ml with n-hexane,
whereby a solution having a concentration of 0.1 mole/
liter in te~ns of Ti,
i .
1 (2) Copolymerization of ethylene, propylene and
5-ethylidene-2-norbornene
A 3-liter separable flask was equipped with
a stirring blade, a three-way cock, a gas blowing tube,
a thermometer and a dropping funnel for addition of
5-ethylidene-2-norbornene, and then sufficiently purged
with nitrogen. In this flask was placed 2 liters of n-
hexane which had been dried by use of molecular sieves
and degassed. Into the flask whose temperature was
controlled to 35C were introduced for 10 minutes
dried ethylene at a rate of 4 liters/min, propylene at
a rate of 6 liters/min and hydrogen at a rate of 0.2
liter/min in the form of a mixed gas through the gas
blowing ~ube, immediately after which 2 ml of a tri-
isobutylaluminium solution in n-haxane having a
concentration of 1 mole/liter was added. Thereafter,
the n-hexane solution of the catalyst component ~A)
prepared in above (1) was added in an amount of 0.05
mmole in terms of titanium atom, and polymerization was
2Q initiated.
Simultaneously with the initiation of the
polymerization, a mixed solution of 10 ml of 5-
ethylidene-2-norbornene and 200 ml of n-hexane was
added dropwise at a rate of 7 ml/min, and the poly-
merization was effected for 3Q minutes. During thepolymerizaticn, a mixed gas of the monomers at the
respective flow rates described above was introduced
into the flask. At this time, the polymerization
.:
.
5~
1 temperature was controlled to 35C by external cooling.
Duriny the copolymerization, substantially no
gel was produced. After 30 minutes, the polymerization
was stopped by addition of 20 ml of methanol. A small
amount of an antioxidant was added, after which steam
stripping was carried out to obtain solid rubber. The
yield, the Mooney viscosity, and the propylene content
of the copolymer were measured. The results are shown
in Table 3.
The raw rubber physical properties of the
copolymer obtained in Example 3 - 1 were as follows:
100% Modulus = 7 kg/cm2
Tensile strength = 17 kg/cm2
Elongation at break = 3,500%
Shore A hardness + 35
. . ,:
- ~ . .... : , .`, .,
.. :~
`
-
O n
+ n n ~r o
~r ~r ~r 1~ ~l1
.~_ __ ___
~ a
.,~
~ ~ ~ o
e H~ ~/ ~1 ~1 r~
. _ __ a~
~0
~ ~ ~ _
t~o o\o n ~ ~r a~ o
O 3 tn
P~ t~ ,~
~ _
..
_ ~o~ ~~o
.~ n n ~g ~r n
~_ . _ _ O
~ O e
_~ ~ ~1 O O
~0 ~ ~! _ : : :
, _
_ e
o 0 5: ~
E~ ~ ~ t-
o ~ I ~a o o o ~D ~ O _
O ~
o--
rn ~ ~~ . t~
ta _ _ o
J~ O ~ O n
~ ~ ~ o
~ ~ c~ ~ ~ a) ~ I ~ 4~
L~~1-- ~ ~ ~ ~ ~ ~ O
oa~ o ~: .~ o a
n O ~ O N o _ _ Q
~:~ tn-- ~ ~: ~ ~ O
oo ,l ~ o o a~
.~ u~ æ z ~Q _ H
t~ _ __ a~
5~ a
~D ,1 I X ~ I
,.~ ~,~ o ,, I tn a
P~tn x ~ I ~ ~rl O ~
~a) ~_ a) ~1 0 rcJ ,): ~rl
h ~~ ~ ~ 1:: ~:1 ~ -- Pl X 1~:1
o ~:: ~ Q (1~ ,-J_ O
,5: ~:1~ I O ~:: : : I ~ ~ ::~1
P~ 1: P~ ~ x a) tD
tn ~~ I ~ ~n I tn ~ O S
0 ~3 ~ O . rl O ~ ~ rJ O
o~ ~ a) ,C ~ ~ I ~ ~ tn
4 t~~~rC 1:1 . E~ ~ ~
. _ _ __
,~ ..
P~ ~ ~ ~ ~r n
O I I I I I
x æ ~ ~ ~ ~ ~ æ
..
_ _ _
r
5~
1 Example ~-1
(1) Preparation of catalyst component (A)
Under a nitrogen stream, 100 g of magnesium
chloride hexahydrate was placed in a 300-ml flask, and
heated to 300C. It formed a homogenenous solution, and
further heating resulted in a white solid. The solid was
ground in a ni-trogen stream and then heated at 300C for
10 hours under reduced pressure to obtain a powder of
Mg(OH)Cl.
A rotator and lg (13 mmoles) of the Mg(OH)Cl
powder were placed in a 100-ml flask which had sufficiently
been dried and then purged with nitrogen. Thereko was
added 36 mmoles of 2-ethylhexyl(di-2-ethylhexyloxy)-
phosphine oxide dried by use of molecular sieves, and the
resulting mixture was heated to 130C. In this state,
the Mg(OH)Cl powder did not dissolve, but when 13 mmoles
of titanium tetrachloride was placed in the flask, a brown
homogeneous solution was obtained. The homogeneous solu-
tion was further heated at 130C continuously for 2 hours.
A rotator was placed in another 100-ml flask
which had sufficiently been dried and khen purged with
nitrogent and 60 ml of dried n-hexane and 13 mmoles of
titanium tetrachloride were placed therein, after whlch
the resulting solution was maintained at 60C on a hot
water bath. Into this solution was slowly dropped, with
vigorous stirring, the above-mentioned homegeneous solution
containing magnesium, titanium and phosphorus. A yellow,
finely divided, solid complex was immediately produced.
. .
.
''` ' ,
: "
~2~
1 The stirring was continued at 60C for 2 hours. The
stirring was stopped to deposit the yellow, finel~ de~ided
solid, and the supernatant was removed by filtration.
To the residue was added 60 ml of fresh, dried n-hexane
and the resulting mixture was stirred for 30 minutes,
whereby the residue was washed. This washing procedure
was repeated 6 times to obtain a yellowish-white, finely
divided solid. Normal hexane was added to this solid to
make up the total volume to S0 ml. The titanium concentra-
tion of the thus obtained finely divided solid complexslurry was 0.024 mole/liter, and Mg/Ti = 10.5 (molar ratio).
(2) Copolymerization of ethylene, propylene and
5-ethylidene-2-norbornene
A 3-liter separable flask was equipped with a
strring blade, a three-way cock, a gas blowing tube, a
thermometer and a dropping funnel for addition of 5-
ethylidene-2-norbornene, and then sufficiently purged
with nitrogen. In this flask was placed 2 liters of n-
hexane which had been dried by use of molecul r sieves
and degassed. In~o the flask whose temperature was con-
trolled to 35C were introduced for 10 minutes dried
ethylene at a rate of 4 liters/min, propylene at a rate
.of 6 liters/min, and hydrogen at a rate of 0.2 liter/min
in the form of a mixed gas through the gas 10wing tube,
immediately after which 2 ml of a n-he~ane solution of
triisobutylaluminum having a concentration of 1 mole/liter
was added. Thereafter, the n-hexane slurry of the
catalyst component (A) prepared in above (1) was added
.
,
~z~
1 in an amoun~ of 0.05 mmole in terms of titanium atom,
and polymerization was initia~ed.
Simultaneously with the initiation of the poly-
merization, a mixed solution of 10 ml of 5-ethylidene-2-
norbornene and 200 ml of n hexane was added dropwise ata rate of 7 ml/min, and the polyrnerization was effected
for 30 minutes. During the polymerization, a mixed gas
of the monomers at the respective ~low rates described
above was introduced into the flask. At this time, the
polymerization temperature was controlled to 35C by
external cooling.
During the copolymerization, substantially no
gel was produced. After 30 minutes, the polymerization
was stopped by addition of 20 ml of methanol. A small
amount of an antioxidant was added, after which steam
stripping was carried out to obtain a solid rubber. The
yield, the Mooney viscosity, and the propylene content of
the copolymer were measured. The results are shown in
Table 4.
The raw rubber physical properties of the
copolymer obtained in Example 4-1 were as follows:
100% Modulus = 5 kg/cm2
Tensile strength = 15 kg/cm2
Elongation at break = 4,000 %
Shore A hardness = 30
3~
S~
1 Example 4-2
(1) Preparation of catalyst component (A)
The same procedure as in Example 4-1 was
repeated to obtain a n-hexane slurry of a yellowish-
white, finely divided, solid complex. To the slurry ~asadded 10 ml of titanium tetrachloride, and the resulting
mixture was stirred at 60C for 2 hours. The stirring
was stopped, and the supernatant was removed by ~iltra-
tion, after which the same washing procedure as in
Example 4-1 was repeated 6 times. Normal hexane was
added to the thus washed residue to adjust the total
volume to S0 ml. The titanium concentration of the thus
obtained finely divided solid complex slurry was 0.025
mole/liter, and Mg/Ti = 9.2 (molar ratio).
lS (2) Copolymerization
Copolymerization was effected by repeating the
same procedure as in (2) of Example 4-1. The results are
shown in Table 4.
Example 4-3
The same procedure as in Example 4-1 was re-
peated, except that the phosphorus compound used in
Example 4-1 was replaced by 36 mmoles o tri-n-butyl
phosphate and 20 ml of monochlorobenzene.
~ light-yellow, finely divided, solid complex
was obtained. Normal hexane was added to the complex to
adjust the total volume to 50 ml, whereby a slurry was
` obtained. The titanium concentration of the slurry was
33
C - ~ _
' "~
1 0.01 mole/liter, and Mg/Ti = 26 (mola~ ratio).
The copolymerization results are shown in Table
4.
Example 4-4
The same procedure as in Example 4-1 was re-
peated, except that the phosphorus compound used in
Example 4-1 was replaced by 36 mmoles of n-butyl(di-n-
butoxy)phosphine oxide and 20 ml of monochlorobenzene.
A light-yellow, finely divided, solid complex
was obtained. Normal hexane was added ko the complex to
adjust the total volume to 50 ml, whereby a slurry was
obtained. The titanium concentration of the slurry was
0.027 mole/liter, and Mg/Ti = 8.7 (molar ratio).
The copolymerization results are shown in
Table 4.
Example 4-5
The same procedure as in Example 4-1 was re-
peated, except that 20 ml of Isoper-E was used as a
solvent, to obtain a light-yellow, finely divided, solid
complex. Normal hexane was added to the complex to adjust
the total volume to 50 ml, whereby a slurry was obtained.
The titanium concentration of the slurry was 0.022 mole/
liter, and Mg/Ti = 10.8 (molar ratio).
The copolymerization results are shown in
Table 4.
,.. . . .
' '
_
~
~ O In ~9 ~ 1~ ~r
~ ~ l I` a~ ~ ~1 O
c~ .~ Y ~ ~r ~ ~r ~ ~
~,l -
_ ~r ~ ~ ~9
,~ ~ ~ ~r o r~
o ~
-~
s, -
.,~ ~ O m ~ t~ oo
E~ . . .
- o ~ o ~ ~o c~ o
_~ ~ ~ ~ ~ ~ ~1
~ -
~r _
~r In co
~1 ~ o a
~ ~ o ~ o o o o o
E~ O ,~ 0~ o o o o o
~ E-~ -
~, _ _
~ u~ ~o ~ l ~ l
~ ~ ~ ~ o ~l ~ ~
~ ~ .C _ O O N _
r-l r~ _ ~ ~ O O
1~ o o o t~ o o ~ a) ~`I u
Z :~ ~ R
t~
~o l a
~: rl I a) ~ ~1 1 a
O ~ ~ ~ ,1 r~ _
~1 U~ ~ rl I ~ ~
~I X X ~: Ql ~1 X X
s~ ra ~ O O ~ I ta ~ o o
~ O ~ X ~ ~ ~rl O X
(~ ~ ~ ~J ~1 0 _ ~ O ~ 0
~ Q. O ,C X ~:: ~ ~ --~:4 .C X
a~ o~ ~s~ ~ ~^ ~
~ s: O ~ ~ ~ ~ ~ ~ X a) ~ ,~ ~
~ O ~ ~ O .1 0 ~ O ~ ~ ~ O
I ~ ~ ~1 ~ I ~5 ~C I .IJ
E~ ~ ~ ~ O ~
_
a~
~0 l l l l
~Z ~ el~ ~r ~ ~r
x -I
3s~
t V
.
,
.
o o
~+ ~ ~r c~ ~ n
.C ~ _ . ~_
_ ~o~ co I_ r~ ~ ~
~ ~ _ _ _.
~ ~ G\O ~ ~n ~ ~ ~
., O~C~ ~ ~ ~D n ~
.
.
" ,
,
~ ~. ' ' ; ,
1 Examples 5-1 to 5-4
(1) Preparation of catalys-t component (A)
A 100-ml flask containing a rotator was suf-
ficiently purged with nltrogen, after which 1 g (10.5
mmoles) of MgCl2 was placed in the flask. There~o was
added 14.5 ml (31.5 mmoles) of dried 2-ethylhexyl(di-2-
ethylhexyloxy1phosphine oxide (phosphorus compound (b)),
and the resultlng mixture was heated to 70C to dissolve
the MgCl2. A homogeneous solution was obtained.
Another 100-ml flask containing a rotator was
sufficiently purged with nitrogen, and 20 ml of dried
n-hexane, 1.44 ml (13.125 mmoles) of TiC14 and the pre-
determined amount of the phosphorus compound (a) shown
in Table 5 were placed in this flask, allowed to react at
the boiling point of n-hexane (about 70C), and heated
and stirred until no more HCl was produced (the reaction
time: 3 hours). An orange, homegeneous solution was
obtained.
The whole amount of the orange, homogeneous
solution was added to the homogeneous MgCl2 solution pre-
viously prepared. The resulting mixture was diluted to
a total volume of 100 ml by further addition of n-hexane.
When 10 ml of TiCl4 was gradually added to the
diluted mixture with stirring while the temperature of
the flask was maintained at 50 to 60C, a yeLlow, finely
divided solid was deposited. The flask was malntained
at S0 to 60"C for 30 minutes after the addition of TiC14.
The stirring was stopped, and the flask was allowed to
_,~
,.
1 stand overnlght to precipi~ate the finely divided solid,
after which the supernatant was taken out. To the resi~ue
was freshly added 80 ml of n-hexane, and after stirring and
washing, precipitation was carried out. This washing pro-
cedure was repeated 6 times. Normal hexane was added tothe thus washed residue to adjust the total volume to
100 ml. The analytical values for the thus obtained slurry
of the finely divided solid complex in n-hexane are shown
in Table 5.
(2) Copolymerization of ethylene, propylene and
5-ethylidene-2-norbornene
A 3-liter separable flask was equipped with a
stirring blade, a three-way cock, a gas blowing tube, a
thermometer and a dropping unnel for addition of 5-
ethylidene-2-norbornene, and then sufficiently pwrged with
nitrogen. In this flask was placed 2 liters of n-hexane
which had been dried by use of molecular sieves and then
degassed. Into the flask whose temperature was controlled
to 35C were introduced for 10 minutes dried ethylene at
a rate of 4 liters/min, propylene at a rate of 6 liters/
min, and hydrogen at a rate of 0.2 liter/min in the form
of a mixed gas through the gas blowing tube, immediately
after which 2 ml of a n-hexane solution of triisobutylalu-
minum having a concentration of 1 mole/liter was added.
Thereafter, the n-hexane slurry of the finely divided
solid complex (the catalyst component (A)) prepared in
above (1) was added in an amount of 0.05 mmole in terms
of titanium atom, and polymerization was initiated.
1 Simultaneously with ~he initiation of the poly-
.erization, a mixed solutlon of 10 ml of 5-ethyli~ene-2-
norbornene and 200 ml of n-hexane was added dropwise at
a rate of 7 ml/min, and the polymerization was effected
for 30 minutes. During the polymerization, a mixed gas
of the monomers at the respective flow ra-tes described
above was introduced into the flask.
The polymerization temperature was controlled
to 35C by external cooling. During the copolymerization,
to substantially no gel was produced. After 30 minutes, the
polymerization was stopped by addition of 20 ml of meth-
anol. A small amount of an antioxidant was added, after
which steam stripping was carried out to obtain a solid
rubber. The yield, the Mooney viscosity, and the pro-
pylene content of the copolymer were measured. The resultsare shown in Table 5.
The raw rubber physical properties of the
copolymer obtained in Example 5-1 were as follows:
100 ~ Modulus = 5 kg/cm2
Tensile strength = 9 kg/cm2
Elongation at break = 4,020 %
Shore A hardness = 29
Example 5-5
The same procedure as in Example 5-1 was re-
peated, except that the phosphorus compound (b) used for
dissolving MgC12 in Example 5-1 was replaced by
.. .
~, .
1 tri-n-butyl phosphate and -th~t 20 ml of monochloro-
benzene was used as the solvent for dissolving the MgCl2.
The results are shown in Table 5.
Example 5-6
The same procedure as in Example 5-5 was repeated,
except that the tri-n-butyl phosphate used in Example 5-5
was replaced by tri-2-ethylhexyl phosphate. The results
are shown in Table 5.
Examples 5-7 to 5-9
(1) Preparation of catalyst component (A)
A 100-ml flask containing a rotator was suffi-
ciently purged with nitrogen, after which MgCl2 (10.5
mmoles) was placed in the flask. Thereto was added 14.5 ml
(31.5 mmoles) of dried 2~ethylhexyl(di-2-ethylhexyloxy)-
prosphine oxide (phosphorus compound (b)), and the result-
ing mixture was heated to 70C to dissolve the MgC12.
To the thus obtained solution were added 20 ml of dried
n-hexane and the predetermined amount of the phosphorus
compound (a) shown in Table 5, and the resulting mixture
was allowed to react at the boiling point of n-hexane
(about 70C), and heated and stirred until no mare HCl was
produced (the reaction time: 7 hours). A colorless,
transparent, homogeneous solution was obtained. After
this solution was adjusted to a total volume of 100 ml
with dried n-hexane, 10 ml of TiC14 was gradually added
thereto with strring while maintaining the temperature of
0~
~ 3
l the system at 50 to 60C, upon which a yellow, finel~
divided solid was deposite~. The temperature of the
system was maintained at 50 to 60C for 30 minutes
a~ter the addition of TiC14. The stirring was stopped,
and the system was allowed to stand overnight to precipi-
tate the finely divided solid, after whlch the supernatant
was taken out. The residue was washed by adding thereto
80 ml of n-hexane and stirring the resulting mixture,
and then precipitated. This washing procedure was re-
peated 6 times. Normal hexane was added to the thuswashed residue to adjust the total volume to 100 ml. The
analytical values for the thus obtained slurry of the finely
divided solid complex in n-hexane are shown in Table 5.
(2) Copolymerization of ethylene, propylene and
5-ethylidene-2-norbornene
The copolymerization was effected by repeating
the same procedure as in Example 5-1. The results are
summarized in Table 5.
Example 5-10
(1) Preparating of catalyst component (A)
A 100-ml flask containing a rotator was suffi-
ciently purged with ritrogen, after which 1 g (10.5
mmoles) of MgC12 was placed in the flas~. Thereto was
added 14.5 ml (31.5 mmoles) of dried 2-ethylhexyl(di-
2-ethylhexyloxy)phosphine o~ide (phosphorus compound (b)),
and the resulting mixture was heated to 70C to dissolve
` the MgC12. To the thus obtained solution were added
~ 4~
,
.
, . '
~ .
1 20 ml of dried n-hexane and 10.5 mmoles of dihydroYy-
n-butoxyphosphine oxide (phosphorus compound (a)~, an~
they were subjected to reaction at the boiling point of
n-hexane and continuously heated and stirred until no
more HCl was produced (the reaction time: 6 hours). A
colorless, transparent, homogeneous solution was obtained.
To this solution was added 10.5 mmoles of TiC4, and
the resulting mixture was continuously heated and stirred
at the boiling point o~ n-hexane until no more HCl was
produced (the reaction time: 6 hoùrs). An orange, homo-
geneous solution was obtained. The solution was adjusted
to a total volume of 100 ml with n-hexane, after which
10 ml of TiC14 was gradually added to the system with
stirring while the temperature of said system was main-
tained at 50 to 60C. A yellow, finely divided solid wasdeposited. The stirring was continued while the tempera-
ture of said system was maintained at 50 to 60C for
30 minutes. The stirring was stopped, and said system
was allowed to stand overnight, after which the finely
divided solid was precipitated, and the supernatant was
taken out. The residue was washed by adding 80 ml of n-
hexane freshly and stirring the resulting mixtur2, and
then precipitated. This washing procedure was repeated
6 times. Normal hexane was added to the thus washed
residue to adjust the total volume to 100 ml. The analyt-
ical values or the thus obtained suspension of the finely
divided solid complex in n-hexane are shown in Table 5.
lZ~
1 (2) Copolymerizatlon of ethylene, propylene and
5-ethylldene-2-norbornene
The copolymeriæation was effected by repeatiny
the same procedure as in Example 5-1. ~he results are
shown in Table 5.
3 , 3 ~ ~ ~ Va
O ~ a ~ ~ ~ rl ~ O ~, O O
O D 1-.1 ~ __ _ _ _
o o~ O o ~I o ~r d' O O O O L~
,~ !L i~
~:'' ~XZ __ l .Ir I l l l l
~5~
__ o _ ~ ~'
O+ O r~ ~ ~ ~I O ~r o~ ~ ~g
~ ~ ~ f'l ~r ~r ~1 ~ r~
,~-~- _ _ _ ~
3 H ~ C)~ In CO CO co 5~ C5~ co co O
~ _ _ _ _ .
_
a~ d~ 00 ~ a~ 1- ~ ~ ~ U~
:~ o~ 3 n ~r u~ ~ ~ In ~ ~o ~ u:
o s~ o --
O ~ ) ___ ___ _
s~
~ r~l 0~ E~ o o oO oO o oO o o o o
E ~ N ~ In ~ IJ~ ~ ~1 t~ t~ r~ CO ~
~ __ _ _ _ _
~ _~ o co ~ a~ ~ ~ ~ ~ ~
_I_ _. _ .
O 1~ 11') 111 U~ .
~ rl CO r~ r~ co Cl~I_ ~ ~ a~
u~ E~ O ~\ . . . . . . . . .
~ ~ ~ ~ O O O O O O ~ ~ O
G ~ ~-- S~
O ~ ~ O ' _ . _ _ _ _ _
P~ E~ ~rl 1~7 n o o o L~ ~D ~r Lr~
E~ u~ -- ~ ~ r~ ~ ~ u~ r~ ,1 ~1 ~ ~1
0'~ ~ )
~1 1 - - ------ -- .
d' ~ ~ In ~ ~ ~D ~ ~O ~r
~1 ~ O ~ ~ O O O O O O O O O r-
V~ ~ o o o o o o o o o o
^ ~ O O . . . . . . . . .
~ .~ o o o o o o o o o o
' ' .'
r ~S~
id ~4 -- --
~s~
1 Example 6-1 ~ombination of the catalyst cornponents
(A)(a) and (B)
(1) Preparation of catalyst component (A)(a)
Into a 300-ml flask purgecl wlth nitrogen were
charged 1 g of dried palladium carbon powder r 200 ml of
1,2-dichloroethane and 100 ml of titanium tetrachloride,
and 200 mmoles of di-n-butyl ether was added with stirr-
ing. Subsequently, hydrogen was fed to the flask for
6 hours at a rate of 0.3 liter/min to obtain a yellowish-
black solution.
The soluti.on was filtered to remove the pal-
ladium carbon, whereby a yellowish-black, homogeneous
solution was obtained. The reduction of the titanium
tetrachloride was approximately 100%. Subsequently, the
concentration of titanium trichloride was adjusted to
0.4 mole/liter with 1,2-dichloroethane.
On the other hand, 25 g (0.262 mole) of an-
hydrous magnesium chloride was placed in a l,000-ml flask
purged with nitrogen and was dissolved by addition of
361.5 ml (0.787 mole) of 2-ethylhexyl(di-2-ethylexyloxy)-
phosphine oxihe. After the dissolution, the resulting
solution was adjusted to a total volu~e of 524 ml with
n-hexane.
Subsequently, in a.200-ml flask were placed
20 ml of the above-mentioned magnesium chloride solution,
then 20 ml of the above-mentioned titanium trichloride
solution, and lastly 145 ml of n-hexane to obtain a green,
homegeneous solution.
~i
"
1 Into this solution was gradually dropped 10 ml
of titanium tetrachloride with stirring. After completion
of the dropping, the stirriny was continued for 3 hours,
and the thus obtained mixture was then allowed to stand.
As a result, the mixture was separated into a black homo-
geneous supernatant and a finely divided solid. The
supernatant was removed, after which 200 ml of n-hexane
was added to the finely divided solid to wash the finely
divided solid. After this washing procedure was repeated
4 times, the total volume of the thus washed finely devided
solid slurry was adjust to a total volume of 200 ml. The
final state of the product was a n-hexane suspension of
a slightly yellow finely divided solid.
The Ti concentration was 0.011 mole/liter, the
Mg/Ti molar ratio was 4.5, and the phosphorus compound/Ti
molar ratio was 0.23.
(2) Preparation o catalyst component (B)
A sufficiently dried 500-ml flask was purged
with dried nitrogen, and 200 ml of n-hexane was charged
thereinto. S~bsequently, 18.8 ml (0.0747 mole) of tri-
isobutylaluminum was added with stirring, and the stirring
was continued for 10 minutes after the addition.
On the other hand, a 100-ml flask was purged
with dried ni~rogen, after which 50 ml of n-hexane was
charged thereinto, and 4.6 ml (0.050 mole) of n-butyl
alcohol was added with stirring.
Subsequently, a 200-ml flask was purged with
` nitrogen, after which 100 ml o the above-mentioned
_~_
L~L' t3
1 n-hexane solution of triisobutylalurninurn was charyed there~
into, and 3.8 ml of the n-he~ane solution of n-butyl
alcohol was gradually dropped thereinto wi-th stirring while
nitrogen was blown thereinto (n-butyl alcohol/triisobutyl-
aluminum molar ratio = 0.10). During the dropping, thetemperature was maintained at 20C. After completion of
the dropping, the stirring and the blowing of nitrogen
were continued at 20C for 1 hour.
The thu~ obtained solution was colorless,
transparent and homogeneous.
(3) Copolymerization procedure
A 3-liter autoclave equipped with a stirrer was
purged with nitrogen, after which 800 g of propylene was
charged thereinto in a liquid state, and the temperature
was raised to 50C. Subsequently, ethylene was fed to
the autoclave while the feeding pressure was kept con-
stant at 32.0 kg/cm2G. After the pressure in the auto-
clave became constant at 32.0 kg/cm G, 15 g of 5-
ethylidene-2-norbornene was added.
Subsequently, the catalyst components (A)(a)
and (B) were fed to the autoclave in amounts of 0.0388
mmole (in terms of ~i) and 1.552 mmoles (in terms of Al),
respectively, over a period of 30 mlnutes. Simultaneously
with the initiation of feeding of the catalyst components,
the beginning of polymerization was observed.
Durlng the polymerization, the polymerization
temperature was maintained at 55~1C by using cooling
water. Ethylene was continuously fed to the autoclave
1 so as to keep the pol~merization pressure constant at
32.0 kg/cm G.
The feeding of ethylene was stopped 4~ minutes
after the beginning of the polymeriza-tion, and 50 ml of
methanol was fed to the au-toclave, after which stirriny
was conducted for iO minutes to remove the unreacted gas,
whereby a rubber-like copolymer was obtained. The rubber-
like copolymer was dried, and thereafter allowed to
stand at 150C for 6 hours and then at 20C for 20 hours.
The yield, Mooney viscosity, propylene content,
iodine value, and quantity of heat of fusion of crystal
of the thus treated rubber-like copolymer were measured.
The results are shown in Table 6.
Example 6-2 Combination of the catalyst components
(A)la) and (B)
(1) Preparation of catalyst component (A)(a)
The catalyst component (A)(a) prepared in
Example 6-1 was used.
(2) Preparation of catalyst component (B)
A triisobutylaluminium solution in n-hexane
and a n-butyl alcohol in n-hexane were prepared by the
same procedure as in Example 6-1.
Subsequently, a 200-ml flask was purged with
nitrogen, after which 100 ml of the triisobutylaluminum
solution in n-hexane was charged thereinto, and 18.9 ml
of the n-butyl alcohol solution in n-hexane was gradually
dropped thereinto with stirring while nitrogen was bubbled
.. ..
1 into the contents of the flask (n-butyl alcohol/tri-
isobutylaluminum molar ratio = 0.50).
After completion of the droppiny, the same
procedure as ln Example 6-1 was repeated to obtain a
colorless, transparent, homogeneous solution.
(3) Copolymerization procedure
Copolymerization, heat treatment and measure-
ment were carried out under the same conditions as in
Example 6-1.
The results are shown in Table 6.
Example 6-3 Combination of the catalyst components
(A)(b) and (B)
(1) Preparation of catalyst component (A)(b)
Into a 200-ml flask purged with nitrogen was
charged 1.0 g (10.5 mmoles) of anhydrous magnesium
chloride, and 14.5 ml (31.5 mmoles) of dried 2-ethyl-
hexyl(di~2-ethylhexyloxy)phosphine oxide was added
thereto, after which the resulting mixture was heated to
80C and stirred, whereby the magnesium chloride was
dissolved to obtain a homogeneous solution.
On the other hand, a 100-ml flask was purged
with nitrogen, and 20 ml of dried n-hexane, 1.44 ml
(13.125 mmoles) of titanium tetrachloride and 3.5 ml
(10.49 mmoles) of monohydroxydi-2-ethylhexyloxyphosphine
oxide were placed therein, subjected to reaction at
about 70~C, and continuously heated and stirred for 3 hours
until no more hydrogen chloride was produced. The thus
! ~ ~jZ)
'', ' ''
~l~S'~ 3
1 o~tained solution was dark-yellow and homogeneous. The
whole dark-yellow homogeneous solution was added to the
above-mentioned magnesium chloride solution, and n-hexane
was ~urther added to adjust the total volume to 100 ml.
When 10 ml of titanium tetrachloride was
gradually dropped with stirring in the thus obtalned
solution con~aining magnesium chloride and titanium
tetrachloride whlle this solution was maintained at about
60C, a yellow, finely divided solid was deposited.
After the addition of titanium tetrachloride, the system
was maintained at 60C for 1 hour, and thereafter the
stirring was stopped, after which the system was allowed
to stand to precipitate the finely divided solid, and the
supernatant was removed.
To the residue was freshly added 80 ml of n-
hexane to wash the residue, and the resulting mixture
was allowed to stand, after which the supernatant was
removed. After this washing procedure was repeated 6
times, n-hexane was added to the residue to adjust the
total volume to 100 ml.
The thus obtained liquid was a n-hexane sus-
pension of a slightly yellow finely divided solid, and
the Ti concentration was 0.004 mole/liter, the Mg/Ti
molar ratio was 25, and the phosphorus compound/Ti molar
ratio was 0.85.
(2) Preparation of catalyst component (B)
A n-hexane solution of triethylaluminum and a
n-hexane solution of 2-ethylhexyl alcohol were prepared
. . .
1 by the same procedure as in Example 6~1.
Subsequently a 200-ml flask was purged with
nitrogen, after which 100 ml. of khe triethylaluminum
(triethylaluminum: 0.0~ mole) solution in n-hexane was
charged thereinto, and 24.3 ml of the 2-ethylhexyl alcohol-
(2-ethylhexyl alcohol: 0.012 mole) solution in n-hexane
was gradually added with stirring while nitrogen was
bu~bled into the contents of the flask (2-ethylhexyl
alcohol/triethylaluminum molar ratio = 0.30).
After the addition, the same procedure as in
Example 6-1 was repeated to obtain a colorless, trans
parent, homogeneous solution.
(3) Copolymerization procedure
Copolymerization was effected by using the same
3-liter autoclave as in Example 6-1. The polymerization
pressure was 30.5 kg/cm2 and hence the feeding pressure
of ethylene was 30.5 kg/cm2, and other conditions were
the same as in Example 6-1.
The catalyst components (A)(b) and (B) were fed
in amounts of 0O0505 mmole (in terms of Ti) and 2.02
mmole (in terms of Al), respectively, by the same method
as in Example 6-1. Polymerization stoppage, heat treat-
ment and measurement were carried out by the same, methods
as in Example 6~
The results are shown in Table 6.
.
. .
,:
,
1 Comparative Example 6-1 [A case where the arnount of the
alcohol used in the catalyst component (B) was increased.]
(1) Preparation of catalyst component (A)(a)
The catalyst component (A)(a) prepared in
Example 6-1 was used.
(2) Preparation of catalyst component (B)
A triisobutylaluminum solution in n-hexane and
a n-butyl alcohol solution ln n-hexane were prepared by
the same procedure as in Example 6-1, ancl subjected to
reaction in a molar ratio of n-butyl alcohol/triisobutyl
alcohol of 1.0 to obtain a co',orless, transparent homo-
geneous solution.
(3) Copolymerization procedure
Copolymerization, heat treatment and measurement
were carried out by the same methods as in Example 6-1.
The results are shown in Table 6.
Comparative Example 6-2 [A case where the amount of the
alcohol used in the catalyst component (B) was increased]
(1) Preparation o~ catalyst component (A)(b)
The catalyst component (A)(b) prepared in
Example 6-3 was used.
(2) Preparation o catalyst component (B)
A triethylaluminum solution in n-hexane and
a 2-ethylhexyl alcohol solution in n-hexane were prepared
in the same manner as in Example 6-3 and subjected to
reaction in a molar ratio of 2-ethylhexyl alcohol/tri-
ethylaluminium o~ 1.0 to obtain a colorless, transparent,
l~ ~'3
, .
. . .
:.
~f,>~ 3
l homegeneous solution.
(3) Copolymerization procedure
Copolymerization, heat treatment and measure-
ment were carried out by the same methocls as in Example
6~3.
The results are shown in Table 6.
Comparative Example 6-3 [A case where an alkylaluminum
alkoxide was used as the catalyst component (B)]
(1) Preparation of catalyst component (A)(a)
The catalyst component (A)(a) prepared in
Example 6-1 was used.
(2) Preparation of alkylaluminum alkoxide
A sufficiently dried 200-ml flash was purged
with nitrogen, and 100 ml of n-hexane was charged thare-
into. In the n-hexane was dissolved 34.5 mmoles of
diisobutylaluminum monobutoxide with stirring to obtain
a homogeneous solution.
(3) Copolymerization procedure
By use of the same 3-liter autoclave as in
Example 6~-1, copolymerization was effected under the same
conditions as in Example 6-1, except that the polymeriza-
tion pressure was 32.0 kg/cm2G and the polymerization
temperature was 55C.
The amounts of the catalysts fed were 0.0388
mmoLe (in terms of Ti) for the component (A)(a) and 1.552
mmoles for the diisobutylaluminum monobutoxide, and the
'' copolymerization was effected while these catalyst
.. ~
'.
~zs~
1 components were fed by the same method as in Example 6-1.
The treatment method and the measurement methods of the
thus obtained copolymer were the same as in Example 6-1,
The results are shown in Table 6.
Comparative Example 6-4 [A case where an alkylaluminum
alkoxide was used as the catalyst component (B)]
(1) Preparation of catalyst component (A)(b)
The catalyst component (A)(b) prepared in
Example 6-3 was used for polymerization.
(2) Preparation of the alkylaluminum alkoxide
A diethylaluminum 2-ethylhexoxide solution in
n-hexane was prepared by the same process as in Comparative
Example 6-3.
(3) Copolymerization procedure
By use of the same 3-liter autoclave as in
Example 6-3, copolymerization was effected by the same
method as in Example 6-5, except that the pressure was
30.5 kg/cm2G, the temperature was 55C, and the amounts
of the catalysts fed were 0.505 mmole (in terms of Ti)
for the component (A)(b) and 2.02 mmoles for the diethyl-
aluminum 2-ethylhexoxide. The treatment method and the
measurement methods of the thus obtained copolymer were
the same as in Example 6-3.
The results are shown in Table 6.
S~
'
~ _ ~ o o o o _ ~ o ~ '
~1 Yr- l r~ O O O O O O O O
r-l OO E-l r-l r-l r-l CO r-~ C_)
-r~
(~ r~
r-l _ ~ tY~ ~ r-l ~0
r r.r~ ~ r-l r~l ~I ~ r-l ~ t'`l
~) I _ _
I~; ~r~ ~ ~r~
r ~ O X r ~ O X
~ r-l 1~1 ~ ~ r; X
r-l ~ r-l 11 r~l
~ ~v~
~E~ E~ ~ ~ t~ 3
_ . _ ~_ _
. ~D~- _ ~ ~ ~ _ _
_ ~ _
a~ a) ~ a) ~ ~ a)
)~1 ~ ~r-l ~ ~ 1 t~l r ~ r ~
. . __ X _E P ~1 ~ . ~q~-~ X
l ¦ a' ~, ~ ~
~ ~ Co ~ ~ ~ ~ ~ ~
~0 ~ _ _ __
U~ ~ I~ ~D a~
. . . . . .
O ~ In a~ o 1` u~ a~
H ~ _ N
~_
P ~ O I~ ~ O er 00
3) ~ ~ ~ ~;r el~ ~r d'
~1 _~ _ _ . _
~ o Ln ~ 1_ ~9 ~ o ~_
O t~ ~ r~ Ln ~ ~o ~ ~
I ~
. ~
. , ' ` '', .
. .
`:, ' `-` , ;
