Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
This invention relates to a process for polymerizing ~-olefins
in the presence of a catalyst capable of ~aintaining its superior catalytic
activity for prolonged periods of time thereby to afford a highly stereo-
regular ~-olefin polymer or copolymer in a high yield which has a higher
apparent density and a reduced content of halogen ascribable to the catalyst
used; and to said catalyst.
Catalyst systems composed of solid titanium halides and organo-
aluminum compounds have previously been used for preparing highly stereo-
regular polymers of ~-olefins. Polymerizations using these catalyst systems
afford highly stereoregular polyrners; but the yield of the polymer per unit
amount of the titanium catalyst component is still low, and an additional
step is required to remove the catalyst residue from the resulting polymer.
ReceNtly, some methods, for example, those disclosed in Japanese Laid-Open
Patent Publications Nos. 16986/73, 16987/73 and 16988/73 (published March 3,
1973 in the name of Montedison S.p.A.), have been proposed to remove the
. .
defects of the prior art techniques. These methods attempt to obtain highly
stereoregular poly(~-olefins) by polyrr.erizing ~-olefins such as propylene
using a catalyst comprising a solid component which is obtained by copolymer-
izing a complex compound formed between a titanium halide and a specific
electron donor together with an anhydrous magnesiuTn halide, and the reaction
product of a triaIkyl aluminum and a specific electron donor. With these
methods, however, the stereoregularity of the resulting polymer is still
insufficient, and the yield of the polymer per titanium atom is still unsat-
isfactory. In addition, these methods still suffer
- 2 -
.~~J ,~
from the defect that the yield of the polymer per chlorine atGm in t~le
catalyst is low because the co-pulverlzed produc-t has a low level of
titanium content, that the polymeIizatiorl must be performed with a low
slurry concentration because of the low apparent density of the resulting
polymer, thus rendering the methods economically disadvantageous, and that
the polymerization activity of the catalyst is lost within short periods of
time.
French ~aid-Open Patent Publication No. 2,113,313 (published
~ay 29, 1972 in the name of Montedison S.p.A.), discloses a process for
10 selectively preparing either an atactic polymer as a main product or a
stereoregular polymer as a main product. This Patent Publication states
that when a Ti catalyst component obtained by contacting a titanium compound
with a mixture of an active-type magnesium halide carrier and an anhydrous
compound of an element of Groups I to IV, for example, Si is used in the
above process preferably in the form supported on a carrier and subsequently
modified with an electron donor, a stereoregular polyrner is obtained as a
main product. This Publication3 however, illustrates only SiO2 as the
anhydrous compound of Si. Furthermore, this Publication discloses that
ethers, thioethers, amines, phosphines, ketones and esters can be utilized
; 20 as the electron donors, but do not exemplify any specific compounds that
fall within the esters. The isotacticity of the polymer shown by the
boiling n-heptane extraction residue in all of the Examples of the above
Patent Publication is at most about 70%, and therefore, the process of this
patent is far from satisfactory for preparing highly stereoregular
~L~4~
polymersO On the other hand, the electron donor used
in this patent ~or production of isotactic polymers
is onl~ ,N', N",N"'-tetra~eth,vl eth~ler,e diamineO More-
over, only an~ydrous lith,ium chloride and SiO2 are specifi-
cally used in -this patent as the anhydrous cornpound of an
element of Groups I to IV.
'~e nave made investigations with a view to
removing the defec-ts of the conventional techMiques, and
consequently found that a titaniu~--containing catalyst
component composed of an organic complex derived from (i)
a magnesium halide, (ii) an organo-polysiloxane, (iii)
an organic carboxylic acid ester and (iv) a specific ~i
compound, w~len-combined wi-th an organoaluminum compound,
becomes a superior catalyst for preparation of highly
stereoregular polyolefinsO Our investigations also led
to the discovery that by using this catalyst, highly
stereoregular ~-olefin polymers or copolymers can be pre-
pared in high yields while maintaining the superior catalytic
activity over a long period of time, and that the halogen
~O content of the resulting polymer or copolymer ascribable
to -the ca-talyst can be reduced and the resulting polymers
or copolymers have a high apparen-t density.
Accordingly, an objec-t of -this inven-tion is to
provide a process for preparing highly stereoregular
pol~olefins having -the above-mentioned improved effects~
- ~nother object of this invention is to provide
a ca-talyst for use in the process of this inven-tionO
, - 4 -
~any other objects and advantages of this invention will become
more apparent from the followi.ng descript:ion.
! The polymerization or copolymerization of ~-olefins having at
least 3 carbon atoms, as referred to in this application, includes homo-
polyrr,erization of ~ olefins having at lea,t 3 carbon atoms, copolymerizations
of at least two of ~-olefins having at least 3 carbon atoms with each other,
- and copolymerization of ~-olefins having at least 3 carbon atoms with
ethylene and/or diolefins in an amount of preferably up to 30 mol ~.
Examples of the ~-olefins are propylene, l-butene, 4-methyl-1-
pentene, and 3-methyl-1-butene, and examples of the diolefins include con-
jugated diolefins such as butadiene and non-conjugated dienes such as di-
cyclopentadiene, ethylidenenorbornene and 1,5-hexadiene.
The catalyst used in this invention is composed of the following
titanium-containing solid catalyst component (A) and organoaluminum catalyst
component (B).
Component (A) consists of an organic complex prepared from
(i) a magnesium halide, (ii) an organo-polysiloxane, (iii) an organic
carboxylic acid ester, and (iv) a titanium compound of the formula
Ti(OR)QX4 Q
wherein R is an alkyl group, for example, a Cl-C4 alhyl group, X is a
halogen atom such as Cl, Br and I and Q is an integer of 0 to 4.
.. ~
z
Examples of co~pon~n-t (i) are mag~e$ium chloride,
magnèsium bromlde and magnesium iodide 9 the magnesium
chloride (MgC12) being especially preferred.
Examples of component (ii) are organic
polysiloxanes of the formula
Q(Q25iO)nSiQ3
wherein Q groups are identical or different,
; and each represent a hydrogen atom 9 an alkyl
group, for example 9 an alkyl group containing
1 to 4 carbon atoms 9 a cycloalkyl group9 for
example9 a cycloalkyl group containing
to 8 carbon atoms9 or an aryl group9 for
example 9 an aryl group contaim~ng 6 -to 8
carbon atoms with the proviso that all Q
groups are not hydrogen atoms at the sa~e
. time9 n is an integer of 1 to 10009
organic polysiloxanes of the formula
.~ (Q25iO)n
wherein Q and n are the same as defined above 9
.~ 20 and organic polysiloxanes of the formula
`,
X ( Q2sio~)nsiG2x
. wherein Q, and n are the same as defined
above and X is a halogen atom.
Examples of the organic carboxylic acid es-ters
(iii) include esters formed between Cl-C89 preferably
Cl-C4, saturated or unsaturated aliphatic carboxylic
- acids which may optionally be su.bstituted by a halogen
atom and alcohols selected from the group consisting of
. Cl-C8, preferably Cl-C49 saturated or unsaturated aliphatic
primary alcohols, C3-C8, preferably C5-C6, saturated or
. unsaturated alicyclic alcohols and Cl-C4 saturated or un-
saturated aliphatic primary alcohols substituted by C6-C10,
preferably C6-C89 aromatic groups or halogen atoms; esters
formed between C7-C12, preferablY C7 C10, a
carboxylic acids and alcohols selected from the group
c3nai~sting o~ Cl-C8~ preferablyoC~C~, $atu~ated or un-
saturated aliphatic primary alcohols9 C3~C89 preferably
C5-C6 9 saturated or unsaturated alicyclic alcohols and
Cl-C4 saturated or unsaturated alipha-tic primary alcohols
substituted by CC-Cl09 preferably C6-C8 aromatic groups
or halogen atoms; and alicyclic carboxylic acid esters
such as methyl cyclopentanecarboxyla~te, methyl hexahydro~
benzoate, ethyl hexahydrobenzoate 9 methyl hexahydrotoluate,
and ethyl hexahydrotoluate.
In the present invention, a part or -the whole
of the organic carboxylic acid ester (iii) can be used
in the form of ester-trea-ted produc-ts or adducts of the
compounds (i), (ii) and (iv) by bringing i-t in advance
. into contact w:ith these compounds (i), (ii) and (iv).
Desirably 9 the magnesium halide (i) as a con-
. stitutent or the titanium-containing solid catalyst com-
ponent (A) is as anhydrous as possible 9 but the inclusion
of moisture is permissible to an extent such tha~t ~the
moisture does not subst~ntially affect the performance
of the catalyst. The halide may be one obtained by de-
hydrating a commercially available grade at 100 to 400C.
under reduced pressure prior to use. For convenience of
use, the ma~nesium halide is preferably used in the form
of a powder having an average par-ticle diameter of 1 to 50
microns~ But when i-t is to be pulverized by a mechanical
contacting treatmen-t during catalys-t preparation, powders
of larger particle sizes can also be used. The average
particle diameter of 1 to 50 microns mean that at least
80% by weight of the -total particles have a par-ticle
diameter of 1 to 50 microns.
Specific examples of linear polysiloxanes of
the formula Q(Q2SiO)nSi~3 as the Si component (ii) are
hexamethyldisiloxane9 decamethyl-tetrasiloxane9 tetra-
cosamethylundecasiloxane, 3-hydroheptamethyltrisiloxane 3
3~-dihydrooctamethyltetrasiloxane9 3,5 9 7-trihydronona-
methylpenta ~ 9 te-tramethyl-l 9 3-diphenyldisi].oxane 9
pentamethyl-1,3 9 5-triphen-yltrisiloxane9 heptaphenyldisiloxane,
. and octaphenyltrisiloxane
Specific examples of cyclopolysiloxanes of the
formula (Q2SiO)n asthe Si component (ii) include 2,496-
trimethylcyclo-trisiloxane, 2,4,6,~-tetracnethylcyclote~tra-
siloxane9 hexarnethylcyclotrisiloxane9 octamethylcyclo-
tetrasiloxane, decamethylcyclopentasiloxane, dodecame-~hyl-
cyclohexasiloxane, triphenyl-19395-trimethylcyclotrisiloxane,
hexaphenylcyclo-trisiloxane9 and octaphenylcyclotetrasiloxane.
Specific examples of linear a9~-dihalo poly-
siloxanes of the formula X(Q2SiO)nSiQ2X as the Si compo
nent include 193-dichlorotetramethyldisiloxane9 1,5-
-- 8 --
'?
~6~2
:
dichlorohexamethyltrisiloxarle, and 1,7-dichlorooctame-thyl
tetrasiloxane.
Of these organic polysiloxanes, the linear
alkylpolysiloxanes are preferredO Methylpolysiloxane and
- 5 ethylpolysiloxane having a viscosity of no-t more than 200
centipoises at 25 C. are especially preferred.
Specific examples of -the organic carboxylic acid
ester as component (iii) of the titanium-contai~i~ng
solid catalyst component (A) are primary alkyl esters
of mono~alent saturated fatty acids such as methyl formate,
ethyl acetate 9 n-amyl acetate, 2-ethylhexyl acetate,
n-butyl formate, ethyl butyrate, or ethyl valerate, pen~yl
acetate; allyl acetate; primary alkyl esters of halo-
alipha-tic carboxylic acids such as ethyl chloroacetate 9
n-propyl dichloroacetate and ethyl chlorobutyrate9 primary
alkyl esters of unsaturated fatty acids such as methyl
acrylate 9 methyl methacryla-te OI` i-butyl crotonate; primary
alkyl esters of benzoic acid such as;~ethyl benzoate9
:- et.~yl benzoate, n-propyl benzoate, n- and i-butyl benzoates,
n- and i-amyl benzoates 9 n-hexyl benzoate, n-octyl benzoate
and 2-ethylhexyl benzoate; primary alkyl esters of toluic
acid such as methyl tolua-te, ethyl tolua-te9 n-propyl toluate,
n~ and i-butyl toluates, n- and i-amyl toluates or 2-ethyl-
hexyl toluate; primary alkyl ~s-ters of ethylbenzoic acid
such as methyl ethylbenzoate, ethyl ethylbenzoate, n-propyl
. ethylbenzoate9 and n- and i-butyl ethylbenzoates 9 primary
alkyl esters of xylylenecarboxylic acid such as ~e-thyl
3,4-xylylene-l-carboxylate9 ethyl 3,5-xylylene-1 carboxylate,
and n-propyl 2~4-xylylene-l carboxylate9 primary alkyl
g _
esters of anisic acid such as metnyl anlsate 9 e-thyl anisa-te 9
n-propyl anisate9 and n- and irbutyl anisates9 and primary
alkyl esters of naphthoic acid such as methyl naphthoate9
ethyl naph-thoate9 n-propyl naphthoate9 and n- and i-
butyl naphthoates.
Of these primary alkyl esters of arornatic carbo-
xylic acids,primary Cl-C4 alkyl esters are preferred.
Methyl benzoa-te and ethyl benzoates are especially
preferred,
As already mentioned9 a par~t or -the whole of
the organic carboxylic acid ester (i:ii) can be used in -the
form of ester-treated products or adduc-ts of the compounds
(i)9 (ii) and (iv) by bringing it in advance into contact
with these compounds (i)9 (ii) and (iv).
Specific examples of the titanium compound of
formula Ti(OR)~,,Y4 ~componen-t (iv)) include titanium
tetrahalides such as titanium tetrachloride9 titanium
-te-trabromide or titanium tetraiodide9 alkoxy titanium
trihalides such as methoxy -titanium -trichloride, ethoxy ti-
: 20 -tanium trichloride9 n-butoxy titanium trichloride, e~thoxy
titanium tribromide or i-bu-toxy ti-tanium tribromide;
dialkoxy titanium dihalides such as dime-thoxy -ti~tar.ium
dichloride9 dicthoxy titanium dichlorideS di-n-butoxy
titanium dichloride or diethoxy ti-tanium dibromide;
trialkoxy ti-tanium monohalides such as -trimethoxy -ti-tanium
cllloride 9 tri.ethoxy titanium chloride9 tri-n-bu-toxY
titanium chloride and -trie-thoxy ti-tanium bromidt9 and
.,. tetraalkoxy titaniums such as te-tramethoxy ti.tanium9
tetrae-thoxy titanium and tetra-n-butoxy -titanium. Of
-- 10 --
~4~
these, the titanium te-trahalides, especially ti-tanium
tetrachloride, are preferr~d.
I~hen a magnesium halid.e (i) treated with the
organic carboxylic acid ester (iii~ is used in -the f`orm-
ation of the titanium-containing solid catalyst component
(A) used in this invention, it is preferred to use a
mechanical pulverizing means for contacting both with each
otne.r According to this pulverizing contact, the organic
acid ester in a wide r~nge of proportions acts effectively
on the magnesium halide. A sufficierlt treating effect
can be obtained even if -the proportion of the former is
small as compared with the latter (in a molar ratio of
... about 1/1 to 1/20).
When the Si component (ii) treated with the organic
carboxylic acid ester (iii) is used~ the treatment is
effected, for example, by a method comprising adding the
organic carboxylic acid ester at room temperature to a
silicon compound itself or its solution in a suitable inert
solvent such as pentane 9 hexane, heptane or kerosene 9 or
or a method comprising preparing a solution of the organic
carboxylic acid ester in the above inert solvent 5 and -then
adding the silicon compound to -the solution. Of course,
the treatment can be completed within short periods of
: time a-t an elevated temperature9 but if desired, the
; 25 trea-tment can also be carried out under cooling.
~1hen the titanium compound (iv) is used in -the
.. form of an adduct of` it with the organic carboxylic acid
ester (iii), the adduct can be prepared by adding the
organic carboxylic acid ester (iii) in an equimol&r or
larger amount (calcula-ted based on the ester) to the tita-
nium compound ltself (if it is l:Lquid) or a solu-tion of it
in the above inert solvent (if it is solid) 9 and separating
the resulting precipitate by filtration. Even when -the
titanium compound is liquid9 it can be used in the adduct-
forming reflction in the form of its solution in the above
inert solvent. The washing of the resultin~ precipitate
(the removal of the unreacted ti-tanium compound and organic
carboxylic acid ester) can also be carried out using the
above solventO
The ratio of the anhydrous magnesium halide (i)/
: the Si component (ii)/the organic carboxylic acid ester (iii)/
the titanium compound (iv) as the starting materials for
the catalyst componen-t (A) is not particularly restricted,
but i.s usually 1/1000-0,01/10-0.005/100 0.0019 preferably
1/10-0.01/1-0.01/30-0.01.
Preferably 9 the titanium-containing solid catalys-t
component (A) is prepared by bringing the components (i),
(ii) 9 (iii) and (iv) into contact with each other under
the pulverizing conditions. A nurrlber of modes are possible
in regard to the order of addi-tion of these componen-ts,
the method of addition and the method of contacting, and
some examples are shown below,
(1) The anhydrous magnesium halide (i), the
organic polysiloxane (ii) 9 the organic carboxyli.c acid ester
(iii) and the titanium compound (iv) are con-tac-ted with each
other intimately by a mechanical pulverizing means (to
be referred to as pulverizing contact) 9 and -the resulting
titanium-can-taining solid component is treated preferably
12
~ 29
with -the coMpound (iv) or its solution in an inert solvent~
(2) Th~ magn~s um halide (i) 9 the organic poly
silox2ne (ii) 9 and the organic carboxylic acid
es-ter are pulverizingly contactecl. The resulting solid
component is treated by suspending in -the titanium
compound (iv) or its solution in an jnert solven-t. Or
the solid component and the titanium compound (iv) are
pulverizingly contacted in the substantially dry s-tate 9
and then treated by suspending preferably in the -ti-tanium
compound (iv) or its solution in an inert solven-t.
(3) The ar~lydrous magnesium halide (i) and the
organic carboxylic acid ester (iii) are pulverizingly
contacled and then further contacted pulverizingly with
the organic polysiloxane (ii) to form a solid component. Or
the magnesiurn halide (i) and the Si component (ii) are
first pulverizlngly contacted and then wi-th the organic
carboxylic acid ester (iiiJ;to form a solid component.
~ither of such solid components is suspended in the titanium
compound (iv) or its solu-tion in an inert solvent to
treat it. Or ^the solid component is pulverizingly con-
tacted wi-th the -titanium component (iv) substantially
in the dry sta-te 9 and then suspended preferably in ~the
titanium compound (iv) or i-ts solution in an iner-t solven-t
to treat ito
(4) The anhydrous magnesium halide (i)9 the
organic polysiloxane (ii) and an adduct of the -titanium
compound (iv) and the organic carboxylic acid ester (iii)
are pulverizingly contac-ted 9 and the resulting titaniu~l-
con-taining solid component is suspended preferably in the
9~
titanium compound (iv) or its solution in an inert solvent
to trea-t it.
(5) The anhydrous magnesium halide (i) and the
organic polysiloxane (ii) are pulverizingly contacted, and
then further pulverizingly contacted with an adduct of the
titanium compound (iv) and the organic carboxylic acid
ester (iii). The resulting titaniu~-containing solid
component is suspended preferably in the titanium
compound (iv) or its solution in an inert solvent to
treat it.
(6) In the procedures of (1) and (3) aboveg
the titanium compound (iv) is used in the form of an adduct
of it with the organic carboxylic acid ester (iii).
(7) The anhydrous magnesium halide (i), the
- 15 organic polysiloxane (ii) 9 the titanium compound (iv) 9 and
an adduct of the titanlum compound (iv) and the organic
7 carboxylic acid ester (iii) are pul-verizingly contacted,
and the resulting titaniurn-containing solid component is
suspended preferably in the titanium compound (iv) or its
solution in an inert solvent to treat i-t.
(8) In the procedure in paragraph (7) above,
the organic carboxylic acid ester (iii) itself is also
added to the pulverizing contact system.
The pulverizingly contact means in the prepara-
tion of the titanium-containing solid titaniurn componen-t
(A) in the present invention Lay9 for example9 include
means using a rotary ball mill 9 a vibratory ball mill, or
an impact mill. As a result of contact by such a pulveri-
zing contact ~eans 9 the organic carboxyllc acid ester
. .
' :
(iii)9 the organic polysiloxane (ii) and -the ti~tanium
compound (iv) immediately act on the ac~tive surface resul-
ting from the pulverization of the magnesium halide (i)
to form an organic complex whose chemical structure has
not been elucidated yet. This can be confirmed by the
fact ~that the diffraction patterrl of the magnesium nalide
powder changes.
The trea-ting condi-tions employed for pulverizingly
cont,acting two or more of the starting ma-terials for -the
catalyst component (A) using various mills can be selected
as followso
Taking up the use of a ro-tary ball mill flS an
example 9 100 balls each with a diame-ter of 15 mm made of'
stainless steel (SUS 32) w*re accomodated in a ball cylin-
drical receptacle made of stainless steel (SUS 32) and
having an inner capacity of 800 ml. and an inside diameter
of 100 mmc ~lhen 20 to 40 g of the materials are placed
in it 9 the pulveriza-tion treatmenl, is carried out usually
for at least 48 hours 9 preferably at least 72 hours at a
speed of 125 rpm. The temperature for the pulverization
treatmen-t is usually a point in the vicini~ty of room tem-
perature, ~lhen -there is a marked exovherm, the system is
preferably cooled~ and the pulverizing con-tact is performed
a-t a temperature lower than room -temperature.
The treat~ent of the solid component obtained
by pulverizing contac-t of the star-ting materials o~ the
solid component (A) with the titanium compound (iv) can
be suitably carried out by stirring the mixture usually
a~t 40~C. to the boiling point of -the treating mixture ~or
- 15 -
~L~4~
at least l hour. Alttrnatively9 this can be accomplished
by pulverizing contact un~er the above pulveriza1;ion con-
ditions for ei; least lO0 hours usLng the ball mill.
~en titanium compourlds are used vn two differ~nt
occasions in the above treatment proc~dure9 they may
be the same as 9 or different from9 each other so long as
they are chosen from compounds of the above general
formula.
The titanium-contalning solid catalyst cornponent
(A) results after separating the organic complex solid
prepared in the above manner from -the suspension. Pre-
ferablyg i-t is fully washed with hexane or other inert
liquid media so tha-t the free -titanium compound (iv) is
no longer detected in -the wash liquidO
The catalyst component (B) to be combined with
the catalys-t componen-t (A) ir -the present invention is an
organoaluminum compound of the general formula R'mAl(OR')3 m
wherein R' is an alkyl group9 preferably a Cl-C4 s-traight-
chain or branched-chain alkyl group9 the two or more R'
groups being identical or different9 and m is a number in
the range of l.5 = m - 3,
Examples of the organoaluminum compound are as
follows;
~ hen m is 3, the compound is a -crialkyl
aluminurnO Specific examples are -trimethyl aluminum3
triethyl aluminum3 tri-n- and -i-propyl aluminums9 tri-n-
and -i-butyl ,~luminum9 and trihexyl aluminum. The
triethyl aluminum and tributyl aluminum are preferred.
They may also be used in combination of two or more.
- 16 -
" .
', '
If desired 9 the trialkyl aluminurlrnay be rtac-ted
with the organic carboxy:':c acid ester prior to use. rl'his
reaction may be carried out in -the polymerization system
before the lnitiation of polymerization9 or it may be
carried out separately 9 and then the reaction product is
added to the polymerization system. rl'he reaction proceeds
sufficiently by contacting the trialkyl aluminum directly
with an organic carboxylic acid ester (or using one of
them as a solution in an inert solvent). The ratio between
the amounts of these materials is such -that the proportion
of the trialkyl ~luminum is usually 2 to 100 mols (based on
the aluminum atom) per gram equivalen-t of the ester group
of the organic carboxylic acid ester. The organic
carboxylic acid ester may be selected from the various
organic carboxylic aci~ esters as component (iii) in the
formation of the catalyst component (A). Usually9 it may
be the same kind of acid ester as that used in forming
the catalyst component (A)o
(2) ~rhen m is at least 1.5 bu-t below 3 (1.5-m <3) 9
the above aluminum compound is a partially alkoxylated alkyl
- aluminumO Such an alkyl aluminum is prepared9 for example9
by adding a calculated amount of an alcohol to a trialkyl
aluminum or dialkyl alumiIlum hydride. Since -this reaction
is vigorous 9 at leas-t one of them is preferably used as a
solution in an inert solvent in order -to cause the reac-
tion to proceed mildly.
In order -to polymerize or copolymerize ~-olefins
having a-t least 3 carbon atoms using -the catalys~t composed
of the -titanium~cor.taining solid catalyst component (A)
and -the organoaluminurn ca-talys-t cornponent (~) 9 polymeriza-
-tion conditiorls known -t~, ~e ~mployed in polymeriza-tions
or copolyrr.eriz~tions of .~-olefins using Zieglcr-type
catalysts can be properlv chosen, Usually9 polymeriza~-
-tion termperatures of from room ternpera-ture to abou-t 200C.
and pressures from atmospheric pressure to about 50 Kg/cm2
can be used. The polymerizations or copolymerizations can
be carried out either in the preserlce or in -the absence of
an inert liquid medlurll. Examples of the l,iquid meclium are
pentane 9 hexane 9 heptane 9 iso-octane and keroserle. Where
the polymeriza-tlon or copolymerlzation is carrled out in
the absence of a liquid medium, it rr,ay be performed in
the presence of a liquid olefin monomer, or l-t may be
carrled ouc ln -the vapor phase 9 for example 9 by uslng a
fluldized bed catalyst.
The concentration of -the catalyst to be charged
into the polymerization system for polyrnerization can be
changed as desired. For example 9 in solid~phase polyme-
rizations 9 the tltanium-containlng solld catalyst cornponen-t
(A) is used in a concentra-tion of usually 0.0001 to 1.0
m-mol/liter calcula~ted as tit.aniurr a-tom 9 and -the ca-talyst
component (B) is used in a concen-tration of usually 1/1 to
; 100/1 9 preferably 1/1 to 30/1, in terms of the alurninum
atom/-titanium atom ratio, In vapor-phase polymerizations 9
the ti~tanium-con~taining solid catalyst comp~nen-t (A) can
be used in a concentra-tion of 0.001 - 0.5 m-mol (_alcula-ted
as titanium atom) 9 and the catalyst component (B) 9 in
an amount of 0.01 - 5 m-mol (calculated as aluminurn atom),
bo-th per llter of the volume of the reac-tion zone,
" 1~
'
In order to lower the molecular weight of the
resulting polymer (in order to increase the melt index of
the polymer), hydrogen may be caused to be present in
the polymerization system.
The following Examples and Comparative Examples
illustrate the present invention more specifically.
Exam~
Preparation of Catalyst Component (A):-
A 800 ml. stainless steel (SUS 32) ball mill with
an inside diameter of 100 mm accomodating therein 100
stainless steel (SUS 32) balls each with a diameter of 15 mm
was charged with 20 g of anhydrous magnesium chloride,
6.0 ml. of ethyl benzoate and 3.0 ml. of methyl polysilo-
xane (having a viscosity of 20 centipoises at 25C.) in
an atmosphere of nitrogen, and pulverizingly contacted for
100 hours at a rotating speed of 125 rpm. The resulting
solid product was suspended in 150 ml. of titanium
tetrachloride, and the suspension was stirred at 80C.
for 2 hours. Then, the solid component was collected by
filtration, and washed with purified hexane until free
titanium tetrachloride was no longer detected. The result-
ing component contained 4.1% by weight of titanium and
58.2% by weight of chlorine as atoms.
Polymerization:-
A 2-liter autoclave was charged with 0.05 ml.
(0.375 m-mol) of triethyl aluminum, 43.8 mg (0.0375 m-mol cal-
culated as titanium atom) of the titanium-containing solid
component (A) obtained above and 750 ml. of kerosene (purified
-19-
~ ~h
~0~ 2
kerosene) sufficiently free from oxygen and mois-ture.
The polymeriza-tion system was hea-ted9 and when thP tempera-
ture reached 70C.9 propylene was in-troducedO Polymeriza-
tion of the propylene was started at a total pressure of
7.0 Kg/cm2. After contimlirlg the polymerization a-t 70C,
for 3 hours 9 the in-troduction of propylene was stopped.
The inside of tne autoclave was cooled to room -tempera-
ture 9 and the catalyst was decomposed by addition of
methanol, The solid component was collected by fil~tration,
washed with methanol, and dried to afford 410.3 g of
polypropylene as a white powder. The boiling n-heptane
extraction residue (II) of the powder was 94.5%9 and its
- apparent density was 0.30 g/rnlO
On the ot,her hand 9 concen-tration of the liquid
phase afforded 15.1 g of a solvent~soluble polymer.
The average specific polymeriza-tion activity
per titanium atom of the ca-talyst used above was 540 g/
Ti-m M hr~atm.
~ rative Exam~
Preparation of a titanium-con-taining catalyst component~-
A ball mill of -the same type as used in Example
1 was charged with 20 g of anhydrous magnesium chloride
and 17.8 g of an adduc-t having -the average composition of
the formula TiClL~-C6H5COOC2~-l59 and they were con-tacted
pulverizingly under -the same conditions as in Example 1
for 100 hours at a speed of 125 rpr.l. The resul-ting solid
titanium catalyst component ~corresponding to the component
(A) in Example 1) was considerably agglomerated in a ball
- 20 ~
mill, and was difficult to obtain in powder form. A part
of the solid component was washed with 1 liter of purified
hexane to the same extent as in Example l, and dried to
form a titanium catalyst component. The titanium catalyst
component contained 4.2% by weight of titanium and 6.30% by
weight of chlorine calculated as atoms.
Polymerization:-
Propylene was polymerized under the same conditions
as in Example 1 using ll~ mg of the titanium catalyst
component obtained above. There were only obtained
8.8 g of polypropylene as a white powder and 1.7 g of a
solvent-soluble polymer.
Examples 2, 3, 4 and 5
: In each runl a titanium catalyst component (A)
was prepared in the same way as in Example 1 except that
each of the polysiloxanes described in Table l was used.
Propylene was polymerized under the same conditions as in
- Example 1 using the resulting titanium catalyst component
in the amount indicated in Table 1. The results are
also shown in Table l.
. -21-
~i) ~ r I -i~
> (\J ~J- Ll--~
r I t~Jr--i C~l
~ -J i~
,, ,Q, t)
~ ~ U~
~ rl --- . . . __
-i~ J_~ ~_
(`~ r >~
N (i) ~ ~
rl ~ ~1 i--' C~
a~ u~ ~\I (~ (\I (\J
a) ~ ,~ ~
~ ~ Q~ ~C~ O O O
.~ a~ ~d ___ _ . __
O .
I .
o ~
~ ~1 ~d
.- o ~a
., o ~ o a), ~ Lr ~ o~
G~ ~ ~ . . o
~ ,~ ~ ~ ~ ~r\~ i~ ~r,i
.~ +~ 1 O~
X a) ~ o h
~q ~ 5~ ~
(1~ _ --
i" -1
:. C) ~ o
5~ r O ~) O r~l
~: O ,~ r~ i~O ~ i--~ ~ ~1
~ 1~ ~1 0 O`-- ~ -1 ~
:, r ~ O ~ _ _ r
~ ~ ~, a) .~
E~ ~ ~ ~ ~_
r t ~d ~ i~o O L~ ~ Lr, F~
O ~ , i~ o~ CO ~ O
~1 0 0.~ i~ i~ h
,.~ ___ <~op~ _. ~
.,. .~ ~ O Lr~ J r~J O
., r,~ V~ O . . . .~
' ;; ,V -i' C3 C~ O
i-~ Lr~ L~ ~O
',~ , rn
~d ___ ~ d
O ~rl ~ J ~ a) t\l h
+~~) E-1. . o ~ ~t i~O
~ ~ rl I t O i-- O
a~,--E- l ~ i~ i~ ~ *
~.,.,~ ~ ''
. . . O a) .
~; 0 X X ~d :~
. .~ + ) o ~ I O F~
~;,............... rq .~ .
~' r~l ~r r~l Orn -1~ X (I)
. ~li ~) L~,~rl O O ~d
,~" +~ r--I r OrC~ h -1 -i~ a)
.~ 0 O rl .~r~ O ~ t',
. V ,1,rd ~ -1 rna~ ~d
.,, . -+~~,. a) ~.5 ~ ~ ,s:~ ~r~ ~ ~ X ~~
~ tr~i~ ~ i~\-i~ ~ ~,) rd i~l O O
.r,J -rl ,~r-l 0 ~~ (~ r--I ~ h
.~ r~ O ~ ~ ~ rd ~r~
,. 0 ~~ o rd I r~~ rn
", b~+~ ~ X i~-i-)~ ~r~
~, , al ,~ llt ~ a) I .-,
O ~ rn ~:C ~ Ei i~
~
.,
rn
0 a~
: . X .~ ~ ~ L~
, ..
.;
. -- 22 --
Ex~ es 6 to ~
In each run9 a cat~lyst, colnpon~n-t (A) was pre-
pared under the same conditions as in Example 1 except
that each of tne substituted benzoic acid es-ters showr
in Table 2 was used in -the ~mount shown in Table 2.
P.ropylene was polymerized in the same wa~ as in Example
1 using the c?talys-t cornponen-t (A) in the amoun-t shown in
Table 2. The results are shown in Table 2.
. .
- 23 -
~ ~ -- -~
~ r`> ~ O C\J
r~ r ~ k
'' L~, ~ o ~
c~ u~ t~ ~ -1~
_ . _ __ . _ ___
r r~
a)-
~
~ ~ ~ (~ a~ c~
~ '~ --' O O O
.~, __
~ I (~) ~ ~
1~ C~ ~ h
N t~ ~ ("I u~ c
,1 h '~
h ~ o u~ ~: rr~ ~ J
Cù X 1 ~D ~1 0 ___
,~ h a) h
o a
n, ~ :~
t,~ ,-~ ,~ ,~ ~ ~ U~
o o o o ,~
~ V~
+~ ~H r~
r-l o ~ r~ h
~ ~ h
:. (V r--l ~ r~ r--I 15~ O t~
L~: ~I) O O O C ~_~ E~
_ ~ _ P~ __ _ O
+
. ~D +J ~ (~ ~D ~ +O
~ 3 Ei ~ ~ ~ +o
." _ ~ ~o
r ~ S
.' (D r--l~D O t~l ~)
; . . r 1 V J O~ a~ ~
. ~) ~ ~ I s~ td
r-l __ _ I E~
.. , ~ V r U~
¢ ~d æ 1~ J
;.: , h .~ . L~ O ~D *
.. h ~1 E~ +~ J J 1
CD E-l _
h CD
O +~ r~ +~ tD
-1~ (D r tl) ~ r~ ~ O
r-l r~ ~ ,D '1 CD 1~ r--I
t rl ~ r-l 0 '9 J ~ ~ J
. . r o ~ +~ ~, CD
.,~...................... t td rl r, F~l td
r'`~' _~_ .. _ _ .. . , .. __
. . t~d tD
. ~r,~ O ~ C~
2 Lr
Ex~ le 9
,. .~ ._
Prepara1;ion of Catalyst Componerlt (A)-
A solid cornponent- was prepared by the ball rnill
treatment of anhydrous magnesium chloride 9 e-thyl ben~oa-te
and methylhydropolysiloxane in -the same way as in ~?xample l.
The resulting solid cornpontnt was suspended in lO0 ml, of
- kerosene containing 50 ml, of ti-tanium -tetrachloride 9 and
-thus treated at 100C, for 2 hours with stirring, The
solid component was collected by filtration9 and washed
with purified hexane unt;il free ti-tanium tetrachloride was
no longer detectedO l'he resulting catalyst cornponen-t
(A) contained 3.0% ~y weight of titaniur,l and 61,2% by
weight of chlorine calculated as a-toms,
Polymerization.-
15A 2-liter autoclave was charged wi-th 750 ml, of
purified kerosene7 0.095 n1l, (0,375 m-mol) of triisobutyl
aluminum and 59,5 ml. (0~0375 m-mol calculated as titanium
atom) of the catalyst comporent (A). The polymeriza-tion
sys+em was hea-ted9 and when -the tempera-ture reached 70C, 9
propylene was in-troducedO The polymerization of propylene
was started at a -to-tal pressure of 7.0 Kg/cm2. With
stirring 9 the polymeriza-tion was carried out for 5 hours at
70 C. with s-tirring 9 and then -the in-troduc-tion of propylene
was stopped. The inside of the au+oclave was cooled to
room temperature 9 and the solid componen-t was collected
by fil-tration, washed with methanol and dried to afford
390.4 g of polypropylene as a whi-te powder and 12,l ~ of
a solvent-soluble polyrner. The powdery polymer had an
n-hep-tane extraction residue of 96,4%9 and an apparent
25 -
density of 0.31 g/ml. The average specific polymerization
ac-tivity of -t~le catalyst was 306 g of polypropylene/Ti-
rmnol~hr a-tm.
Examples_10 -to 14
. 5 In each run9 a catalyst component (A) was pre-
pared under the same conditions as in Example 1 except
that each of the polysiloxanes shown in Table 3 was
used instead of the methyl polysiloxane. Propylene was
polymerized in the same way as in Example 1 using the
catalyst component (A) in the amount shown in Table 3,
The results are shown in Teble 3,
;
:
; - ~6 -
~1) rl ~ r-- ~_ . _ _
~`~
* O O ~ ~D
0 ~1 (~ ~ O ~D
rr~ ~ J
r~, o ~
~ U~ ~ ~ _ _
1~
r-l
r~ h rl E3 0~ 0~ CO 0~ O~)
I\~ ~d u~ ~ ~ N N N (~I
r~ L~l r ~10 O O O O O
¢~ . _
___ _ _ v - _
rO ~ S~ O
a) ~ .~ a) ~ o~
h ~ ~1 ~ ~ ~ . o
tH -1~ 0 U~ ~ r-l
O ~ ~rl 0 ~1 0 0~~ 0~ ~ (~ ~ 0~
u F~ ~ h o p~ p~ _ _ _
r _~_ r~
u r-l ~ El 1-- ~D C~ (~
r-l r I ~D ~D 0~ L~`\ ~i
; ~ r-l r l r-l r-l r-l
u~ ~
r.~ __ _ ~ _ . r-l
~o~ s~ a)
~ ~ ~ a) ~o r-l 0 ) LO 1~ r-l
r-l 0 ~3 o o ~ o ~ f~
a) ~:) ~ N r-l CU N O (a
rl ~: r-l rJ~ 0~ (~ 0~ CO E~
r~ _ _ _ O o N N N N r~J I O
rv ~)
r-l u~
~ ~ ~V
0 ~ ~ .~
E~ ~ r-l ~ C~ N Lr~ O O
~1; ~ ~ ) 0~ O 0~ r-l O
o ~3: L~ \~ Lr~ ~D \.D O
~ ~_ O
r-l -- - ~ . ____ ~1
C~ ~V
~ ~r~ ~
. L~ rr~ L~ o ~
~_ 0 rl -~ ~\ il- Lr~ O O Ul
E~ ~ O . O . . 0
~i t ~ ~' rr~ r ~ r ~ rr~ r ~ ~v
~V ___ _ l l El
~ rl) l 0
O rl~ ~ 0 U~
Pl ~ ~ ~
. o ,~ ~ ~v r~
o o . _~ ~v o r~, 0
r-l r-l 1~r-l ~ r-l O ~C
~rlE~ ~_:>. 0 o r-l
u~ U~ ~' ~ ~ ~r~) ~ r-l
~ ~ i~ -~ o ~ r(~ r~ r~ rl
r--I r~ (Vtv r-l ~ r~) ~ u
0 O r-l ~r~ ~1 r-l rlr-l 0
~;lrl u~ ~ ~> >~~ S~
0 ~ ~ X~ ~r-l ~ ~ rv ~ (Vr~ +~
v ,~ :~ v o~ ~, ~ r~ ~ ,r~. ~D rl)
rl O .~ r~¦I ~> rv 0 rv ~11 ~, -1-~
~. ~ r~ r I~C) O ~3 X ~I Xr~ o
r.~i 0 r~J u~r~ ~--1 (1~ O 1.~ O ~) r-l
~10 --~ ~ ~1~ r~) -1~ r-l r~) r-l ~ r,~
h O ho~ ~ t) ,1 rv ,1 r~ ~,
__ O O -1-)N r~ I --~ 9~__r~ r~)
U~
rv
rr
E3 Or-l N r~ ~
. r~ ~1r-l r-l r Jr-l
.'- - ~_ __ __
' '
-- 27 --
