JPH04175312A - Alpha-olefin polymerization catalyst - Google Patents

Abstract

PURPOSE:To obtain a polymerization catalyst which can keep an ability to perform highly stereoregular polymerization of an alpha-olefin and can exhibit high polymerization activity by mixing activated titanium trichloride with an organometallic compound and a specified organosilicon compound. CONSTITUTION:An alpha-olefin polymerization catalyst comprising activated titanium trichloride (A), an organometallic compound (B) and an organosilicon compound of the formula (C) (wherein R<1> is a 1-10 C hydrocarbon group or R<7>O; R<2> is a 1-10 C hydrocarbon group or R<8>O; R<3> is a 1-10 C hydrocarbon group or R<9>O; R<4> and R<5> are the same or different 1-10 C hydrocarbon groups; R<6> is a 1-10 C hydrocarbon group or OR<11>; and R<7> to R<11> are the same or different 1-10 C hydrocarbon groups). The mixing ratio among components A, B and C is such that 0.5-100g mol of component B is used per g atom of the titanium atoms of component A, and 0.001-10mol of component C is used per mol of component B.

Description

[Detailed description of the invention] Industrial applications The present invention relates to a catalyst for α-olefin polymerization.

Conventional technology α-olefin polymerization catalysts consisting of activated titanium trichloride and organic phosphorous compounds are polymers with different properties from catalysts whose components are so-called magnesium-supported catalysts, in which a titanium compound is supported on a magnesium compound. It also has the characteristics of being able to produce

However, activated titanium trichloride has problems in that it has lower polymerization activity and slightly lower stereoregularity than magnesium-supported catalysts.

A catalyst that combines a magnesium-supported catalyst and an organoaluminum compound further has a 5i-0-'C bond, or one ship's SiR'R', (OR3) a-1, (n
It is known that the use of organosilicon compounds represented by 0 to 2) improves the stereoregularity of the resulting polymer (for example, JP-A-54-94690, JP-A-56-36).
No. 203, No. 57-63310, No. j8-83016
No. 62-11705, etc.).

On the other hand, a catalyst consisting of activated titanium trichloride and an organoaluminum compound was further added with one shipura R', 5i (OR2),
By combining organosilicon compounds represented by h (0≦n4), α-
A method for producing olefin polymers has been proposed (Japanese Unexamined Patent Publication No.
3-238110).

However, despite the improvement in stereoregularity, the polymerization activity may be reduced to less than half of that when no organosilicon compound is used, and the relationship between the improvement in stereoregularity and the decrease in polymerization activity is Depends on the type of.

Problems to be Solved by the Invention An object of the present invention is to provide a polymerization catalyst that maintains high stereoregularity and exhibits high polymerization activity in the polymerization of α-olefins.

Means for Solving the Problems The present inventors have discovered that activated titanium trichloride and organic
As a result of intensive research on organosilicon compounds to be combined with miniram compounds, it was discovered that the objects of the present invention can be achieved by using specific organosilicon compounds having 5i-3i and 5i-0-C bonds. Completed the invention.

The gist of the invention, that is, the gist of the present invention is as follows: (A) activated titanium trichloride, (B) organometallic compound, and (C) -Shinzo [However, R' is a hydrocarbon group having 1 to 10 carbon atoms or R'iSi, R2 is a hydrocarbon group having 1 to 10 carbon atoms, or R60, R3 is a hydrocarbon group having 1 to 10 carbon atoms, or R90, R' and R5 are the same or different groups having 1 to 10 carbon atoms;
10 hydrocarbon groups, R6 is a hydrocarbon group having 1 to 10 carbon atoms, 0R10 or 3i11i11, R7-
R11 is the same or different hydrocarbon group having 1 to 10 carbon atoms. ] is an α-olefin polymerization catalyst consisting of a silicon compound and an organic silicon compound.

Activated titanium trichloride Activated titanium trichloride (hereinafter referred to as component) used in the present invention is obtained by further activating β-type titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound. It is something.

Activation of β-type titanium trichloride is performed by treating the titanium trichloride with an electron-donating compound such as an alcohol, ether, ester, lactone, amine, acid halide, acid anhydride, or the like.

Furthermore, the activated titanium trichloride is treated with an activator such as titanium tetrachloride, silicon tetrachloride, halogen-containing compounds such as hydrogen halides, halogenated hydrocarbons, and halogenated organic aluminum compounds, or halogen elements such as iodine and chlorine. It is also possible to carry out the treatment with the above-mentioned electron-donating compounds in the presence of these activators.

For more detailed preparation methods for the components, see, for example, JP-A-47-34.
No. 478, No. 50-74594, No. 50-74595
No. 50-123090, No. 50-123091, No. 52-107294, No. 53-14192, No. 53-65286, No. 53-65287, etc.

That is, (1) TiCl4 is reduced with an organoaluminum compound, and the obtained solid (hereinafter referred to as reduced solid) is treated with a complexing agent (
A method of treating with an electron-donating compound) and further reacting with TiCl4 (Japanese Patent Application Laid-open No. 34478/1983).

■ A method in which the reduced solid is treated with a complexing agent and further treated with a monoalkylaluminium cibaride (Japanese Patent Laid-Open No. 50-7
No. 4594).

(2) A method in which the catalyst component obtained in (1) above is further treated with a complexing agent (Japanese Patent Application Laid-open No. 74595/1983).

■ A method of treating the reduced solid with a complexing agent and further treating 40 with TiC1 at a temperature below (Japanese Patent Application Laid-open No. 50-1
No. 23090).

(2) A method in which the catalyst component obtained in (1) above is further treated with carbon tetrachloride (Japanese Patent Application Laid-open No. 123091/1983).

■ A method of treating the reduced solid with a chlorinated hydrocarbon having 2 carbon atoms in the presence of a complexing agent (Japanese Unexamined Patent Publication No. 107294/1983)
.

■ A method of treating the reduced solid with a chlorinated hydrocarbon having 3 or more carbon atoms in the presence of a complexing agent (Japanese Unexamined Patent Publication No. 53-141.92
issue).

■ A method of treating the reduced solid with hydrogenated hydrogen under chlorine having 2 or more carbon atoms in the presence of a complexing agent and TiC1 (Japanese Patent Application Laid-open No. 53
-65286).

(2) A method of treating the reduced solid with a chlorinated hydrocarbon having 2 or more carbon atoms in the presence of a complexing agent and AlCl3-ether (
Japanese Patent Publication No. 53-65287).

Component A is prepared as described above, and if necessary, component A may be washed with the above-mentioned inert medium and may be further dried.

In addition, component A further comprises, in the presence of an organoaluminum compound,
Olefin polymers formed in component A upon contact with olefins may also be included. The organoaluminum compound is selected from the organometallic compounds described below, which are one of the components of the catalyst of the present invention.

In addition to ethylene, the olefins include propylene, 1-7
α-olefins such as /tene, 1-hexene, 4-methyl-1-pentene, etc. can be used.

Contact with the olefin is preferably carried out in the presence of the inert medium described above. The contact is usually carried out at a temperature of 100°C or less, preferably -10°C to +50°C. The amount of olefin polymer contained in component A is usually 0 per gram of component A.
．． It is 1-100g.

In the contact between component A and the olefin, an electron-donating compound may be present together with the organoaluminum compound. Particularly preferable electron-donating compounds include carboxylic acid esters, amines, and phosphites. Component A that has been in contact with the olefin can be washed, if necessary, with the above-mentioned inert medium or further dried.

Organometallic compoundsOrganometallic compounds (hereinafter referred to as component B) are listed in No.■ of the periodic table.
It is an organic compound of a group metal to a group II metal. As component B, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly suitable. As organoaluminum compounds that can be used, - Funagura R,, ^lX
3-. ．． (However, R is an alkyl group or a ryoryl group, X is a halogen atom, an alkoxy group, or a hydrogen atom, and n is an arbitrary number in the range of 1≦n≦3.) 1 to 1 carbon atoms such as trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminum monoalkoxide, dialkyl aluminum monohydride, etc.
Particularly preferred are alkylaluminum compounds having 8, preferably 2 to 6 carbon atoms, or mixtures or complexes thereof. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diisobutylaluminum chloride, etc. dialkylaluminum monohalides, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, isobutylaluminum dichloride, monoalkylaluminum dihalides, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, Dialkyl aluminum monoalkoxides such as dimethyl aluminum methoxide, diethylaluminum ethoxide, diethylaluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum Examples include dialkyl aluminum tram hydride such as hydride. Two or more of these compounds can be used in combination.

Furthermore, an organic aluminum compound in which two or more pieces of aluminum are bonded via an oxygen atom or a nitrogen atom can also be used. Such compounds include, for example, (C2L) 2A
10A1 ([:2)1s) 2 .

2H5 etc. can be exemplified.

Organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride, diethylzinc, etc., as well as LiAl(C2Hs), LiAI(C711,s), etc.
), and the like.

Organosilicon Compound The organosilicon compound (hereinafter referred to as component C), which is one component of the catalyst of the present invention, is represented by the above general formula. In training, the hydrocarbon group of R'-R'' is an alkyl group,
Examples include an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkagenyl group, an aryl group, and an aralkyl group.

Alkyl groups include methyl, ethyl, propyl, i-
Propyl, butyl, 1-butyl, S-butyl, t-butyl, amyl, l-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, decyl, etc., and alkenyl groups include vinyl, allyl, propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-octenyl, 1-dekenyl, 1-methyl-1-pentynyl, 1-methyl-1-hebutenyl, etc., cycloalkyl groups include cyclopentyl, cyclohexyl, Methylcyclohexyl group etc., cycloalkenyl group such as cyclopentenyl, cyclohexenyl, methylcyclohexenyl group, etc., cycloalkagenyl group such as cyclopentagenyl, methylcyclopentagenyl, indenyl group, etc. Examples of the allyl group include phenyl, tolyl, and xylyl groups, and examples of the aralkyl group include benzyl, phenethyl, and 3-phenylpropyl groups. For R4 and R5, methyl and ethyl groups are particularly desirable.

Specific examples of component C will be listed below. Note that the general formula is expressed as R'/R2/R'10R'10R5/R6.

In addition, in the following, Me=methyl, Bt-ethyl, Pr
= propyl, Bu = butyl, Amy = amyl, Hex
= indicates hexyl.

■R', R'' and R3 are hydrocarbon groups, and R6 is 0R1
In the case of 0, [R', R'' and R3 are the same, R1,
When R' and R2 are the same, R mountain/R3, OR',
When OR' and OR'' are the same, OR' and OR' and OR
When ' are the same, ([]R') and /OR'' are displayed respectively.]Me10Me, MeloBt,
BtloMe, EtloBt, Mez/
n-n-Pr1O, Mez/n-Pr10Bt.

Mea/l-BuloMe, Mez/1-Bul
oat, Bt2/Me10Me, Btz
/Me10Bt S Me/ (OMe)210Bt
.

Me/ (OMe)z/ 0i-Pr, Me/ (
OMeL/ 0t-Bu, Me/ (DBt)zl
on-Hex, Et/(OMe)z/Di
-Pr.

Me2/ t-Bu/ (OMe) 2/old=Bu,
8t2/ Me/ (OMe)zlon-Hex
0 ■ When R' is R; Si, R2 and R3 are hydrocarbon groups, and R6 is 0R10 [When R2 and R3 are the same, R:iS+/R: and OR
4゜When OR' and OR'' are the same, display as OR', and OR' and [When OR5 are the same, display as (OR') and 10R10, respectively.] Me3Si/Me, 10Me, Me+Si/Mez
/[]OBt.

BtsSt/ Me2/ OMe, Bt3S+/
Me2/OBt, MeaS+/Bt210Me
, MesSi/Bt210Bt, Bt3Si/B
t210Me, Bt+Si/Btz/OBt
, Me3Si/Me/BtloMe, Bta
S+/Me/Bt/OBt, MeaS+/
Bt/1-Pr10Bt, BtsSi/Me/
l-BuloMe, MesSi/Me2/ (
OMe) 210t-Bu, Me3Si/M82/
(OBt)2/ 0nilex, Bt3St/
Me2/(OMe)2/Us-8my.

Me+Si/Me/Bt/ (OMe)210t-Bu
, Bt3Si/Me/Bt/ (OBt)21
0n-Hex, Bt3Si/Me/1-Pr
/(Oat)2/1-Bu, Bt+S+/Me/1
-Bu/(OMe)210S-8mY.

■When R', R2 and R3 are hydrocarbon groups and R6 is a hydrocarbon group [When R', R2 and R3 are the same, R1, R2 and R
When 2 are the same, it is displayed as Rkichi/R3, and when OR' and OR5 are the same, it is displayed as (OR') and /R', respectively. ]M
e/ (OM”e) 2/ Me, Me/ (O
at) 2/ Me, Me/(OMe) 2/
Bt, Me/ (OBt) 2/ Bt, Me/
(OMe) 2/ i -Pr, Me/ (OB
t) 2/ 1-Pr, Me/ (OMe) 2
/ t-Bu.

Me/ (OBt) 2/ t-Bu, Me/
(OMe) 2/ n-Bu, Me/ (OBt
) 2/ n-Bu, Me/ (OMe) 2/
5-Bu, Me/(OBt)z/5-Bu
, Bt/ (OMe)2/ Me, E! t/ (
OBt)z/ Me, Bt/ (OMe> 2/
1-Pr, Bt/ (Of!t)2/ 1-P
r, Me2/n-Pr/(OMe)2/M
e, Mez/n-Pr/(0[1t)2/Me
, Me2/t-Bu/ (OMeL/Bt,
Me2/1-Bu/ (OEt)2/Bt, Me
2/n-Bu/(OBt)2/Me.

Me2/ n-Bu/ (OBt)2/ Me,
Mez/n-Hex/(OMe)2/Me,
Mea/ n-Hex/ (OBt) 2/ Me
, Me2/ s-Amy/ (OMe) 2/
Me, Mez/ s-Amy/ (OBt) 2
/Me.

Me/ (OMe) 2/Cyclopliers JL/, M
e/(OMe)2/cyclopentadienyl.

■When rl' is R1:Si, R2 and R3 are hydrocarbon groups, and R6 is a hydrocarbon group [When R'' and R3 are the same, R:S+/RΔ, OR'
When and OR5 are the same, each is displayed as ([]R')2/R6. ] Me3Si/ Me2/ (OMe) 2/ Me,
MeaSi/Me, /(Oat)2/Me,
BtsSi/Mea/ (OMe)z/ 1-Pr
.

Bt+Si/ Mez/ (OMe) 2/ n He
x.

■R', R2 and R3 are hydrocarbon groups, and R6 is 3i[+
In the case [R', R' and R3 are the same, R1, R2 and R3
When OR' and OR5 are the same, R:/R3 is displayed, and (OR')2/5IRA' is displayed when OR' and OR5 are the same.

]Me/ (OMe) 2/ SiMe, , Me/
(Oat) 2/ SiMe3゜Me/ (OMe)
2/5iBt3, Et/ (OMe)z/SiM
e3, Bt/(OBt)i/SiMe5. Bt
/ (OMe)z/S+Bt+, Bt/(OBt)
z/5iBt3, Mez/n-Pr/ (OM
e) z/SiMe+.

Me2/1-Bu/(OMe)2/SiMe+, B
t,/1-Pr/(OBt)2/S+BL.

■It' is RH5+, R2 and R3 are hydrocarbon groups, and R
When 6 is Si[+ [When R2 and R3 are the same, R:S+/R壬 and OR'
When and OR5 are the same, (OR') =/5iR4' is displayed. ] MeaSi/ Mea/ (OMe) 2/ SiMe
3. Me+Si/ Bt2/(OMe)z/ SiM
es, MesSi/Me2/(OBtL/S
iMe3゜Me+Si/ Mez/ (OMe) 2/
5ifts, MeaSi/Me/Bt/(O
Bt)z/SiMes, Bt3Si/Btz/(O
Bt)2/SiMe+, Bt3S+/Btz/
(OEt)2/S+Bta, MeaSi/M
e/ n-Bu/ (OBt) 2/ SiMe+.

■When R' and R2 are hydrocarbon groups, R3 is R90, and R6 is 0R10 [When R' and R2 are the same, it is called R/R90, and when OR4 and OR5 and OR'' are the same, it is called OR'. OR' and 0f
When t5 is the same, (OR')210ff" is displayed respectively.] Mea/Men10Me, Me2/Men10B
t, Me2/Btu/ OMe, Me2/
Btu/OBt, Mez/1-Pr[]10
Me, Me2/1-PrO/OBt,
Me2/t-BuO/OMe.

Me2/1-BuOloBt, Me2/n-He
xOloMe, Me2/n-)1exO/OB
t, Et2/ Men/ OMe, Bt2
/MeO/OBt, Me/t-Bu/M
en/OMe, Me/t-Bu/MeOl
oBt, (i-Pr)a/MeO10Me,
(i-Pr)z/Men10Bt, Me/s-
^my/ Men/ OMe, Me/ 5-An
y/Men/ OBt, Me2/ Men/ (
OMe) 2/ OBt, Mez/ Men/
(,0Bt) 2/ 0t-Bu, Me-/B
tu/ (OMe) -10n-Hex, Me2/
BtO/ (OBt)zloi-Pr, BLa/
Men/ (OMe) 2/ Oat, Bt2/
Men/ (OBt) 2/ Ot-Bu, B
t2/ Eta/ (OMe)z/ 0n-Hex,
Bt2/ Btu/(OBt) 2/ 0i-Pr
, Me/t-Bu/ Men/ OMe/ OBt
/Di-Pr, Bt/ 1-Pr/ [EtO/
OMe/[]Bt/On-Amy.

■R" is RaSi, R' is a hydrocarbon group, R3 is R90
So, if R6 is OR■, then CUR'; if OR' and OR'' are the same, then OR', and if OR' and OR5 are the same, then (Off') 2/O
Each is indicated as R'. ] Me3Si/ Me/ Man/ [1Me, M
e:+Si/Me/Men/[]Be,
Me+Si/Me/Btu/OMe,
Bt3Si/ Bt/Me(]/ [1Me, B
t3Si/Me/Btu/OMe, Bt3
Si/Me/ Men/ DBt, Bt3Si/
Bt/Eta/OBt.

Me3Si/t-8u/Men/OMe,
Bt3Si/1-Pr/EtO/OBt,
MesSi/ Me/ Men/ (OMe) 2/
0t-Bu.

Me3Si/ Et/ MeO/ (DBt) 2/
[]n-Pr, MesSi/ Bt/ Eta/
(OBt)2/ Di-Pr, Bt3S
i/Me/MeO/(OBLL/Di-Pr,
[1it3Si/ Bt/ Btu/ (OBt)
210i-Pr, BtsSi/Me/BtD
/ (OMe) 2/ Us-Amy.

■When R' and R2 are hydrocarbon groups, R3 is R'O, and R6 is a hydrocarbon group [When R' and R2 are the same, RΔ/R90, and when OR' and OR5 are the same, ( OR') 2/R6, respectively. ] Me2/ MeD/ (OMe) 2/ Me,
Me2/ Men / (OBt) 2/ Me,
Mez/ Btu/ (OMe) 2/ Me,
Me2/Btu/(D[!t)a/Me, M
e2/ 1-Pro / (OMe)2/Me, M
82/ 1-Pro/ (O[Et)2/Me, M
e2/5-BuO/ (OMe)2/Me, Mea
/5-Bun/ (Of'!t)2/Me, Mez
/t-AmyO/(OMe)2/Me,
Mez/ wo -8myo/ (OBt)2/ Me
.

Mez/n-11exO/(OMe)2/Me,
Mez/n-HexO/(OEt)2/Me,
已t2/ Men/ (OMe)2/ Me,
Bt2/Men/(OBt)2/Me, Me/
n-Pr/Men/(OMe)2/ Bt, Me
/ n-Pr/ MeO/ (OBt) 2/ Bt
, Me/1-Bu/Men/(OMe)2/Me
, Me/1-Bu/MeO/(OBt)2/ Me
, Men/ Men/ (OMe)z/ Bt
, Mea/Men/ (OBt)2/Bt , Me
2/Men/ (OMe)2/1-Pr.

Mez/ Men/ (OBt) 2/ 1-Pr,
Me2/ Men/ (OMe) 2/ t-Bu
, Me2/ Men/ (OBt) 2/ t-
Bu, Me2/ Men/ (OMe) 2/cyclohexyl, Mez/ Men/ []Me/
OBt/ Bt, Mez/ Btu/ OMe/
OBt/ t-Bu, Bt2/ Men/ O
Me/OBt/1-Pr, Me/t-Bu
/ Men10Me/ OBt/ Me, Bt/
1-Pr/Btu/OMe/OBt/n-He
x.

(I R' is R'iSi, R2 is a hydrocarbon group, R3 is R
When 'O' and R6 is a hydrocarbon group [When OR4 and OR5 are the same, it is expressed as (OR')2/R'. ] Me3Si/ Me/ Men/ (OMe> 2/
Me, Me3Si/ Bt/Men/ (DMe)
2/ Me, Me+Si/ Bt/mouth to
/ (OMe)2/Me, Me3S+/ Bt/
[! to/ (OBt)z/ Bt, EtaS+
/Me/Men/(OMe)z/Me, Bt3Si
/Bt/MeO/(OMe) 2/Me, Bta
Si/ Bt/ Eta/ (OMe) 2/ Me
.

Bt+S+/ Bt/mouth to/ (OBt)2/ Bt
, MeaS+/ Et/Men/ (OBt)
2/t-Bu, BtsSi/Me/IEt
ll/ (OMe) 2/ 5-Bu, MesSi
/ Me/ Men/ OMe/ []lEt/ Me
.

Bt3Si/ Bt/ Men/ OMe/ OBt/
1-Pr'.

When OR1 and R2 are hydrocarbon groups, R3 is R'0, and R8 is S+RA' [When R' and R2 are the same, R'2/R'O and OR'
and OR' are the same, (OR') 2/5iRA'
are displayed respectively. ] Me2/ Men/ (OMe) 2/ SiM+,
, Me2/ Btu/(OMe) 2/ SiMea
, Mez/ Men/ (Oat) 2/ SiM
ea.

Mez/ Men/ (OMe) 2/ 5iBt+
, Eta/ Men/ ([]Me) 2/ SiM
e3. [! t2/ Btu/ (OMeL/ SiM
e3. Btz/Men/(OMe)z/5i8t+
, Bt2/BtO/(0[l!t)a/5iBt3
, Me/Bt/MeO/(OBt)z/51M8s
, Me/Et/Btu/(OMe)2/5iRt+
, Me/1-Br/Btu/(OMe)2/SiMe+
, Bt/s-Amy/Man/ (OBt)2/S
iMe+, 1-Pr/n-Bu/Men/ (
DMe) 2/5iBta.

Me/Bt/Men/DMa10at/SiMe3
, Bt/1-Bu/MeO10Me10at/5iBt
＋.

@R' KaRH5i, R''-/)<Hydrocarbon M, R3
KaR'aOte, R6 Ka5IRa' 0:) [When OR4 and [lR' are the same, (OR') 2/
Display on SiR8l. ] Me, Si/ Me/ MaO/ (OMe) 2/
SiMea, MeaSi/ at/ MeO/ ((
]Me) 2/SiMas, Me3Si/Me
/ BtO/(OMe) 2/ SiMe+, Bt
sSi/ Me/ Men/ (OMe) 2/SiM
e+, II! t+Si/Bt/Man/(DMe
)a/SiMes.

Bt3S+/ Bt/ Btu)/ (OMe) 2/
SiMe3. BtaS+/Me/MeO/ (
OMeL/ 5iBta, BtaSi/ Bt/
BtO/ (OBt) 2/ 5ifts, Mes
S1/Me/Men/OMe10Bt/SiM
e+, Bt3Si/ Bt/ Btu/ OMe
/ OBt/S+Bti.

@ R' b < 1 tM of hydrocarbon, R2 Ka R'0 , R3 Ka R1 l0 Te, If R6 is "OR" [If R80 and R90 are the same, R'/ (Il'O)
, and Of', when OR5 and 0R10 are the same, OR', and when OR' and OR5 are the same, (OR')
2/OR” respectively.] Me/ (Men)zloMe, Me/ (Men
>210at, Bt/(MeO)z/OMe,
[! t/ (Men)2/ OBt, Me/ (
BtO)210Me, Me/ (BtO)zloB
t, Me/(n-PrO)zloMe, Me
/ (n-PrO)10Bt, Me/ (Men)
/ (t-BuO)/OMe, Me/ (Men
) / (t-Bun) / OBt.

Me/ (Men) 2/ (OMe) 2/ 0t-
Bu, Me/ (Men) 2/(Oat) 2/
Di-Pr, Me/Men/t-Bun/
(OMe) 2/0n-Hex, Bt/Bt
u/ 1-PrO/ (OBt)2/ 0i-Bu,
Me/ Eta/ n-Bun/ OMe/ Btu
/ 0n-)1ex 0■R1 is RaSi, R2 is R
[When 1O1R3 is R'0 and R6 is OR'' [When R80 and R1l0 are the same, R:S+/ (R'
O) When 2, Of', OR5 and OR'' are the same, it is OR', and when OR' and OR5 are the same, it is (OR')
2/OR” respectively.] M+, Si/ (MeO)210Me, Me
+Si/(BtO)210Me.

Me+Si/ (Men)210at, Bt3Si/
(Btu)210Me.

Bt3S+/ (Men)z/ OBt, Bt3
SI/(BtO)2/OBt.

Me3Si/ (n-Pro)210Me, Bts
Si/Btu/1-PrOloBt, Me+
Si/MeO/n-BuOloMe, Me3S
i/(Men)2/ (OMe)210t Bu,
Me3S+/ (BtO)a/(OMe)2/ 0
n-Hex, Bt3Si/ (Me0)2/ (O
BtL2/Old-Pr, MesSi/Men/
1-BuO/(OMe)210s-^my.

Bt3Si/Btu/i-ProloMeloBtl
on-flex 0■R1 is a hydrocarbon group, R2 is R1l
01 When R3 is RIIO and R6 is a hydrocarbon group [When R60 and R90 are the same, R'/ (RIIO)
2, and when OR' and OR5 are the same, (OR')2/
Each is indicated as R'. ] Me/ (Men) 27 (OMe) 2/ Me
, Me/ (Men) 2/(OBt) 2/ M
e, Bt/ (Men), / (OMe) 2
/Me.

Bt/ (BtO)2/ (OBt)z/ Me,
i Pr/ (MeO)2/(OMe)2/ Me
, 1-Pr/ (Men) 2/ (OBt)
2/Me.

n-flu/, (Men) 2/ (OMe) 2/
Me, n-Bu/ (Men), /(OBt)2
/ Me, Me/ (n-PrO)z/ (OM
e) 2/Me.

Me/ (n-PrO)2/ (OBt)z/Me
, Me/ (s-Bun)z/ (OMe)z/
Me, Me/ (El-BLIO)2/ (
OBt)z/Me.

Me/Men/n-HexO/ (OMe)2/Me
, Me/Men/n-tlexo/ (Oat
)2/Me, Bt/ (Men)2/ (O
Me) 2/Bt, Bt/ (Men)z/ (
OBt) 2/ Bt, Vinyl/(Men) 2/ (
OMe) 2/vinyl, vinyl/ (Bto) 2/(
Oat) , /vinyl, Me/ (Men) 2/
OMe/ OBt/Me, Me/ (EtO
)2/[]Me10Bt/Bt , Bt/ (BtO
)z10Me10Bt/Me, Et/ (Bt
u) 210Me10at/at, Me/Men
/ Btu/ OMe/Kanot/Bt, Bt/Me
n/Btu10Me10Bt/Bt.

@R' is a hydrocarbon group, R2 is R''O, R3 is R90,
When R6 is St RA l [R'0 and R90-b<same (7) then R'/(R
'0), G, OR' and HOR' M same (D, H (OR)
')2/5IRA' Display each. ] Me/ (Men) 2/ (OMe) 2/ SiM
e3. Me/ (Men) 2/(OBt) 2/
SiMea, Me/ (Men) 2/ (OMe
) 2/5iBt*.

Bt/ (Men)2/ (OMe)z/ S+Me+
, Bt/ (BtOL/(OMe) 2/ SiM
e3. Bt/ (Men) 2/ (OBt) 2/
SiMe+.

Bt/ (Men)z/ (OMe)2/5iBt3
, Bt/ (RtO)2/(OEt) 2/ 5iBt
, , Me/ Men/ Btu/ []Me/
OBt/S+Me3, Bt/Men/Btu10Me
10Et/S+[t,.

1-Pr/ (Men), / (OMe>2/ SiM
e3. n-Bu/ (MeO)2/ (OMe)
2/5ift3. Me/ (s-BIIO) 2
/ (OBt) 2/ SiMe3. vinyl/ (
Men) 2/ OMe/ OBt/ SiMe3゜＠
R' KaR: St, R"KaR"0, R3 KaR'0
Te, in the case of R6ka5iR4' [When R80 and R90 are the same, R:S+/ (R80
)2 and OR' and OR' are the same 1;! (OR
') 2/ S+RA' c! : Display each. ] MeaSi/ (Men)2/ (OMe)z/ Si
Mea, Me+Si/(Btu) 2/ (OMe
) 2/ SiMe3, Me3Si/ (Men
) 2/(OBt) 2/ SiMes, Me3
Si/ (Men) 2/ (OMe) 2/ 5iE
ta, MeaSi/(BtO)2/(OBt)z/
5 iBt.

Bt+Si/(Men>2/(OMe)2/5iBt3
．． Bt+Si/(Btu) 2/ (OBt) 2
/ 5ift3. Me+Si/ Men/ Btu
/(OMe) 2/ SiMe3. Me3Si/
(Btu) 2/OMe/OBt/SiMe3,
BtsSi/ Men/ Btu/ (OMe)
2/ SiMe3゜Bt+Si/ Men/口tO/
OMe/OBt/S+Bt+.

The catalyst of the present invention consists of component A, component B, and component C.
The composition ratio of component B is 0.5 to 100 g mol, preferably 1 to 100 g mol per 1 gram atom of titanium in component A.
40 g mol, component C is 0.0 for 81 mol of component
It is used in an amount of 0.01 to 10 mol, preferably 0.01 to 1.0 mol.

Polymerization of α-olefins The catalyst of the present invention is suitable for homopolymerization of α-olefins having 3 to 10 carbon atoms or other monoolefins or monoolefins having 3 to 1 carbon atoms.
It is particularly useful as a catalyst for copolymerization with C3 to C6 alpha-olefins, such as propylene, 1-butene, 4-methyl-1-pentene,
It exhibits extremely excellent performance as a catalyst for homopolymerization of 1-hexene, etc., or random and block copolymerization with each other and/or with ethylene.

The polymerization reaction may be performed in either a gas phase or a liquid phase, and when polymerizing in a liquid phase, normal butane, isobucune, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. (7) It can be carried out in activated hydrocarbons and in liquid liquid. Polymerization temperature is usually -80°C to +150°C,
Preferably it is in the range of 40 to 120°C. The polymerization pressure is
For example, the pressure may be 1 to 60 atmospheres. The molecular weight of the resulting polymer can also be controlled by the presence of hydrogen or other known molecular weight regulators. In addition, the amount of other olefin to be copolymerized with α-olefin in copolymerization is
Usually up to 30% by weight, especially 0.3% by weight based on α-olefin.
-15% by weight. The polymerization reaction using the catalyst system according to the present invention may be carried out in a continuous or batchwise reaction, and the conditions may be those commonly used. Further, the copolymerization reaction may be carried out in one stage, or may be carried out in two or more stages.

Effects of the Invention The catalyst of the present invention can produce a highly stereoregular polymer in high yield in the polymerization of α-olefins.

EXAMPLES The present invention will be specifically explained by examples and application examples. Note that percentages (%) in the examples are based on weight unless otherwise specified.

The heptane-insoluble content (hereinafter abbreviated as 81), which indicates the proportion of crystalline polymer in the polymer, is the residual amount when extracted with N-hebutane for 6 hours using an improved Soxhlet extractor.

Example 1 Preparation of component A (activated titanium trichloride) Twenty-one flasks equipped with a stirrer were placed in a constant temperature water bath kept at 0°C, and 700 mjl! of purified hebutane and 250 rnl of titanium tetrachloride were added and mixed. Next, set the temperature of this hebutane solution of titanium tetrachloride to 0°C.
315-diethylaluminum chloride, 117-ethylaluminum dichloride and 40
A mixture consisting of 0rd purified hebutane was mixed dropwise over a period of 3 hours. After completion of the dropwise addition, the contents were heated with a stirrer and brought to 65° C. after 1 hour, and further stirred at this temperature for 1 hour to obtain a reduced solid. The resulting reduced solid was separated, washed with purified heptane, and then incubated at 65°C under reduced pressure for 3
Dry for 0 minutes.

Next, a suspension of 25 g of this reduced solid is dispersed in 100 mf of purified hebutane is prepared, and then an amount of hexachloroethane corresponding to 1 gram mole of hexachloroethane per gram atom of titanium in the reduced solid is added to the suspension. was added in the form of a solution containing 25 g of hexychloroethane in 100 d, and a further 0.0 g of titanium per gram atom of titanium in the reduced solid. Di-n-butyl ether in an amount corresponding to 100 g moles was added and mixed with stirring.

Next, this mixed solution was heated to 80°C with stirring, and after stirring for 5 hours, the obtained solid was washed 5 times with 100-purified butane and dried at 65°C for 30 minutes. Component A was prepared.

1, 51 with a propylene polymerization stirrer installed! Component A1 obtained above was placed in a stainless steel autoclave under a nitrogen gas atmosphere.
A solution containing 2.7 mg, 1 mol of diethylaluminum chloride (DEAC) in n-hebutane 11 and 0.2 mol of 1.1 in n-hebutane 1β
-dimethoxy1.2,2.2-tetramethyldisilane (
Hereinafter, it will be referred to as XMMS. ) containing solution 1- was mixed and held for 5 minutes. Next, after adding 750 d of hydrogen gas as a molecular weight control agent and 11 ml of liquid propylene, the temperature of the reaction system was raised to 70° C., and propylene was polymerized for 1 hour. After the polymerization was completed, unreacted propylene was purged to obtain a white polypropylene powder containing 2.9% HIO.

The polymerization activity (RT) of the catalyst was 5.5 kg/g/component A.

Example 2.3 Propylene polymerization was carried out in the same manner as in Example 1, except that the organosilicon compounds shown in Table 1 were used instead of XMMS, and the results are shown in Table 1.

Comparative Example I Polymerization of propylene was carried out in the same manner as in Example 1, except that XMMS was not used. The results are shown in Table 1.

Examples 4 to 6 Polymerization of propylene was carried out in the same manner as in Example 1, except that triethylaluminum was used instead of DEAC as the organometallic compound, and the compounds shown in Table 1 were used instead of XMMS as the organosilicon compound. The results are shown in Table 1.

Comparative Example 2 Propylene was polymerized in the same manner as in Examples 4 to 6 except that no organosilicon compound was used, and the results are shown in Table 1.

Table 1 Example Organosilicon Compound RT
Hl (Kg/g・Component A) (%) Example I Me, Si-3i (51-3i (O5
,497,9〃2 MeaSi-3i(OBt)
35J 97,3〃3
Me, 5i-5i (mouth Me) 2 (Ot-Bu)
5.9 97.8 Comparative Example 1 2.0
97.0 Example 4 Me, 5i-3i (
OMe), 11.8 96.
1〃5 Bt3Si-3i (OMe)s
14.9 95.7〃 6
MesSi-3i(OMe)2cyclopentyl 16.8 9
6.6 Comparative Example 2 1
8.5 '84J

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing the steps for preparing the catalyst of the present invention.

Claims (1)

[Claims] (A) Activated titanium trichloride, (B) Organometallic compound, and (C) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, R^1 has 1 to 10 carbon atoms] or R^7_3Si, R^2 is a hydrocarbon group having 1 to 10 carbon atoms, or R^8O, R^3 is a hydrocarbon group having 1 to 10 carbon atoms, or R^9O, R^4 and R^5 are the same or different hydrocarbon groups having 1 to 10 carbon atoms, R^6 is a hydrocarbon group having 1 to 10 carbon atoms, OR^1^0 or SiR
^1^1_3, and R^7 to R^1^1 are the same or different hydrocarbon groups having 1 to 10 carbon atoms. ] An α-olefin polymerization catalyst comprising an organosilicon compound represented by: