JPH02286703A - Liquid catalyst component, polymerization catalyst comprising the same component, and production of ethylene/alpha-olefin copolymer by using the catalyst - Google Patents

Abstract

PURPOSE:To obtain the title liquid catalyst component for the production of the title copolymer having a narrow compositional distribution and a high MW and improved in weathering resistance, coloration and anticorrosiveness by reacting a specified titanium compound with a specified compound. CONSTITUTION:A liquid catalyst component for the production of an ethylene/alpha- olefin copolymer is obtained by reacting a titanium compound of formula I [wherein R<1> and R<2> are each a 1-30C hydrocarbon group; X is a halogen atom; Y is an alkoxyl; 1<=m<=3; 0<=n< and 1<=(m+n)<=3] with a compound of formula II (wherein R<3> and R<4> are each a 1-30C hydrocarbon group or a 1-30C alkoxy). By using a polymerization catalyst obtained by reacting the obtained component with an organoaluminum compound, it is possible to produce an ethylene/alpha-olefin copolymer having a narrow compositional distribution and excellent weathering resistance, colorability, anticorrosiveness and mechanical properties.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a liquid catalyst component for producing an ethylene-a-olefin copolymer, a catalyst, and a production method using the same. More specifically, the present invention relates to catalyst components for producing ethylene-α-olefin copolymers, catalysts, and production methods using the same, which have a narrow composition distribution and are excellent in weather resistance, color resistance, corrosion resistance, and mechanical properties.

<Prior art> In general, a method for producing an ethylene-α-olefin copolymer is to use a so-called Ziegler-Natsuta catalyst consisting of a transition metal compound of groups 1 to 2 of the periodic table and an organometallic compound of groups 1 to 2 of the periodic table. The methods used are widely known.

On the other hand, it is desirable that the composition distribution of the ethylene-α-olefin copolymer odor be narrow in terms of practical physical properties.
It is produced using a catalyst system consisting of a vanadium compound such as VCts, VOCls, V○(OR)5, etc. and an alkyl aluminum halide such as Et3At2Cl3.

However, in such a catalyst system, the obtained ethylene-α-
Although the composition distribution of olefin copolymers is narrow, there are problems such as low productivity due to low polymerization activity at high temperatures, and problems such as coloration, weather resistance, and corrosion due to residual vanadium and chlorine. In addition, when these catalysts are used to copolymerize with α-olefins having a large number of carbon atoms, the molecular weight of the resulting ethylene/α-olefin copolymer decreases. Therefore, it is difficult to say that it is necessarily sufficient in terms of practical physical properties.

In order to solve the above-mentioned problems, a method using a catalyst system consisting of a titanium compound or a zirconium compound and an aluminum compound has been disclosed.
In particular, a method using a catalyst system consisting of a titanium compound or a zirconium compound and aluminoxane has recently been proposed.

However, since the ethylene-α olefin copolymer obtained from this catalyst system has a low molecular weight, it cannot be said that it has sufficient practical properties.

In addition, as a method for polymerizing or copolymerizing olefins using a catalyst system consisting of a compound having a titanium nitrogen bond and an organoaluminum compound, a solid component in which a titanium amide compound or an alkali metal salt of a titanium amide compound is supported on magnesium halide is used. and a method of polymerizing ethylene using a catalyst system consisting of an organoaluminum compound (DE
2030753), a method of copolymerizing ethylene and α-olefin using a catalyst system consisting of a titanium amide compound containing a π-aryl ligand and aluminoxane (Japanese Unexamined Patent Publication No. 6
2-121708), using a catalyst system consisting of a titanium Schifnylamide compound and an organoaluminium compound,
A method of copolymerizing ethylene or ethylene with α-olefin (EP O10'4374), a method of copolymerizing α-olefin or ethylene with α-olefin using a catalyst system consisting of a titanium amide compound having an aryl substituent and an organoaluminum compound. Polymerization method (Japanese Patent Publication No. 42-226
91), and a method of homopolymerizing ethylene and α-olefins or copolymerizing ethylene and α-olefins using a catalyst system consisting of a titanium amide compound having a lower alkyl group such as diethylamide titanium trichloride and an organoaluminum compound ( Special public show 4l-5379
), (J, Polym, Sci, Part A
-1,241,6 (1968)) A method for polymerizing ethylene using a catalyst system consisting of titanium tetrakis diphenylamide and an organoaluminum compound (Japanese Patent Publication No. 42-11
646) etc. have been disclosed.

However, even if the copolymerization of ethylene and α-olefin is carried out using the catalyst system disclosed therein (German Patent No. 2030753), the method disclosed in this publication does not produce an ethylene-α-olefin copolymer. The composition distribution of is wide, and the molecular weight of the copolymer obtained by the method disclosed in JP-A-62-121708 is low, and (E, P 0
104374, Special Publication No. 41-5379, Special Publication No. 42
-22691. J, PolVm, 5ciPart
A-1, 241, 6 (1968)), the narrow composition distribution of the resulting copolymer is still far from satisfactory;
) In the disclosed method, the narrow composition distribution and catalytic activity of the resulting copolymer were still far from satisfactory.

Further, as a method for producing an α-olefin polymer using an electron donating compound such as a diketone compound or a diester compound, for example, a method consisting of a titanium halide, an electron donor such as a digtone compound or an ester compound, and magnesium halide can be used. A method for producing an α-olefin polymer using a catalyst system consisting of a solid catalyst and an organoaluminum is known. (Japanese Patent Application Laid-open No. 57-151603) However, even if ethylene/α-olefin copolymerization is carried out using such a catalyst, the composition distribution of the resulting copolymer is wide, and it cannot be said that the composition is necessarily sufficient in terms of practical physical properties. hard.

<Problems to be Solved by the Invention> Under the present circumstances, the problem to be solved by the present invention, that is, the purpose of the present invention is to use a new catalyst that has a narrow composition distribution, a high molecular weight, and a weather-resistant color, It is an object of the present invention to provide a liquid catalyst component for polymerizing ethylene and α-olefin for producing an ethylene-α-olefin copolymer with improved corrosivity, a polymerization catalyst, and a manufacturing method using the same.

Means for Solving the Problems> The present invention provides (A> (a) - Clothes cost (R'R2N +4(m+
n) 'ri XmYn (However, R1 and R2 have 1 carbon number
~30 hydrocarbon groups (RI, R2 may be the same or different from each other), X is a halogen, Y is an alkoxy group, m is a number of 1≦m≦3, and n is a number of O≦n3. m-hn) is 1≦(m1n)≦3. ), and (b) -clothing cloth''-c-cH2-c-R4 (where R3 and]111 R4 is a hydrocarbon group having 1 to 30 carbon atoms and/or 1 carbon number);
A liquid for producing an ethylene-α-olefin copolymer, which is obtained by reacting a compound represented by ~30 alkoxy groups (R' and R' may be the same or different from each other). A catalyst component and a polymerization catalyst for producing an ethylene-α-olefin copolymer characterized in that it is obtained by reacting the liquid catalyst component with (5) an organoaluminum compound, and a production method using the same. It is.

Hereinafter, the present invention will be explained in detail.

The titanium compound (a) used in the synthesis of the catalyst component hole in the present invention is -R'R2N +a-(m+
n) TiXmYn (However, R1 and R2 have 1 or more carbon atoms
30 hydrocarbon groups (R' and R2 may be the same or different), X is /'trogen, Y is an alkoxy group, m is 1≦m≦3, n is 0≦n (3) The number (m+n) is 1≦(m+n)≦3. ) is a titanium compound represented by

Next, a specific example of such a suitable titanium compound is dimethylamide titanium trichloride.

Bis(dimethylamide) titanium dichloride tric(dimethylamide) titanium chloride.

Diethylamide butane trichloride, bis(diethylamide) titanium dichloride, bis(diethylamide)
Titanium dichloride, tric(diethylamide) titanium chloride, di-isofuropyramide titanium trichloride, bis(di-isofurobilamide) titanium dichloride.

tric(di-isopropylamide) titanium chloride,
Di-isobutyramide titanium trichloride, bis(di-isobutyramide) titanium dichloride, tric(di-isobutyramide) titanium chloride, i;-ter
t-Butyramide titanium trichloride, bis(di-t)
ert-butyramide) titanium dichloride, tris(
Di-tert-butylamide) titanium chloride, dibutylamide butane trichloride 1 Bis(dibutylamide) titanium dichloride, tris(digtylamide)
Titanium chloride, dioctylamide titanium trichloride, bis(dihexylamide) titanium dichloride,
Tris(dihexylamide) titanium chloride, dioctylamide titanium trichloride, bis(dioctylamide) titanium dichloride, tris(dioctylamide) titanium chloride, didecylamide titanium trichloride, bis(didecylamide) titanium dichloride, tris(´;decylamide) Titanium chloride, dioctadenylamide titanium trichloride, bis(dioctadecylamide) titanium dichloride, tris(dioctadecylamide) titanium chloride, di-arylamide titanium trichloride, bis(di-arylamide) titanium dichloride, tris( di-arylamide) titanium chloride, di-propenylamide titanium trichloride, bis(di-propenylamide) titanium dichloride, tris(di-propenylamide) titanium chloride,
Ethoxy (dimethylamide) titanium dichloride, ethoxy (dioctylamide) titanium dichloride, butoxy (dioctylamide) titanium dichloride, hexyloxy (dioctylamide) titanium dichloride, 2-ethylhexyloxy (dioctylamide) titanium chloride, decyloxy (dioctylamide) titanium dichloride Titanium dichloride, ethoxy ('; didecylamide titanium chloride, hexyloquine (didenylamide) titanium dichloride, 2-ethylhexyloxy (didecylamide) titanium chloride, decyloxy (dioctylamide) titanium dichloride, ethoxy (dioctadecylamide) titanium dichloride , 2-ethylhexyloxy(dioctadecylamido)titanium dichloride.

Desyloxy (dioctylamide) titanium dichloride,
Hexyloxybis(dioctylamide) titanium chloride, 2-ethylhexyloxybis(dioctylamide)
Titanium chloride, desiloquinbis(dioctylamide) titanium chloride, hexyloxybis(didecylamide)titanium chloride, 2-ethylhexyloxybis(
didecylamide cutitan chloride, desyloxibis (
Examples include (didecylamide) titanium chloride.

Among such titanium compounds, when R1 and R2 are linear aliphatic hydrocarbon groups (because the composition distribution becomes narrower, dimethylamide titanium trichloride, bis(dimethylamide)titanium dichloride, trichloride ( dimethylamide) titanium chloride, digtylamido titanium trichloride, bis(dibutylamide) titanium dichloride, tric(dibutylamide) titanium chloride, dioctylamide titanium trichloride, bis(dioctylamide) titanium dichloride, tric(dioctylamide) titanium chloride , didecylamide titanium trichloride, bis(didecylamide) titanium dichloride, tris(didecylamide) titanium chloride, dioctadecyl, ruamide titanium trichloride, bis(dioctadecylamide) titanium dichloride, tris(dioctadecylamide) titanium chloride, ethoxy( dioctylamide) titanium dichloride, ethoxy(didenylamide) titanium dichloride, (dioctadecylamide) titanium dichloride, etc. Among these titanium compounds, especially when R' and R2 are linear aliphatic saturated hydrocarbon groups, If the number of carbon atoms is 8 or more, the titanium compound becomes liquid and the composition distribution becomes narrower.
Bis(dioctylamide) titanium dichloride, tris(dioctylamide) titanium chloride, didecylamide titanium trichloride, bis(didecylamide) titanium dichloride, tris(didecylamide) titanium chloride, dioctadecylamide titanium trichloride,
Bis(dioctadecylamide) titanium chloride, tris(dioctadecylamide) titanium chloride, 2-
Examples include ethyloxy(didecylamide) titanium dichloride, decyloxy(dioctylamide) titanium dichloride, and ethoxy(dioctadecylamido)titanium dichloride.

Further, the present invention is directed to the above-mentioned compounds (the nature of which should not be limited to these).

The method for synthesizing such a transition metal compound containing a secondary amide group is described in Japanese Patent Publication No. 42-11646, H, Btir
ger et al. J. Organomet.
Chem.

108 (1976) 69-84, H, Bii
rger et al J.

Organomet, Chem, 20 (1969
) 129-139 etc. can be used.

The present invention (herein, according to these methods, (i)
- R'R8NH (R' and R8 are saturated hydrocarbon groups having 8 to 30 carbon atoms, and from the viewpoint of liquefaction of the titanium compound to be produced, preferably R7 and R8 are 8 to 30 carbon atoms.
30 aliphatic saturated hydrocarbon groups, more preferably R7 and R8 are linear aliphatic saturated hydrocarbon groups having 8 to 30 carbon atoms. ) with a secondary amine compound represented by (11)-R9M (R9 is a hydrocarbon group having 1 to 30 carbon atoms, M is L
1+ Represents an alkali metal such as K. ) to synthesize an alkali metal amide compound, and then react with the alkali metal amide compound and (iii) general 2 Tlx4 (X, chlorine, bromine,
Halogen such as iodine, preferably chlorine. ) was synthesized by reacting titanium tetrahalide represented by

The compound (b) used in the synthesis of the catalyst component (g) in the following (this invention G) is as follows: 30 hydrocarbon groups and/or 1 carbon number
It is a compound represented by ~30 alkokyne groups (R' and R' may be the same or different from each other).

Specific examples of such compound (b) include the compounds described below.

CH3(CO)CH2(CO) CHs, CHs
(Co) CH2(CO)C2H5゜CH3(CO)C
H2(Co)C3H5, CH3(CO)CH2(Co)
is.

C3H7, CHs (CO) CH2(CO)C4H9
,CH3(CO)CH2(CO)C6H,3,CHx(
CO)CH2(CO)C10H2+, CH3(Co
)CH2(CO) cyclo C6HI2,
C2H3(CO)CH2(Co)C2H5.

C2H3(Co)CH2(Co)CaI7. C2H
3(CO)CH2(CO)C4H7C2H5CCO)C
H=CH2)C6H,3,C2H3(Co)CH2(C
O) C, CH21゜C2H5(Co) CH2(Co)
CI2 H25, C2Hs (Co)CH2(Co)
CyC10C6H,2,C6H,5(Co)CH2(
Co)CH3,C6Hl3(Co)CH2(Co)C,
H7,C6H,3,(Co)CH2(CO)iso
C3H7, C6H1s(Co)CH2(Co)ter
tc4H9, C6H+3(Co)CL(CO)C6H1
3C6H,5(Co) CH2(CO) cyclo
C6H52, cyclo C6HI2(Co)CH
2(Co)cyclo-C6H,2,CHx(CO)C
Hz(Co)CH=CH2,CI(3(CO)CH2
(Co) CH2CH= CH=CH2(Co)CH2
(Co) (CH2) 2 CH= CH2, CHs
(Co) CH2(CH=CH2)4CH=CH2,
CH=CH2)CH2(Co) C(CH3)=CH
2CH3(CO)CH2(Co)CH2-C(CH3)
= CH2, CI(t(Co)CH2(CO)C
H= CHCHs, C2H5(CO)CH2(CO
)CH=CH2゜C2E(S(Co)CH2(Co)
(CH2)2CH=CH2,C285(Co)CH2(
C■C(CHx)=CH2CHs(Co)CH2(Co
)CH2CH=CH2゜C4H9(CO)CH2(CO
)CH=CH2,C4H9(CO)CH2(CO)C
(CI(3)=CH2,C6Hl3(CO)CH2(C
O) CH= CH2, C6H4x(Co)CH2(C
o) CH2CH=CH2, CyC10C6F(1□(C
O) CH2(CO)CH=CH2,C,CH21(Co
)CH2(CO)CH=CH2゜C,OH2,(Co)
CH2(CO) C(CH5) = CH2, CL(C
O)CH2(Co)C6H5,C2H3(CO)CH2
(CO)C6H5, C5H7CC○)CH2(CHCH
2.

iso C5Hy (Co)CH2(CO)C6H5
,C4H9(CO)CH2(CO)C6H.

ter t C4H9(CO)CH2(CO)C6H
s, C6H+3(Co)CH2(Co)CJ(sCI
OH21(CO)CH2(CO) CA H5, Cyc
10 C6HI2 (Co)CH2(CO)C6Hs
, CHs (Co)CH2(CO)C,2H,. ,
C5H7(Co)CH2(Co)C,2H,o.

CaI2(Co)CH2(Co)C+2H+a, C1
oH2, (Co)CH2(CO)C+2H+.

Cl2H25(CO)CH2(Co)CI2H,o,
CH2= CH(CO) CH2(CO)CHCH2,
CH2=CH(CO)CH2(Co)CH2CH=CH
2CH2=CH(CO)CH2(CO)CH2-CH=
CH2, CH2=CH(Co) CH2(Co) (C
H2) 2 CH= CH2, CH2= CH(Co)
CH2(Co)C(CH3)CH= CH2, CH2=
CH(CH3)C(Co)CH2(Co)C(CL)C
H=CH2, CH2=CH(CO)CH2(Co)C,
tH5, CH2=CH(CH5)C(Co)CH2(C
O) C6H5, C4H9CH= CI CH2(Co
)CH2(Co)CH2(Co)C6H5, CH2=
CH(Co)CH2(CO)C42H4゜, CH2=C
H(CH3)C(Co)CH2(Co)C42HI. .

C4H9-CH= CH-CH2-(Co)CH2(C
o) β-diketone compounds such as C, 2H, O, etc.

CH3(Co)CH2(Co)OCHs, CH3(
Co)CH2(CO)○C5H7CH3(Co)CH2
(CO)Oiso C3H7,CH3(Co)CH2(
CO)○C-H9CH5(CO)CH2(Co)Ot
-C4H9,CH,(Co)CL(Co)OC6H,3
CH, (CO)CL(Co)O-cycloC6H,2
,CL(Co)CL(Co)○C,oH21,C2H3
(CO)CH2(CO)○C2H5, C2H5(CO)
CH2(Co)OC,H9,C2H3(CO)CH2(
Co)αtC4H9), C2H3(CO)CH
2(Co)OC4°H21, C2H5(Co)CH2(
CO)CI2H2S, C2H3(Co)CH2(C
O) cyc lo -C6H+2. C4H9(Co
)CH2(CO)OC3H7゜C-H9(Co)CH2
(Co) 0C4H9, C4H9(CO)CH2(Co
)QC+oH2iCJ(+x(Co)CL (CO)O
CH,,C6H,5(Co)CH2(Co)OC,H7
.

C6H, (Co)CH2(CO)O-1so-CsHy
, C6Hl3(CO)CH2(Co)OC6H+s
, C6Ht3(Co)CH2(Co)O(cyclo
-C6HI2) C6H+3(Co)CH2(CO)
0CIOH2+, Cyclo C6HI2(Co)
CH2(Co)cyclo-C6HI2. CHg(
Co)CH2(Co) 0-CH2CH=CH2゜CH
5(CO)CH2(CO)O-(CH2)2CH=CH
2, CH3(CO)CH2(Co)O(CH2)aCH
= CH2, CH3(Co)CH2(Co)OCH2=
CH5)=CH2,CH3(Co)CH2(Co)-0
-CH=CH-CHa.

C2H5(Co)CH2(CO) 0CH2=CH=
CH2, C2H5(Co) CH2(CO)OC(CH
3) = CH2, C2H3(Co) CH2(Co)
0CH2-CHCH2, C-H9(Co)CH2(CO
)○CH2-CH=CH2C4H9(Co)CH2(C
O) QC(CH3)= CH2,C6H,5(CO)
CH2(Co)-〇CH2CH=CH2, CycloC
6H+2(CO)CH2(Co)OCH2= CH=
CH2, C, OH2, (Co)CH2(Co)OCH2
-CH=CH2,C,. H21(CO)CH2(Co)
OCCCHs ) = CH2, CHs (CO)C
H2(Co)OC6H5, C2H3(Co)CH2(C
o) OC6H5, is.

C3Hv (Co)CH2(CO)○C6H5,ter
t C4H9(CO)CH2(CO)OC6Hs,
Cyclo C6HI2(CO)CH2(CO)Q
C6H5, C6H,! (CO)CH2(Co)0C6
H5, C4゜H21(Co)CH2(CO)○C6H3
CH,(Co) CH2(CO)OC,2H,. , C
,H7(Co)CH2(Co)QC,2H,. .

C4H9(Co)CH2(Co)OC,2HIO,C,
0H21(Co)CH2(Co)OC,2H,. .

β-keto acid compounds such as C+2Ls (Co)CH2(Co)C+2H+o.

cHgo(CO)CH2(COX)CH,,CH30(
Co)CH2(Co)OC2H5CH30(Co)CH
2(CO)01 CJ7, CH30(CO)CH
2(Co)○(t-C4H9), CH,O(CO)
CH2(Co) 0C6H+g.

CH30(Co)CH2(Co)O(cyclo-C6
H,2), CHs○(CO)CH2(Co)QC,
. H24, C2H50(Co)CH2(Co)OC5H
7, C2H5○(CO)CH2(Co)O(t-C4H
9), C2H50(CO)CH2(CO)OC6H5
゜C2H5○(CO)CH2(Co) O(CyClo
C6HT2), C2H50(CO)CH2(C
O)○Cl0H21,C6H+50(Co)CH2(C
o)○C3H7.

C6H,O(CO)CH2(CO)QC4H9,C6H
430(CO)CH2(Co)OC6H1S, C6H
430(CO)CH2(Co)O(cyclo C6H
I2), C6H5○(Co)CH2(CO)OC4
OH21, CJv○(CO)CH2(CO)○CI[1
H21CH,0(CO)CH2(CO)OCH2-CH
=CH2, CHg○(CO)CH2(Co)○(CH2
)2-CH=CH2,CL○(CO)CH2(CO)O
C(CH15) = CH2, CHs○(CO) CH2
(Co)○-CH=CH-CH,.

C4H90(Co)CH2(Co)OCH2CH=CH
2, C4H90(Co)CH2(Co)○(CH2)2
-CH=CH2,C4H90(CO)CH2(CO)Q
C(CH5)=CH2,C4H90(Co)CH2(
Co)○CH=CHCH=CH150(Co)CH2(
CO)○CH2-CH=CH2,C6HI30(CO)
CH2(CO)O(CH2)2- CH= CH2,C
6H,30(Co)CH2(CO)QC(CH5)=C
H2,C6H,,0(Co)CH2(Co)OCH=C
H-CH3゜(Cyc IQ C6H12) O(C
o) CH2(Co)O(CH2) 2 CH= CH
2C4゜H2,○(Co)CH2(Ce))OCH2-
CH= CH2, C[HffiO(CO)CH2(Co
)OC(CH3)=CH2,CH,○(CO)CH2(
CO)○C6H5.

CgH,0(Co)CH2(CO)QC6H5,1so
-C3H7O(CO)CL(Co)OC6H5,ter
t C4H90(Co)CH2(CO)OC6H5,
C6H,30(CO)CH2(CO)○C6H5,(C
yclo-C6HI2)○(Co) CH2(Co)○
CbH5, Cl0H210(CO) CH2(Co)
0C6Hs, CHs○(Co)CH2(Co) O
C128. , CxH70(Co)CH2(CO)QC
,2H,. .

C4H90(Co)CH2(Co)0CI2HTO,
(Cyclo C6HI2)○(Co)CH2(Co
) OCl2H10, Cl2H250(Co) CH2
(Co)OCI2H+o.

CH2=CH-CH2-0(Co)CH2(Co)OC
H2CH=CH2CH2=CH-CH20(Co)CH
2(CO)OC(CH5) = CH2.

CH2=CH-CH20(Co)CH2(Co)O(C
H2) 2CH=CH2゜CH2=CH-CH20(CO
) CI(2(Co)OC6H5, C4Hq CH=C
H-CH2-○(CO)CH2(Co) 0CH2CH
= CH-C4H9.

C6H50(Co)CH2(Co)○C6H5,C6H
50(CO)CH2(Co)OC,2H,o, C6H
50(Co)CH2(Co) 0CH2-CH= CH
Examples include malonic acid diester compounds such as No. 2.

Among these, β-diketone compounds and β
-keto acids, particularly preferably β-diketone compounds. Furthermore, the present invention is not limited to the above compounds.

In the present invention, known organoaluminum compounds can be used as the organoaluminum compound used as the catalyst component.

Preferably an organoaluminum compound represented by R5aAjMs-a or -E-At(R')-0+
A chain or cyclic aluminoxane having the structure shown in E can be exemplified.

R5 and R6 are hydrocarbon groups having 1 to 8 carbon atoms and may be the same or different. M is a hydrogen atom and/or an alkoxy group. a is O (a≦3, t is an integer of 1 or more.

A specific example of the organoaluminum compound represented by R5aAAMs-a is trimethylaluminum.

triethylaluminum, tripropylaluminum,
Trialkylaluminum such as triisobutylaluminum and trihexylaluminum, dimethylaluminum hydride, diethylaluminum hydride,
Dialkyl aluminum hydride such as dipropyl aluminum hydride, diisobutyl aluminum hydride, diakyl aluminum hydride, dimethyl aluminum methoxide.

Methylaluminium dimethoxide, diethylaluminum methoxide, ethylaluminum dimethoxide, diisoptylaluminum notoxide, isobutylaluminum jetoxide.

Dihexyl aluminum methoxide, hexyl aluminum dimethoxide, dimethyl aluminum ethoxide,
Examples include alkyl aluminum alkoxides such as methyl aluminum jetoxide, diethylaluminium ethoxide, ethyl aluminum jetoxide, diisobutyl aluminum ethoxide, and isobutyl aluminum jetoxide.

Specific examples of the aluminoxane represented by -E-Az(R')-0-3-t include tetramethylsialuminoxane,
Examples include tetraethylsialuminoxane, tetrabutylsialuminoxane, tetrahexylsialuminoxane, methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexylaluminoxane, and the like.

■Component (A) is 1 mole of titanium atom in component
-100,000 (this can be used, but preferably 1-10,000, more preferably 1-50
Used in the range 00.

Next, the synthesis of catalyst component (2) in the present invention will be described.

The catalyst component (8) of the present invention is synthesized by reacting the titanium compound (a,) and the compound (b) and removing solids from the resulting reaction mixture.

The reaction between titanium compound (a) and compound (b) can be carried out by adding titanium compound (a) + compound (b), or vice versa (adding titanium compound (a) to compound (b)). Either is fine.

Further, the titanium compound (a) and the compound (b) are preferably used after being dissolved or diluted in a suitable solvent.

Such solvents include hexane and heptane.

Examples include aliphatic hydrocarbons such as octane and decane, aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as chlorohexane, methylcyclohexane, and decalin, and ether compounds such as diethyl ether, diisoamyl ether, and tetrahydrofuran. It will be done.

The reaction temperature is -50 to 150°C, preferably -130 to 12°C.
The temperature range is 0°C, particularly (preferably 0 to 100°C).

The reaction time is not particularly limited, but 30 minutes to 6 hours is usually suitable.

Incidentally, the time for dropping the titanium compound (a) or the compound (b) is not particularly limited, but is usually about 30 minutes to 6 hours.

The amount of compound (b) to be used is 0.01 to 1.0, preferably 0.05 to 0.8, particularly preferably 0.1 to 0. .6
is within the range of

The present invention (the catalyst component and catalyst are ethylene-α
- Can be used for the production of olefin copolymers. The copolymer refers to a copolymer consisting of ethylene and one or more olefins.

In the present invention, the monomers constituting the copolymer are ethylene and one or more α-olefins.

Propylene is a specific example of the a-olefin.

Butene-1, Pentene-1, Hexene-1,4 Methylpentene-1, Octene-1, Decene-1, Octadecene=1. Examples include eicosene-1 and the like.

Furthermore, it is also possible to copolymerize a non-conjugated diene in order to improve the vulcanizability of the copolymer. Specific examples of such non-conjugated dienes include dicyclopencdiene, tricyclopentadiene, 5-methyl-2,5-norbornadiene, 5-methylene-2-norbornene, 5-ethyrythene-2-norbornene, and 5-isoflobenyl-2- norbornene.

5-(2-butenyl)-2-norbornene.

1,5,9-cyclododecatriene, 6-methyl4,7
．． 8.9-Tetrahydroindene, trans-1,2-
Divinylcyclobutane, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 1,3 hexadiene, 1
．． Examples include 6-octadiene, 6-methyl-1,5-heptadiene, etc., but the present invention is not limited to the above-mentioned compounds.

The copolymer of the present invention has a density Cf/ad) of 0.85 to 0.
．． Although a wide range such as 95 can be taken, it is preferably 0.8 from the viewpoint of flexibility at particularly low temperatures.
5 to 094, more preferably 0.85 to 0.92, particularly preferably 0.85 to 0.90, and the infrared absorption spectrum (wherein the ethylene crystal chain group < 73
It is a rubbery random copolymer with a narrow composition distribution in which no absorption at 0 cm' is observed.

Further, the copolymer may contain two or more types of α-olefin and non-conjugated diene.

Using the catalyst components or catalysts according to the invention, ethylene-
An example of a method for producing an α-olefin copolymer will be described below.

First, there are no particular restrictions on the method of supplying each catalyst component to the polymerization tank, except that it is supplied in an inert gas such as nitrogen or argon without moisture. Catalyst component (9)
They may be supplied individually for one day, or they may be supplied by bringing the three parties into contact with each other in advance.

The polymerization temperature can range from -30 to 300°C, preferably from -10°C to 200°C, particularly preferably from 20°C to 150°C.

The polymerization pressure is not particularly limited, but is preferably about 3 to 1500 atm from the viewpoint of industrial and economical aspects.

The polymerization method can be continuous or batchwise. Further, slurry polymerization using an inert hydrocarbon solvent such as propane, butane, pentanehexane, heptane, or octane, liquid phase polymerization without a solvent, or gas phase polymerization is also possible.

Furthermore, in order to adjust the molecular weight of the copolymer of the present invention, it is also possible to add a chain transfer agent such as hydrogen.

<Examples> Below, Examples and Comparative Examples (thus, the present invention will be described in further detail)
I will explain this.

In addition, the α-olefin content, iodine value, and intrinsic viscosity in the examples are values measured by the following method.

The α-olefin content was determined by the characteristic absorption of ethylene and α-olefin using an infrared spectrophotometer (manufactured by JASCO Corporation) JASCOA-302.

The iodine value was determined from the characteristic absorption of the diene using the infrared spectrophotometer.

The intrinsic viscosity [η] is 135° using an Ubbelohde viscometer.
Measured in tetralin solution at C.

The titanium content in the catalyst component was measured by atomic absorption spectrometry.

Example 1 (1) Synthesis of catalyst component (9) 300 equipped with a stirrer, dropping funnel 1, reflux tube, and thermometer
- After replacing the flask with argon, the composition formula (C8H+
7) 5mm of titanium compound represented by 2N-Tics
23.8 y of hexane solution containing ol was charged.

Next, 0.399 (2.5 mmol) of benzoylacetone diluted with 10 parts of hexane was added dropwise from the dropping funnel over 30 minutes while keeping the temperature of the solution in the flask at 75°C. The reaction was carried out for an additional hour.

Next, 33.8 d of a hexane solution containing catalyst component particles was obtained by removing the solid produced by the reaction from the mixed solution obtained by the above reaction. is 0.07 from atomic absorption spectrometry
It was 5 mmol/ml.

(ii) Copolymerization of ethylene and propylene After purging a 300-meter flask equipped with a stirrer, reflux pipe, blowing pipe, and thermometer with argon, 200 m of heptane and 5.0 ml (5 mmol) of lysoptylaluminium were charged. , then a mixed gas of C2/C; (gas phase composition (all expressed in volume below) C2/C; = 2/8
) into the solution through the blowing tube (after saturating it (1)
3.6 d of hexane solution containing the catalyst component (g) obtained in
(0.25 mmol of titanium atoms) was added to start polymerization.

Thereafter, the mixed gas was continuously supplied while maintaining the temperature at 30° C., and polymerization was carried out for 1 hour. Then, 20 units of ethanol were added to stop the polymerization.

The generated polymer was mixed with 950 ml of ethanol and 50 ml of 1N hydrochloric acid.
j! After washing was repeated three times with 1000 mg of a mixed solution of 1000 mg, vacuum drying was performed to obtain 5.95 r of an ethylene-propylene copolymer (hereinafter referred to as "rEP copolymer"). The activity per hour per mole of T1 atoms (hereinafter simply referred to as "activity") is 2,4 X 10' fl / mol Ti
Met.

The obtained polymer has an infrared absorption spectrum with an absorption of <730 tyn' (hereinafter referred to as r
IRy3a) was not observed, indicating that it is a copolymer with a narrow composition distribution.

The propylene content (wt%) in the copolymer is 33.3%,
The intrinsic viscosity (hereinafter referred to as "[η]") is [η) = 3
．． It was 0.

Example 2 Copolymerization of ethylene and butene-1 Example 1 (
In the copolymerization of ethylene and propylene in ii), C:
/C: Instead of mixed gas (C2/ C: Mixed gas (C2
/C4=2/8), and 1.8d (titanium atom 0.125 mmol) of hexane solution containing the catalyst component (g).
) Copolymerization of ethylene and butene-1 was carried out under the same conditions as in Example 1 except that ethylene-butene-1 copolymer (hereinafter referred to as rEB copolymer) 5.3f was obtained.

The activity was 42 × 10′ S′/molTi.

The obtained polymer was a copolymer with a narrow composition distribution, with no 1R730 observed. Butene-1 content 407%, [
η] = 37° Example 3 Copolymerization of ethylene and hexene-1 After purging a 300 rnl flask equipped with a stirrer, reflux tube, blowing tube, and thermometer with argon, 1200 mg of hexene-1,
Triisobutylaluminum 5.0mrriol
), then ethylene gas (375mg/M
In) was blown into the solution through a blowing tube (after saturation, 0.036 mg of the hexane solution containing catalyst component holes obtained in (1) of Example 1 (titanium atoms 0.0025 m
mol) was added to start polymerization.

Thereafter, the temperature was kept at 30°C (gas supply was continued and polymerization was carried out for 1 hour), and then 20 rn! of ethanol was added to stop the polymerization.

The resulting polymer was mixed with 950 m of ethanol and 50 m of 1N hydrochloric acid.
After repeating washing three times with a mixed solution of 1000ml of ethylene-hexene-1 copolymer (rE
H copolymer. ) 1.92 was obtained. Activity is 7. '
l×105r/molTi.

The obtained polymer had no IR730 and had a narrow composition distribution. Hexene-1 content 493%
, [η] = 69° Example 4 Copolymerization of ethylene and decene-1 In the copolymerization of ethylene and hexene-1 in Example 3, except that 200 rr=tt of decene-1 was used instead of hexene-1. Ethylene and decene-1 were copolymerized under the same conditions as in Example 3 to obtain 0.7r of ethylene-decene-1 copolymer (hereinafter referred to as rED copolymer). Activity is 2.6xlO
It was 5r/mol Ti.

The obtained polymer was a copolymer with a narrow composition distribution, with no lR73G observed. Decene-1 content 573%, [
η') = 6.3゜Example 5 Same as Example 1 except that 2.5 mmol of ethyl 3-oxobutanoate was used instead of benzoylacetone in the synthesis of catalyst component (i) of Example 1). Copolymerization of ethylene and propylene was carried out under the same conditions as in Example 1 to obtain 1.3 g of rEP copolymer j.

The activity was 1.5 x 10' r/molTi.

The obtained polymer did not contain IRyso and was a copolymer with an irregular composition distribution. Furopyrene content 31.2%,
[η) = 3.1° Example 6 Synthesis of the catalyst component (g) of (i) of Example 1 (herein,
2. Dibenzoylmethane instead of pageylacetone.
Copolymerization of ethylene and propylene was carried out under the same conditions as in Example 1, except that 5 mmol was used, and rEP copolymer 387 was obtained. The activity is 1,5 x 10' f /
mol Ti.

The obtained polymer was a copolymer with a narrow composition distribution, with no 1R730 observed. Propylene content 29.3%,
[η) = 3.2° Example 7 Copolymerization of ethylene and propylene in (i) of Example 1 (here, 5 mmol of di-isobutyl aluminum methoxide was used instead of triisobutyl aluminum,
Copolymerization was carried out in the same manner as in Example 1, except that 0.72 mA (0.05 mmol of titanium atoms) of a hexane solution containing the catalyst component (2) was used, and EP co-Tc polymer 5. '
I got ty. Activity 1.1 x 105y/molTi
.

The obtained polymer had no 1R730 and had a narrow composition distribution. Propylene content 32.1%,
[η] = 3.4° Example 8 Copolymerization of ethylene and propylene in (n) of Example 1 (here, 6.7 mmol of methylaluminoxane was used instead of triisobutylaluminum, and the catalyst component G copolymerization was carried out in the same manner as in Example 1, except that a hexane solution containing (a) was used at 0.014 mA (titanium atom 0.001 mmol) to obtain EP copolymer 0142.Activity 1. OX 105? / mol Ti 0 The obtained polymer had a narrow composition distribution with no lR730 observed.Propylene content 33.1%, [
η] = 3.2° Example 9 Synthesis of catalyst component (9) in (i) of Example 1,
(39) Instead of the titanium compound represented by (C817L7)2N TICt3 ((C+oH2+)2N TiCt,
Example 1 ((
The same procedure as i) was carried out (this catalyst component was synthesized, except that in (i) of Example 1, 3.6 hexane solutions (625 mmol of titanium atoms O) containing the catalyst component (a) were used. Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1 (■) to obtain EP copolymer 3.02.

Activity 1. I X 10' 9 /mol Ti 0 The obtained polymer had no IR7xo and had a narrow composition distribution. Propylene content 30.6%, [
η]-30゜Example 10 Copolymerization of ethylene, propylene and dicyclopentadiene After purging a 300-meter flask equipped with a stirrer, reflux tube, blowing tube, and thermometer with argon, 200 mg of heptane,
Synchropentagene 1.24d (10mmol)
) diisobutylaluminum 5.0 (5 mmol
), and then a mixed gas of C:/C: (gas phase composition (
After saturated G in the solution through a blowing tube, the hexane solution 36-(Titanium atoms 0. 25 mmol) was added to start polymerization.

Thereafter, the mixed gas was continued to be supplied while maintaining the temperature at 30'Cf, and polymerization was carried out for 1 hour, after which 20 ml of ethanol was added to stop the polymerization.

The resulting polymer was washed three times with 1000 m6 of a mixed solution of 950 rnl of ethanol and 50 ml of 1N hydrochloric acid, and then dried under vacuum to obtain ethylene-propylene dicyclopentadiene copolymer (EPDM) 3.02 mm. The activity was 4.2 x 10'f/rriol Ti. Furopylene content 27.0%, [η:] = 3.1.
Moreover, the iodine value is 12.0 (r/1009).

Comparative Example I Ti CLa G Copolymerization Example 1
In the copolymerization of ethylene and propylene in (i), the copolymerization of ethylene and propylene was carried out in the same manner as in Example 1, except that 0.5 mmol of TlC14 was used instead of (CaH+7)2NTiCz3 as the catalyst component (5). Polymerization was carried out to obtain EP copolymer 2.3f. Activity is 4500
r/molTi.

The obtained copolymer was a polymer in which I Ryso was recognized and had a wide composition distribution. Propylene content 375%, [
η] = 27° Comparative Example 2 Copolymerization of ethylene and propylene (ii) of Example 1 (
Here, (C3HI7)2N as the catalyst component (a)
An alternative to Ti CLs is titanocene dichloride (
0.5 mmol of Cp2TIC42), 25 mmol of aluminoxane instead of lysobutylaluminum
Same as in Example 1 except that ethylene and propylene were copolymerized to obtain an EP copolymer of 0.6'S+.The activity was 12000 f//mol Ti.

The obtained copolymer had a fluoropylene content of 399%, [η:] = 0.2, although I R73o was not observed.
9, which was a copolymer with a very low molecular weight.

<Effects of the Invention> As described above, the use of the catalyst component, catalyst, and production method using the same of the present invention (thereby, it becomes possible to produce ethylene polymers and ethylene-α-olefin copolymers with excellent randomness, and they have excellent weather resistance. It is possible to provide an ethylene-α-olefin copolymer having excellent properties such as hardness, corrosion resistance, transparency, colorability, stickiness, and mechanical properties.

[Brief explanation of drawings]

FIG. 1 is a flowchart diagram to aid understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited thereto in any way. (43 Complete)

Claims (18)

[Claims] (1) (A) (a) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^1 and R^2 are hydrocarbon groups having 1 to 30 carbon atoms (R^1 and R^2 are mutually (can be the same or different), X is a halogen, Y is an alkoxy group, m is a number of 1≦m≦3, n is a number of 0≦n<3, and (m+n) is 1≦(m+n)≦3. ) and (b) general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^3 and R^4 are hydrocarbon groups having 1 to 30 carbon atoms and/or Production of an ethylene-α-olefin copolymer characterized by being obtained by reacting a compound represented by ~30 alkoxy groups (R^3 and R^4 may be the same or different from each other) Liquid catalyst component for use. (2) (A) (a) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^1 and R^2 are hydrocarbon groups having 1 to 30 carbon atoms (R^1 and R^2 are mutually (can be the same or different), X is a halogen, Y is an alkoxy group, m is 1≦m≦3, n is a number of 0≦n<3, and (m+n) is 1≦(m+n)≦3. ) and (b) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^3 and R^4 are hydrocarbon groups with 1 to 30 carbon atoms and/or carbon numbers Reacting a liquid catalyst component obtained by reacting a compound represented by 1 to 30 alkoxy groups (R^3 and R^4 may be the same or different from each other) and (B) an organoaluminum compound. A polymerization catalyst for producing an ethylene-α-olefin copolymer, characterized in that it is obtained by. (3) The liquid catalyst component for producing an ethylene-α-olefin copolymer according to claim 1, wherein (a) R^1 and R^2 are saturated hydrocarbon groups having 1 to 30 carbon atoms. (4) Ethylene-α- according to claim 1, wherein (a) R^1 and R^2 are aliphatic saturated hydrocarbon groups having 1 to 30 carbon atoms.
Liquid catalyst component for producing olefin copolymers. (5) The liquid catalyst component for producing an ethylene-α-olefin copolymer according to claim 1, wherein (a) R^1 and R^2 are linear aliphatic saturated hydrocarbon groups having 1 to 30 carbon atoms. (6) The liquid catalyst component for producing an ethylene-α-olefin copolymer according to claim 1, wherein (a) R^1 and R^2 are hydrocarbon groups having 8 to 30 carbon atoms. (7) The liquid catalyst component for producing an ethylene-α-olefin copolymer according to claim 1, wherein (a) R^1 and R^2 are saturated hydrocarbon groups having 8 to 30 carbon atoms. (8) Ethylene-α- according to claim 1, wherein (a) R^1 and R^2 are aliphatic saturated hydrocarbon groups having 8 to 30 carbon atoms.
Liquid catalyst component for producing olefin copolymers. (9) The liquid catalyst component for producing an ethylene-α-olefin copolymer according to claim 1, wherein (a) R^1 and R^2 are linear aliphatic saturated hydrocarbon groups having 8 to 30 carbon atoms. (10) The polymerization catalyst for producing an ethylene-α-olefin copolymer according to claim 2, wherein (a) R^1 and R^2 are saturated hydrocarbon groups having 1 to 30 carbon atoms. (11) Ethylene-α according to claim 2, wherein (a) R^1 and R^2 are aliphatic saturated hydrocarbon groups having 1 to 30 carbon atoms.
- Polymerization catalyst for producing olefin copolymers. (12) The polymerization catalyst for producing an ethylene-α-olefin copolymer according to claim 2, wherein (a) R^1 and R^2 are linear aliphatic saturated hydrocarbon groups having 1 to 30 carbon atoms. (13) The polymerization catalyst for producing an ethylene-α-olefin copolymer according to claim 2, wherein (a) R^1 and R^2 are saturated hydrocarbon groups having 8 to 30 carbon atoms. (14) Ethylene-α according to claim 2, wherein (a) R^1 and R^2 are aliphatic saturated hydrocarbon groups having 8 to 30 carbon atoms.
- Polymerization catalyst for producing olefin copolymers. (15) The polymerization catalyst for producing an ethylene-α-olefin copolymer according to claim 2, wherein (a) R^1 and R^2 are linear aliphatic saturated hydrocarbon groups having 8 to 30 carbon atoms. (16) The organoaluminum compound (B) has the general formula R^5
An organoaluminum compound represented by _aAlM_3_-_a or a chain or cyclic aluminoxane having a structure represented by the general formula ▲Mathematical formula, chemical formula, table, etc.▼ (However, R^5 and R^6 have 1 to 1 carbon atoms 8 hydrocarbon group, M
represents hydrogen and/or an alkoxy group, a represents a number of 0<a≦3, and l represents an integer of 1 or more. ) Ethylene-α according to claims 2 or 10 to 15
- Polymerization catalyst for producing olefin copolymers. (17) A method for producing an ethylene-α-olefin copolymer, which comprises using the polymerization catalyst according to claim 2 or 10 to 15. (18) Density of ethylene-α-olefin copolymer is 0
．． 18. The method for producing an ethylene-α-olefin copolymer according to claim 17, wherein the copolymer is 85 to 0.95 (g/cm^2).