JPH072924A - Use of titanium and zirconium as homogeneous catalysts, and new titanium and zirconium compounds - Google Patents

Abstract

PURPOSE: To improve reaction efficiency by using a homogenous catalyst consisting of specific compds. containing Ti and Zr when an olefinic or an acetylenic unsaturated hydrocarbon is polymerized or oligomerized.

CONSTITUTION: A compd. represented by formula I (wherein M is Ti or Zr; X¹ and X² are each a halogen or a 1-20C aliphatic or aromatic hydrocarbon; O-O is groups represented by formulae II, III; R¹ and R² are each a steric hinderance alkyl, OR' or silyl; R' is a 1-20C aliphatic or aromatic hydrocarbon; R³ and R⁴ are each H, a 1-20C aliphatic or aromatic hydrocarbon, silyl or OR'; Y is methylene, ethylene or a divalent crosslinking group such as S, O or the like; (n) is 0 or 1) [e.g.; 2,2'-S(4-Me, 6-tBuC₆H₂O)₂Ti(CH₂Ph)₂] is prepared. In the presence of a heterogenous catalyst comprising this compd., an olefinic or acetylenic unsaturated hydrocarbon (e.g.; ethene) is polymerized or oligomerized.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

This invention relates to the use of titanium and zirconium compounds with chelated alkoxide ligands as homogeneous catalysts for olefin polymerization or oligomerization involving cyclotrimerization of terminal acetylenes, and chelates containing silyl groups. And novel zirconium and zirconium compounds having a fluorinated alkoxide ligand.

[0002]

U.S. Pat. No. 4,452,914 discloses titanium complexes or compounds which can be used as transition metal components in Ziegler-Natta catalysts. This titanium complex or compound has the general formula Ti (OR) _n X _4-n (wherein R
Represents a hydrocarbon group having 1 to 20 carbon atoms, X represents halogen, and n is an integer of 0 to 4) and is reacted with at least one compound containing at least one hydroxyl group. Can be obtained. The at least one compound includes an optionally substituted bisphenol compound and an optionally substituted binaphthol compound, the two aromatic rings of which are a divalent bridging group such as a hydrocarbon group or a sulfur-containing group. Can be coupled to each other via. However, said US patent does not describe the presence of a silyl group as a substituent on the aromatic ring of a compound containing at least one hydroxyl group.

European Patent Application 0,433,943
JP-A No. 1994-242242 discloses a catalyst for producing 1,4-polybutadiene, which catalyst comprises a transition metal compound, an organoaluminum compound, and an organic compound having at least two hydroxyl groups. The organic compound may be an optionally substituted bisphenol or binaphthol compound and the aromatic rings containing hydroxyl groups may be linked to each other via divalent bridging groups such as hydrocarbon groups or sulfur containing groups. However, said European patent application makes no mention of its use as an olefin polymerization or oligomerization catalyst, nor does it disclose the presence of silyl substituents on aromatic rings containing hydroxyl groups.

US Pat. No. 4,798,903 discloses optically active 3,3'-disilylbinaphthol derivatives useful as ligands. More specifically, the 3,3′-disilylbinaphthol derivative is reacted with a trialkylaluminum, thus providing an active aluminum useful as a catalyst for an asymmetric heterogeneous Diels-Alder reaction in a reaction between an aldehyde and a conjugated diene. It is said to be useful for obtaining reagents. In general, 3,
The 3'-disilylbinaphthol compound is described as being useful as a ligand for an optically active catalyst. However, no mention is made of its use as an olefin polymerization or oligomerization catalyst, nor of any complex with zirconium or titanium compounds.

It is therefore known to date to use titanium or zirconium compounds with chelated bisphenol or binaphthol ligands as homogeneous catalysts in the polymerization or oligomerization of olefinically unsaturated compounds and the cyclotrimerization of terminal acetylenes. Not not. Furthermore,
Titanium and zirconium compounds with chelated 3,3'-disilylbinaphthol ligands are also unknown.

[0006]

Therefore, the purpose of the invention is to
It is to provide an improved homogeneous catalyst for the polymerization or oligomerization of olefinically unsaturated compounds and terminal acetylenes.

[0007]

Accordingly, the present invention is directed to a process for polymerizing or oligomerizing olefinic or acetylenically unsaturated hydrocarbons in the presence of a homogeneous catalyst, the process wherein said catalyst is of the general formula (I):

[0008]

[Chemical 5]

[Wherein M is Ti or Zr; X ¹ and X ² are independently halogen, an optionally substituted aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, a silyl group, or General formula -OR '(In the formula, R'is 1 to 2 carbon atoms.
0 represents an alkoxy group of an aliphatic or aromatic hydrocarbon group of 0); OO represents the general formula (II) or (III):

[0010]

[Chemical 6]

[Wherein R ¹ and R ² are independently a sterically hindered alkyl group, an alkoxy group of the general formula OR '(wherein R'is as defined above) or the general formula SiR ^a R ^b R ^c (In the formula,
R ^a , R ^b and R ^c independently represent a lower alkyl group, an aryl group, an arylalkyl group or an alkylaryl group); and R ³ and R ⁴ are independently hydrogen and optionally substituted. And an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, a silyl group or a general formula OR ′ (in the formula,
R ′ represents the same as defined above); Y is a divalent bridging group selected from the group consisting of methylene, ethylene, —S— and —O—; n is 0 or 1. Represents a chelated alkoxide ligand of [1]].

Although the homogeneous catalysts are particularly useful for the polymerization or oligomerization of ethene, propene or hexene, the best results are obtained for the polymerization or oligomerization of ethene. The term "olefinically unsaturated hydrocarbon" as used herein should be broadly construed to include both monounsaturated compounds and diolefinically unsaturated compounds. Examples of diolefinically unsaturated compounds include 1,
3-Butadiene can be mentioned. Monoolefins can have terminal unsaturation (α-olefins) or internal unsaturation, as in, for example, 2-hexene or 3-hexene.

On the other hand, the titanium and zirconium compounds are also useful as a homogeneous catalyst in the oligomerization of terminal acetylenes, and more particularly in the cyclotrimerization of terminal acetylenes. Preferably, the acetylene has the general formula (I
V):

[0014]

[Chemical 7]

(Wherein R represents a hydrocarbylsilyl group, an optionally substituted aryl group or an alkyl group having 1 to 20 carbon atoms other than tertiary alkyl). According to a more preferred embodiment, said R group is selected from the group consisting of trimethylsilyl, phenyl and p-tolyl.

The polymerization or oligomerization is carried out in a manner known per se and can be carried out in bulk, solution, slurry or gas phase reaction. The usual temperature range is 95 to 150 ° C., the pressure is generally 1 to 100 bar, preferably 3 to 70 bar.
r.

Preferably in formula (I), X ¹ and X ² are the same and are selected from the group consisting of halogen, alkylenetrialkylsilyl, aryl, alkylaryl, arylalkyl and lower alkyl. Of this group of preferred substituents, chlorine, benzyl, methylenetrimethylsilyl and methyl are the optimal members.

When the chelated alkoxide ligand is of the class represented by general formula (II), n may be 0 or 1, and when n = 1 Y is preferably a methylene group or --S--. Is. Further, it is preferred that R ¹ and R ² are the same and represent a bulky alkyl group having 1 to 10 carbon atoms, preferably tertiary butyl. The other substituents R ³ and R ⁴
Are preferably arranged both in the meta position relative to R ¹ and R ² , respectively, in which case R ³ and R ⁴ are preferably identical and represent methoxy, methyl or ethyl. Particularly preferred is 2,2 ′-(4-OMe, 6-tBuC ₆ H
₂ O) ₂ Ti (CH ₂ Ph) ₂ , 2,2′-S (4-Me,
_{6-tBuC 6 H 2 O)} 2 Ti (CH 2 Ph) 2 and 2,
_{2'-CH 2 (4-Et} , 6-tBuC 6 H 2 O) 2 Ti
(CH ₂ Ph) ₂ and 2,2′-S (4-Me, 6-tBuC ₆ H for use as an olefin polymerization catalyst
₂ O) ₂ Ti (CH ₂ Ph) ₂ is most suitable.

On the other hand, when the chelated alkoxide ligand is a class represented by the general formula (III), R
¹ and R ² are both of the general formula SiR ^a R ^b R ^c (wherein R ^a ,
R ^b and R ^c independently represent a lower alkyl group, an aryl group, an arylalkyl group or an alkylaryl group). In that case R ¹ and R ² are selected from trimethylsilyl, diphenylmethylsilyl, triphenylsilyl and dimethylphenylsilyl,
R ¹ and R ² are preferably the same.

The present invention further includes the general formula (V):

[0021]

[Chemical 8]

[Wherein M is Ti or Zr; X ¹ and X ² are independently halogen, an optionally substituted aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, a silyl group, or General formula -OR '(In the formula, R'is 1 to 2 carbon atoms.
And R ^a , R ^b and R ^c are independently a lower alkyl group, an aryl group, an arylalkyl group or an alkylaryl group, preferably methyl and Representing phenyl].

According to a preferred embodiment of the present invention, X ¹ and X ² are the same and are selected from the group consisting of halogen, alkylenetrialkylsilyl, aryl, alkylaryl, arylalkyl and lower alkyl. Of these, chlorine, benzyl, methylenetrimethylsilyl and methyl are the optimal members.

Suitable novel compounds are those in which any of R ^a , R ^b and R ^c is selected from methyl and phenyl, or M =
Zr or Ti, R ^a = R ^b = R ^c = independently methyl or phenyl and X ¹ = X ² = Cl or benzyl or methyl, or M = Zr and R ^a = R ^b = ^Rc =
The compound of formula V is phenyl and X ¹ = X ² = methylenetrimethylsilyl.

When the chelated alkoxide titanium and zirconium compounds as described above are used as a homogeneous catalyst for the polymerization of olefins such as ethene and propene, a cocatalyst is required to activate the catalyst. In principle, all cocatalysts known to the person skilled in the art can be used, but preference is given to using organoaluminium compounds such as diethylaluminium chloride or methylaluminoxane. The best results are obtained with methylaluminoxane.

When used as a catalyst in the cyclotrimerization of terminal acetylene to produce benzene, there is a terminal triple bond which results in the terminal hydrogen atom being acidic and the titanium or zirconium atom and X. ^The catalyst does not require cocatalyst activation as the bond to the ¹ and X ² groups is basic. This is further

[0027]

[Chemical 9]

And that the internal acetylene does not undergo the cyclization trimerization reaction, ie

[0029]

[Chemical 10]

Is only very weakly acidic, and internal acetylene such as but-2-yne is

[0031]

[Chemical 11]

It is not acidic at all due to the absence of acidic hydrogen atoms directly attached to. The cyclization trimerization reaction is performed as follows.

[0033]

[Chemical 12]

The more bulky binaphthol or bisphenol ligands, ie those having bulky X ¹ and X ² groups, are symmetrical 1,3,5-
Tri-substituted benzene is unsuitable. Therefore, 1, 2, 4
The ratio of the tri-substituted benzene to its 1,3,5-isomer can be controlled by the type of X ¹ and X ² groups attached to the metal atom.

The invention is further described below by means of non-limiting examples.

[0036]

EXAMPLES All experiments for producing chelated alkoxide titanium and zirconium compounds were conducted by Schlenk.
Type glassware under an argon atmosphere or under a nitrogen atmosphere in a Braun single station drybox with a -40 ° C fridge (Schle.
nk and Braun are trademarks).

Nuclear magnetic resonance (NMR) spectrum is Var
ian XL-200, Varian VXR-300
Or recorded on a Bruker-500 MHz spectrometer (Varian and Bruker are trademarks). Chemical shifts (δ) are expressed in ppm relative to the residual protons in the deuterium-substituted solvent. The coupling constant J _AB is expressed in Hertz (Hz). The solvent is P.I. A. Graded, dehydrated with sodium wire and suitable desiccant under argon atmosphere before use (sodium benzophenone ketyl for ether and THF, sodium for hexane and toluene)
Was distilled from. The deuterium-substituted solvent was dehydrated with a 4Å molecular sieve.

Binaphthol and bisphenol ligands are described in J. Org. Chem. 1981, 46 , 39
3; Bull. Chem. Soc. Japan 19
88, 61 , 2975; Tet. Lett. 198
3, 24 , 5611; Chem. Soc. ，
C 1971, 1750 and J. Org. Chem. 1
983, 48 , 4948.

Zr (CH ₂ Ph) ₂ Cl ₂ and M (CH ₂ P
h) ₄ (M = Ti, Zr) is described in J. Organomet.
Chem. 1981, 205 , 319 and J. Or
ganomet. Chem. 1971, 26 , 35
It was prepared according to the method described in 7.

The melting point of the polymer is determined by the differential scanning calorimetry (D
SC).

[0041] Example ^{1 M = Zr, R a =} R b = R c = methyl and X ¹ = X ² = Cl
Corresponding to the compound of formula (V) (1,1 ′-{2,
_{2 ', 3,3'-OC 10 H} 5 SiMe 3} 2) was prepared ZrCl ₂ as follows.

Zr (CH ₂ Ph) ₂ Cl ₂ 0.494 g
(1.18 mmol) was dissolved in 5 ml of toluene at 25 ° C. 3,3'-bis (trimethylsilyl) in this solution
-1,1'-bi-2,2'-naphthol 0.338 g
A solution prepared by dissolving (1.18 mmol) in 5 ml of toluene was added. After stirring at 20 ° C. for 16 hours, toluene was removed under reduced pressure and the reddish brown powder was washed with hexane. -4
Recrystallize from ether / hexane 1: 1 mixture at 0 ° C.,
A yellow powder was obtained. Yield 0.383 g (73% yield).

¹ H NMR (C ₆ D ₆ , 25 ° C.): δ
8.10 (s, 2H); 7.8-7.7 (d, 2)
H); 7.2-6.95 (m, 4H); 6.86-
6.75 (m, 2H); 0.70 (s, 18H, Si
Me ₃ ).

¹³ C NMR (C ₆ D ₆ ): δ158.
1; 135.7; 129.6; 128.4; 12
8.3; 128.2; 125.7; 124.7;
123.6; 111.4; -0.58 (Si Me
₃ ).

Elemental analysis: C ₂₆ H ₂₈ O ₂ Si ₂ Cl ₂ Zr
Calcd for: C52.86; H4.78; Si9.
51; Cl 12.00; Zr 15.44. Measured value:
C53.12; H5.04; Si9.20; C
111.86; Zr15.30.

Example 2 M = Zr, R ^a = methyl, R ^b = R ^c = phenyl and X ¹ =
Corresponds to a compound of formula (V) where X ² = Cl (1,
1 '- {2,2', 3,3' -OC 10 H 5 SiMeP
h ₂ } ₂ ) ZrCl ₂ was prepared as described in Example 1.

¹ H NMR (C ₆ D ₆ , 25 ° C.): δ
7.75 (br, 6H); 7.62 (d, 2H);
7.52 (d, 2H); 7.43 (m, 6H);
7.27 (m, 6H); 7.17 (t, 2H);
7.06 (t, 2H); 6.73 (d, 2H);
1.17 (s, 6H, Me ).

Elemental analysis: C ₄₆ H ₃₆ O ₂ Si ₂ Cl ₂ Zr
Calculated for: C65.76; H5.08; Si6.
15; Cl 7.76; Zr 9.99. Measured value: C
65.58; H5.14; Si6.19; Cl
8.00; Zr 10.10.

[0049] Example ^{3 M = Zr, R a =} R b = R c = phenyl and X ¹ = X ² = C
corresponding to the compound of formula (V) which is l (1,1'-
_{{2,2 ', 3,3'-OC 10} H 5 SiPH 3} 2) Zr
Cl ₂ was prepared as described in Example 1.

¹ H NMR (C ₆ D ₆ / d ⁸ -THF, 25
C): δ 8.07 (s, 2H); 8.0 (m, 12)
H); 7.35 (d, 2H); 7.25-7.15.
(M, 18H); 7.35 (d, 2H); 6.86
(T, 2H, 7.7 Hz); 6.75 (t, 2H, 7.
7 Hz).

¹³ C NMR (C ₆ D ₆ ): δ160.
2; 142.1; 137.1; 137.0; 13
5.5; 129.9; 129.8; 128.8;
127.4; 126.8; 124.5; 12
4.0; 117.9.

Elemental analysis: C ₅₆ H ₄₀ O ₂ Si ₂ Cl ₂ Zr
Calcd for: C69.47; H4.86; Si5.
41; Cl 6.48; Zr 8.79. Measured value: C
69.22; H5.04; Si5.30; Cl
6.69; Zr 8.61.

Example 4 Corresponds to a compound of formula (V) where M = Ti, R ^a = R ^b = R ^c = methyl and X ¹ = X ² = benzyl (1,1′-
_{{2,2 ', 3,3'-OC 10} H 5 SiMe 3} 2) Ti
(CH ₂ Ph) ₂ was prepared as follows.

Ti (CH ₂ Ph) ₄ 0.153 g (0.3
71 mmol) is dissolved in 10 ml of toluene and -40 ° C.
(HOC ₁₀ H ₅ SiMe ₃ ) ₂ 0.
16 g (0.372 mmol) was added. The solution was heated to 20 ° C. with stirring and stirred at this temperature for 15 hours.
Toluene was removed under reduced pressure to give a red oil which was recrystallized to give a solid product.

¹ H NMR (C ₆ D ₆ , 25 ° C.): δ
8.17 (s, 2H); 7.2-6.8 (m);
2.87 (2H, AB, CH ₂ ); 2.35 (AB,
2H, CH ₂ ); 0.48 (s, 18H, Si M
e ₃ ).

EXAMPLE 5 Using Zr (CH ₂ Ph) ₄ , a compound of formula (V) in which M = Zr, R ^a = methyl, R ^b ═R ^c = phenyl and X ¹ ═X ² = benzyl. Corresponding to (1,1 '-{2,2',
_{3,3'-OC 10 H 5 SiMePh 2} } 2) Zr (CH 2 P
h) ₂ was prepared as described in Example 4.

[0057] EXAMPLE ^{6 M = Ti, R a =} R b = R c = phenyl and X ¹ = X ² = corresponds to the compound benzyl a is Formula (V) (1,1'
_{{2,2 ', 3,3'-OC 10} H 5 SiPh 3} 2) Ti
(CH ₂ Ph) ₂ was prepared as in Example 4.

¹ H NMR (C ₆ D ₆ , 25 ° C.): δ
8.33 (s, 2H); 8.0-7.92 (m, 12
H); 7.2-6.8 (m + C 6 D 5 H); 6.75
(M, 4H); 6.45 (m, 4H); 1.4 (A
B, J _AB = 11 Hz, 2H, C H ₂ ); 1.05 (A
B, J _AB = 11 Hz, 2H, C H ₂ ).

Elemental analysis: Calculated for C ₇₀ H ₅₄ O ₂ Si ₂ Ti: C81.53; H5.28; Ti4.64.
Found: C81.24; H5.41; Ti4.7.
5.

[0060] Example ^{7 M = Zr, R a =} R b = R c = phenyl and X ¹ = X ² = corresponding to compounds of methyl a is Formula (V) (1,1'
_{{2,2 ', 3,3'-OC 10} H 5 SiPh 3} 2) Zr
Me ₂ (ether) ₂ was prepared as follows.

In a small Schlenk tube (C ₁₁₀ H ₅ OSi
Ph ₃ ) ₂ ZrCl ₂ · toluene 0.896 g (0.83
(mmol) was suspended in 60 ml of ether. The solution was cooled to −40 ° C. and 2 eq MeLi (1.
6M solution 1.04 ml) was added dropwise. After 10 minutes, the orange suspension became a clear yellow solution and began to turn cloudy.
The solution was filtered, concentrated under reduced pressure, crystallized at -40 ° C,
A white crystalline solid was obtained.

¹ H NMR (C ₆ D ₆ , 25 ° C.): δ
8.28 (s, 2H); 7.92 (m); 7.53
(M); 7.16 (m); 6.97 (m);
14 (q, 8H, ether); 0.78 (t, 12
H, ether); -0.136 (s, 6H, Me);
6.75 (t, 2H, 7.7Hz).

¹³ C NMR (C ₆ D ₆ ): δ159.8
6; 142.0 (d, 149 Hz); 138.2;
136.2; 129.3; 127.1; 12
5.8; 123.3; 118.2.

Naphthyl and phenyl resonances: 66.1
(T, 141 Hz, ether); 46.04 (q, 1
18Hz, Me ); 14.22 (q, 129Hz, ether).

Elemental analysis: C ₅₆ H ₄₀ O ₂ Si ₂ Cl ₂ Zr
Calcd for: C74.48; H5.21; Zr8.
33. Found: C74.75; H5.32; Zr.
8.60; Li0.0; Cl <0.2.

[0066] EXAMPLE ^{8 M = Zr, R a =} R b = R c = phenyl and X ¹ = X ² = corresponds to the compound benzyl a is Formula (V) (1,1'
_{{2,2 ', 3,3'-OC 10} H 5 SiPh 3} 2) Zr
(CH ₂ Ph) ₂ was prepared as follows.

0.795 g (1.7) of Zr (CH ₂ Ph) ₄
4 mmol) was dissolved in 30 ml of toluene, and 1.4 g (1.74 mmol) of 3,3′-bis (triphenylsilyl) -1,1′-bi-2,2′-naphthol was added to the solution.
Was added. After stirring for 16 hours at 20 ° C., toluene was removed under reduced pressure. Wash the resulting yellow oil with hexane,
A yellow powder was obtained. Yield 1.70 g (91% yield).

¹ H NMR (CD ₂ Cl ₂ , 25 ° C.):
δ 8.15 (s, 2H); 7.75 (d, 2H);
7.65 (m, 10H); 7.35 (m, 24H);
6.78 (d, 2H); 6.55 (m, 6H);
5.70 (d, 4H, benzyl H _o); 0.88 (A
B, 2H, 9.8 Hz); 0.64 (AB, 2H,
9.8 Hz).

¹³ C NMR (CD ₂ Cl ₂ ): δ15
7.7; 143.9; 138.9; 137.5;
137.1; 134.9; 130.9; 13
0.0; 129.9; 128.3; 128.1;
127.5; 127.1; 125.9; 124.
6; 124.3; 116.1; 68.1 (t, C
H ₂ , J _CH = 133 Hz).

Example 9 (1,1 '-{2,2) corresponding to the compound of formula (V) wherein M = Zr, R ^a = R ^b = R ^c = phenyl and X ¹ = X ² = methylene trimethylsilyl. ', 3,3'-OC ₁₀ H ₅ S
iPh _{3} 2)} was prepared in the same manner as Zr (CH ₂ SiMe _{3) 2} Example 8.

¹ H NMR (CD ₂ Cl ₂ , 25 ° C.):
δ 8.35 (s, 2H); 8.0-7.92 (m, 1
2H); 7.2-6.8 (m + C 6 D 5 H); 7.1
5 (d, 2H); 0.5 (AB, 2H, C H 2);
-0.50 (AB, 2H, C H 2); -0.4 (s,
18H, Si Me _3).

¹³ C NMR (CD ₂ Cl ₂ ): δ15
6.0; 142.9; 137.3; 137.0;
130.1; 130.0; 128.8; 12
8.7; 128.4; 128.0; 127.0;
126.1; 124.4; 117.2.

Fetyl and Phenyl Resonance: 67.6
_{(C H 2); 1.3 (} Si Me 3).

Example 10 This example illustrates the use of several chelated alkoxide titanium and zirconium catalysts in the polymerization of ethene and propene.

2,2'-S (4-Me, 6-tBuC ₆
H ₂ O) This compound was prepared in _{2 Ti (CH 2 Ph) 2} (Cat1) is, n = 1, Y = -S- , with R ¹ = R ² = tert-butyl and R ³ = R ⁴ = methyl Corresponds to a compound of formula (I) in which X ¹ = X ² = benzyl with certain ligands of formula (II) as alkoxide ligands.

2,2'-S (4-Me, 6-tBuC ₆
A solution of 0.21 g of H ₂ OH) ₂ in 2 ml of toluene was added to Ti (C) in 3 ml of toluene / 5 ml of hexane.
H ₂ Ph) ₄ 0.24 g (0.583 mmol) was added to a cooled (−20 ° C.) solution. Red purple solution at 20 ℃ 1
Stir for hours and remove the solvent under reduced pressure. Extraction with hexane gave a dark red, slightly oily product which was very soluble in hexane. Recrystallized from hexane, analytically pure Cat
Got 1.

2,2'-CH ₂ (4-Et, 6-tBu
_{C 6 H 2 O) 2 Ti} (CH 2 Ph) This compound was prepared in ₂ (Cat2) is, n = 1, Y = methylene, R ¹ = R ² = tertiary butyl and R ³ = R ⁴ = ethyl Corresponds to a compound of formula (I) in which X ¹ = X ² = benzyl with certain ligands of formula (II) as alkoxide ligands.

81 mg (0.20 m) of Ti (CH ₂ Ph) ₄
(mol) was dissolved in 5 ml of hexane to give a solution of -40
The mixture was cooled to 0 ° C., 72 mg (0.20 mmol) of 2,2′-bis (3-t-butyl-5-ethylphenol) was suspended in 5 ml of hexane, and the suspension was similarly added to the suspension cooled to −40 ° C. . After addition at -40 ° C, the suspension was slowly warmed to 20 ° C. After stirring for 2 hours at 20 ° C., the resulting red solution was stripped under reduced pressure to give a red foam. The concentrated hexane solution was crystallized at -40 ° C to give a microcrystalline C
I got at2.

2,2 '-(4-OMe, 6-tBuC _{6
H 2 O) 2 Ti (CH} 2 Ph) This compound was prepared in ₂ (Cat3) ^{is, n = 0, R 1 =} R 2 = tert-butyl and R ³
Corresponds to a compound of formula (I) where X ¹ = X ² = benzyl, having as ligand an alkoxide ligand of formula (II) where = R ⁴ = methoxy.

Ti (CH ₂ Ph) ₄ 1 in 5 ml of toluene
14 mg (0.275 mmol) were added to a suspension of 99 mg (0.275 mmol) 2,2'-bis (3-t-butyl-5-methoxyphenol) in 5 ml toluene. After stirring for 16 hours at 20 ° C., toluene was removed under reduced pressure. A purple oil was thus obtained and recrystallized from hexane or ether at -40 ° C to give red lumps.

Polymerization Experiments Table 1 shows the ethene polymerization results of several titanium and zirconium compounds. The following conditions were applied in each polymerization experiment.

-Ethylene pressure: 3 bar; -Polymerization temperature: 20 ° C, except for the catalysts of Example 4, Cat1 and Cat3, the polymerization temperature was 40 ° C; -0.02 mmol catalyst; -5 mmol methyl as a 10% solution in toluene. Aluminoxane; -200 ml toluene; -Polymerization time: 15 to 30 minutes, except that in Cat 3, the polymerization time was 1.5 hours.

[0083]

[Table 1]

In the above table, M _w is the weight average molecular weight, M _n is the number molecular weight, and Pd is the polydispersity M _w / M _n . Molecular weight data was determined by GPC. The melting point (mp) of the obtained polyethylene was determined by DSC.

Example 11 The catalyst of Example 1 was likewise used for the polymerization of propene. Polymerization temperature 45 ° C, propene pressure 6 bar and polymerization time 60
Polymerization was carried out under the same conditions as applied during the ethene polymerization, except that the time was 0.43 (kg / g Zr / hr), M _w 1.2 × 10 ⁵ , M _n 7600, PD 15.8.
I got the data of.

Example 12 0.02 mol of the catalyst of Example 5 in 200 ml of toluene
To 200 equivalents

[0087]

[Chemical 13]

(R is defined in Table 2) was added at 20 ° C. Trimerization was completed within 5 minutes at 20 ° C. The same experiment was conducted using the catalyst of Example 8. The results are shown in Table 2.

[0089]

[Table 2]

As is clear from Table 2, the bulky substituent R
^{The use of 1} and R ² (SiPh ₃ relative to SiMePh ₂ ) is unsuitable for forming 1,3,5-trisubstituted benzenes.

Example 13 1-Hexene Polymerization About 2 × 10 ⁻⁵ mol of a catalyst was dissolved in 5 ml of 1-hexene at 20 ° C. in a dry box. About 100 times the amount of MAO
Was added as a solution in 3 ml of toluene. The formed homogeneous solution was stirred for 16 hours at 20 ° C. Then, remove the reaction vessel from the dry box, and then MeOH, then 1M.
HCl was added to destroy excess MAO. The toluene solution was decanted and evaporated. Polyhexene was identified by ¹ H and ¹³ C NMR spectroscopy and GPC analysis. Molar mass was determined by GPC. The polymer was dissolved in CDCl ₃ for NMR analysis. The end groups were confirmed by APT experiments and were fully linked to ¹³ C NMR. D
According to the SC Analysis (-40 ℃ "100 ℃) T g or the T _m was shown.

Table 3 shows the results of hexene polymerization experiments for the above catalysts.

[0093]

[Table 3]

1,3-Butadiene Polymerization 2 × 10 ⁻⁵ mol catalyst in 25 ml autoclave, 1
A 00-fold amount of MAO and 15 ml of toluene were added. The autoclave was pressurized at 20 ° C. with 1.5 bar butadiene. After 3 hours, open the autoclave and wash with MeOH and 1
Excess MAO was destroyed by adding M HCl. The organic layer was decanted and the solvent was evaporated to give polybutadiene as a rubber-like polymer. ^The structure was identified by ¹ H and ¹³ C NMR spectroscopy. The ratio of 1,2-methylene to 1,4- cis / trans unit was determined by ¹ H NMR spectroscopy. Reflux with C ₂ D ₂ Cl ₄ for 1 hour under an inert atmosphere to dissolve the polymer. 1,2-methylene units were resonant at 4,8 and 1.3 ppm, 1,4- trans units were 1.98 and 5.4 ppm, and 1,4- cis units were 5.32 and 2.03 ppm. did. The ratio can be calculated from the integral of the individual peaks. E. R. San
tee, Jr. R.K. Chang and M.D. Morto
n Polymer Lett. Ed . 1973,
11 . 453.

Table 4 shows the results of butadiene polymerization for the above catalysts.

[0096]

[Table 4]

Claims (12)

[Claims] 1. A process for polymerizing or oligomerizing olefinic or acetylenically unsaturated hydrocarbons in the presence of a homogeneous catalyst, said catalyst having the general formula (I): [In the formula, M is Ti or Zr; X ¹ and X ² are independently halogen, an optionally substituted aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, a silyl group or a general formula-
OR '(in the formula, R'is an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms) alkoxy group; O-
O is represented by the general formula (II) or (III): {In the formula, R ¹ and R ² are independently a sterically hindered alkyl group, an alkoxy group of the general formula OR ′ (in the formula, R ′ is as defined above), or a general formula SiR ^a R ^b R ^c (wherein , R ^a , R ^b and R ^c independently represent a lower alkyl group, an aryl group, an arylalkyl group or an alkylaryl group); and R ³ and R ⁴ are independently hydrogen and optionally substituted. Represents an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, a silyl group or an alkoxy group represented by the general formula OR '(wherein R'is as defined above); Y is methylene, ethylene, Is a divalent bridging group selected from the group consisting of -S- and -O-; and n is 0 or 1, and represents a chelated alkoxide ligand. 2. Process according to claim 1, characterized in that the unsaturated hydrocarbon is ethene or propene and the polymerization is carried out in the presence of an organoaluminum cocatalyst. 3. Formula (IV): embedded image (In the formula, R represents a hydrocarbylsilyl group, an optionally substituted aryl group, or a carbon atom number other than tertiary alkyl having 1 to 1 carbon atoms.
The process according to claim 1, comprising the step of cyclo-trimerization of a terminal acetylene having 20 alkyl groups). 4. In formula (I), X ¹ and X ² are the same,
Halogen, alkylenetrialkylsilyl, aryl,
4. The method according to any one of claims 1 to 3, characterized in that it is selected from the group consisting of alkylaryl, arylalkyl and lower alkyl. 5. R ¹ and R ² are the same and have 4 carbon atoms.
Process according to any one of claims 1 to 4, characterized in that it represents a sterically hindered alkyl group from 10 to 10. Claims 1 wherein R ³ and the R ⁴ is characterized in that it is arranged in the meta position with respect to each R ¹ and R ² 5
The method according to any one of 1. 7. The method according to claim 6, wherein R ³ and R ⁴ are the same and represent methoxy, methyl or ethyl. 8. A compound represented by the general formula (V): [In the formula, M is Ti or Zr; X ¹ and X ² are independently halogen, an optionally substituted aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, a silyl group or a general formula-
OR '(in the formula, R'is an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms) alkoxy group;
R ^a , R ^b and R ^c independently represent a lower alkyl group, an aryl group, an arylalkyl group or an alkylaryl group]. 9. A compound according to claim 8, wherein X ¹ and X ² are selected from the group consisting of chlorine, benzyl, methylenetrimethylsilyl and methyl. 10. A compound according to claim 8 or 9, characterized in that R ^a , R ^b and R ^c are selected from methyl and phenyl. 11. M = Zr or Ti, and R ^a = R ^b =
R ^c = independently methyl or phenyl, X ¹ = X ² =
A compound according to any one of claims 8 to 10, characterized in that it is Cl or benzyl or methyl. 12. M = Zr, R ^a = R ^b = R ^c = phenyl, and X ¹ = X ² = methylenetrimethylsilyl, according to any one of claims 8 to 10. The described compound.