JP2003517056A - Method for producing highly branched amorphous polyolefin using homogeneous catalyst - Google Patents

Abstract

(57) Abstract: In a method for producing a highly branched amorphous polyolefin having a rubber elastic property profile derived from ethene using a homogeneous catalyst, the method comprises the following steps: 1) ^[Wherein, R 1, ^{R 2} is, _C 4 _{-C 16} having two vicinal hydrogen substituents relative connection between the aryl or heteroaryl and ^{N a} or ^{N b} - is heteroaryl Ethene in an inert solvent in the presence of a transition metal compound of the formula (I) and, if desired, a cocatalyst, and in a next step b) a compound of formula (II): To the oligomer mixture from a) and continuing the reaction in the presence of ethene, then in step c) isolating the resulting polymerization product, A method for producing a crystalline polyolefin using a homogeneous catalyst.

Description

Detailed Description of the Invention

The present invention relates to a process for producing highly branched amorphous polyolefins starting from ethene and having a rubber elastic property profile using homogeneous catalysts.

Those skilled in the art recognize that if the hyperbranched polyolefin is sufficiently amorphous, it can be mixed with a polymer blend or homopolymer as a rubber elastic component to improve hardness (Kunststoffe). , 1999, 89, 154-162). Hyperbranched polyolefins typically include a polyethylene backbone with randomly dispersed alkyl side chains of varying length. Unlike polybutadiene rubbers, for example, hyperbranched polyolefins usually do not have double bond units and are therefore only slightly or not affected by climate.

Various methods have been developed for producing branched polyolefins. US-
According to the method described in A-5272236, 1-alkenes such as 1-hexene or 1-octene are used as catalysts for [(η ⁵ -C ₅ Me ₄ ) SiMe ₂ (
Branched polyethylene can be produced by copolymerization with ethene in the presence of η ¹ -NCMe ₃ ] TiCl ₂ . In this type of method, it is always necessary to independently produce 1-olefin in advance.

Beach and Kissin, Polym. Sci., 1984, 22, 3027 combine two Ziegler-Natta catalysts to produce a branched polyolefin from ethene. A catalyst mixture consisting of titanium alkoxide and triethylaluminum was first used to produce the main 1-butene, which was co-catalyzed with ethene in the presence of titanium tetrachloride supported on magnesium chloride with triethylaluminum. Polymerize. But,
The degree of branching of 20 alkyl branches per 1000 carbon atoms is too low to obtain a sufficiently amorphous material. Furthermore, since the yield is low, it cannot be used on an industrial scale.

According to the method of Barnhart and Bazan, J. Am. Chem. Soc., 1998, 120, 1082-1083, a branched polyolefin is likewise obtained from ethene by combining two metallocene complexes with each other. To be However, this method succeeds only when the polymerization activities of the transition metal compounds used for ethene are well coordinated with each other.
This is because otherwise neither the polyolefin backbone nor the copolymerizable 1-alkene will be produced. In addition, Barnhart and Bazan point out that care must be taken that the transition metal compound used does not result in a dimer binding product of the 1-alkene formed. Leads to a heterogeneous product mixture. In addition, two metallocene compounds having different reactivities must not chemically react with each other. Many such preconditions for the production of branched olefins from ethene, according to Barnhart and Bazan, are achieved only by a well-defined zirconocene complex, which is complexed with two boratbenzene rings. , The free valence on the boron atom must bond with the ethoxy group. Simply replacing the ethoxy group with a phenol group does not form the desired branched polyolefin at all.

According to Brookhart et al., J. Am. Chem. Soc. 1995, 117, 6414-6415, nickel diimine catalysts can be used to similarly produce branched polyethylene starting from ethene. . However, most of the alkyl branches are methyl groups, which makes the resulting polyolefin's rubber elastic property profile less strong. Although a highly branched amorphous polyolefin can be obtained from ethene by using a corresponding palladium complex, its productivity is very low and its industrial use is not conceivable.

The use of a combination of several olefin polymerization catalysts as described in Ahn. Et al., Polymer Engineering and Science, 1999, 39, 1257-1264 has been shown to use polyethylene with a bimodal particle size distribution or a very wide molar range. Derives polyethylene showing a mass distribution.
The authors first reacted the ethene with a metallocene compound such as bis (cyclopentadienyl) zirconium dichloride or bis (indenyl) zirconium dichloride (wherein the reactivity of the catalyst used was reduced by addition of triethylaluminum). The reaction is continued after the addition of a Ziegler-Natta compound, for example titanium tetrachloride-vanadium oxide trichloride.

Synthesis of a polyolefin blend from ethene using a catalyst composite of a polymerization catalyst based on a high numbered transition metal compound and a polymerization catalyst based on a low numbered transition metal compound is described in DE-A -197070236. The higher numbered transition metal compounds used are Ziegler-Natta catalysts, for example those based on titanium tetrachloride, or metallocene catalysts based on cyclopentadienyl complexes of titanium, zirconium or hafnium. Slow transition metal compounds are, for example, nickel or palladium diimine complexes. In addition to branched polyethylene, linear or slightly branched polyethylene is present in the resulting polymer blend.

In Fink et al., Macromol. Chem. Rapid Commun., 1991, 12, 697-701, a nickel-ylide complex was combined with a bridged and unbridged metallocene complex to produce branched polyethylene from ethene. ing. However, the proportion of α-olefin incorporated is generally very low. Further, suitable reactivity can be obtained only when a large amount of methylaluminoxane is used as a cocatalyst, but as a result, the dimerization tendency is unavoidable.

EP-A-0250999 discloses the use of a combination of a nickel-ylide complex as an oligomerization catalyst and a heterogeneous chromium polymerization catalyst supported on silica gel to produce a branched polyolefin from ethene. ing. However, this yields only polyolefins with very long alkyl branches, which results in partially crystalline or crystalline materials, but without achieving an amorphous property profile.

WO 99/10391 describes both simultaneous and sequential use of several different polymerization catalysts. However, even when using bulky nickel diimine complexes and bis (cyclopentadienyl) zirconium dichloride complexes, only partially crystalline materials are obtained.

According to WO 99/50318, for example, the production of branched polyolefins from ethene is carried out by simultaneous or sequential addition of a tridentate iron bisimine complex and a metallocene catalyst to the reaction mixture. However, branched polyolefins having a sufficiently high proportion of alkyl branching, exhibiting a suitable alkyl branching pattern, while having a sufficient rubber elastic property profile such that they can be used as impact modifiers, are described in the methods described. Therefore, it cannot be obtained with reproducibility. This means that Tm ≧ 100
It is evidenced by the thermal properties of the described polymers with melting points of ° C. Furthermore, the method described does not ensure that the α-olefins formed are incorporated into the copolymer chain, so that these compounds remain as residues in the copolymer and cause contamination, and therefore additional cost. It is necessary to separate by such a purification process.

Ethene to hyperbranched polyolefins using a two-component or multi-component catalyst system that is easy to handle, exhibits high activity and leads to a high degree of branching, and thus yields an amorphous rubber elastic product. Are required to be manufactured.

The object of the present invention is to provide a process in which amorphous or predominantly amorphous rubber-elastic polyolefins are satisfactorily obtained even on an industrial scale by means of simple and efficient preparation. Is to provide.

It has been found that this object is achieved by a method for producing a highly branched polyolefin having an ethene-derived rubber elastic property profile using a homogeneous catalyst, in which in the first step, a) At least one formula (I):

[0016]

[Chemical 6]

[0017] wherein substituents and indices have the following meanings: R ^1, R ² is hydrogen to two vicinal position with respect to the binding part between the aryl or heteroaryl and N ^a or N ^b C ₄ -C ₁₆ -heteroaryl having a substituent or C ₆ -C ₁₆ -aryl, R ³ , R ⁴ are hydrogen, C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₆ - aryl, the alkyl portion has 1 to 10 carbon atoms and an alkylaryl or Si having 6 to 14 carbon atoms in the aryl portion ^(R _{8) 3,} wherein ^{R 8} is , _C 1 _{-C 10} - _alkyl, C 3 _{-C 10} - _{cycloalkyl, C 6 ~C 1} 6 - aryl, having from 1 to 10 carbon atoms in the alkyl part and 6 to the aryl portion
Alkylaryl having 14 carbon atoms, R ⁵ , R ⁶ , R ⁷ are hydrogen, C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₆ -aryl, alkyl An alkylaryl having 1 to 10 carbon atoms in the moiety and 6 to 14 carbon atoms in the aryl moiety, or Si (
R ⁸ ) ₃ or a functional group based on an element from group IVA to VIIA of the Periodic Table of Elements, or R ⁵ and R ⁶ and / or R ⁶ and R ⁷ are each fused together to form a 5-membered A 6- or 7-membered aliphatic or aromatic substituted or unsubstituted carbocycle or heterocycle, M ^I is Fe, Ru, Co, Rh, Ni or Pd, and T, Q are Uncharged or monoanionic monodentate ligands or T and Q
Alkylene or C ₃ - - C ₂ having an alkyl ester or nitrile end groups _- are Jiketoenorato units or methyl ketone end groups or a linear C ₁ -C 4 together form an alkylene unit, A is not coordinated Or a non-coordinating anion, m, p is 0, 1, 2 or 3, q is 1, 2 or 3, and n is 1, 2 or 3] In the presence of the compound and, if desired, one or more cocatalysts in the form of an uncharged Lewis strong acid, an ionic compound having a Lewis-acid cation or an ionic compound having a Bronsted acid as the cation, Oligomerizing ethene in an active solvent, and in the next step b) at least one formula (II):

[0018]

[Chemical 7]

[0019] [Wherein the substituents and indices have the following meanings: R⁹~ R¹²Is hydrogen, C₁~ C₁₀-Alkyl, C_Three~ C₁₀-Cycloalk
Le, C₆~ C₁₆-Aryl, having 1 to 10 carbon atoms in the alkyl part and
Alkylaryl having 6 to 14 carbon atoms in the reel part or Si (R⁸) _Three Or a functional group based on an element of group IVA to VIIA of the periodic table of elements
Or R⁹And R¹⁰And / or R¹¹And R¹²Respectively
Substituted or unsubstituted with 5-, 6- or 7-membered aliphatic or aromatic condensed together
Forming a carbocycle or heterocycle of M^IIIs a Group IIIB, IVB, VB or VIB metal of the Periodic Table of the Elements
, T'and Q'are a hydrogen atom and C, respectively.₁~ C₁₀-Alkyl or C₆~ C₂₀ -Aryl group, halogen atom, -OR ', -SR', -OSiR '_Three, -SiR
’_Three, -CR "_TwoSiR ’_Three, -PR '_Two, -NR '_Two, Toluenesulfonyl,
Trifluoroacetyl, trifluoromethanesulfonyl, nonafluorobutanes
Rufonyl, 2,2,2-trifluoroethanesulfonyl, Z is -CR '_Two-, -SiR '_Two-, GeR '_Two-, -SnR '_Two-, -BR
'-Or -O-, where R'is C₁~ C₂₀-Alkyl, C_Three~ C₁₀-Cycloalkyl, C₆~ C_{1 6} -Aryl, having 1 to 10 carbon atoms in the alkyl part and 6 to in the aryl part
Alkylaryl having 10 carbon atoms, C₁~ C₂₀-Alkoxy, C_Three ~ C₁₀-Cycloalkoxy, C₆~ C₁₆-Aryloxy or alkyl moieties
Having 1 to 10 carbon atoms in the and 6 to 10 carbon atoms in the aryl portion
Alkylaryloxy, k is 1, 2 or 3, G is -O-, -S-, -NR "-, -PR"-, -BR "-, -OR"-,-.
SR "-, -NR"_Two, PR ”_Two-Or formula (III):

[0020]

[Chemical 8]

(Wherein the substituents R ^{9 to} R ¹² are as defined above), R ″ is hydrogen, C ₁ -C ₂₀ -alkyl, C ₃ -C ₁₀ -cyclo _alkyl, C 6 to C1 ₅ - aryl, alkylaryl or _C 3 _{-C 30} having 6 to 10 carbon atoms in the and aryl portion has from 1 to 10 carbon atoms in the alkyl part - are organosilyl, Or Z _k and G together form a substituted or unsubstituted aromatic or heteroaromatic structure having 4 to 16 ring carbons or Z _k and R ⁹ and / or R ¹² are Together, monocyclic or polycyclic,
A transition metal compound forming an aliphatic, aromatic or heteroaromatic ring system, and, if desired, another cocatalyst as described in step a) is added to the oligomer mixture derived from a) to produce ethene The reaction is continued in the presence, after which the polymerization product obtained in step c) is isolated.

The compounds (I) ^the radicals ^{R 1} and ^{R 2} in the, ^{N a} or ^{N b} and aryl or _{C 4} substituted with two vicinal (ortho) groups relative to the junction between the heteroaryl group Is a C ₁₆ -heteroaryl or C ₆ -C ₁₆ -aryl group, for example in the case of a phenyl group, the hydrogen is in the ortho position with respect to the conjugated bond between the phenyl group and the imine nitrogen.

The substituents R ¹ and R ^{2 in} compound (I) may be the same or different from each other with respect to the aromatic ring or heteroaromatic ring system and / or another substituent present at a non-vicinal position.

[0024]   Heteroaryl or aryl group R¹And R^TwoIs the two vicinals listed
In addition to the ortho hydrogen atom, it may have one or more other substituents. like this
Substituents are, for example, elements of group IVA, VA, VIA or VIIA of the Periodic Table of the Elements.
It may be a base-based substituent. Examples of suitable groups are straight or branched chain C ₁ ~ C₁₀-Alkyl, preferably C₁~ C₆-Alkyl, such as methyl, ethyl
, N-propyl, i-propyl, n-butyl, i-butyl or t-butyl,
Halogenated or perhalogenated C₁~ C₁₀-Alkyl, preferably C₁ ~ C₆-Alkyl, such as trifluoromethyl or trichloromethyl or 2
, 2,2-trifluoroethyl, triorganosilyl, such as trimethylsilyl,
Triethylsilyl, tri-t-butylsilyl, triphenylsilyl or t-butyl
Tyldiphenylsilyl, nitro, cyano or sulfonate groups, amino, eg
NH_Two, Dimethylamino, di-i-propylamino, di-n-butylamino, di
Phenylamino or dibenzylamino, C₁~ C₁₀-Alkoxy, preferably
C1-C₆-Alkoxy, such as methoxy, ethoxy, i-propoxy or t
Butoxy, or halogen, such as fluorine, chlorine, bromine or iodine.

Of the aryl groups R ¹ and R ² , preference is given to phenyl, naphthyl and anthracenyl groups. Particularly preferred are phenyl and naphthyl groups,
Very particular preference is given to phenyl radicals, which aryl radicals may in each case have further substituents as defined above in the positions which are not vicinal or ortho.

In the phenyl group, a hydrogen atom or methyl, i-propyl, t-butyl, trichloromethyl, trifluoromethyl, methoxy, ethoxy, chloro or bromo substitution at a position para to the bond to the imine nitrogen. Phenyl groups bearing groups are particularly useful. Particularly preferred radicals R ¹ , R ² are, for example, 4-i-propylphenyl, 4
-Methylphenyl, 4-methoxyphenyl and phenyl.

[0027]   For the purposes of the present invention, suitable C_Four~ C₁₆-Heteroaryl group R¹And R ^Two Includes a hydrogen atom at two vicinal positions with respect to the bond to the imine nitrogen.
And both substituted and unsubstituted heteroaryl groups are included. Advantageously, C _Four ~ C₉-Heteroaryl groups, eg pyrrolidyl (via ring carbon to imine nitrogen
Or a pyrrolide (bonded to the imine nitrogen via the pyrrole nitrogen) group or
Imidazoyl (C-N-bond), imidazolide (NN-bond), benzimidazole
Zolyl, benzimidazolide, pyrazolyl, pyrazolide, pyridinyl, pyrimidy
A nyl, quinolyl or isoquinolyl group. Among these, pyrrolidyl and especially
The pyrrolido group is particularly noteworthy.

Possible groups R ³ and R ^{4 in} (I) are hydrogen, C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₆ -aryl, 1 to the alkyl part. Alkylaryl having 10 carbon atoms and 6 to 14 carbon atoms in the aryl part, silyl group (Si (R ⁸ ) ₃ ), amino group (N (R ⁸ ) ₂ ), ether group (
OR ⁸ ) or a thioether group (SR ⁸ ). Preferred as radicals R ³ and R ⁴ are hydrogen, methyl, ethyl, i-propyl, t-butyl, methoxy, ethoxy, i-propoxy, t-butoxy, trifluoromethyl, phenyl, naphthyl, tolyl, 2 -I-propylphenyl, 2-t-butylphenyl, 2,6-
It is di-i-propylphenyl, 2-trifluoromethylphenyl, 4-methoxyphenyl, pyridyl or benzyl, especially hydrogen, methyl, ethyl, i-propyl or t-butyl. Ligand compounds containing these groups are described by K. Vriez
e and G. vvan Koten, Adv. Organomet. Chem., 1982, 21, 151-239, and J.
Matei, T. Lixandru, Bul. Inst. Politeh. Isai, 1967, 13, 245. Furthermore, the 1,4-dithianes described in WO 98/37110 are advantageous as heterocyclic systems R ³ , R ⁴ .

The groups R ⁵ , R ⁶ and R ⁷ are, independently of one another, hydrogen, C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₆ -aryl, alkyl in the alkyl part. 1 to
Alkylaryl or silyl groups having 10 carbon atoms and 6-14 carbon atoms in the aryl part (Si (R ⁸ ) ₃ ) or VA to V of the Periodic Table of the Elements
It is a functional group based on a Group IIA element. Suitable functional groups are, for example, amino, such as NH ₂ , dimethylamino, di-i-propylamino, di-n-butylamino, diphenylamino or dibenzylamino, C ₁ -C ₁₀ -alkoxy,
Preference is given to C ₁ -C ₆ -alkoxy, such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, t-butoxy, or halogen, such as fluorine, chlorine, bromine or iodine.

R ⁵ and R ⁶ or / and R ⁶ and R ⁷ together are also substituted or unsubstituted with a fused, 5-, 6- or 7-membered aliphatic or aromatic containing pyridyl system. Carbocycles or heterocycles are formed, ie, for example, substituted or unsubstituted isoquinoline systems are obtained.

The groups R ⁵ , R ⁶ and R ⁷ are preferably hydrogen or methyl, especially hydrogen.

[0032]   Suitable groups R⁸Is C₁~ C₁₀-Alkyl, preferably C₁~ C₆-Alkyl, C ₆ ~ C₁₆-Aryl, preferably C₆~ C₁₀1 on the aryl or alkyl part
10 to, preferably 1 to 6 carbon atoms and 6 to 14 carbon atoms in the aryl part
Alkylaryl, preferably having 6 to 10 carbon atoms. Suitable groups are
For example, triorganosilyl groups such as trimethylsilyl, triethylsilyl,
It is triphenylsilyl or t-butyldiphenylsilyl.

Unless otherwise stated, the alkyl, cycloalkyl, aryl and alkylaryl radicals of the radicals R ^{3 to} R ⁸ include the following substituents: C ₁ -C ₁₀ -alkyl radicals are, for example, preferably methyl, Ethyl, n-propyl, i
-Propyl, n-butyl, i-butyl, t-butyl groups and straight-chain and branched pentyl, hexyl or heptyl groups are included. C ₁ -C ₁₀ -Alkyl groups also include groups substituted with functional groups based on elements of group IVA, VA, VIA or VIIA of the Periodic Table of the Elements, ie, for example, partially halogenated. Or a perhalogenated alkyl group such as trichloromethyl, trifluoromethyl,
2,2,2-Trifluoroethyl, pentafluoroethyl or pentachloroethyl and alkyl groups having one or more epoxy groups, such as propenoxy. Of the C ₁ -C ₁₀ -alkyl groups, the C ₁ -C ₆ -alkyl groups are generally preferred.

Suitable C ₃ -C ₁₀ -cycloalkyl groups include both carbocycles and heterocycles, ie substituted and unsubstituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, pyrrolyl, Pyrrolidonyl or piperidinyl. Of the suitable substituted cycloaliphatic radicals, mention should be made of, for example, 1-methylcyclohexyl, 4-t-butylcyclohexyl and 2,3-dimethylcyclopropyl.

[0035]   Suitable C₆~ C₁₆-Aryl groups include very common substituted and unsubstituted ari.
Group is included. Among the unsubstituted aryl groups, C is preferably₆~ C₁₀− Ally
Group, such as phenyl and naphthyl groups. Phenyl is particularly advantageous
It Unsubstituted and substituted C₆~ C₁₆-In any of the aryl groups,
Display (eg C₆-, C₁₀-Or C₁₆−) Is a carbon atom forming an aromatic system
Means the number of. The carbon atoms of the possible alkyl and / or aryl substituents are
Not included in this number. Therefore, C₆~ C₁₆-For example, the expression aryl
Replace C₆~ C₁₆-Aryl groups such as substituted anthracenyl are also included. C ₆ ~ C₁₆-The aryl group therefore follows from IVA, VA, VIA and VIA of the Periodic Table of the Elements.
And mono-, poly- or super-substituted with substituents based on Group VIIA elements.
Included groups are also included. A preferred functional group is C₁~ C₁₀-Alkyl, preferably C₁~
C₆-Alkyl, C₆~ C₁₆-Aryl, preferably C₆~ C₁₀-Aryl,
Triorganosilyl, such as trimethylsilyl, triethylsilyl, triphenyl
Rusilyl or t-butyldiphenylsilyl and amino, eg NH_Two, Jime
Cylamino, di-i-propylamino, di-n-butylamino, diphenylami
No or dibenzylamino, C₁~ C₁₀-Alkoxy, preferably C₁~ C₆−
Alkoxy, such as methoxy, ethoxy, n-propoxy, i-propoxy, n
-Butoxy, i-butoxy, t-butoxy, or halogen, such as fluorine, salts
Elemental, bromine or iodine.

[0036]   Substituent R^Three~ R⁸As C₆~ C₁₆-For aryl groups, substituted and unsubstituted
A heteroaryl group of eg C_Four~ C_Thirteen-Heteroaryl, preferably C_Four~ C ₉ -Heteroaryl, such as pyridyl, pyrimidyl, quinolyl or isoquinoli
Included.

Suitable alkylaryl groups R ^{3 to} R ⁸ generally have 1 to 10, preferably 1 to 6 carbon atoms in the alkyl part and 6 to 14 in the aryl part, Those having 6 to 10 carbon atoms are preferably included, in particular the benzyl group.

Suitable metals M ^{I in} (I) are the elements iron, cobalt, ruthenium, rhodium, palladium or nickel. In the transition metal compound (I), iron, cobalt, ruthenium, palladium and nickel are usually present in a formal divalent or trivalent positively charged form, whereas rhodium is usually monovalent. Alternatively, it exists in a trivalent positively charged form. Preferred metals M ^I are cobalt and iron, particularly preferably iron.

T and Q, in one form, are uncharged and / or monoanionic monodentate ligands. Suitable uncharged ligands are Lewis bases such as acetonitrile,
Benzonitrile, diethyl ether, tetrahydrofuran, amines, ketones, phosphines, ethyl acetate, dimethylsulfoxide, dimethylformamide or hexamethylphosphoramide. Other suitable uncharged Lewis base ligands are ethene and common olefinically unsaturated compounds. Monoanionic ligands are, for example, carbanions based on substituted or unsubstituted alkyl, aryl or acyl groups or halide ions.

T in (I) is preferably a monoanion and has, for example, a sulfonate, borate, chloride, bromide or iodide, methyl, phenyl, benzyl or a hydrogen atom in the β-position to the metal center M ^I. Not C ₁ -C ₁₀ -alkyl.
The C ₁ -C 4 _- also includes radicals having alkyl ester end groups or nitrile end groups. Particularly preferred are chloride and bromide as halide or trifluoromethyl sulfonate as sulfonate and methyl as alkyl group.

Like T, the ligand Q preferably has no hydrogen atom in the β position relative to the trifluoromethyl sulfonate, chloride, bromide, iodide, methyl, phenyl, benzyl or metal center M ^I , _{C 1 ~C 4 - C 1 ~C} 10 having an alkyl ester end groups or nitrile end groups - alkyl. Another example of an advantageous ligand Q is
Acetonitrile, benzonitrile, ethene, triphenylphosphine as a monodentate phosphite, pyridine as a monodentate aromatic nitrogen compound, acetate, propionate and butyrate, especially acetate as a suitable carboxylate,
Linear alkyl ethers, for example Chokukusariji -C 2 _-C 6 _- alkyl ethers, such as diethyl ether or di--i- propyl ether, preferably diethyl ether, cyclic ethers such as tetrahydrofuran or dioxane, preferably tetrahydrofuran, A straight-chain C ₁ -C ₄ -alkyl ester, such as ethyl acetate, dimethylsulfoxide, dimethylformamide, hexamethylphosphoramide or a halide. In the case of the iron complex (I) (M ^I = Fe), Q is preferably a halide, eg chloride or bromide, whereas the cobalt complex (I
In the case of M ^I = Co), Q is preferably chloride.

[0042]   Further, the ligands T and Q are taken together to form a methyl ketone end group, a straight chain C₁ ~ C_FourC with alkyl ester or nitrile end groups_TwoOr C_Three Can be an alkylene unit or a diketoenolate, for example acetylacetone
. In this case, T and Q are advantageously combined together in -CH_TwoCH_TwoCH_TwoC (O) O
CH_ThreeUnits, in this case M^IAnd together form a 6-membered ring. The terminal methylene group is M ^I When a metal-carbon bond is formed with the carbonyl group,^ICoordinate with.

[0043]   For the purposes of the present invention, the anion A, which is uncoordinated or difficult to coordinate, is
Is an anion in which the charge density of the nion center is reduced by electronegative groups and /
Or an anion in which the group structurally blocks the anion center. Good
Suitable anions A are, for example, antimonates, sulphates, sulphonates, boraxes.
Salts, phosphates or perchlorates, eg B [C₆H_Three(CF_Three)_Two]_Four ^- , (Tetrakis (3,5-bis (trifluoromethyl) phenyl) borate),
B [C₆H₅]_Four ^-, BF_Four ^-, SbF₆ ^-, AlF_Four ^-, AsF₆ ^-, PF₆ ^-Or
Trifluoroacetate (CF_ThreeSO_Three ^-). Advantageous is B [C₆H_Three (CF_Three)_Two]_Four ^-, SbF₆ ^-And PF₆ ^-Is. Particularly advantageously, borate,
Especially B [C₆H_Three(CF_Three)_Two]_Four ^-To use. Suitable non-coordinated or weakly coordinated ani
On-A and its production are described, for example, in S. H. Strauss, Chem. Rev. 1993, 93, pp. 92.
7-942, and W. Beck and K. Suenkel, Chem. Rev. 1988, 88, pp. 1405-142.
Described in 1.

Advantageous transition metal compounds (I) are, for example: 2,6-bis [1- (phenylimino) ethyl] pyridine-iron (II) chloride,
2,6-Bis [1- (4-methylphenylimino) ethyl] pyridine-iron (II)
Chloride, 2,6-bis [1- (4-isopropylphenylimino) ethyl] pyridine-iron (
II) chloride, 2,6-bis [1- (4-methoxyphenylimino) ethyl] pyridine-iron (II
) Chloride, 2,6-bis [1- (4-trifluoromethylphenylimino) ethyl] pyridine-iron (II) chloride and the corresponding iron (II) bromide and cobalt (II).
It is a chloride complex.

The transition metal compound (I) includes a tridentate bisimine chelate ligand as a structural element (structural element excluding the components MI, T, Q and A in the formula (I)). These tridentate ligands can be reacted with primary amines such as aniline, 4-methylphenylamine, 4-methoxyphenylamine, 4-trifluoromethylphenylamine or 4-t-butylphenylamine. It can be prepared from 2,6-diacetylpyridine (see J. Org. Chem. 1967, 32, 3246).

Regarding the method for producing the transition metal compound (I), Brookhart et al., Macromolecules,
1999, 32, 2120-2130, which are hereby expressly incorporated by reference.

In step a), one or more transition metal compounds (I) may be used together for olefin oligomerization.

In step a), an uncharged Lewis strong acid, an ionic compound having a Lewis acid cation or an ionic compound having a Bronsted acid as a cation may be added as a cocatalyst to the transition metal compound (I).

[0049]   Suitable ionic compounds having a Lewis acid cation have, for example, the formula:
: L^{l +}(Y X¹  X^Two  X^Three  X^Four)_l- In the formula, L is an element of main group I or II of the periodic table of elements, for example lithium, sodium,
Potassium, rubidium, cesium, magnesium, calcium, strontium
Or barium, especially lithium or sodium or silver, carbonium or
Supersubstituted with oxonium cations or alkyl and / or aryl groups or
Partially substituted ammonium, sulfonium or 1,1'-dimethylferrose
Is a nickel cation, Y is an element of main group III of the periodic table of the elements, especially boron, aluminum or gallium.
Um, preferably boron, X¹~ X^FourAre, independently of one another, hydrogen, straight chain or branched chain C₁~ C₁₀-Archi
Le, favorably C₁~ C₈-Alkyl, such as methyl, ethyl, n-propyl, i-
Propyl, n-butyl, i-butyl, t-butyl or n-hexyl, mono-substituted
Or a poly-substituted halogen such as fluorine, chlorine, bromine or iodine
Have C₁~ C₁₀-Alkyl, preferably C₁~ C₈-Alkyl, C₆~ C₁₆−
Aryl, preferably C₆~ C₁₀-Aryl, such as fluorine, chlorine, bromine or yo
Phenyl mono- or poly-substituted with halogens such as arsenic, eg pentaflu
Orophenyl, having 1-10, preferably 1-6, carbon atoms in the alkyl part
And alkyl having 6 to 14, preferably 6 to 10 carbon atoms in the aryl part
Aryls such as benzyl, fluorine, chlorin, bromine, iodine, C₁ ~ C₁₀-Alkoxy, preferably C₁~ C₈-Alkoxy, for example methoxy, et
Toxy or i-propoxy, or C₆~ C₁₆-Aryloxy, preferably C ₆ ~ C₁₀-Aryloxy, such as phenoxy, and l is 1 or 2.

The anion (Y X ¹ X ² X ³ X ⁴ )-in the compound of formula (IVa) is preferably a non-coordinating counterion. Boron compounds, such as those described in WO9109882, are worthy of description, the specification of which is expressly incorporated herein by reference. Particularly suitable cations L are derived from sodium or triphenylmethyl cations or are tetraalkylammonium cations, such as tetramethylammonium, tetraethylammonium or tetra-n-butylammonium, dimethylanilinium, or tetraalkylphosphonium cations,
For example tetramethylphosphonium, tetraethylphosphonium or tetra-n
-Derived from butylphosphonium. Preferred compounds (IVa) are, for example, sodium tetrakis (pentafluorophenyl) borate or sodium tetrakis.
It is [bis (trifluoromethyl) phenyl] borate.

[0051]   Suitable uncharged Lewis strong acids are, for example, compounds having the formula: Y X⁵  X⁶  X⁷        (IVb) In the formula, Y is an element of main group III of the periodic table of elements, in particular boron, aluminum or
Is gallium, preferably boron, X⁵~ X⁷Are, independently of one another, hydrogen, straight chain or branched chain C₁~ C₁₀-Archi
Le, preferably C₁~ C₈-Alkyl, such as methyl, ethyl, n-propyl, i
-Propyl, n-butyl, i-butyl, t-butyl or n-hexyl, mono
Substituted or polysubstituted halogens such as fluorine, chlorine, bromine or iodine
C with an atom₁~ C₁₀-Alkyl, preferably C₁~ C₈-Alkyl, C₆~ C ₁₆ -Aryl, preferably C₆~ C₁₀-Aryl, such as fluorine, chlorine, bromine
Or phenyl mono- or poly-substituted with a halogen atom such as iodine, for example
Pentafluorophenyl, 1-10, preferably 1-6 carbons in the alkyl part
Having atoms and 6 to 14, preferably 6 to 10 carbon atoms in the aryl part
Alkylaryl, such as benzyl, or fluorin, chlorin, bromine
Or Iodine.

Particularly preferred radicals X ^{5 to} X ⁷ are radicals having halogen substituents. An advantageous example is
It is pentafluorophenyl. Particular preference is given to compounds of the formula (IVb) in which X ⁵ , X ⁶ and X ⁷ are identical, preferably tris (pentafluorophenyl) borate. Furthermore, aluminum alkyl compounds or alkylaluminium halide compounds, such as triethylaluminium, tri (n-hexyl) aluminum or di-i-propylaluminium chloride, are also particularly suitable as cocatalysts (IVb). Furthermore, lithium alkyl and / or magnesium alkyl, such as (n-butyl) (n-octyl) magnesium, can also be used as compound (IVb). Any mixture of compound (IVb) can also be used.

Another uncharged Lewis strong acid that is advantageous as a cocatalyst is an aluminoxane compound.
Suitable aluminoxane compounds are almost all compounds having an Al-C bond. Particularly suitable cocatalysts are open-chain and / or cyclic aluminoxane compounds of formula (IVc) or (IVd):

[0054]

[Chemical 9]

Wherein R ¹³ are each, independently of one another, a C ₁ -C ₄ -alkyl group, preferably a methyl or ethyl group, r is an integer of 5 to 30, preferably 10 to 25. Is].

The preparation of these oligomeric aluminoxane compounds is generally carried out by the reaction of trialkylaluminium with water and is described in particular in EP-A-0284708 and US-A4794096.

In general, the oligomeric aluminoxane compounds obtained in this way are in the form of a mixture of straight-chain and cyclic-chain molecules with different lengths, so that r is considered to be an average value. The aluminoxane compound can also be present in a mixture with another metal alkyl, preferably an aluminum alkyl, such as triisobutylaluminum or triethylaluminum. Preference is given to using methylaluminoxane (MAO), especially in the form of a solution in toluene. Methylaluminoxane can be produced, for example, by E
P-A 284708 is described in detail.

Other compounds that can be used as co-catalysts are aryloxyaluminoxanes described in US-A 5391793, amidoaluminoxanes described in US-A 5371260, aminoaluminoxane hydrochlorides described in EP-A 0633264,
A siloxyaluminoxane and aluminoxane mixture described in EP-A0621279.

The aluminoxanes described are, by themselves or in aliphatic or aromatic hydrocarbons,
It is used, for example, in the form of a solution or suspension in toluene or xylene, or a mixture thereof.

[0060]   The cocatalysts mentioned can be used alone or in any mixture.

The process of the invention for producing hyperbranched polyolefins can be carried out in non-polar aliphatic or aromatic neutral solvents such as heptane, i-butane, toluene or benzene or polar neutral solvents. Suitable polar neutral solvents are, for example, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and chlorobenzene and similar linear or cyclic ethers such as diethyl ether or tetrahydrofuran, as well as acetone, dimethyl, sulfoxide, dimethylformamide, hexa. Methylphosphoramide or acetonitrile. Of course, any mixture of these solvents may be used as long as the mixture is homogeneous. Particularly advantageous are dichloromethane, toluene, i-butane, pentane, heptane, chlorobenzene and acetonitrile and mixtures thereof, especially toluene, i-butene and chlorobenzene.

The amount of solvent is generally chosen such that the starting compound can be present in dissolved form at the beginning of the reaction.

The oligomerization in step a) is usually from −40 to 160 ° C., preferably −20.
It is carried out at -100 ° C and particularly preferably at 0-80 ° C. The reaction time is generally in the range of 0.1 to 120 minutes, depending on the reaction conditions selected.

The oligomerization is generally in the range 0.1 to 1000 bar, preferably 0.5 to 1.
00 and particularly preferably at pressures in the range from 1 to 80 bar.

[0065] The concentration of the transition metal compound (I) is generally 10 ^- 9 ~0.1mol / l, preferably ^{5 × 10 - 8 ~10 - 2} mol / l and particularly preferably 10 ^- 6 to 5 × 10 ^- 2 mol
/ L range.

[0066] starting concentration of ethene is usually 10 ^- 3 ~10mol / l range of, preferably from 10 ^- 2 -
It is in the range of 5 mol / l.

[0067]   Addition of one or more transition metal compounds of formula (II) to the reaction mixture after step a).
Add Advantageous transition metal compounds are derived from the compounds of formula (II) below: M^IIIs titanium or zirconium, R⁹~ R¹²Is C₁~ C₁₀-Alkyl or C_Three~ C₂₁-Organosilyl
Where two adjacent groups may form a fused aromatic ring, T'and Q'are a hydrogen atom and C, respectively.₁~ C₁₀-Alkyl or C₆~ C₂₀ -Aryl group, halogen atom, -OR ', -SR', -OSiR '_Three, -SiR
’_Three, -CR "_TwoSiR ’_Three, Eg CH_TwoSiMe_Three, -PR '_Two, -NR ' _Two , For example -NMe_Two, Toluenesulfonyl, trifluoroacetyl, triflu
Oromethanesulfonyl, nonafluorobutanesulfonyl or 2,2,2-trif
Is luoroethanesulfonyl, Z is CH_Two, CH_TwoCH_Two, CH (CH_Three) CH_Two, CH (C_FourH₉) C (C
H_Three)_Two, C (CH_Three)_Two, (CH_Three)_TwoSi, (CH_Three)_TwoGe, (CH_Three) _Two Sn, (C₆H₅)_TwoSi, (C₆H₅) (CH_Three) Si, (C₆H₅)_TwoS
n, (CH_Two)_FourSi or CH_TwoSi (CH_Three)_TwoAnd k is 1, 2 or 3, G is -O-, -S-, -NR "-or -PR"-or a group of formula (III)
Yes:

[0068]

[Chemical 10]

Here, the substituents R ^{9 to} R ¹² are as defined above, and R ″ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, Cyclohexyl or phenyl or cyclopentadienyl,
3-methylcyclopentadienyl, 3-n-butylcyclopentadienyl, indenyl, tetrahydroindenyl, tetramethylcyclopentadienyl, 3-trimethylsilylcyclopentadienyl or 3-phenylcyclopentadienyl, or Z _k And G are taken together are a substituted or unsubstituted aromatic or heteroaromatic structure having from 4 to 10 ring carbons, or Z _k and R ⁹ and / or R ¹² are taken together It can be a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system.

Suitable central metals M ^II of the transition metal compounds (II) are high-numbered transition metals, ie metals of group IIIB of the periodic table of the elements, lanthanide metals such as lanthanum or yttrium, IVB metals such as titanium. , Zirconium or hafnium, VB metals such as vanadium, VIB metals such as chromium or molybdenum (Lehrbuch der anorganischen Chemie, Holleman-Wiberg, de Gruyt
See also er Berlin, 1985). Preference is given to titanium, zirconium or hafnium. In the latter case, the metal M ^II of the mononuclear complex (II) is substantially 4
It has a positive charge of valence.

The monoanionic η ⁵ -bonded cyclic ligand having the substituent — (Z _k ) — is cyclopentadienyl (R ^{9 to} R ¹² ═H) or one or more functional groups other than Z, For example halogen, such as fluorine, chlorine or bromine, straight or branched C ₁ -C ₂₀ -alkyl, preferably C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-. butyl or t- _butyl, C 3 _{-C 10} - cycloalkyl, preferably _C 3 -C ₇ - cycloalkyl, such as cyclopropyl or cyclohexyl, or _C 6 _{-C 16,} - aryl, preferably _C 6 _{-C 10} -Aryl,
It may be, for example, a slightly charged 5-membered aromatic carbocycle substituted with phenyl or naphthyl. Suitable aryl substituents include, for example, C ₁ -C ₆ -alkyl, such as methyl or i-propyl or halogen, such as C ₆ -C ₁₆ -aryl substituted with fluorine, chlorine or bromine, preferably C _6- . C ₁₀ - aryl are also included.

Two adjacent groups, for example R ⁹ and R ¹⁰ or R ¹⁰ and R ¹¹ are taken together to form a saturated or unsaturated ring having 4 to 18 carbon atoms, preferably 4 to 15 carbon atoms. Or forming a heterocycle. Such moieties include, for example, fused aryl units. Thus, substituted and unsubstituted indenyl, fluorenyl or benzindenyl systems are likewise suitable monoanionic η ⁵ -linked cyclic ligands.

[0073]   Another suitable group R⁹~ R¹²Is C_Three~ C_Thirty-Organosilyl, preferably C_Three ~ C₂₁-Organosilyl group-Si (R^*)_ThreeIs. Group R^*Are independent of each other
C₁~ C₁₀-Alkyl, preferably C₁~ C₇-Alkyl, such as methyl,
Ethyl or i-propyl, C_Three~ C₁₀-Cycloalkyl, preferably C_Three~ C ₇ -Cycloalkyl, such as cyclopropyl or cyclohexyl, C₆~ C_{1 0} -Aryl, preferably phenyl, or having 1 to 4 carbon atoms in the alkyl part.
And an alkylaryl having 6 to 10 carbon atoms in the aryl portion, such as
This is

The groups R ^{9 to} R ^{12 in} compound (II) may be the same or different.

Particularly useful metal M ^II complexed η ⁵ -bonding ligands are derived from cyclopentadienyl, tetra-C ₁ -C ₆ -alkylcyclopentadienyl, indenyl, fluorenyl or benzindenyl. Where the latter three ligands may be mono- or poly-substituted with C ₁ -C ₆ -alkyl groups. Thus, preferred groups having the substituent Z are cyclopentadienyl substituted with _{1 to} 3 C ₁ -C ₄ -alkyl groups, tetra-C ₁ -C ₄ -alkylcyclopentadienyl, indenyl, Benzindenyl, and indenyl or benzindenyl. Particular preference is given to using cyclopentadienyl, tetramethylcyclopentadienyl or indenyl substituted by the group Z, especially tetramethylcyclopentadienyl.

Complexes (II) with two η ⁵ -bonding ligands are generally used. In these compounds G is a group of formula (III). The η ⁵ -bonding ligands may have the same substitution pattern or may differ from each other in the ring system itself and / or the ring substitution pattern.

[0077]   Suitable groups Z are monoanionic linkages whose free valence is occupied by the organic group R '.
It is a divalent structural unit based on members. An example of a suitable bonding member is silylene (-S
iR ’_Two-), Alkylene (-CR '_Two-), Germanyl (-GeR '_Two-),
Stanil (-SnR '_Two-), Boranyl (-BR'-) and oxo (-O-)
It is a base. Two covalent bond units Z (k = 2) are monoanionic η⁵-Binding ligand
And a unit G is formed. In a 2-membered bond, Z is not necessarily two
It does not have to exist in the form of the same structural unit. Suitable 2-membered bonds are especially those of the system -S.
iR ’_Two-SiR '_Two-, SiR '_Two-CR '_Two-, CR '_Two-CR '_Two-, C
R '= CR'-, -O-CR'_Two-And-O-SiR '_TwoIs. However,
In particular, a bond part having a single bond atom (k = 1) is used, and especially in the system —SiR ′._Two−
And -CR '_Two− Is used. The group R'is C₁~ C₂₀-Alkyl, preferably
C₁~ C₁₀-Alkyl, such as methyl, ethyl or i-propyl, C_Three~ C ₁₀ -Cycloalkyl, preferably C_Three~ C₇-Cycloalkyl, such as cyclohexyl
Kicil, C₆~ C₁₅-Aryl, preferably C₆~ C₁₀-Aryl, especially fe
Having 1 to 10 carbon atoms in the nyl or alkyl part and 6 to 10 in the aryl part
Alkylaryls with 1 carbon atom are used, eg benzyl. Z is 1
One or more groups R⁹~¹²Together with monocyclic or polycyclic aliphatic, aromatic or heteroaromatic
Form an aromatic ring system. Of the groups Z, di-C is particularly advantageous.₁~ C₇-Al
Kill-substituted silyl groups such as dimethylsilyl, diethylsilyl or di-i
-Propylsilyl.

Unit G also includes, for example, oxo (—O—), thio (—S—), amide (—NR ″)
-) Or a phosphide (-PR "-) group. These groups are generally conjugated and / or coordinated to the metal center M ^II . In addition, G is also uncharged 2-. It may be an electron donor, for example -OR ", -SR", -NR " ₂ or -PR" _{2. The} latter group G is generally coordinated to the metal center M via a free electron pair. G is preferably an oxo or thio group, particularly preferably an amide unit. The groups -NR "-, -PR"-, -OR ", -SR", -NR " ₂ or -PR.
As "substituents R _2", typically _hydrogen, C 1 _{-C 20} - alkyl, for example methyl, ethyl, t- butyl or n- _octyl, C 3 _{-C 10} - cycloalkyl, such as cyclohexyl, C ₆ -C ₁₅ - aryl, such as phenyl or _naphthyl, C 4 _{-C 16} - heteroaryl, such as pyridyl, furyl or quinolyl, 6 to 10 to have and aryl portions 1 to 10 carbon atoms in the alkyl portion alkylaryl having a carbon atom or a _C 3 _{-C 30,} - using organosilyl, for example, trimethylsilyl. Particularly preferred radicals R "are bulky groups, e.g. _C 3 _{-C 10} - alkyl group, for example, i- propyl or t- _butyl, C 6 _{-C 10} -
Aryl groups such as phenyl or substituted phenyl and alkylaryl groups having 1 to 6 carbon atoms in the alkyl portion and 6 to 10 carbon atoms in the aryl portion, such as benzyl. -N (t-butyl) -is particularly frequently used as the unit G. Further, the unit G is taken together with the unit Z or Z _k to form a ring carbon 4 to 16
Substituted or unsubstituted aromatic or heteroaromatic structures having one, preferably four to ten, are formed.

The ligands T ′ and Q ′ in compound (II) have the same meaning as the corresponding ligands T and Q of formula (I). T ′ and Q ′ are preferably halides, particularly preferably chloride or bromide, especially chloride.

Suitable transition metal compounds (II) are disclosed in DE-A 19707236, the essence of which is hereby incorporated by reference.

Particularly preferred compounds (II) are dimethylsilanediylbis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride, dimethylsilanediylbis (indenyl) zirconium dichloride, dimethylsilanediylbis (2-). Methylindenyl) zirconium dichloride, dimethylsilanediylbis (2-methylbenz [e] indenyl) zirconium dichloride, [dimethylsilanediyl (tetramethylcyclopentadienyl) (t-butyl) amido] titanium dichloride, (quinoline-8- Ill)-
2-indenyl titanium trichloride, (quinolin-8-yl) -2-indenyltrimethyl titanium, (quinolin-8-yl) -2-indenyl titanium dichloride, (quinolin-8-yl) -2-benz [ e] indenyl titanium trichloride, (
Quinolin-8-yl) -2-benz [e] indenyltrimethyl titanium, (quinolin-8-yl) -2-benz [e] indenyl titanium dichloride, (2-methylquinolin-8-yl) -2, 3,4,5-tetramethylcyclopentadienyl-titanium trichloride, (2-methylquinolin-8-yl) -2,3,4,5-tetramethylcyclopentadienyltrimethyl titanium and (2-methylquinoline -8-yl) -2,3,4
It is 5,5-tetramethylcyclopentadienyl titanium dichloride.

By adding the transition metal compound (II) to the reaction mixture of step a),
The polymerization of step b) can be initiated. If desired, another solvent component may be added to dilute the reaction mixture before addition of compound (II). In addition, a transition metal compound (II
), As such or in dissolved form, can be added to the reaction mixture, if desired, together with another cocatalyst of the type mentioned above.

In step b), methylaluminoxane, magnesium alkyl, lithium alkyl or aluminum alkyl, such as butyloctylmagnesium, butyllithium or triisobutylaluminum or any mixture of compounds thereof, borane and / or borate, eg tris ( Advantageously, it is added together with pentafluorophenyl) borate or dimethylanilinium tetrakis (pentafluorophenyl) borate as a cocatalyst.

The polymerization of step b) is generally from −100 ° C. to 300 ° C., preferably from 0 to 200 ° C.
, And particularly preferably at 25 to 150 ° C., 0.5 to 300 bar, preferably 1 to 10
It is carried out in the pressure range from 0 bar and particularly preferably from 1 to 60 bar.

The process of the invention may be carried out either in a single reactor or in two or more reactors linked in a cascade. Transition metal compounds (I) and (II
The ratio of) can be varied during the process by the amount added to each reactor cascade. The ratio of compound (I): compound (II) is generally 200.
: 1 to 1:50, preferably 50: 1 to 1:10.

A particularly beneficial effect on the number of alkyl branches is that in step b) the ethene feed is stopped and the polymerization is continued under the pressure conditions established in reaction step a) while consuming the ethene residue. It is achieved by Of course, ethene can also be interrupted only during step b). In another form, the ethene feed is first interrupted in step b) and then restarted during the polymerization.

The (co) polymerization reaction of step b) may be interrupted and the treatment carried out in a conventional manner.
For example, the reaction mixture is introduced into a product which has been precipitated by treatment with an excess of a low molecular weight alcohol, such as methanol, ethanol or i-propanol and, if desired, a mineral acid diluted in a mixture of low molecular weight alcohols, such as hydrochloric acid. be able to.

The method of the present invention comprises at least 12 for every 1000 carbon atoms in the polymer backbone.
A highly branched olefin having 0, in particular at least 150, very preferably at least 170 and even more preferably at least 205 alkyl branches is reproducibly provided.

The polyolefin obtained by the method of the present invention contains 10,000 to 2,000,000 g /
It has an average molecular weight Mw in the range of mol, preferably 15,000 to 1,000,000 g / mol and particularly preferably 20,000 to 500,000 g / mol. The polydispersity is in the range of 1.5 to 5.0, preferably 1.5 to 3.0, particularly preferably 1.6 to 2.5.

Furthermore, the hyperbranched polymers obtainable by the process according to the invention have a high proportion of ethylene branches, no or substantially no methyl branching, a small proportion of butyl and hexyl or It has more branches. The method of the invention preferably has at least 60%, preferably at least 70%, particularly preferably at least 80% of the alkyl branches.
Is ethyl side branch, at most 20% of the alkyl branch, preferably at most 15%,
Particularly preferred is a hyperbranched polyolefin in which at most 10% is either butyl and hexyl and higher side chains.

The hyperbranched polyolefin obtained has a rubber elastic property profile and is generally completely amorphous. They do not exhibit a melting point and generally have a glass transition temperature below −10 ° C., preferably below −30 ° C., particularly preferably below −50 ° C.

The hyperbranched polyolefins obtainable by the process according to the invention are suitable, for example, for improving the impact resistance of polymer mixtures containing linear polyolefins or thermoplastic processable materials. Suitable thermoplastic materials are, for example, polyamides such as polyamide 6 or polyamide 6.6, polyacetals such as polyoxymethylene or polyesters such as polybutylene terephthalate.

In the method of the invention, no 1-alkene dimer binding product produced is found. Furthermore, no problematic interactions are found between the olefin oligomerization catalyst and the polymerization catalyst as described. Also, in step a) no unreacted 1-alkane is detected in the branched polyolefin formed, so that these compounds are fully incorporated into the polymer chain in step b) and thus a homogeneous product is obtained.

[0094]   The present invention is explained in detail by the following examples.

Example Gel filtration chromatography of the polymer from Experiment 9 was performed on a Waters apparatus (150
C) using 1,2,4-trichlorobenzene as the eluent against polyethylene standard (flow rate: 1 ml / min) and using the method of DIN 55672
It was carried out at 40 ° C.

Gel filtration chromatography of the polymers from experiments 1-6 using tetrahydrofuran as the eluent against polystyrene standards (flow rate: 1.2 ml /
min) was carried out at 35 ° C.

¹ H-NMR and ¹³ C-NMR spectra were taken on a Bruker instrument (ARX300).
, Recorded using C ₂ D ₂ Cl ₄ as solvent.

DSC spectra were recorded on a Perkin-Elmer instrument (series 7) at a heating rate of 20 K / m.
recorded in.

Tetrahydrofuran and toluene were refluxed over sodium / benzofuran and distilled under inert gas.

Methylaluminoxane (MAO) in toluene, commercially available from Witco.
Used as a 53 molar solution.

The preparation of the catalyst complexes (Ia, Ib) and (II) and the polymerization reaction were carried out in the absence of air and moisture using the protective gas technology known in organic chemistry. Nitrogen was used as a protective gas.

A. Preparation of catalyst complex 1. Transition metal compound (Ia, Ib) a) 2,6-bis [1- (2-methylphenylimino) ethyl] pyridine 2,6-diacetylpyridine (1.5 g) , 2-Methylaniline (2.1 g) and p-toluenesulfonic acid (160 mg) were refluxed in benzene (50 ml) with a water separator for 24 hours. The cooled reaction mixture was added to diethyl ether (100 m).
1) diluted with sodium hydrogen carbonate solution (100 ml) and water (100 ml)
Washed with. The organic layer was dried over sodium sulfate and evaporated under reduced pressure. The resulting residue was washed with cold methanol (50 ml) and dried under reduced pressure. The yield of yellow solid was 80%.

B) 2,6-Bis [1-phenylimino) ethyl] pyridine Synthesis of this ligand was carried out using aniline (1.86 g) instead of 2-methylaniline.
Was carried out in the same manner as in A.1.a). The yield was 82%.

C) Transition metal compounds (Ia) (comparative catalyst) and (Ib) (catalyst according to the process of the invention) 2,6-bis [1- (2-methylphenylimino) dissolved in tetrahydrofuran (10 ml) ethyl] pyridine (A.1.A)) or 2,6-bis [1- (phenylimino) ethyl] pyridine (A.1.b)) (1mmol), FeCl 2 · 4H in tetrahydrofuran (10ml) Add to ₂ O with stirring. After stirring for 2 hours at room temperature, the volatile constituents were removed under reduced pressure and the residue was washed with diethyl ether (50 ml) and n-pentane (50 ml). The final distillate of solvent was removed under high vacuum. Products (Ia) and (Ib
) Got.

2) Transition Metal Compound (II) Dimethylsilanediylbis (2-methyl-4- (1-naphthyl) indenyl)
Zirconium dichloride The transition metal compound (II) was prepared according to the method of Spaleck et al., Organometallics 1994, 13
, 954-963.

A.) Preparation of hyperbranched polyolefin The transition metal compound (Ib) or (Ia) is stirred (600 rpm),
A 2.0 liter autoclave (runs 1-6: 1000 ml, runs 7-9: 800 ml) and methylaluminoxane (1.53 molar solution in toluene) and pre-flashed with ethene gas (runs 1- 6) or 1.6l
It was introduced into the autoclave (Experiments 7-9) at 40 ° C. The ethene pressure was set to 2 bar and kept this pressure during the first reaction step (step a)). The ethene feed was interrupted before the addition of the transition metal compound (II). Transition metal compound (II)
Was added, the polymerization reaction was carried out while consuming ethene present in the reaction vessel (step b)). After cooling to room temperature, the reaction vessel was degassed, the polymer solution was slowly introduced into 200 ml of ethanol and the reaction mixture was evaporated to a volume of about 400 ml, after which a mixture of diluted hydrochloric acid and methanol was added in excess (about 1.5l)
Used to precipitate the polymer product. The product was filtered off and methanol (300 m
It was washed with l) and the final residual solvent was removed under high vacuum at 40 ° C. Details relating to the polymerizations carried out in the customary manner as well as the reaction parameters characterizing the product properties of the polymers produced are given in the table below.

[0107]

[Table 1]

(A) Alkyl branching in the polyolefins obtained in Experiments 1-6 as determined by ¹³ C-NMR spectroscopy consisted of ethyl branching (80%), butyl branching (10%) and hexyl and higher. (B) first number = reaction time of step a), second number = reaction time of step b); (c) comparative experiment; (d) catalyst (Ib) Polymerization in the simultaneous presence of (II) and (II)
Using catalysts (Ib) and (II) simultaneously, ie steps a) and b
It is proved that the hyperbranched amorphous polyolefin does not occur when () is carried out simultaneously).

─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Joachim Kvaiser             Federal Republic of Germany Mannheim Morsch             Trace 13 (72) Inventor Gerrit Leinstra             Germany Mannheim Burga             -Meister-Fuchs-Strasse 7 (72) Inventor Michael Gepleks             Federal Republic of Germany Ramsheim Bouvet             6 F-term (reference) 4J128 AA02 AB01 AC09 AC27 AC45                       AC46 AC47 BA01B BB01B                       BC25B EA02 EB01 EB02                       ED01 EF02 GA16

Claims (7)

[Claims] 1. A highly branched amorphous having an ethene to rubber elastic property profile.
A method for producing a polyolefin using a homogeneous catalyst, wherein the method comprises the first step
In steps a) at least one general formula (I):     [Chemical 1] [Wherein the substituents and indices have the following meanings: R¹, R^TwoIs aryl or heteroaryl and N^aOr N^bConnection between and
With C having hydrogen substituents at two vicinal positions with respect to_Four~ C₁₆-Heteroaryl
Or C₆~ C₁₆-Aryl R^Three, R^FourIs hydrogen, C₁~ C₁₀-Alkyl, C_Three~ C₁₀-Cycloalkyl
, C₆~ C₁₆-Aryl, having 1 to 10 carbon atoms in the alkyl part and
Alkylaryl having 6 to 14 carbon atoms in the aryl moiety, or Si (R⁸) _Three And here R⁸Is C₁~ C₁₀-Alkyl, C_Three~ C₁₀-Cycloalkyl, C₆~ C_{1 6} -Aryl, having 1 to 10 carbon atoms in the alkyl part and 6 to in the aryl part
An alkylaryl having 14 carbon atoms, R⁵, R⁶, R⁷Is hydrogen, C₁~ C₁₀-Alkyl, C_Three~ C₁₀-Cycloa
Rukiru, C₆~ C₁₆-Aryl, has 1-10 carbon atoms in the alkyl part?
Alkyl moiety having 6 to 14 carbon atoms in the aryl part or Si (R ⁸ )_ThreeOr a functional group based on an element of group IVA to VIIA of the periodic table of elements
Or R⁵And R⁶And / or R⁶And R⁷Are together
Substituted or non-substituted with a 5-, 6- or 7-membered aliphatic or aromatic condensed to
Forming an alternative carbocycle or heterocycle, M^IIs Fe, Ru, Co, Rh, Ni or Pd, T, Q is an uncharged or monoanionic monodentate ligand, or T and
Q together are a diketo enolate unit or a methylketone end group or a straight chain
C₁~ C_FourC having an alkyl ester or nitrile end group_Two-Alkylene
Or C_ThreeForming an alkylene unit, A is an anion that does not coordinate or is difficult to coordinate, m and p are 0, 1, 2 or 3, q is 1, 2 or 3, and n is 1, 2 or 3] and optionally an uncharged
Lewis strong acid, Lewis-as an ionic compound or cation having an acid cation
In the presence of one or more cocatalysts in the form of ionic compounds with Bronsted acids
To oligomerize ethene in an inert solvent, and in the next step, b) at least one general formula (II):     [Chemical 2] [Wherein the substituents and indices have the following meanings: R⁹~ R¹²Is hydrogen, C₁~ C₁₀-Alkyl, C_Three~ C₁₀-Cycloalk
Le, C₆~ C₁₆-Aryl, having 1 to 10 carbon atoms in the alkyl part and
Alkylaryl having 6 to 14 carbon atoms in the reel part or Si (R⁸) _Three Or a functional group based on an element of group IVA to VIIA of the periodic table of elements
Or R⁹And R¹⁰And / or R¹¹And R¹²Respectively
Substituted together with a condensed 5-, 6- or 7-membered aliphatic or aromatic group or
Form an unsubstituted carbocycle or heterocycle, M^IIIs a Group IIIB, IVB, VB or VIB metal of the Periodic Table of the Elements
, T'and Q'are hydrogen atoms, C₁~ C₁₀-Alkyl or C₆~ C₂₀− Ally
Group, halogen atom, -OR ', -SR', -OSiR '_Three, -SiR '_Three,-
CR ”_TwoSiR ’_Three, -PR '_Two, -NR '_Two, Toluenesulfonyl, triflu
Oroacetyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl
2,2,2-trifluoroethanesulfonyl, Z is -CR '_Two-, -SiR '_Two-, GeR '_Two-, -SnR '_Two-, -BR
'-Or -O-, where R'is C₁~ C₂₀-Alkyl, C_Three~ C₁₀-Cycloalkyl, C₆~ C_{1 6} -Aryl, having 1 to 10 carbon atoms in the alkyl part and 6 to in the aryl part
Alkylaryl having 10 carbon atoms, C₁~ C₂₀-Alkoxy, C_Three ~ C₁₀-Cycloalkoxy, C₆~ C₁₆-Aryloxy or alkyl moieties
Having 1 to 10 carbon atoms in the and 6 to 10 carbon atoms in the aryl portion
Alkylaryloxy, k is 1, 2 or 3, G is -O-, -S-, -NR "-, -PR"-, -BR "-, -OR"-,-.
SR "-, -NR"_Two, -PR "_TwoOr formula (III):     [Chemical 3] (In the formula, the substituent R⁹~ R¹²Is as defined above), R "is hydrogen, C₁~ C₂₀-Alkyl, C_Three~ C₁₀-Cycloalkyl, C₆ ~ C₁₅-Aryl, an aryl part having 1 to 10 carbon atoms in the alkyl part
Alkylaryl having 6 to 10 carbon atoms or C_Three~ C_Thirty-Olga
Is nosilyl, or Z_kAnd G, taken together, are substituted or non-substituted having 4 to 16 ring carbon atoms.
Forming a substituted aromatic or heteroaromatic structure, or Z_kAnd R⁹And / or R¹²Together, are monocyclic or polycyclic,
Transition metal compounds forming an aliphatic, aromatic or heteroaromatic ring system, and
If desired, described in step a) for the oligomer mixture described in a).
Add another cocatalyst similar to the above, continue the reaction in the presence of ethene,
In c) the resulting polymerization product is isolated Using a homogeneous catalyst of hyperbranched amorphous polyolefin, characterized in that
Manufacturing method. 2. In the formulae, the substituents and indices have the following meanings: R ¹ , R ² is 4-i-propylphenyl, 4-methylphenyl, 4-methoxyphenyl or phenyl, R ³ , R ⁴ is hydrogen, methyl, ethyl, i-propyl, t-butyl or triorganosilyl, R ⁵ , R ⁶ , R ⁷ are hydrogen or methyl, M ^I is iron or cobalt, Process according to claim 1, characterized in that the transition metal compound (I) in which T, Q is a halide ion or trifluoromethanesulfonate is used. 3. In the formula, the substituents and indices have the following meanings: R ¹ , R ² is 4-i-propylphenyl, 4-methylphenyl, 4-methoxyphenyl or phenyl, R ³ , R ⁴ is hydrogen, methyl, ethyl, i-propyl, t-butyl or triorganosilyl, R ⁵ , R ⁶ , R ⁷ are hydrogen or methyl, M ^I is iron or cobalt, T is methyl, Q is chloride, bromide or trifluoromethanesulfonate, and A is tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
B [C ₆ H ₅ ] ₄ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , AlF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ or a transition metal compound (I) which is trifluoroacetate is used, The method according to claim 1 or 2. 4. Substituents and indices have the following meanings: M^IIIs titanium or zirconium, R⁹~ R¹²Is C₁~ C₁₀-Alkyl or C_Three~ C₂₁-Organosilyl
Where the two adjacent groups may form a fused aromatic ring, T'and Q'are a hydrogen atom and C, respectively.₁~ C₁₀-Alkyl or C₆~ C₂₀ -Aryl group, halogen atom, -OR ', -SR', -OSiR '_Three, -SiR
’_Three, -CR "_TwoSiR ’_Three, -PR '_Two, -NR '_Two, Toluenesulfonyl,
Trifluoroacetyl, trifluoromethanesulfonyl, nonafluorobutanes
Rufonyl or 2,2,2-trifluoroethanesulfonyl, z is CH_Two, CH_TwoCH_Two, CH (CH_Three) CH_Two, CH (C_FourH₉) C (C
H_Three)_Two, C (CH_Three)_Two, (CH3)_TwoSi, (CH_Three)_TwoGe, (CH_Three) _Two Sn, (C₆H₅)_TwoSi, (C₆H₅) (CH_Three) Si, (C₆H₅)_TwoS
n, (CH_Two)_FourSi or CH_TwoSi (CH_Three)_TwoAnd k is 1, 2 or 3, G is -O-, -S-, -NR "-or -PR"-or formula (III):     [Chemical 4] [In the formula, the substituent R⁹~ R¹²Is as defined above], R "is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl.
L, t-butyl, cyclohexyl or phenyl or cyclopentadienyl,
3-methylcyclopentadienyl, 3-n-butylcyclopentadienyl, in
Denyl, tetrahydroindenyl, tetramethylcyclopentadienyl, 3-to
Limethylsilylcyclopentadienyl or 3-phenylcyclopentadienyl
Is 4. Use of a transition metal compound (II), characterized in that
The method according to item 1. 5. Steps a) and / or b), characterized in that borane, magnesium alkyl, lithium alkyl or aluminum alkyl, aluminum halide alkyl or aluminoxane is used as cocatalyst. The method according to any one of 1. 6. A process according to claim 1, characterized in that steps a) and b) are carried out in a cascaded stirred vessel. 7. The general formula (I):     [Chemical 5] [Wherein the substituents and indices have the following meanings: R¹, R^TwoIs aryl or heteroaryl and N^aOr N^bConnection between and
With C having hydrogen substituents at two vicinal positions with respect to_Four~ C₁₆-Heteroaryl
Or C₆~ C₁₆-Aryl R^Three, R^FourIs hydrogen, C₁~ C₁₀-Alkyl, C_Three~ C₁₀-Cycloalkyl
, C₆~ C₁₆-Aryl, having 1 to 10 carbon atoms in the alkyl part and
Alkylaryl having 6 to 14 carbon atoms or Si (R⁸)_Three And here R⁸Is C₁~ C₁₀-Alkyl, C_Three~ C₁₀-Cycloalkyl, C₆~ C_{1 6} -Aryl, having 1 to 10 carbon atoms in the alkyl part and 6 to in the aryl part
An alkylaryl having 14 carbon atoms, R⁵, R⁶, R⁷Is hydrogen, C₁~ C₁₀-Alkyl, C_Three~ C₁₀-Cycloa
Rukiru, C₆~ C₁₆-Aryl, has 1-10 carbon atoms in the alkyl part?
Alkyl moiety having 6 to 14 carbon atoms in the aryl part or Si (R ⁸ )_ThreeOr a functional group based on an element of group IVA to VIIA of the periodic table of elements
Or R⁵And R⁶And / or R⁶And R⁷Are together
Substituted or non-substituted with a 5-, 6- or 7-membered aliphatic or aromatic condensed to
Forming a carbocyclic or heterocyclic ring, M^IIs Fe, Ru, Co, Rh, Ni or Pd, T, Q are uncharged or monoanionic monodentate ligands or T and Q
Taken together, a diketo enolate unit or a methyl ketone end group or a straight chain C ₁ ~ C_FourC with ester or nitrile end groups_Two-Alkylene or C_Three Forming an alkylene unit, A is an anion that does not coordinate or is difficult to coordinate, m and p are 0, 1, 2 or 3, q is 1, 2 or 3, and n is 1, 2 or 3] and optionally an uncharged
Lewis strong acid, Lewis-as an ionic compound or cation having an acid cation
An ethene of one or more cocatalysts in the form of ionic compounds with Bronsted acids.
Use for producing highly branched amorphous polyolefins with rubber-elastic properties from polymers
.