Catalyst and process for preparing same

文档序号：914020 发布日期：2021-02-26 浏览：6次中文

阅读说明：本技术 催化剂 (Catalyst and process for preparing same ) 是由 N·阿杰拉尔 V·维克库恩 L·M·C·雷斯科尼 V·V·伊兹默 D·S·科诺诺维奇 A· 于 2019-06-28 设计创作，主要内容包括：式(I)的配合物：M为Hf；每个X是σ配体；L是式-(ER~8_2)_y-的桥；y是1或2；E是C或Si；每个R~8独立地为C_1-C_(20)-烃基、三(C_1-C_(20)-烷基)甲硅烷基、C_6-C_(20)-芳基、C_7-C_(20)-芳基烷基或C_7-C_(20)-烷基芳基,或者L为亚烷基基团,例如亚甲基或亚乙基；Ar和Ar’各自独立地为任选被1至3个R~1或R~(1’)基团分别取代的芳基或杂芳基基团；R~1和R~(1’)各自独立地相同或可以不同,并且是直链或支链的C_1-C_6-烷基基团、C_(7-20)芳基烷基、C_(7-20)烷基芳基基团或C_(6-20)芳基基团,条件是如果总共存在四个或更多个R~1和R~(1’)基团,R~1和R~(1’)中的一个或多个不是叔丁基；R~2和R~(2’)相同或不同,且为CH_2-R~9基团,其中R~9为H或者直链或支链的C_1-C_6-烷基基团、C_(3-8)环烷基基团、C_(6-10)芳基基团；每个R~3为-CH_2-、-CHRx-或C(Rx)_2-基团,其中Rx为C_(1-4)烷基,且其中m为2-6；R~5是直链或支链的C_1-C_6-烷基基团、C_(7-20)芳基烷基、C_(7-20)烷基芳基基团或C_6-C_(20)-芳基基团；R~6为C(R~(10))_3基团,其中R~(10)为直链或支链的C_1-C_6烷基基团；以及R~7和R~(7’)相同或不同,并且为H或者直链或支链的C_1-C_6-烷基基团。本发明还涉及固体形式的催化剂,其包含(i)式(I)的配合物和(ii)铝化合物的助催化剂和(iii)硼化合物的助催化剂。(A complex of formula (I): m is Hf; each X is a sigma ligand; l is a group of the formula- (ER) 8 2 ) y -a bridge of; y is 1 or 2; e is C or Si; each R 8 Independently is C 1 ‑C 20 -hydrocarbyl, tri (C) 1 ‑C 20 Alkyl) silyl, C 6 ‑C 20 -aryl, C 7 ‑C 20 Arylalkyl or C 7 ‑C 20 -alkylaryl, or L is an alkylene group, such as methylene or ethylene; ar and Ar' are each independently optionally substituted with 1 to 3R 1 Or R 1’ Aryl or heteroaryl groups substituted with the respective groups; r 1 And R 1’ Each independently being the same or different and being a straight or branched C 1 ‑C 6 -alkyl radical, C 7‑20 Arylalkyl radical, C 7‑20 Alkylaryl group or C 6‑20 Aryl group, provided that if there are four or more R in total 1 And R 1’ Group, R 1 And R 1’ Is not a tert-butyl group; r 2 And R 2’ Are the same or different and are CH 2 ‑R 9 Group, wherein R 9 Is H or straight or branched C 1 ‑C 6 -alkyl radical, C 3‑8 Cycloalkyl radical, C 6‑10 An aryl group; each R 3 is-CH 2 -, -CHRx-or C (Rx) 2 -a group wherein Rx is C 1‑4 Alkyl, and wherein m is 2-6; r 5 Is straight-chain or branched C 1 ‑C 6 -alkyl radical, C 7‑20 Arylalkyl radical, C 7‑20 Alkylaryl group or C 6 ‑C 20 -an aryl group; r 6 Is C (R) 10 ) 3 Group, wherein R 10 Is straight-chain or branched C 1 ‑C 6 An alkyl group; and R 7 And R 7’ Identical or different and is H or C which is linear or branched 1 ‑C 6 -an alkyl group. The invention also relates to a catalyst in solid form comprising (I) a complex of formula (I) and (ii) a cocatalyst of an aluminium compound and (iii) a cocatalyst of a boron compound.)

1. A complex of formula (I):

m is Hf;

each X is a sigma ligand;

l is a group of the formula- (ER)⁸ ₂)_y-a bridge of;

y is 1 or 2;

e is C or Si;

each R⁸Independently is C₁-C₂₀-hydrocarbyl, tri (C)₁-C₂₀Alkyl) silyl, C₆-C₂₀-aryl, C₇-C₂₀Arylalkyl or C₇-C₂₀-alkylaryl, or L is an alkylene group, such as methylene or ethylene;

ar and Ar' are each independently optionally substituted with 1 to 3R¹Or R^1’Aryl or heteroaryl groups substituted with the respective groups;

R¹and R^1’Each independently the same or different, and is a straight or branched C₁-C₆-alkyl radical, C_7-20Arylalkyl radical, C_7-20Alkylaryl group or C_6-20Aryl group, provided that if there are four or more R in total¹And R^1’Group, R¹And R^1’Is not a tert-butyl group;

R²and R^2’Are the same or different and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C_1-6-alkyl radical, C_3-8Cycloalkyl radical, C_6-10An aryl group;

each R³is-CH₂-, -CHRx-or C (Rx)₂-a group wherein Rx is C_1-4Alkyl, and wherein m is 2-6;

R⁵is straight-chain or branched C₁-C₆-alkyl radical, C_7-20Arylalkyl radical, C_7-20Alkylaryl group or C₆-C₂₀-an aryl group;

R⁶is C (R)¹⁰)₃Group, wherein R¹⁰Is straight-chain or branched C₁-C₆An alkyl group; and

R⁷and R^7’Identical or different and is H or C which is linear or branched₁-C₆-an alkyl group.

2. The complex of claim 1 which is a complex of formula (Ia)

M is Hf;

each X is a sigma ligand;

l is a group of the formula- (ER)⁸ ₂)_y-a bridge of;

y is 1 or 2;

e is C or Si;

each R⁸Independently is C₁-C₂₀-hydrocarbyl, tri (C)₁-C₂₀Alkyl) silyl, C₆-C₂₀-aryl, C₇-C₂₀Arylalkyl or C₇-C₂₀-alkylaryl, or L is an alkylene group;

each n is independently 0,1, 2 or 3;

R²and R^2’Are the same or different and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C_1-6-alkyl radical, C_3-8Cycloalkyl radical, C_6-10An aryl group;

each R³is-CH₂-, -CHRx-or C (Rx)₂-a group wherein Rx is C_1-4Alkyl, and wherein m is 2-6;

R⁵is straight-chain or branched C₁-C₆-alkyl radical, C_7-20Arylalkyl radical, C_7-20Alkylaryl group or C₆-C₂₀-an aryl group;

R⁶is C (R)¹⁰)₃Group, wherein R¹⁰Is straight-chain or branched C₁-C₆An alkyl group; and

R⁷and R^7’Identical or different and is H or C which is linear or branched₁-C₆-an alkyl group.

3. The complex of claim 2, wherein L is of the formula-SiR⁸ ₂-, wherein each R⁸Independently is C₁-C₂₀-hydrocarbyl, tri (C)₁-C₂₀Alkyl) silyl, C₆-C₂₀-aryl, C₇-C₂₀Arylalkyl or C₇-C₂₀-alkylaryl.

4. The complex of claim 1, which is a complex of formula (Ib):

wherein

M is Hf;

each X is a sigma ligand;

l is an alkylene bridge or of the formula-SiR⁸ ₂A bridge of (a) wherein each R⁸Independently is C₁-C₂₀-hydrocarbyl, tri (C)₁-C₂₀Alkyl) silyl, C₆-C₂₀-aryl, C₇-C₂₀Arylalkyl or C₇-C₂₀-an alkylaryl group;

each n is independently 0,1, 2 or 3;

R²and R^2’Are the same or different and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C_1-6-alkyl radical, C_3-8Cycloalkyl radical, C_6-10An aryl group;

R⁵is straight-chain or branched C₁-C₆-alkyl radical, C_7-20Arylalkyl radical, C_7-20Alkylaryl group or C₆-C₂₀-an aryl group;

R⁶is C (R)¹⁰)₃Group, wherein R¹⁰Is straight-chain or branched C₁-C₆An alkyl group; and

R⁷and R^7’Identical or different and is H or C which is linear or branched₁-C₆-an alkyl group.

5. The complex of claim 4, wherein each n is 1 or 2.

6. The complex according to any one of the preceding claims, which is a complex of formula (II)

Wherein

M is Hf;

x is a sigma ligand, preferably each X is independently a hydrogen atom, a halogen atom, C_1-6Alkoxy radical, C_1-6An alkyl, phenyl or benzyl group;

l is an alkylene bridge or of the formula-SiR⁸ ₂A bridge of (a) wherein each R⁸Independently is C₁-C₆Alkyl radical, C_3-8Cycloalkyl or C₆-an aryl group;

each n is independently 1 or 2;

R¹and R^1’Each independently the same or different, and is a straight or branched C₁-C₆-an alkyl group, with the proviso that if four R's are present¹And R^1’Group, all 4 ofCan be simultaneously tert-butyl;

R²and R^2’Are the same or different and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C_1-6-an alkyl group;

R⁵is straight-chain or branched C₁-C₆-an alkyl group; and

R⁶is C (R)¹⁰)₃Group, wherein R¹⁰Is straight-chain or branched C₁-C₆An alkyl group.

7. The complex according to any one of the preceding claims, which is a complex of formula (III)

Wherein

M is Hf;

each X is a sigma ligand, preferably each X is independently a hydrogen atom, a halogen atom, C_1-6Alkoxy radical, C_1-6An alkyl, phenyl or benzyl group;

l is-SiR⁸ ₂-, wherein each R⁸Is C₁-C₆-alkyl or C_3-8A cycloalkyl group;

each n is independently 1 or 2;

R¹and R^1’Each independently the same or different, and is a straight or branched C₁-C₆-an alkyl group, with the proviso that if four R's are present¹And R^1’All 4 of which cannot be tert-butyl at the same time;

R⁵is straight-chain or branched C₁-C₆-an alkyl group; and

R⁶is C (R)¹⁰)₃Group, wherein R¹⁰Is straight-chain or branched C₁-C₆An alkyl group.

8. The complex according to any one of the preceding claims, which is a complex of formula (IV)

Wherein

M is Hf;

each X is a hydrogen atom, a halogen atom, C_1-6Alkoxy radical, C_1-6An alkyl, phenyl or benzyl group;

l is-SiR⁸ ₂-, wherein each R⁸Is C_1-4Alkyl or C_5-6A cycloalkyl group;

each n is independently 1 or 2;

R⁵is straight-chain or branched C₁-C₆-an alkyl group; and

R⁶is C (R)¹⁰)₃Group, wherein R¹⁰Is straight-chain or branched C₁-C₆An alkyl group.

9. The complex according to any one of the preceding claims, which is a complex of formula (V)

Wherein

M is Hf;

x is a hydrogen atom, a halogen atom, C_1-6Alkoxy radical, C_1-6An alkyl, phenyl or benzyl group;

l is-SiMe₂；

Each n is independently 1 or 2;

R⁵is straight-chain or branched C₁-C₄-an alkyl group; and

R⁶is C (R)¹⁰)₃Group, wherein R¹⁰Is straight-chain or branched C₁-C₄An alkyl group.

10. The complex according to any one of the preceding claims, which is a complex of formula (VI)

Wherein

M is Hf;

x is a hydrogen atom, a halogen atom, C_1-6Alkoxy radical, C_1-6An alkyl, phenyl or benzyl group;

l is-SiMe₂；

Each n is independently 1 or 2;

R⁵is a straight chain C₁-C₄-alkyl groups, such as methyl; and

R⁶is a tert-butyl group.

11. The complex according to any one of the preceding claims, which is a complex of formula (VII)

Wherein

M is Hf;

x is a hydrogen atom, a halogen atom, C_1-6Alkoxy radical, C_1-6Alkyl, phenyl or benzyl groups, especially chlorine;

l is-SiMe₂；

Each n is independently 1 or 2;

R¹and R^1’Each independently the same or different, and is a straight or branched C₁-C₄-an alkyl group, with the proviso that if four R's are present¹And R^1’All 4 of which cannot be tert-butyl at the same time;

R⁵is methyl; and

R⁶is a tert-butyl group.

12. The complex according to any one of the preceding claims, which is a complex of formula (VIII)

Wherein

M is Hf;

x is Cl;

l is-SiMe₂；

Each n is independently 1 or 2;

R¹and R^1’Each independently being methyl or tert-butyl, provided that if four R's are present¹And R^1’All 4 of these radicals, which cannot be simultaneously tert-butyl,

R⁵is methyl; and

R⁶is a tert-butyl group.

13. The complex of any one of the preceding claims, wherein at least one of the C (4) or C (4') phenyl rings is 3, 5-dimethylphenyl.

14. The complex of any one of the preceding claims, wherein at least one of the C (4) or C (4') phenyl rings is 4- (tert-butyl) -phenyl.

15. The complex according to any one of the preceding claims, wherein R¹、R^1’And each value of n is selected such that the C (4) or C (4') phenyl ring is a 3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl and/or 4- (tert-butyl) -phenyl group.

16. A catalyst in solid form comprising:

(i) the complex according to any one of claims 1 to 15;

(ii) cocatalysts of aluminum compounds, e.g. aluminoxanes, and

(iii) a promoter for boron compounds, such as borate.

17. The catalyst of claim 16, which is supported on an external support or in the form of solid particles without an external support.

18. A process for the manufacture of the catalyst system of claim 16 or 17, comprising obtaining the complex (i) of any one of claims 1 to 15 and the cocatalysts (ii) and (iii);

the method comprises forming a liquid/liquid emulsion system comprising a solution of catalyst components (i), (ii) and (iii) dispersed in a solvent in the form of dispersed droplets and solidifying the dispersed droplets to form solid particles of the catalyst system.

19. A process for the preparation of a propylene polymer comprising polymerising propylene optionally with ethylene and/or a C4-10 alpha olefin in the presence of a catalyst as claimed in any one of claims 16 to 17.

Technical Field

The present invention relates to novel bisindenyl ligands, complexes thereof and catalysts comprising these complexes. The invention also relates to the use of the novel bisindenyl metallocene catalysts for the preparation of propylene polymers, in particular heterophasic propylene copolymers and propylene homopolymers, having a high molecular weight and therefore a low MFR, having an improved activity, and having a high melting point.

Background

Metallocene catalysts have been used for many years to make polyolefins. Numerous academic and patent publications describe the use of these catalysts in the polymerization of olefins. Metallocenes are used industrially, in particular polyethylene and polypropylene are generally produced using cyclopentadienyl-based catalyst systems having different substitution patterns.

The present inventors have sought new metallocene catalysts which are capable of providing high melting temperature propylene polymers, particularly in the case of propylene homopolymers. In addition, the desired catalysts should also have improved properties in the production of high molecular weight propylene homopolymers, have good activity and be able to produce propylene heterophasic copolymers with a high melting polymer matrix and a high molecular weight rubber phase. Various prior art references are directed to one or more of these features.

C is disclosed, for example, in WO2007/116034₂Symmetrical metallocenes. This document reports, inter alia, metallocene rac-Me₂Si(2-Me-4-Ph-5-OMe-6-tBuInd)₂ZrCl₂And used as a polymerization catalyst after activation with MAO for the homopolymerization of propylene and the copolymerization of propylene with ethylene and higher alpha-olefins in solution polymerization。

WO02/02576 describes, inter alia, rac-Me₂Si[2-Me-4-(3,5-tBu₂Ph)Ind]₂ZrCl₂And rac-Me₂Si[2-Me-4-(3,5-tBu₂Ph)Ind]₂ZrCl₂(see also WO2014/096171) and its use in the manufacture of high Mw and high melting point polypropylene.

WO06/097497 describes, inter alia, racemic-Me supported on silica₂Si (2-Me-4-Ph-1,5,6, 7-tetrahydro-s-indacen-1-yl)₂ZrCl₂And their use in the homopolymerization of propylene and the copolymerization of propylene and ethylene.

WO2006100258 describes C₁-use of a symmetric metallocene for the production of a heterophasic ethylene/propylene copolymer.

WO2011/076780 describes rac-Me activated with methylaluminoxane in solid particulate form₂Si (2-Me-4-Ph-1,5,6, 7-tetrahydro-s-indacen-1-yl)₂ZrCl₂Without an external carrier, for propylene homopolymerization.

US 6,057,408 describes the effect of 4-aryl substituents on the molecular weight of ethylene-propylene copolymers produced in liquid slurries. It has been described in this document that asymmetric metallocenes are capable of producing isotactic polypropylene. WO2013/007650 describes certain asymmetric catalysts comprising an alkoxy group in the 5-position of one of the rings, e.g. dimethylsilylene (. eta.) (eta.)⁵-6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl) - (η⁵-6-tert-butyl-2-methyl-4-phenyl-1H-inden-1-yl) zirconium dichloride. Despite good performance, the catalysts based on this reference are limited in terms of polypropylene homopolymer melt temperature, productivity at low MFR. In addition, the overall productivity of the catalyst still needs to be improved.

In Ewen et al J.Am.chem.Soc.1987,109,6544-6545, it is described that hafnocenes improve the Tm of polypropylene relative to the corresponding zirconocenes. Activation was accomplished by MAO, but Tm was still low.

Furthermore, most metallocenes, the structure of which is optimized to produce high molecular weight isotactic PP, exhibit limitations in molecular weight capability when used to produce ethylene-propylene copolymers in the gas phase. It is known that for a given rubber comonomer composition, the tensile and impact properties of a heterophasic PP/EPR blend can be improved by increasing the molecular weight of the rubber phase. In addition, if the Tm of the hPP matrix of the heterophasic copolymer is low, the material stiffness is not as high as desired.

Even with the improvements described in the literature, there is still a need to provide metallocene catalysts which are capable of providing propylene polymers with improved activity, providing high melting temperature polypropylenes and having high molecular weights, i.e. low MFR values, and further providing propylene heterophasic copolymers having a high melting polymer matrix and a high molecular weight rubber phase.

The catalysts of the invention should ideally be suitable for use in conventional solid supported forms, for example using silica or alumina supports, or may be used in solid form without an external support or carrier.

The applicant has previously developed alternatives to conventional inorganic supports. In WO03/051934, the inventors propose an alternative form of catalyst which is provided in solid form but which does not require a conventional external support material, such as silica. The invention is based on the following findings: homogeneous catalyst systems containing organometallic compounds of transition metals can be converted in a controlled manner into solid, homogeneous catalyst particles by first forming a liquid/liquid emulsion system comprising a solution of the homogeneous catalyst system as the dispersed phase and a solvent immiscible therewith as the continuous phase, and then solidifying the dispersed droplets to form solid particles comprising the catalyst.

The invention described in WO03/051934 enables the formation of solid spherical catalyst particles of the organic transition metal catalyst without the use of external porous support particles such as silica, as is typically required in the art. The catalyst of the invention should be able to utilize the process.

The present inventors have developed a novel metallocene catalyst, with the currently achievable use of an alternative C₁A symmetric metallocene-based catalyst having improved polymerization properties compared to the symmetric metallocene-based catalyst,higher catalyst productivity, improved performance in producing high molecular weight and high melting temperature polypropylene polymers (particularly propylene homopolymers and propylene heterophasic copolymers) as described above.

Known metallocene catalysts exhibit moderate activity and provide moderate melting point polypropylenes. However, it would be desirable to provide catalysts that provide higher molecular weight rubber phases of higher molecular weight polymers or heterophasic copolymers, and even higher melting temperature propylene homopolymers. The present invention solves this problem.

The inventors have now found that the inclusion of a specific C₁Specific catalysts of symmetrical metallocenes provide improved properties in the polymerization of propylene, in particular in the homopolymerization of propylene and in the production of heterophasic copolymers of propylene.

In particular, the catalyst of the present invention can realize

Improved performance in the production of high molecular weight propylene homopolymers;

improved, i.e. higher melting, propylene homopolymers;

improved, i.e. higher melting point, of the propylene homopolymer matrix of the heterophasic propylene copolymer;

improved, i.e. higher molecular weight, of the rubber phase of the heterophasic propylene copolymer;

high catalyst activity for the production of high Mw propylene polymers,

it has now been surprisingly found that these improvements can be achieved by using a catalyst of the present invention comprising a specific metallocene as defined below and at least two cocatalysts, i.e. aluminium-based and boron-based cocatalysts.

Disclosure of Invention

Viewed from one aspect, the invention provides a complex of formula (I):

m is Hf;

each X is a sigma ligand;

l is a group of the formula- (ER)⁸ ₂)_y-a bridge of;

y is 1 or 2;

e is C or Si;

ar and Ar' are each independently optionally substituted with 1 to 3R¹Or R^1’Aryl or heteroaryl groups substituted with the respective groups;

R¹and R^1’Each independently being the same or different and being a straight or branched C₁-C₆-alkyl radical, C_7-20Arylalkyl radical, C_7-20Alkylaryl group or C_6-20Aryl group, provided that if there are four or more R in total¹And R^1’Group, R¹And R^1’Is not a tert-butyl group;

R²and R^2’Are the same or different and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C_1-6-alkyl radical, C_3-8Cycloalkyl radical, C_6-10An aryl group;

each R³is-CH₂-, -CHRx-or C (Rx)₂-a group wherein Rx is C_1-4Alkyl, and wherein m is 2-6;

R⁵is straight-chain or branched C₁-C₆-alkyl radical, C_7-20Arylalkyl radical, C_7-20Alkylaryl group or C₆-C₂₀-an aryl group;

R⁶is C (R)¹⁰)₃Group, wherein R¹⁰Is straight-chain or branched C₁-C₆An alkyl group; and

R⁷and R^7’Identical or different and is H or C which is linear or branched₁-C₆-an alkyl group.

Viewed from a further aspect the invention provides a complex of formula (Ia)

M is Hf;

each X is a sigma ligand;

l is a group of the formula- (ER)⁸ ₂)_y-a bridge of;

y is 1 or 2;

e is C or Si;

each n is independently 0,1, 2 or 3;

R²and R^2’Are the same or different and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C_1-6-alkyl radical, C_3-8Cycloalkyl radical, C_6-10An aryl group;

each R³is-CH₂-, -CHRx-or C (Rx)₂-a group wherein Rx is C_1-4Alkyl, and wherein m is 2-6;

R⁵is straight-chain or branched C₁-C₆-alkyl radical, C_7-20Arylalkyl radical, C_7-20Alkylaryl group or C₆-C₂₀-an aryl group;

R⁶is C (R)¹⁰)₃Group, wherein R¹⁰Is straight-chain or branched C₁-C₆An alkyl group; and

R⁷and R^7’Identical or different and is H or C which is linear or branched₁-C₆-an alkyl group.

In a preferred embodiment of formula (Ia), L is of the formula-SiR⁸ ₂-, wherein each R⁸Independently is C₁-C₂₀-hydrocarbyl, tri (C)₁-C₂₀Alkyl) silyl, C₆-C₂₀-aryl, C₇-C₂₀Arylalkyl or C₇-C₂₀-alkylaryl.

Viewed from another aspect, the invention provides a complex of formula (Ib):

wherein

M is Hf;

each X is a sigma ligand;

l is an alkylene bridge (e.g. methylene or ethylene) or of the formula-SiR⁸ ₂A bridge of (a) wherein each R⁸Independently is C₁-C₂₀-hydrocarbyl, tri (C)₁-C₂₀Alkyl) silyl, C₆-C₂₀-aryl, C₇-C₂₀Arylalkyl or C₇-C₂₀-an alkylaryl group;

each n is independently 0,1, 2 or 3;

R²and R^2’Are the same or different and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C_1-6-alkyl radical, C_3-8Cycloalkyl radical, C_6-10An aryl group;

R⁵is straight-chain or branched C₁-C₆-alkyl radical, C_7-20Arylalkyl radical, C_7-20Alkylaryl group or C₆-C₂₀-an aryl group;

R⁶is C (R)¹⁰)₃Group, wherein R¹⁰Is straight-chain or branched C₁-C₆An alkyl group; and

R⁷and R^7’Identical or different and is H or C which is linear or branched₁-C₆-an alkyl group.

Viewed from another aspect the invention provides a catalyst in solid form comprising

(i) A complex of formula (I) as defined above, and

(ii) a cocatalyst comprising an aluminium-based compound, and

(iii) a cocatalyst comprising a boron-based compound.

Thus, the catalyst of the present invention is used as a heterogeneous catalyst.

The catalysts of the invention are used in solid form, preferably in the form of solid particles, and may be supported on an external support material such as silica or alumina or be free of an external support, but still in solid form. For example, the solid catalyst can be obtained by:

(a) forming a liquid/liquid emulsion system comprising a solution of catalyst components (i), (ii) and (iii) dispersed in a solvent to form dispersed droplets; and

(b) solid particles are formed by solidifying the dispersed droplets.

Viewed from a further aspect the invention provides a process for the manufacture of a catalyst as defined above comprising obtaining a complex of formula (I) as described above and at least two cocatalysts;

forming a liquid/liquid emulsion system comprising a solution of catalyst components (i), (ii) and (iii) dispersed in a solvent and solidifying the dispersed droplets to form solid particles.

Viewed from a further aspect the invention provides the use of a catalyst as defined above in the polymerisation of propylene, particularly for forming propylene polymers, particularly polypropylene homopolymers and propylene heterophasic copolymers, optionally with a comonomer selected from ethylene or a C4 to C10 alpha-olefin or mixtures thereof.

Viewed from a further aspect the invention provides a process for the polymerisation of propylene comprising reacting propylene and optionally a comonomer with a catalyst as described above, for example for the formation of a propylene homopolymer or for example with ethylene to form a propylene copolymer, especially a propylene homopolymer and a propylene heterophasic copolymer.

Drawings

FIG. 1 illustrates the use of comparative and inventive catalysts CE1, CE2 and IE 1; and the polypropylene homopolymer melt temperatures of the samples produced by CE4, CE5, and IE 2. The catalysts of the present invention provide propylene homopolymers having a melt temperature at least about 4 degrees higher than the polymer produced using the comparative catalyst.

FIG. 2 illustrates the use of comparative and inventive catalysts CE1, CE2, and IE 1; and MFR of the propylene homopolymer samples produced from CE4, CE5, and IE2₂₁And (6) obtaining the result. The MFR values of the polymers produced with the catalysts of the invention are significantly lower compared to the polymers produced with the comparative catalysts, indicating higher moleculesAmount of the compound (A).

FIG. 3 illustrates the use of comparative and inventive catalysts CE1, CE2, and IE 1; and the activity of CE4, CE5 and IE2 as catalysts in the production of propylene homopolymers. In which the activity of the catalyst of the present invention is higher than that of the related comparative example.

Analytical testing

The measuring method comprises the following steps:

determination of Al, Zr and Hf (ICP-method)

Elemental analysis of the catalyst was performed by taking a solid sample of mass M and cooling on dry ice. By dissolving in nitric acid (HNO)₃65%, 5% of V) and fresh Deionized (DI) water (5% of V), the samples were diluted to a known volume V. The solution was then added to hydrofluoric acid (HF, 40%, 3% of V), diluted with DI water to a final volume V, and stabilized for two hours.

Analysis was performed at room temperature using a Thermo Elemental iCAP 6300 inductively coupled plasma emission spectrometer (ICP-OES) using a blank (5% HNO)₃3% HF in DI water) and 6 standards of 0.5ppm, 1ppm, 10ppm, 50ppm, 100ppm and 300ppm Al with 0.5ppm, 1ppm, 5ppm, 20ppm, 50ppm and 100ppm HF and Zr at 5% HNO₃3% HF in DI water.

Immediately prior to analysis, the calibration was "slope re-determined" (respoped) "using a blank and 100ppm Al, 50ppm Hf, Zr standards, and quality control samples (20ppm Al, 5ppm Hf, Zr at 5% HNO) were run₃3% HF in DI water) to confirm the re-determined slope (respope). QC samples will also run after every 5 th sample and when the planned analysis is clustered.

The hafnium content was monitored using the 282.022nm line and the 339.980nm line, and the zirconium content was monitored using the 339.198nm line. The aluminium content was monitored via the 167.079nm line when the Al concentration in the ICP sample was between 0-10ppm (calibrated to 100ppm only), and for Al concentrations above 10ppm, via the 396.152nm line.

The reported values are the average of three consecutive aliquots taken from the same sample and correlated to the original catalyst by inputting the original mass and dilution volume of the sample into the software.

In case of analyzing the elemental composition of the offline prepolymerized catalyst, the polymer fraction was digested by ashing so that the elements could be freely dissolved by acid. The total content is calculated to correspond to the weight% of the prepolymerized catalyst. In the examples disclosed below, no off-line prepolymerization step was used.

DSC analysis of propylene homopolymerization example

According to ISO11357-3, in a heating/cooling/heating cycle at a scan rate of 10 ℃/min in a temperature range of +23 ℃ to +225 ℃, at 50ml min^-1About 5mg of sample was subjected to a measurement of the melting temperature Tm using a Mettler-Toledo 822e Differential Scanning Calorimeter (DSC) under a nitrogen flow rate of (1). The melting temperatures were taken as the endothermic peaks in the second heating step, respectively. According to ISO 11357-1, H is used₂And O, lead, tin and indium are used for calibrating the instrument.

DSC analysis of the Main melting temperature (T) of the heterophasic propylene copolymer examples_m) Heat of fusion (H)_m) And crystallization temperature (T)_c)

DSC analysis was performed on 5mg to 7mg samples using Mettler TA Instrument Q2000 Differential Scanning Calorimetry (DSC). DSC was run in heating/cooling/heating cycles at a scan rate of 10 ℃/min over a temperature range of-30 ℃ to +225 ℃ according to ISO 11357/part 3/method C2. Determination of the crystallization temperature (T) from the Cooling step_c) And determining the main melting temperature (T) from the second heating step_m) And heat of fusion (H)_m)。

Melt flow rate

The Melt Flow Rate (MFR) is determined according to ISO 1133 and is expressed in g/10 min. MFR indicates the flowability, and therefore the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. MFR is determined at 230 ℃ and may be determined at different loads, e.g. 2.16kg (MFR)₂) Or 21.6kg (MFR)₂₁)。

Intrinsic viscosity

The intrinsic viscosity (iV) was measured according to DIN ISO 1628/1 (in decalin at 135 ℃) at 10 months 1999.

Xylene cold soluble fraction

According to ISO 16152; 2005 xylene cold soluble (XCS, wt%) was determined at 25 ℃.

Crystex analysis

Crystalline fraction and soluble fraction process

The Crystalline Fraction (CF) and the Soluble Fraction (SF) of the polypropylene (PP) composition, as well as the comonomer content and the intrinsic viscosity of the respective fractions, were analyzed by CRYSTEX QC, Polymer Char (valencia, spain).

The crystalline and amorphous fractions were separated by temperature cycling of dissolution at 160 ℃, crystallization at 40 ℃ and re-dissolution in 1,2, 4-trichlorobenzene (1,2,4-TCB) at 160 ℃. The quantification of SF and CF and the determination of the ethylene content (C2) were carried out by means of an infrared detector (IR4) and an in-line 2-capillary viscometer for determining the Intrinsic Viscosity (IV).

The IR4 detector is a multi-wavelength detector that detects IR absorbance in two different wavelength bands (CH3 and CH2) to determine the concentration and ethylene content in the ethylene-propylene copolymer. The IR4 detector was calibrated with 8 EP copolymers having known ethylene contents of 2 to 69 wt.% (from¹³C-NMR determination) and the concentration of each EP copolymer used for calibration is between 2mg/ml and 13 mg/ml.

By XS calibration, the amount of Soluble Fraction (SF) and Crystalline Fraction (CF) is related to the amount of "xylene cold soluble" (XCS) and Xylene Cold Insoluble (XCI) fractions, respectively, as determined by standard gravimetric method according to ISO 16152. XS calibration was achieved by testing various EP copolymers with XS content in the range of 2-31 wt%.

The Intrinsic Viscosity (IV) of the parent EP copolymer and its soluble and crystalline fractions were determined using an online 2-capillary viscometer and correlated with the corresponding IV determined by standard methods in decalin according to ISO 1628. Calibration was achieved with various EP PP copolymers with IV ranging from 2 to 4 dL/g.

The concentration of the PP composition sample to be analyzed is weighed out in the range of 10mg/ml to 20 mg/ml. After automatically filling the sample bottle with 1,2,4-TCB containing 250mg/l 2, 6-tert-butyl-4-methylphenol (BHT) as antioxidant, the sample was dissolved at 160 ℃ until completely dissolved, usually for 60 minutes, with stirring at 800 rpm.

A defined volume of sample solution is injected into a column equipped with an inert support, where crystallization of the sample is performed and the soluble fraction is separated from the crystalline fraction. This process was repeated twice. During the first injection, the entire sample was measured at elevated temperature to determine the IV [ dl/g ] and C2[ wt% ]ofthe PP composition. During the second implantation, the soluble fraction (at low temperature) and the crystalline fraction (at high temperature) with the crystallization period were measured (Wt% SF, Wt% C2, IV). (EP stands for ethylene propylene copolymer. PP stands for polypropylene).

The Crystex test is further described in WO 2019/002345. We cross-reference their fig. 1a and 1 b.

Flexural modulus

Flexural modulus was determined at 23 ℃ according to ISO 178 on injection molded test specimens (80X 10X 4mm) as described in EN ISO 1873-2.

Charpy notch impact

Charpy Notched Impact Strength (NIS) was determined according to ISO179/1eA on injection-molded test specimens (80X 10X 4mm) as described in EN ISO 1873-2.

Dynamic Mechanical Thermal Analysis (DMTA)

Dynamic Mechanical Thermal Analysis (DMTA) was performed according to ISO 6721-7. Compression molding samples (40X 10X 1 mm) at a heating rate of 2 ℃/min and a frequency of 1Hz between-130 ℃ and +150 DEG C³) The measurement is done in torsional mode. The storage modulus (G') and glass transition temperatures of the EPR phase (Tg1) and matrix (Tg2) at 23 ℃ are reported.

Examples

Metallocene synthesis

Reagent

2, 6-dimethylaniline (Acros), 1-bromo-3, 5-dimethylbenzene (Acros), 1-bromo-3, 5-di-tert-butylbenzene (Acros), bis (2, 6-diisopropylphenyl) imidazolium chloride (Aldrich), triphenylphosphine (Acros), NiCl₂(DME) (Aldrich), dichlorodimethylsilane (Merck), ZrCl₄(Merck)、HfCl₄，<1% Zr (Strem Chemicals), trimethyl borate (Acros), Pd (OAc)₂(Aldrich)、NaBH₄(Acros), 2.5M nBuLi in hexane (chemical), CuCN (Merck), magnesium turnings (Acros), silica gel 60, 40-63 μ M (Merck), bromine (Merck), 96% sulfuric acid (Reachim), sodium nitrite (Merck), copper powder (Alfa), potassium hydroxide (Merck), K₂CO₃(Merck)、12M HCl(Reachim)、TsOH(Aldrich)、MgSO₄(Merck)、Na₂CO₃(Merck)、Na₂SO₄(Akzo Nobel), methanol (Merck), diethyl ether (Merck), 1, 2-dimethoxyethane (DME, Aldrich), 95% ethanol (Merck), dichloromethane (Merck), hexane (Merck), THF (Merck), and toluene (Merck) were used as received. Hexane, toluene and dichloromethane for organometallic synthesis were dried over molecular sieve 4a (merck). The ether, THF and 1, 2-dimethoxyethane used for organometallic synthesis were distilled over sodium benzophenone free radical (sodium benzophenone). Drying of CDCl with molecular sieves 4A₃(Deutero GmbH) and CD₂Cl₂(Deutero GmbH). 4-bromo-6-tert-butyl-5-methoxy-2-methylindan-1-one is obtained as described in WO 2013/007650.

Synthesis of MC CE1 (comparative)

4- (4-tert-butylphenyl) -1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-indacene

The precursor 4-bromo-1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-indacene was prepared according to the procedure described in WO2015/158790a2 (pages 26-29).

To 1.5g (1.92mmol, 0.6 mol.%) of NiCl₂(PPh₃) To a mixture of IPr and 89.5g (318.3mmol) of 4-bromo-1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-indacene was added 500ml (500mmol, 1.57 equivalents) of 1.0M 4-tert-butylphenyl magnesium bromide in THF. The resulting solution was refluxed for 3 hours, then cooled to room temperature and 1000ml of 0.5M HCl was added. Further, the mixture was extracted with 1000ml of dichloromethane, the organic layer was separated, and the aqueous layer was extracted with 250ml of dichloromethane. The combined organic extracts were evaporated to dryness to give a green oil. In thatThe title product was isolated by flash chromatography on silica gel 60(40-63 μm; eluent: hexane-dichloromethane ═ 3:1 (vol), then 1:3 (vol)). This procedure yielded 107g (ca. 100%) of 1-methoxy-2-methyl-4- (4-tert-butylphenyl) -1,2,3,5,6, 7-hexahydro-s-indacene as a white solid mass.

For C₂₄H₃₀O, analytical calculation: c, 86.18; h, 9.04. Measured value: c, 85.99; h, 9.18.

¹H NMR(CDCl₃) Cis-isomers δ 7.42-7.37(m,2H),7.25-7.20(m,3H),4.48(d, J ═ 5.5Hz,1H),3.44(s,3H),2.99-2.47(m,7H),2.09-1.94(m,2H),1.35(s,9H),1.07(d, J ═ 6.9Hz, 3H); trans-isomers δ 7.42-7.37(m,2H),7.25-7.19(m,3H),4.39(d, J ═ 3.9Hz,1H),3.49(s,3H),3.09(dd, J ═ 15.9Hz, J ═ 7.5Hz,1H),2.94(t, J ═ 7.3Hz,2H),2.78(tm, J ═ 7.3Hz,2H),2.51-2.39(m,1H),2.29(dd, J ═ 15.9Hz, J ═ 5.0Hz,1H),2.01(quin, J ═ 7.3Hz,2H),1.36(s,9H),1.11(d, J ═ 7.1, 3H).¹³C{¹H}NMR(CDCl₃) Cis-isomers delta 149.31,142.71,142.58,141.46,140.03,136.71,135.07,128.55,124.77,120.02,86.23,56.74,39.41,37.65,34.49,33.06,32.45,31.38,25.95, 13.68; trans-isomers delta 149.34,143.21,142.90,140.86,139.31,136.69,135.11,128.49,124.82,119.98,91.53,56.50,40.12,37.76,34.50,33.04,32.40,31.38,25.97,19.35.

4- (4-tert-butylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-indacene

To a solution of 107g of 1-methoxy-2-methyl-4- (4-tert-butylphenyl) -1,2,3,5,6, 7-hexahydro-s-indacene (prepared above) in 700ml of toluene, 600mg of TsOH was added, and the resulting solution was refluxed for 10min using a Dean-Stark head. After cooling to room temperature, the reaction mixture was quenched with 200ml of 10% NaHCO₃And (6) washing. The organic layer was separated and the aqueous layer was additionally extracted with 2X 100ml dichloromethane. The combined organic extracts were evaporated to dryness to give a red oil. Flash chromatography on silica gel 60(40-63 μm; eluent: hexane, then hexane-bisMethyl chloride 5:1 (vol)) and then distilled under vacuum, b.p.210-216 ℃/5-6mm Hg. This procedure yielded 77.1g (80%) of 4- (4-tert-butylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-indacene as a pale yellow glassy material.

For C₂₃H₂₆C, 91.34; h, 8.66. Found C, 91.47; h, 8.50.

¹H NMR(CDCl₃):δ7.44-7.37(m,2H),7.33-7.26(m,2H),7.10(s,1H),6.45(br.s,1H),3.17(s,2H),2.95(t,J＝7.3Hz,2H),2.78(t,J＝7.3Hz,2H),2.07(s,3H),2.02(quin,J＝7.3Hz,2H),1.37(s,9H).¹³C{¹H}NMR(CDCl₃):δ149.37,145.54,144.79,142.91,139.92,138.05,137.15,134.06,128.36,127.02,124.96,114.84,42.11,34.53,33.25,32.16,31.41,25.96,16.77.

2-methyl- [4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] (chloro) dimethylsilane

To a solution of 22.3g (73.73mmol)4- (4-tert-butylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-indacene in 300ml diethyl ether (cooled to-50 ℃ C.) were added in one portion 30.4ml (73.87mmol) 2.43M nBuLi in hexane. The resulting mixture was stirred at room temperature overnight, then the resulting suspension with the bulk of the precipitate was cooled to-78 ℃ (where the precipitate substantially dissolved to form an orange solution) and 47.6g (369mmol, 5 equivalents) dichlorodimethylsilane was added in one portion. The resulting solution was stirred at room temperature overnight and then filtered through a glass frit (G4). The filtrate was evaporated to dryness to give 28.49g (98%) of 2-methyl- [4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] (chloro) dimethylsilane as a colorless glassy material which was used without further purification.

¹H NMR(CDCl₃):δ7-50-7.45(m,2H),7.36(s,1H),7.35-7.32(m,2H),6.60(s,1H),3.60(s,1H),3.10-2.82(m,4H),2.24(s,3H),2.08(quin,J＝7.3Hz,2H),1.42(s,9H),0.48(s,3H),0.22(s,3H).¹³C{¹H}NMR(CDCl₃):δ149.27,144.41,142.15,141.41,139.94,139.83,136.85,130.19,129.07,126.88,124.86,118.67,49.76,34.55,33.27,32.32,31.44,26.00,17.6

2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butyl-indan-1-one

31.1g (100mmol) of 2-methyl-4-bromo-5-methoxy-6-tert-butyl-indan-1-one, 25.0g (140mmol) of 4-tert-butylphenyl boronic acid, 29.4g (280mmol) of Na in 130ml of water and 380ml of DME₂CO₃、1.35g(6.00mmol，6mol.％)Pd(Oac)₂And 3.15g (12.0mmol, 12 mol.%) PPh₃The mixture was refluxed for 6h under argon. The resulting mixture was evaporated to dryness. To the residue were added 500ml of dichloromethane and 500ml of water. The organic layer was separated and the aqueous layer was extracted with 100ml of dichloromethane. The combined organic extracts are purified over Na₂SO₄Dried, evaporated to dryness and the crude product isolated by flash chromatography on silica gel 60(40-63 μm; eluent: hexane-dichloromethane ═ 2:1 (vol)). The crude product was recrystallized from n-hexane to yield 29.1g (81%) of a white solid.

For C₂₅H₃₂O₂Calculated value of C, 82.37; h, 8.85. Found C, 82.26; h, 8.81.

¹H NMR(CDCl₃) δ 7.74(s,1H, 7-H in indenyl), 7.48(d, J ═ 8.0Hz,2H, C₆H₄ ^t2,6-H in Bu), 7.33(d, J ═ 8.0Hz,2H, C₆H₄ ^t3,5-H in Bu), 3.27(s,3H, OMe),3.15(dd, J ═ 17.3Hz, J ═ 7.7Hz,1H, 3-H in indan-1-one), 2.67-2.59(m,1H, 2-H in indan-1-one), 2.48(dd, J ═ 17.3Hz, J ═ 3.7Hz, 3' -H in indan-1-one), 1.42(s,9H, C)₆H₄ ^tIn Bu^tBu),1.38(s,9H, 6 of indan-1-one)^tBu),1.25(d, J ═ 7.3Hz,3H, 2-Me in indan-1-one).

2-methyl-5-tert-butyl-6-methoxy-7- (4-tert-butylphenyl) -1H-indene

To a solution of 28.9g (79.2mmol) 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butyl-indan-1-one in 400ml THF (cooled to 5 ℃ C.) is added 5.00g (132mmol) NaBH₄. Further, 100ml of methanol was added dropwise to the mixture under vigorous stirring at 5 ℃ for about 7 hours. The resulting mixture was evaporated to dryness and the residue was partitioned between 500ml of dichloromethane and 1000ml of 0.5M HCl. The organic layer was separated and the aqueous layer was extracted with 100ml of dichloromethane. The combined organic extracts were evaporated to dryness to give a colourless oil. To a solution of this oil in 500ml of toluene was added 1.0g of TsOH. The resulting mixture was refluxed with Dean-Stark head for 15 minutes and then cooled to room temperature using a water bath. With 10% Na₂CO₃The resulting pale red solution was washed with aqueous solution, the organic layer was separated and the aqueous layer was extracted with 2X 100ml of dichloromethane. The combined organic extracts are purified by₂CO₃Dried and then passed through a short pad of silica gel 60(40-63 μm). The silica gel pad was additionally washed with 50ml dichloromethane. The combined organic eluates were evaporated to dryness to give a pale yellow crystal mass. The product was isolated by recrystallizing the cake from 150ml of hot n-hexane. The crystals precipitated at 5 ℃ were collected and dried in vacuo. This procedure gave 23.8g of crude white crystalline 2-methyl-5-tert-butyl-6-methoxy-7- (4-tert-butylphenyl) -1H-indene. The mother liquor was evaporated to dryness and the residue was recrystallized in the same way from 20ml of hot n-hexane. This procedure gave a further 2.28g of product. Thus, the total yield of the title product was 26.1g (95%).

For C₂₅H₃₂O, calculated as C, 86.15; h, 9.25. Found C, 86.24; h, 9.40.

¹H NMR(CDCl₃):δ7.44(d,J＝8.5Hz,2H,C₆H₄ ^t2,6-H in Bu), 7.40(d, J ═ 8.5Hz,2H, C₆H₄ ^t3,5-H in Bu), 7.21(s,1H, 4-H in indenyl), 6.43(m,1H, 3-H in indenyl), 3.20(s,3H, OMe),3.15(s,2H, 1-H in indenyl), 2.05(s,3H, 2-Me in indenyl), 143(s,9H, 5 in indenyl-^tBu),1.37(s,9H,C₆H₄ ^tIn Bu^tBu).

[ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] dimethylsilane

To a solution of 8.38g (24.04mmol) 2-methyl-5-tert-butyl-7- (4-tert-butylphenyl) -6-methoxy-1H-indene in 150ml diethyl ether at-50 ℃ were added in one portion 9.9ml (24.06mmol) 2.43M in hexaneⁿBuLi. The mixture was stirred at room temperature overnight, then the resulting yellow solution with yellow precipitate was cooled to-50 ℃ and 150mg of CuCN was added. The resulting mixture was stirred at-25 ℃ for 0.5h, then 9.5g (24.05mmol) of 2-methyl- [4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl were added in one portion](chloro) dimethylsilane in 150ml of diethyl ether. The mixture was stirred at room temperature overnight and then filtered through a pad of silica gel 60(40-63 μm), which was additionally washed with 2X 50ml of dichloromethane. The combined filtrates were evaporated under reduced pressure and the residue was dried under vacuum at elevated temperature. This procedure gives 17.2g (ca. 100%) of [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl][ 2-methyl-4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl]Dimethylsilane (approx. 95% purity of the NMR spectrum, approx. 1:1 mixture of stereoisomers) as a yellowish glassy solid which was used in the next step without further purification.

¹H NMR(CDCl₃) Δ 7.50(s,0.5H),7.48-7.41(m,6H),7.37-7.33(m,2.5H),7.26(s,0.5H),7.22(s,0.5H),6.57 and 6.50(2s, sum 2H),3.71,3.69,3.67 and 3.65(4s, sum 2H),3.23 and 3.22(2s, sum 3H),3.03-2.80(m,4H),2.20,2.16 and 2.14(3s, sum 6H),2.08-1.99(m,2H),1.43 and 1.41(2s, sum 9H),1.39(s,18H), -0.19, -0.20, -0.21 and-0.23 (4s, sum 6H).¹³C{¹H}NMR(CDCl₃):δ155.49,155.46,149.41,149.14,149.11,147.48,147.44,146.01,145.77,143.95,143.91,143.76,143.71,142.14,142.10,139.52,139.42,139.34,139.29,139.20,139.16,137.10,137.05,137.03,135.20,130.05,130.03,129.73,129.11,127.25,127.22,126.20,126.13,125.98,125.94,125.05,124.82,120.59,120.52,118.51,118.26,60.51,60.48,47.31,46.89,46.72,35.14,34.55,33.34,33.28,32.30,31.47,31.45,31.24,31.19,26.02,25.99,17.95,17.86.

Trans-dimethylsilanediyl [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] zirconium dichloride

To 17.2g (about 24.04mol) of [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl][ 2-methyl-4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl]Dimethylsilane (prepared above) was added in one portion to a solution of 250ml of diethyl ether (cooled to-50 ℃ C.) 19.8ml (48.11mmol) of 2.43M in hexaneⁿBuLi. The mixture was stirred at room temperature for 4h, then the resulting cherry red solution was cooled to-60 ℃ and 5.7g (24.46mmol) ZrCl was added₄. The reaction mixture was stirred at room temperature for 24h to give a red solution with an orange precipitate. The mixture was evaporated to dryness. The residue was heated with 200ml of toluene and the resulting suspension was filtered through a frit (G4). The filtrate was evaporated to 90 ml. The yellow powder precipitated from the solution overnight at room temperature was collected, washed with 10ml of cold toluene and dried in vacuo. This procedure yielded 4.6g (22%) of an approximately 4 to 1 mixture of trans-and cis-zirconocenes. The mother liquor was evaporated to about 40ml and 20ml of n-hexane was added. An orange powder precipitated from the solution overnight at room temperature was collected and dried in vacuo. This procedure yielded about 6.2g (30%) of a mixture of about 1 to 1 trans-zirconocenes and cis-zirconocenes. Thus, the total yield of trans-and cis-zirconocenes isolated in this synthesis was 10.8g (52%). A4.6 g sample of the above mixture of trans-and cis-zirconocenes in a ratio of about 4 to 1 was obtained after crystallization from 20ml of toluenePure trans-zirconocene. This procedure gives 1.2g of pure trans-zirconocene.

Trans-dimethylsilanediyl [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] zirconium dichloride:

for C₅₀H₆₀Cl₂OSiZr calculated as C, 69.25; h, 6.97. Found C, 69.43; h, 7.15.

¹H NMR(CDCl₃) δ 7.59-7.38 (group of m, 10H),6.74(s,1H),6.61(s,1H),3.37(s,3H),3.08-2.90(m,3H),2.86-2.78(m,1H),2.20(s,3H),2.19(s,3H),2.10-1.92(m,2H),1.38(s,9H),1.33(s,18H),1.30(s,3H),1.29(s,3H).¹³C{¹H}NMR(CDCl₃,):δ159.94,150.05,149.86,144.79,144.01,143.20,135.50,135.41,133.87,133.73,133.62,132.82,132.29,129.23,128.74,126.95,126.87,125.36,125.12,122.93,121.68,121.32,120.84,117.90,81.65,81.11,62.57,35.74,34.58,33.23,32.17,31.37,31.36,30.32,26.60,18.39,18.30,2.65,2.57¹.

¹No resonances originating from one carbon atom were found due to overlap with some other signals.

Synthesis of MC-CE2 (comparative)

4-bromo-2, 6-dimethylaniline

159.8g (1.0mol) of bromine are slowly added (over 2 hours) to a stirred solution of 121.2g (1.0mol) of 2, 6-dimethylaniline in 500ml of methanol. The resulting dark red solution was stirred at room temperature overnight and then poured into a cold solution of 140g (2.5mol) potassium hydroxide in 1100ml water. The organic layer was separated and the aqueous layer was extracted with 500ml of diethyl ether. The combined organic extracts are washed with 1000ml of water and then K₂CO₃Drying and evaporation in vacuo gave 202.1g of 4-bromo-2, 6-dimethylaniline (purity approx. 90%) as a dark red oil which crystallized on standing at room temperature. This material was used further without additional purification.

¹H NMR(CDCl₃):δ7.04(s,2H),3.53(br.s,2H),2.13(s,6H).

1-bromo-3, 5-dimethylbenzene

97ml (1.82mol) of 96% sulfuric acid was added dropwise at a rate to keep the reaction temperature below 7 ℃ to a solution of 134.7g (about 673mmol) of 4-bromo-2, 6-dimethylaniline (prepared above, having a purity of about 90%) in 1400ml of 95% ethanol (cooled to-10 ℃). After the addition was complete, the solution was stirred at room temperature for 1 h. The reaction mixture was then cooled in an ice bath and a solution of 72.5g (1.05mol) of sodium nitrite in 150ml of water was added dropwise over about 1 h. The resulting solution was stirred at the same temperature for 30 min. The cooling bath was then removed and 18g of copper powder was added. After the rapid release of nitrogen was complete, additional portions (about 5g each, a total of about 50g) of copper powder were added every 10min until the gas completely ceased to be released. The reaction mixture was stirred at room temperature overnight, then filtered through a frit (G3), diluted with two volumes of water, and the crude product was extracted with 4 x 150ml dichloromethane. The combined extracts are purified by₂CO₃Drying, evaporation to dryness and then vacuum distillation (b.p.60-63 ℃ C./5 mm Hg) gave a pale yellow liquid. The product was additionally purified by flash chromatography on silica gel 60(40-63 μm; eluent: hexane) and redistilled (b.p.51-52 ℃ C./3 mm Hg) to give 63.5g (51%) of 1-bromo-3, 5-xylene as a colorless liquid.

¹H NMR(CDCl₃):δ7.12(s,2H),6.89(s,1H),2.27(s,6H).¹³C{¹H}NMR(CDCl₃):δ139.81,129.03,128.61,122.04,20.99.

(3, 5-dimethylphenyl) boronic acid

From a solution of 190.3g (1.03mol) of 1-bromo-3, 5-dimethylbenzene in 1000ml of THF and 32g (1.32mol, 28 mol)% excess) to give a 3, 5-dimethylphenylmagnesium bromide solution, cooled to-78 ℃ and 104g (1.0mol) of trimethyl borate are added in one portion. The resulting heterogeneous mixture was stirred at room temperature overnight. The borate ester was hydrolyzed by careful addition of 1200ml of 2M HCl. 500ml of diethyl ether are added, the organic layer is separated and the aqueous layer is additionally extracted with 2X 500ml of diethyl ether. The combined organic extracts are purified over Na₂SO₄Dried and then evaporated to dryness to give a white mass. The latter was triturated with 200ml of n-hexane, filtered through a frit (G3) and the precipitate was dried in vacuo. This procedure gave 114.6g (74%) of (3, 5-dimethylphenyl) boronic acid.

For C₈H₁₁BO₂Calculated value of C, 64.06; h, 7.39. Found C, 64.38; h, 7.72.

¹H NMR(DMSO-d₆) δ 7.38(s,2H),7.00(s,1H),3.44 (very br.s,2H),2.24(s,6H).

2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-indan-1-one

49.14g (157.9mmol) of 2-methyl-4-bromo-5-methoxy-6-tert-butylindan-1-one, 29.6g (197.4mmol, 1.25eq.) of (3, 5-dimethylphenyl) boronic acid, 45.2g (427mmol) of Na₂CO₃、1.87g(8.3mmol，5mol.％)Pd(OAc)₂、4.36g(16.6mmol，10mol.％)PPh₃A mixture of 200ml of water and 500ml of 1, 2-dimethoxyethane was refluxed for 6.5 h. The DME was evaporated on a rotary evaporator and 600ml of water and 700ml of dichloromethane were added to the residue. The organic layer was separated and the aqueous layer was extracted with another 200ml of dichloromethane. The combined extracts are purified by₂CO₃Dried and then evaporated to dryness to give a black oil. The crude product was purified by flash chromatography on silica gel 60(40-63 μm, hexane-dichloromethane ═ 1:1 (vol), then 1:3 (vol)) to give 48.43g (91%) of 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylindan-1-one as a brown-brown oil.

For C₂₃H₂₈O₂Calculated value of C, 82.10; h, 8.39. Found C, 82.39; h, 8.52.

¹H NMR(CDCl₃):δ7.73(s,1H),7.02(s,3H),7.01(s,3H),3.32(s,3H),3.13(dd,J＝17.5Hz,J＝7.8Hz,1H),2.68-2.57(m,1H),2.44(dd,J＝17.5Hz,J＝3.9Hz),2.36(s,6H),1.42(s,9H),1.25(d,J＝7.5Hz,3H).¹³C{¹H}NMR(CDCl₃):δ208.90,163.50,152.90,143.32,138.08,136.26,132.68,130.84,129.08,127.18,121.30,60.52,42.17,35.37,34.34,30.52,21.38,16.40.

2-methyl-5-tert-butyl-6-methoxy-7- (3, 5-dimethylphenyl) -1H-indene

8.2g (217mmol) of NaBH₄To a solution of 48.43g (143.9mmol) 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylindan-1-one in 300ml THF (cooled to 5 ℃ C.) is added. Then, 150ml of methanol was added dropwise to the mixture by vigorous stirring at 5 ℃ over about 7 hours. The resulting mixture was evaporated to dryness and the residue was partitioned between 500ml dichloromethane and 500ml 2M HCl. The organic layer was separated and the aqueous layer was extracted with 100ml of dichloromethane. The combined organic extracts were evaporated to dryness to give a slightly yellowish oil. To a solution of this oil in 600ml of toluene was added 400mg of TsOH, and the mixture was refluxed with a Dean-Stark head for 10 minutes, then cooled to room temperature using a water bath. The resulting solution was passed over 10% Na₂CO₃The organic layer was separated by washing, and the aqueous layer was extracted with 150ml of dichloromethane. The combined organic extracts are purified by₂CO₃Dried and then passed through a short layer of silica gel 60(40-63 μm). The silica gel layer was additionally washed with 100ml dichloromethane. The combined organic eluates were evaporated to dryness and the resulting oil was dried in vacuo at elevated temperature. This procedure gave 45.34g (98%) of 2-methyl-5-tert-butyl-6-methoxy-7- (3, 5-dimethylphenyl) -1H-indene, which was used without further purification.

For C₂₃H₂₈O, calculated as C, 86.20; h, 8.81. Measured in factValue C, 86.29; h, 9.07.

¹H NMR(CDCl₃):δ7.20(s,1H),7.08(br.s,1H),6.98(br.s,1H),6.42(m,1H),3.25(s,3H),3.11(s,2H),2.36(s,6H),2.06(s,3H),1.43(s,9H).¹³C{¹H}NMR(CDCl₃):δ154.20,145.22,141.78,140.82,140.64,138.30,137.64,131.80,128.44,127.18,126.85,116.98,60.65,42.80,35.12,31.01,21.41,16.65.

[ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl ] (chloro) dimethylsilane

To a solution of 9.0g (28.08mmol) 2-methyl-5-tert-butyl-6-methoxy-7- (3, 5-dimethylphenyl) -1H-indene in 150ml diethyl ether (cooled to-50 ℃ C.) were added 11.6ml (28.19mmol) 2.43M in hexane in one portionⁿBuLi. The resulting mixture was stirred at room temperature for 6h, then the resulting yellow suspension was cooled to-60 ℃ and 18.1g (140.3mmol, 5 equivalents) dichlorodimethylsilane was added in one portion. The resulting solution was stirred at room temperature overnight and then filtered through a frit (G3). The filtrate was evaporated to dryness to give [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl](chloro) dimethylsilane, a slightly yellowish oil, was used further without further purification.

¹H NMR(CDCl₃):δ7.38(s,1H),7.08(s,2H),6.98(s,1H),6.43(s,1H),3.53(s,1H),3.25(s,3H),2.37(s,6H),2.19(s,3H),1.43(s,9H),0.43(s,3H),0.17(s,3H).¹³C{¹H}NMR(CDCl₃):δ155.78,145.88,143.73,137.98,137.56,137.49,136.74,128.32,127.86,127.55,126.64,120.86,60.46,49.99,35.15,31.16,21.41,17.55,1.11,-0.58.

1-methoxy-2-methyl-4- (3, 5-dimethylphenyl) -1,2,3,5,6, 7-hexahydro-s-indacene

To a volume of 2.0g (2.56mmol, 1.8 mol.%) NiCl₂(PPh₃) To a mixture of IPr and 40.0g (142.3mmol) 4-bromo-1-methoxy-2-methyl-1, 2,3,5,6, 7-hexahydro-s-indacene was added 200ml (200mmol, 1.4eq) of 1.0M 3, 5-dimethylphenylmagnesium bromide in THF. The resulting solution was refluxed for 3 hours, then cooled to room temperature and 400ml water was added followed by 500ml 1.0M HCl solution. Further, the mixture was extracted with 600ml of dichloromethane, the organic layer was separated, and the aqueous layer was extracted with 2X 100ml of dichloromethane. The combined organic extracts were evaporated to dryness to give a slightly greenish oil. The product was isolated by flash chromatography on silica gel 60(40-63 μm; eluent: hexane-dichloromethane ═ 2:1 (vol), then 1:2 (vol)). This procedure yielded 43.02g (99%) of 1-methoxy-2-methyl-4- (3, 5-dimethylphenyl) -1,2,3,5,6, 7-hexahydro-s-indacene as a colorless thick oil, a mixture of two diastereomers.

For C₂₂H₂₆O, calculated as C, 86.23; h, 8.55. Found C, 86.07; h, 8.82.

¹H NMR(CDCl₃) The cis-isomers δ 7.21(s,1H),6.94(br.s,1H),6.90(br.s,2H),4.48(d, J ═ 5.5Hz,1H),3.43(s,3H),2.94(t, J ═ 7.5Hz,2H),2.87-2.65(m,3H),2.63-2.48(m,2H),2.33(s,6H),2.02(quin, J ═ 7.5Hz,2H),1.07(d, J ═ 6.7Hz, 3H); trans-isomers δ 7.22(s,1H),6.94(br.s,1H),6.89(br.s,2H),4.38(d, J ═ 4.0Hz,1H),3.48(s,3H),3.06(dd, J ═ 16.0Hz, J ═ 7.5Hz,1H),2.93(t, J ═ 7.3Hz,2H),2.75(td, J ═ 7.3Hz, J ═ 3.2Hz,2H),2.51-2.40(m,1H),2.34(s,6H),2.25(dd, J ═ 16.0Hz, J ═ 5.0Hz,1H),2.01(quin, J ═ 7.3Hz,2H),1.11(d, J ═ 7.1H, 3H).¹³C{¹H}NMR(CDCl₃) Cis-isomers δ 142.69,142.49,141.43,139.97,139.80,137.40,135.46,128.34,126.73,120.09,86.29,56.76,39.43,37.59,33.11,32.37,25.92,21.41, 13.73; trans-isomers delta 143.11,142.72,140.76,139.72,139.16,137.37,135.43,128.29,126.60,119.98,91.53,56.45,40.06,37.65,33.03,32.24,25.88,21.36,19.36.

4- (3, 5-dimethylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-indacene

To a solution of 43.02g (140.4mmol) 1-methoxy-2-methyl-4- (3, 5-dimethylphenyl) -1,2,3,5,6, 7-hexahydro-s-indacene in 600ml toluene was added 200mg TsOH and the resulting solution was refluxed with a Dean-Stark head for 15 min. After cooling to room temperature, the reaction mixture was quenched with 200ml 10% NaHCO₃And (6) washing. The organic layer was separated and the aqueous layer was additionally extracted with 300ml dichloromethane. The combined organic extracts were evaporated to dryness to give a pale orange oil. The product was isolated by flash chromatography on silica gel 60(40-63 μm; eluent: hexane, then hexane-dichloromethane ═ 10:1 (vol)). This procedure yielded 35.66g (93%) of 4- (3, 5-dimethylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-indacene as a slightly yellowish oil which spontaneously solidified to form a white mass.

For C₂₁H₂₂Calculated as C, 91.92; h, 8.08. Found C, 91.78; h, 8.25.

¹H NMR(CDCl₃):δ7.09(s,1H),6.98(br.s,2H),6.96(br.s,1H),6.44(m,1H),3.14(s,2H),2.95(t,J＝7.3Hz,2H),2.76(t,J＝7.3Hz,2H),2.35(s,6H),2.07(s,3H),2.02(quin,J＝7.3Hz,2H).¹³C{¹H}NMR(CDCl₃):δ145.46,144.71,142.81,140.17,139.80,137.81,137.50,134.33,128.35,127.03,126.48,114.83,42.00,33.23,32.00,25.87,21.38,16.74.

[ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] dimethylsilane

To a solution of 7.71g (28.1mmol)4- (3, 5-dimethylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-indacene in a mixture of 150ml diethyl ether and 20ml THF at-50 deg.C were added 11.6ml (28.19mmol) 2.43M in hexane in one portionⁿBuLi. The mixture was stirred at room temperature for 6h, then the orange color obtainedThe solution was cooled to-50 ℃ and 150mg of CuCN was added. The resulting mixture was stirred at-25 ℃ for 0.5H, then [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl-was added in one portion](chloro) dimethylsilane (prepared above, about 28.08mmol) in 150ml of diethyl ether. The mixture was stirred at room temperature overnight and then filtered through a pad of silica gel 60(40-63 μm), which was additionally washed with 2X 50ml of dichloromethane. The combined filtrates were evaporated under reduced pressure to give a yellow oil. The product was isolated by flash chromatography on silica gel 60(40-63 μm; eluent: hexane-dichloromethane ═ 10:1 (vol), then 5:1 (vol)). This procedure gave 11.95g (65%) [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl][ 2-methyl-4- (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl]Dimethylsilane (mixture of stereoisomers about 1: 1) as a pale yellow glassy solid.

For C₄₆H₅₄OSi, calculated as C, 84.87; h, 8.36. Found C, 85.12; h, 8.59.

¹H NMR(CDCl₃) δ 7.48 and 7.33(2s, sum 1H),7.26-7.18(m,1H),7.16-7.07(m,2H),7.04-6.95(m,4H),6.51 and 6.45(2s, sum 2H),3.69 and 3.65(2s, sum 2H),3.28 and 3.26(2s, sum 3H),3.01-2.74(m,4H),2.38 and 2.37(2s, sum 12H),2.20 and 2.15(2s, sum 6H),2.09-1.97(m,2H),1.43 and 1.42(2s, sum 9H), -0.17, -0.18, -0.19 and-0.24 (4s, sum 6H).¹³C{¹H}NMR(CDCl₃):δ155.29,147.45,147.39,145.99,145.75,143.93,143.90,143.72,143.69,142.06,142.01,140.08,140.06,139.46,139.37,139.26,139.03,139.00,138.24,137.50,137.34,137.07,136.99,130.39,128.23,128.14,127.92,127.50,127.46,127.26,126.12,126.05,125.99,125.94,120.55,120.51,118.46,118.27,60.49,47.33,46.86,46.76,35.14,33.33,33.28,32.18,31.26,31.21,25.95,25.91,21.44,17.96,17.88,-5.27,-5.39,-5.50,-5.82.

Trans-dimethylsilanediyl [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] zirconium dichloride

To 11.95g (18.36mol) [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl group][ 2-methyl-4- (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl]Dimethylsilane (prepared as above) was added in one portion to a solution of 200ml of diethyl ether (cooled to-50 ℃ C.) 15.1ml (35.7mmol) of 2.43M in hexaneⁿBuLi. The mixture was stirred at room temperature for 3h, then the resulting red solution was cooled to-78 ℃ and 4.28g (18.37mmol) ZrCl was added₄. The reaction mixture was stirred at room temperature for 24h to give a light red solution with an orange precipitate. The mixture was evaporated to dryness. The residue was treated with 250ml of hot toluene and the resulting suspension was filtered through a frit (G4). The filtrate was evaporated to 40 ml. The red powder precipitated from the solution at room temperature overnight was collected, washed with 10ml of cold toluene and dried in vacuo. This procedure gives 0.6g of cis-zirconocene. The mother liquor was evaporated to about 35ml and 15ml of n-hexane was added to the warm solution. The red powder precipitated from the solution at room temperature overnight was collected and dried in vacuo. This procedure gave 3.49g of cis-zirconocene. The mother liquor was evaporated to about 20ml and 30ml of n-hexane was added to the warm solution. The yellow powder precipitated from the solution at room temperature overnight was collected and dried in vacuo. This procedure yielded 4.76g of trans-zirconocene as toluene solvate (× 0.6 toluene), contaminated with 2% of cis-isomer. Thus, the total yield of cis-and trans-zirconocenes isolated in this synthesis was 8.85g (59%).

Trans-dimethylsilanediyl [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] zirconium dichloride:

for C₄₆H₅₂Cl₂OSiZr×0.6C₇H₈Calculated value C, 69.59; h, 6.61. Found C, 69.74; h, 6.68.

¹H NMR(CDCl₃):δ7.47(s,1H),7.40(s,1H),7.37-7.03(m,4H),6.95(s,2H),6.71(s,1H),6.55(s,1H),3.43(s,3H),303-2.96(m,2H),2.96-2.87(m,1H),2.87-2.76(m,1H),2.34 and 2.33(2s, sum 12H),2.19 and 2.18(2s, sum 6H),2.06-1.94(m,2H),1.38(s,9H),1.28(s,3H),1.27(s,3H).¹³C{¹H}NMR(CDCl₃,):δ159.73,144.59,143.99,143.00,138.26,137.84,137.59,136.80,135.35,133.85,133.63,132.95,132.52,128.90,128.80,127.40,126.95,126.87,126.65,122.89,121.61,121.53,120.82,117.98,81.77,81.31,62.62,35.73,33.20,32.12,30.37,26.49,21.47,21.38,18.40,18.26,2.64,2.54.

Cis-dimethylsilanediyl [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] zirconium dichloride

For C₄₆H₅₂Cl₂OSiZr, calculated as C, 68.11; h, 6.46. Found C, 68.37; h, 6.65.

¹H NMR(CDCl₃) δ 7.51(s,1H),7.39(s,1H),7.36-6.99(m,4H),6.95(s,2H),6.60(s,1H),6.44(s,1H),3.27(s,3H),2.91-2.75(m,4H),2.38 and 2.34(2s, sum 18H),1.99-1.87(m,1H),1.87-1.74(m,1H),1.42(s,3H),1.36(s,9H),1.19(s,3H).¹³C{¹H}NMR(CDCl₃Delta 158.74,143.41,142.84,142.31,138.30,137.77,137.55,136.85,135.87,135.73,134.99,134.75,131.64,128.83,128.76,127.97,127.32,126.82,126.22,123.91,121.35,121.02,120.85,118.56,83.47,83.08,62.32,35.53,33.33,31.96,30.33,26.53,21.45 (two resonances), 18.56,18.43,2.93,2.65.

Synthesis of the metallocene MC-IE1 (according to the invention)

2-methyl- [4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl]Chloro-dimethyl-silane

Will be in hexaneⁿBuLi (2.43M, 30.4ml, 73.87mmol) was added in one portion to a solution of 22.3g (73.73mmol)4- (4-tert-butylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-indacene in 300ml diethyl ether (cooled to-50 ℃ C.). Mixing the obtained extractsThe mixture was stirred at room temperature overnight, then the resulting suspension with the large amount of precipitate was cooled to-78 deg.C (where the precipitate substantially dissolved to form an orange solution) and 47.6g (369mmol, 5 eq) of dichlorodimethylsilane was added in one portion. The resulting solution was stirred at room temperature overnight and then filtered through a frit (G4). The filtrate was evaporated to dryness to give 28.49g (98%) of 2-methyl- [4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl]Chlorodimethylsilane, a colorless glassy material, was used without further purification.

[ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl][ 2-methyl-4- (4-tert-butyl) methyl ester Butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl]Dimethylsilane

Will be in hexaneⁿBuLi (2.43M, 9.6ml, 23.33mmol) was added in one portion to a solution of 8.12g (23.3mmol) 2-methyl-5-tert-butyl-7- (4-tert-butylphenyl) -6-methoxy-1H-indene in 150ml diethyl ether (-50 ℃). The mixture was stirred at room temperature overnight, then the resulting yellow suspension was cooled to-50 ℃ and 150mg of CuCN was added. The resulting mixture was stirred at-25 ℃ for 0.5h, then 9.2g (23.29mmol) of [ 2-methyl-4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl were added in one portion]A solution of chlorodimethylsilane in a mixture of 100ml of diethyl ether and 50ml of THF. The mixture was stirred at room temperature overnight and then filtered through a pad of silica gel 60(40-63 μm). The precipitate was additionally washed with 2X 50ml of dichloromethane. The combined filtrates were evaporated under reduced pressure and the residue was taken upThe material was dried under vacuum at elevated temperature. This procedure gives 16.6g (about 100%) [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl][ 2-methyl-4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl]Dimethylsilane (approx. 95% NMR purity, approx. 1:1 mixture of stereoisomers) was a pale yellow glass and was used further without further purification.

Trans-dimethylsilanediyl [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylinden-1-yl] [ 2-methyl-4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl]Hafnium dichloride

Will be in hexaneⁿBuLi (2.43M, 19.2ml, 46.7mmol) was added in one portion to 16.6g (23.3mol) of [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl][ 2-methyl-4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl]Dimethylsilane (prepared as above) was dissolved in 250ml of diethyl ether (cooled to-50 ℃). The mixture was stirred at room temperature overnight, then the resulting cherry red solution was cooled to-60 deg.C,and 7.46g (23.29mmol) of HfCl was added₄. The reaction mixture was stirred at room temperature for 24h to give an orange suspension. The suspension is filtered through a frit (G4) and the precipitate is washed with 30ml of diethyl ether. Evidence of the NMR spectrum shows that the precipitate is pure trans-dichlorohafnocene (with LiCl), while the filtrate contains 77/23 proportions (in favor of cis) of a mixture of cis-dichlorohafnocene and trans-dichlorohafnocene (contaminated with some other impurities). The precipitate was dissolved in 100ml of hot toluene and the resulting suspension was filtered off of LiCl through a frit (G4). The filtrate was evaporated to about 20ml and 40ml of n-hexane was added. The yellow solid which precipitated at room temperature was filtered off (G3), washed with 15ml of cold n-hexane and then dried in vacuo. This procedure gives 4.70g (21%) of pure trans-complex. The mother liquor was evaporated to about 15ml and 40ml of n-hexane was added. The yellow precipitate formed (G3) was filtered off and then dried in vacuo. This procedure yielded 3.60g (16%) of an about 4/1 mixture of cis-hafnocene and trans-hafnocene (in favor of cis). Thus, the total yield of trans-hafnocene and cis-hafnocene isolated in this synthesis was 8.3g (37%).

Trans-dimethylsilanediyl [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] hafnium dichloride

For C₅₀H₆₀Cl₂HfOSi, calculated as C, 62.92; h, 6.34. Found C, 63.11; h, 6.58.

¹H NMR(CDCl₃):δ7.59-7.36(m,10H),6.65(s,1H),6.52(s,1H),3.35(s,3H),3.15-2.91(m,3H),2.91-2.79(m,1H),2.27(s,6H),2.10-1.88(m,2H),1.38(s,9H),1.33(s,18H),1.28(2s,6H).¹³C{¹H}NMR(CDCl₃,):δ159.75,150.01,149.82,144.36,143.58,143.04,135.53,133.86,133.07,132.80,132.26,131.87,131.20,129.23,128.74,126.52,125.34,125.10,121.31,120.85,119.82,119.47,117.81,82.78,82.20,62.56,35.68,34.58,33.13,32.12,31.37,30.36,26.67,18.26,18.15,2.63,2.55.

Synthesis of metallocene MC-IE2 (invention)

[ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl esterbutyl-1H-inden-1-yl]Chloro-dimethyl-silane

Will be in hexaneⁿBuLi (2.43M, 25.2ml, 61.24mmol) was added in one portion to a solution of 19.66g (61.35mmol) 2-methyl-5-tert-butyl-6-methoxy-7- (3, 5-dimethylphenyl) -1H-indene in 300ml diethyl ether (cooled to-50 ℃ C.). The resulting mixture was stirred at room temperature for 4h, then the resulting yellow suspension was cooled to-60 ℃ and 40.0ml (42.8g, 331.6mmol, 5.4 equivalents) dichlorodimethylsilane was added in one portion. The resulting solution was stirred at room temperature overnight and then filtered through a frit (G3). Evaporating the filtrate to dryness to obtain [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl]Chlorodimethylsilane, a slightly yellowish oil, was used without further purification.

[ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-inden-1-yl][ 2-methyl-4- (3, 5-) Dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl]Dimethylsilane

Will be in hexaneⁿBuLi (2.43M, 25.2ml, 61.24mmol) was added in one portion to a solution of 16.83g (61.33mmol) of 4- (3, 5-dimethylphenyl) -6-methyl-1, 2,3, 5-tetrahydro-s-indacene in a mixture of 300ml of diethyl ether and 40ml of THF (cooled to-50 ℃). The mixture was stirred at room temperature overnight, and the resulting mixture was then concentratedThe reddish solution was cooled to-50 ℃ and 300mg of CuCN was added. The resulting mixture was stirred at-25 ℃ for 0.5H, then [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl-was added in one portion]A solution of chlorodimethylsilane (prepared above, ca. 61.24mmol) in 150ml of diethyl ether. The mixture was stirred at room temperature overnight and then filtered through a pad of silica gel 60(40-63 μm), which was additionally washed with 2X 50ml of dichloromethane. The combined filtrates were evaporated under reduced pressure and the residue was dried under vacuum at elevated temperature. This procedure gave 39.22g (98%) of [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl][ 2-methyl-4- (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl]Dimethylsilane (an approximately 3:2 mixture of stereoisomers) is a reddish glass-like material.

Trans-dimethylsilanediyl [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylindene-1- Base of][ 2-methyl-4- (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl]Hafnium dichloride

Will be inIn an alkaneⁿBuLi (2.43M, 49.6ml, 120.5mmol) was added in one portion to 39.22g (60.25mmol) of [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butyl-1H-inden-1-yl][ 2-methyl-4- (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl]Dimethylsilane (prepared as above) was dissolved in 400ml of diethyl ether (cooled to-50 ℃). The mixture was stirred at room temperature overnight. The resulting red solution was then cooled to-78 deg.C and 19.3g (60.26mmol) HfCl was added₄. The reaction mixture was stirred at room temperature for 24h to give an orange suspension. The precipitate is filtered off (G4) and washed with 30ml of cold diethyl ether. Evidence of the NMR spectrum indicates that the precipitate is pure cis-dichlorohafnocene (with LiCl), while the filtrate comprises an about 4/1 mixture of trans-and cis-dichlorohafnocenes (in favor of trans-dichlorohafnocene) (contaminated with some other impurities). The precipitate was dissolved in 150ml hot toluene and the resulting suspension was filtered to remove LiCl through a frit (G4). The filtrate was evaporated to about 45 ml. The orange solid material that precipitated overnight at room temperature was filtered off (G3) and then dried in vacuo. This procedure gives 8.1g (15%) of pure cis-complex. The mother liquor was evaporated to almost dryness and the residue was triturated with 20ml of n-hexane to give 2.6g (4.8%) of cis-hafnocene dichloride as an orange powder. The ether mother liquor was evaporated to about 60ml and the precipitated yellow powder (G4) was filtered off, washed with 20ml cold (0 ℃) ether and then dried in vacuo. This procedure gives 10.2g (19%) of pure trans-dichlorohafnocene. Thus, the total yield of trans-and cis-dichlorohafnocenes isolated in this synthesis was 20.9g (39%).

Trans-dimethylsilanediyl [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] hafnium dichloride:

for C₄₆H₅₂Cl₂OSiHf, calculated as C, 61.50; h, 5.83. Found C, 61.38; h, 6.15.

¹H NMR(CDCl₃):δ7.51(s,1H),7.43(s,1H),7.34-7.02(br.m,4H),6.94(s,2H),6.61(s,1H),6.46(s,1H),3.42(s,3H),3.11-2.79(m,4H),2.33(s,6H),2.32(s,6H),2.27(s,6H),2.07-1.92(m,2H),1.38(s,9H),1.27(s,3H),1.26(s,3H).¹³C{¹H}NMR(CDCl₃,):δ159.55,144.17,143.58,142.84,138.38,137.82,137.57,136.94,133.09,132.67,132.40,132.11,131.23,128.84,128.76,127.40,126.88,126.53,124.97,121.28,120.84,119.76,119.71,117.90,82.92,82.40,62.62,35.68,33.11,32.07,30.43,26.56,21.46,21.38,18.26,18.12,2.63,2.53.

Cis-dimethylsilanediyl [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylinden-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -1,5,6, 7-tetrahydro-s-indacen-1-yl ] hafnium dichloride:

for C₄₆H₅₂Cl₂OSiHf, calculated as C, 61.50; h, 5.83. Found C, 61.59; h, 6.06.

¹H NMR(CDCl₃):δ7.53(s,1H),7.41(s,1H),7.29-7.06(m,4H),6.94(s,2H),6.50(s,1H),6.35(s,1H),3.26(s,3H),2.95-2.77(m,4H),2.49(s,3H),2.46(s,3H),2.33(2s,sum 12H),1.99-1.86(m,1H),1.86-1.73(m,1H),1.40(s,3H),1.37(s,9H),1.18(s,3H).¹³C{¹H}NMR(CDCl₃,):δ158.61,143.03,142.46,142.16,138.42,137.73,137.52,136.98,135.33,134.60,133.69,132.53,131.19,128.79,128.71,127.34,126.85,126.00,125.76,121.95,121.45,119.12,118.91,118.55,84.66,84.26,62.31,35.48,33.25,31.94,30.40,26.60,21.44,18.44,18.31,2.93,2.61

Summary of metallocene examples used in the examples

Catalyst preparation examples

Material

The inventive metallocenes MC-IE1 and MC-IE2 as described above; and the comparative metallocenes MC-CE1 and MC-CE2 were used to prepare the catalysts.

MAO was used as a 30 wt-% solution in toluene. The commercially available triphenylcarbenium tetrakis (pentafluorophenyl) borate (Boulder Chemicals) was used. As the surfactant, a perfluoroalkylethyl acrylate available from Cytonix corporation (CAS No. 65605-70-1) was used, dried over activated molecular sieves (2 times) and degassed by argon blowing before use (S1), or 1H, 1H-perfluoro (2-methyl-3-oxahex-1-ol) (CAS 26537-88-2) available from Unimatec, dried over activated molecular sieves (2 times) before use and degassed by argon blowing (S2). Hexafluoro-1, 3-dimethylcyclohexane (PFC) (CAS No. 335-27-3) was obtained from commercial sources and dried (2 times) over activated molecular sieves prior to use and degassed by argon blowing. Propylene is supplied by Borealis and is fully purified prior to use. Triethylaluminum was purchased from Crompton and used in pure form. Hydrogen is supplied by AGA and purified before use.

All chemicals and chemical reactions were handled under an inert gas atmosphere using Schlenk and glove box techniques, and glassware, syringes, needles or cannulae were oven dried.

Catalyst example CE1 (comparative)

Inside a glove box, 85.9mg of dried and degassed surfactant S2 was mixed with 2mL of MAO in a septum bottle (septum bottle) and allowed to react overnight. The next day, 43.9mg of MC-CE1(0.076mmol, 1 equiv.) was dissolved in another septum bottle with 4mL of MAO solution and stirred in the glove box.

After 60 minutes, 4mL of MAO-metallocene solution and 1mL of surfactant solution were added in succession to a 50mL emulsified glass reactor charged with 40mL of PFC (at-10 ℃) and equipped with an overhead stirrer (stirring speed 600 rpm). The total amount of MAO was 5mL (450 equivalents). A red emulsion formed immediately and was stirred at 0 deg.C/600 rpm for 15 minutes. The emulsion was then transferred to 100mL of hot PFC at 90 ℃ via 2/4 teflon tubing and stirred at 600rpm until the transfer was complete, then the speed was reduced to 300 rpm. After stirring for 15 minutes, the oil bath was removed and the stirrer was turned off. The catalyst was left to settle on top of the PFC and the solvent was siphoned off after 45 minutes. The remaining red catalyst was dried under argon flow at 50 ℃ for 2 hours. 0.62g of a red free-flowing powder is obtained.

Catalyst example CE2 (comparative)

Inside a glove box, a solution of surfactant S2 (28.8mg of a dried and degassed dilution of S2 in 0.2mL of toluene) was added dropwise to 5mL of 30wt. -% Chemtura MAO. The solution was left under stirring for 10 minutes. Then, 98.7mg of the metallocene MC-CE1 was added to the MAO/surfactant. After stirring for 60 minutes, 104.9mg of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added.

After stirring for 60 minutes, the surfactant-MAO-metallocene-borate solution was added to a 50mL emulsion glass reactor charged with 40mL PFC (at-10 ℃) and equipped with an overhead stirrer (stirring speed 600 rpm). A red emulsion formed immediately and was stirred at-10 deg.C/600 rpm for 15 minutes. The emulsion was then transferred to 100mL of hot PFC at 90 ℃ via 2/4 teflon tubing and stirred at 600rpm until the transfer was complete. The speed was then reduced to 300 rpm. After stirring for 15 minutes, the oil bath was removed and the stirrer was turned off. The catalyst was left to settle on top of the PFC and the solvent was siphoned off after 35 minutes. The remaining catalyst was dried under argon flow at 50 ℃ for 2 hours. 0.90g of a red free-flowing powder is obtained.

Catalyst example CE3 (comparative, without B cocatalyst)

After stirring for 60 minutes, the surfactant-MAO-metallocene solution was added to a 50mL emulsion glass reactor charged with 40mL PFC (at-10 ℃) and equipped with an overhead stirrer (stirring speed 600 rpm). A yellow emulsion formed immediately and was stirred at-10 deg.C/600 rpm for 15 minutes. The emulsion was then transferred via 2/4 Teflon tubing to 100mL of hot PFC at 90 ℃ and stirred at 600rpm until the transfer was complete. The speed was then reduced to 300 rpm. After stirring for 15 minutes, the oil bath was removed and the stirrer was turned off. The catalyst was left to settle on top of the PFC and the solvent was siphoned off after 35 minutes. The remaining catalyst was dried under a stream of argon at 50 ℃ for 2 hours. 0.80g of a yellow free-flowing powder is obtained.

Catalyst example IE1 (inventive)

Inside a glove box, a solution of surfactant S2 (28.8mg of a dried and degassed dilution of S2 in 0.2mL of toluene) was added dropwise to 5mL of 30wt. -% Chemtura MAO. The solution was left under stirring for 10 minutes. Then, 108.7mg of the metallocene MC-IE1 was added to the MAO/surfactant. After 60 minutes, 106.0mg of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added. The mixture was reacted in a glove box at room temperature for 60 min.

Then, the surfactant-MAO-metallocene-borate solution was added to a 50mL emulsion glass reactor charged with 40mL PFC (at-10 ℃) and equipped with an overhead stirrer (stirring speed 600 rpm). A yellow emulsion formed immediately and was stirred at-10 deg.C/600 rpm for 15 minutes. The emulsion was then transferred via 2/4 Teflon tubing to 100mL of hot PFC at 90 ℃ and stirred at 600rpm until the transfer was complete. The speed was then reduced to 300 rpm. After stirring for 15 minutes, the oil bath was removed and the stirrer was turned off. The catalyst was left to settle on top of the PFC and the solvent was siphoned off after 35 minutes. The remaining catalyst was dried under argon flow at 50 ℃ for 2 hours. 0.75g of a yellow free-flowing powder is obtained.

Catalyst example CE4 (comparative)

In a glove box, 86.8mg of dried and degassed S2 was mixed with 2mL of 30wt. -% Chemtura MAO in a septum bottle and allowed to react overnight. The next day, 41.1mg of metallocene MC-CE2(0.051mmol, 1 equiv.) was dissolved in another septum bottle with 4mL of a 30wt. -% Chemtura MAO solution and stirred in the glove box.

After 60 minutes, 1mL of surfactant solution and 4mL of MAO-metallocene solution were added in succession to a 50mL emulsified glass reactor charged with 40mL of PFC (at-10 ℃) and equipped with an overhead stirrer (stirring speed 600 rpm). The total amount of MAO was 5mL (300 equivalents). A red emulsion formed immediately and was stirred at-10 deg.C/600 rpm for 15 minutes. The emulsion was then transferred via 2/4 Teflon tubing to 100mL of hot PFC at 90 ℃ and stirred at 600rpm until the transfer was complete, then the speed was reduced to 300 rpm. After stirring for 15 minutes, the oil bath was removed and the stirrer was turned off. The catalyst was left to settle on top of the PFC and the solvent was siphoned off after 35 minutes. The remaining catalyst was dried under argon flow at 50 ℃ for 2 hours. 0.54g of a red free-flowing powder is obtained.

Catalyst example CE5 (comparative)

Inside a glove box, a solution of surfactant S2 (28.8mg of a dried and degassed dilution of S2 in 0.2mL of toluene) was added dropwise to 5mL of 30wt. -% Chemtura MAO. The solution was left under stirring for 10 minutes. Then, 92.3mg of the metallocene MC-CE2 was added to the MAO/surfactant. After stirring for 60 minutes, 106mg of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added.

After stirring for 60 minutes, the surfactant-MAO-metallocene-borate solution was added to a 50mL emulsion glass reactor charged with 40mL PFC (at-10 ℃) and equipped with an overhead stirrer (stirring speed 600 rpm). A red emulsion formed immediately and was stirred at-10 deg.C/600 rpm for 15 minutes. The emulsion was then transferred via 2/4 Teflon tubing to 100mL of hot PFC at 90 ℃ and stirred at 600rpm until the transfer was complete. The speed was then reduced to 300 rpm. After stirring for 15 minutes, the oil bath was removed and the stirrer was turned off. The catalyst was left to settle on top of the PFC and the solvent was siphoned off after 35 minutes. The remaining catalyst was dried under a stream of argon at 50 ℃ for 2 hours. 0.6g of a red free-flowing powder is obtained.

Catalyst example IE2 (inventive)

Inside a glove box, a solution of surfactant S2 (28.8mg of a dried and degassed dilution of S2 in 0.2mL of toluene) was added dropwise to 5mL of 30wt. -% Chemtura MAO. The solution was left under stirring for 10 minutes. 102.23mg of the metallocene MC-IE2 was then added to the MAO/surfactant. After 60 minutes, 104.9mg of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added. The mixture was reacted in a glove box at room temperature for 60 min.

Catalyst results are disclosed in table 1

TABLE 1

M is Zr or Hf

Off-line prepolymerization of the catalysts of examples CE4, CE5 and IE2

The catalysts of examples CE4, CE5 and IE2 were prepolymerized according to the following procedure: the off-line prepolymerization experiment was carried out in a 125mL pressure reactor equipped with a gas feed line and an overhead stirrer. Dried and degassed perfluoro-1, 3-dimethylcyclohexane (15 cm)³) And the required amount of catalyst to be prepolymerized were charged to the reactor in a glove box and the reactor was sealed. The reactor was then removed from the glove box and placed in a water-cooled bath maintained at 25 ℃. The overhead stirrer and feed line were connected and the stirring speed was set at 450 rpm. The experiment was started by opening the propylene feed to the reactor. The total pressure in the reactor was raised to about 5 bar (barg) and kept constant by the propylene feed via mass flow controllers until the target degree of polymerization was reached. By flash evaporationVolatile components to terminate the reaction. Inside the glove box, the reactor was opened and the contents poured into a glass container. The perfluoro-1, 3-dimethylcyclohexane was evaporated until constant weight was obtained to obtain an off-line prepolymerized catalyst.

The offline prepolymerized catalysts were labeled pCE4, pCE5, and pIE2, the degree of pre-polymerization (DP) of which is disclosed in table 2.

The degree of pre-polymerization (DP) is defined as the weight of the polymer matrix/weight of the solid catalyst before the off-line prepolymerization step.

The composition of the catalyst (prior to off-line prepolymerization) can be determined by ICP. The Metallocene (MC) content of the offline prepolymerized catalyst can be calculated from the ICP data as follows:

equation 1

Equation 2

Equation 3

Equation 4

TABLE 2

Off-line prepolymerisation catalysisAgent for treating cancer	pCE4	pCE5	pIE2
				Degree of preliminary polymerization, g/g	3.15	5.47	3.62
Metallocene content in offline prepolymerized catalyst, wt%	0.68	1.05	1.76

Polymerization examples

Homopolymerization of propylene

The polymerization was carried out in a 5L reactor. 200 μ l Triethylaluminium (TEA) was fed as scavenger to 5mL of dried and degassed pentane. The required amount of hydrogen (1mmol) was then loaded and 1100g of liquid propylene was fed into the reactor. The temperature was set to 20 ℃. The required amount of catalyst in 5mL of PFC was flushed into the reactor with nitrogen overpressure. After a prepolymerization time of 5 minutes, the temperature was raised to 70 ℃ over a period of 15 minutes. After 60 minutes, the polymerization was stopped by venting the reactor and flushing with nitrogen before collecting the polymer.

Based on a period of 60 minutes (homopolymerization of propylene), the catalyst activity was calculated according to the following formula:

the polymerization results are disclosed in table 3. The polymerization examples are labeled P-CEn/P-IEn.

TABLE 3 homopolymerization results and Polymer analysis

From the homopolymerization results, it can be seen that the metallocene complex has a ligand structure similar to that of the metallocene complex but takes Zr as metal; or the comparative examples using Hf but no boron promoter, the catalysts of the invention have a significantly higher Tm. Furthermore, in the inventive examples, the activity was at a higher level.

Copolymerization of propylene with ethylene

Step 1: prepolymerization and bulk homopolymerization

A21.2L stainless steel reactor charged with 0.4 bar (barg) propylene was charged with 3950g of propylene. Triethylaluminium was injected into the reactor by an additional 240g of propylene. The solution was stirred at 20 ℃ and 250rpm for at least 20 minutes. Catalyst injection was as follows: the required amount of solid off-line prepolymerized catalyst was charged into a 5ml stainless steel cylinder in a glove box and a second 5ml bottle containing 4ml of n-heptane, pressurized with 10 bar of nitrogen, was added to the top of the first bottle. The catalyst feeder system was mounted on a port on the top of the autoclave. In experiments P-pCE5 and P-pIE2-2, 2NL of H were fed via a mass flow controller immediately within 1 minute₂. The valve between the two bottles was opened and the solid catalyst was contacted with heptane under nitrogen pressure for 2s, then flushed into the reactor with 240g of propylene. The prepolymerization was carried out for 10 minutes. At the end of the prepolymerization step, the temperature was raised to 80 ℃. When the internal reactor temperature reached 71 ℃, 1.5NL of H was added over three minutes via a mass flow controller₂(Process 1 and Process 2) or H of 2.0NL₂(process 3). The reactor temperature was kept constant at 80 ℃ throughout the polymerization. The polymerization time was measured from when the internal reactor temperature reached 2 ℃ lower than the set polymerization temperature.

Step 2: gas phase homopolymerization

After the bulk step was completed, the stirrer speed was reduced to 50rpm and the pressure was reduced to 23 bar (bar-g) by discharging the monomer. The stirrer speed was then set to 180rpm, the reactor temperature was set to 80 ℃ and the pressure was set to 24 bar (bar-g). Hydrogen at 2.0NL was added over 4 minutes via a flow controller. During the gas-phase homopolymerization, both pressure and temperature were kept constant via mass flow controllers (propylene feed) and a thermostat for 40 minutes.

And step 3: gas phase ethylene-propylene copolymerization

After the gas phase homopolymerization step (step 2) was completed, the stirrer speed was reduced to 50rpm, and the pressure was reduced to 0.3 bar (bar-g) by discharging the monomer. Triethylaluminium (0.80ml of a 0.62mol/l solution in heptane) was then injected into the reactor through a further 250g of propylene via a steel cylinder, except for experiment P-pIE2-2 (where TEA was not added in this step). The pressure was then reduced again to 0.3 bar (bar-g) by discharging the monomer. The stirrer speed was set at 180rpm and the reactor temperature was set at 70 deg.C (85 deg.C in experiment P-pIE 2-2). The reactor pressure was then increased to 20 bar (bar-g) by feeding a C3/C2 gas mixture (C2/C3 ═ 0.56 wt/wt). The temperature was kept constant by a thermostat and the pressure was kept constant by feeding a C3/C2 gas mixture (the composition of which corresponds to that of the target polymer) via a mass flow controller until the set time for this step expired.

The reactor was then cooled to about 30 ℃ and the volatile components were vented. By 3 times N₂And a vacuum/N₂After cyclic purging of the reactor, the product was removed and dried overnight in a fume hood. To 100g of polymer was added 0.5% by weight of Irganox B225 (solution in acetone) additive and dried overnight in a fume hood and then dried in a vacuum oven at 60 ℃ for one hour.

The copolymerization conditions are shown in table 4, and the copolymerization results are shown in table 5.

TABLE 4 copolymerization conditions

Amount of catalyst prepolymerized off line

TABLE 5 copolymerization results

Amount of catalyst before off-line prepolymerization

Table 5 shows that catalyst pIE2 produced T in comparison to the Zr analogue_mHigher and rubber phase with higher molecular weight (in iV)_EPRdL/g). In addition, high iV (EPR) can be obtained at polymerization temperatures up to 85 ℃.

The material from P-pIE2-1 and P-pCE5 was complexed on TSE 16 with 1500ppm of B225 and 500ppm of calcium stearate, respectively, with a melting temperature of 210 ℃ and a throughput of 2 kg/h. The complexed products were named IE 1-product (for P-pIE2-1 group) and CE 2-product (for P-pCE5 group), respectively. These properties are listed in table 6.

It can be seen that IE1 gives higher flexural modulus and impact strength at 0 ℃ and-20 ℃.

Table 6 stiffness/impact balance of IE-and CE-products.

		IE 1-product	CE 2-products
				Flexural modulus	MPa	1109	1002
NIS/0℃	kJ/m²	4,97	4,14
				NIS/-20℃	kJ/m²	2,11	1,35
Tg1	℃	-36,3	-39,7
				Tg2	℃	1,4	0,6
G’	MPa	615	572

Detailed Description

Definition of

Throughout the specification, the following definitions apply.

By "free of an external support" is meant that the catalyst does not contain an external support, such as an inorganic support, for example silica or alumina, or an organic polymer support material.

The term "C_1-20Hydrocarbyl radicals "including C_1-20Alkyl radical, C_2-20Alkenyl radical, C_2-20Alkynyl, C_3-20Cycloalkyl radical, C_3-20Cycloalkenyl radical, C_6-20Aryl radical, C_7-20Alkylaryl group or C_7-20Arylalkyl groups or mixtures of these groups, for example cycloalkyl substituted by alkyl. The linear and branched hydrocarbyl groups are free of cyclic units. Aliphatic hydrocarbyl groups do not contain an aryl ring.

Preferred C unless otherwise stated_1-20The hydrocarbon radical being C_1-20Alkyl radical, C_4-20Cycloalkyl radical, C_5-20Cycloalkyl-alkyl radical, C_7-20Alkylaryl group, C_7-20Arylalkyl radical or C_6-20Aryl radicals, especially C_1-10Alkyl radicalRadical, C_6-10Aryl or C_7-12Arylalkyl radicals, e.g. C_1-8An alkyl group. Most particularly preferred hydrocarbyl groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C_5-6Cycloalkyl, cyclohexylmethyl, phenyl or benzyl.

The term "halo" when referring to the complex definition includes fluoro, chloro, bromo and iodo groups, especially chloro or fluoro groups.

The oxidation state of the metal ions depends primarily on the nature of the metal ions in question and the stability of the individual oxidation states of each metal ion.

It is understood that in the complex of the present invention, the metal ion M as a Hf ion is coordinated by the ligand X to satisfy the valence of the metal ion and to fill its available coordination sites. The nature of these sigma-ligands can vary widely.

The terms "C4 phenyl ring" and "C4 'phenyl ring" refer to substituted phenyl rings attached at the 4 and 4' positions of an indenyl (indenyl) ring and an indacenyl (indacenyl) ring, respectively. The numbering of these rings will be apparent from the structure shown herein.

Catalyst activity is defined herein as the amount of polymer produced per gram of catalyst per hour. Catalyst metal activity is defined herein as the amount of polymer produced per gram of metal per hour. The term productivity is also sometimes used to refer to catalyst activity, although in this context it refers to the amount of polymer produced per unit weight of catalyst.

The term "molecular weight" as used herein, unless otherwise indicated, refers to the weight average molecular weight Mw.

A maximum of 6R can be bound in the complex of the formula (I)¹And R^1’A group. All that is required is if there are four or more R¹And R^1’At least one of the radicals is not tert-butyl. The complex may have 0,1, 2 or 3 tertiary butyl groups but not more.

Detailed Description

The present invention relates to a series of novel complexes and, therefore, to catalysts which are ideal for the polymerization of propylene. The complexes of the invention are asymmetric. Asymmetric simply means that the two ligands forming the metallocene are different, i.e., each bears a set of chemically different substituents.

The complexes of the invention are preferably chiral, racemic, bridged bisindenyl C₁Symmetrical metallocenes. Although the complex of the present invention is formally C₁Symmetrical, but since they hold C in a position very close to the metal centre₂Symmetry, although not at the periphery of the ligand, so that the ligand ideally retains the pseudo-C₂-symmetry. Depending on their chemical nature, the trans enantiomer and the cis enantiomer (in C) are formed simultaneously during the synthesis of the complex₁In the case of symmetric complexes). For the purposes of the present invention, rac-trans means that the two indenyl ligands are oriented in opposite directions relative to the cyclopentadienyl-metal-cyclopentadienyl plane, whereas rac-cis means that the two indenyl ligands are oriented in the same direction relative to the cyclopentadienyl-metal-cyclopentadienyl plane, as shown in the structure below.

Formula (I) and any subformulae are intended to cover both the cis and trans configuration. Preferred complexes are in the trans configuration. In formula I, the metal ion is always Hf.

It is preferred if the metallocenes of the invention are used as racemic or racemic-trans isomers. Thus, desirably, at least 95% mol, for example at least 98% mol, especially at least 99% mol of the metallocene is in the racemic or racemic-trans isomer form.

In the catalyst of the present invention, the following preferable conditions are applied. The catalyst according to the invention is of formula (I):

in the complex of formula (I), M is Hf.

Each X is a sigma ligand. Most preferably, each X is independently a hydrogen atom, a halogen atom, C_1-6Alkoxy groups or R groups, wherein R is C_1-6Alkyl, phenyl or benzyl groups. Most preferably X is a chloro, benzyl or methyl group. Preferably both X groups are the same. The most preferred choices are two chlorides, two methyl groups or two benzyl groups, especially two chlorides.

L is- (ER)⁸ ₂)_y-. If E is Si, it is preferred. It is preferable if y is 1. - (ER)⁸ ₂)_yPreferably a methylene or ethylene linker, or L is of the formula-SiR⁸ ₂A bridge of (a) wherein each R⁸Independently is C₁-C₂₀-hydrocarbyl, tri (C)₁-C₂₀Alkyl) silyl, C₆-C₂₀-aryl, C₇-C₂₀Arylalkyl or C₇-C₂₀-alkylaryl. Thus, the term C_1-20The hydrocarbon radical comprising C_1-20Alkyl radical, C_2-20Alkenyl radical, C_2-20Alkynyl, C_3-20Cycloalkyl radical, C_3-20Cycloalkenyl radical, C_6-20Aryl radical, C_7-20Alkylaryl group or C_7-20Arylalkyl groups or mixtures of these groups, for example cycloalkyl substituted by alkyl. Preferred C unless otherwise indicated_1-20The hydrocarbon radical being C_1-20Alkyl radical, C_4-20Cycloalkyl radical, C_5-20Cycloalkyl-alkyl radical, C_7-20Alkylaryl group, C_7-20Arylalkyl radical or C_6-20An aryl group. If L is an alkylene linking group, ethylene and methylene are preferred.

Preferably two R⁸The groups are the same. If R is⁸Is C₁-C₁₀Hydrocarbyl or C₆-C₁₀Aryl radicals, e.g. methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C_5-6Cycloalkyl, cyclohexylmethyl, phenyl or benzyl, are preferred, more preferably two R⁸Are all C₁-C₆Alkyl radical, C_3-8Cycloalkyl or C₆-aryl radicalRadicals, e.g. C₁-C₄Alkyl radical, C_5-6Cycloalkyl or C₆-aryl groups, most preferably two R⁸Both are methyl, or one is methyl and the other is cyclohexyl. The alkylene linker is preferably methylene or ethylene. L is most preferably-Si (CH)₃)₂-。

Ar and Ar' are preferably phenyl rings.

Each substituent R¹And R^1’Independently the same or different, and is preferably a straight-chain or branched C₁-C₆-alkyl radical or C_6-20Aryl radical, more preferably straight-chain or branched C₁-C₄An alkyl group. Preferably, each R¹And each R^1’Independently methyl, ethyl, isopropyl or-CMe₃In particular methyl or-CMe₃. Preferably, each R¹Is the same and each R^1’The same is true.

Each n is independently 0,1, 2 or 3, preferably 1 or 2. The sum of the two "n" values is ideally 2,3 or 4. When n is 1, the ring is preferably substituted in the para (4-or 4' -position) position by a group R¹Or R^1’Is substituted. When n is 2, the ring is preferably substituted in the ortho position (3 and 5 or 3 'and 5') by a group R¹Or R^1’And (4) substitution.

In all embodiments of the invention, the substitution of the C (4) and C (4') phenyl groups is limited by the following conditions: the complex is substituted by a total of 0,1, 2 or 3 CMes on the entire bound C (4) and C (4') phenyl ring₃Substituted by radicals, preferably a total of 0,1 or 2 CMe on the entire combined C (4) and C (4') phenyl ring₃And (4) substituting the group. In other words, if the sum of two values of n is equal to 4 or more, then there is at least one R present¹Or R^1’The group cannot represent a tert-butyl group.

Desirably, none of the C (4) or C (4') rings contain two branched substituents. If the C (4) or C (4') ring contains two substituents (i.e., n is 2), then preferably R¹Or R^1’Is C_1-4Straight chain alkyl groups, such as methyl.

If the C (4) or C (4') ring contains a(i.e., n is 1), then preferably R is¹Or R^1’Is a branched chain C_4-6Alkyl groups, for example, tert-butyl.

In particular embodiments, Ar and Ar' in formula I (or any of the formulae below) are independently selected from the group consisting of C substituted at the 3, 5-position or 4-position with a straight or branched chain₁-C₄An alkyl-substituted phenyl ring; i.e. corresponding to substitution in position 3,5 or 4, wherein R¹And R^1’Is C₁-C₄An alkyl group, n is 1 or 2. In particular embodiments, Ar and Ar' in formula I are independently selected from the group consisting of 3, 5-dimethylphenyl, 3, 5-di-tert-butyl, and 4- (tert-butyl) -phenyl. Thus, in particular embodiments, in the complex of formula I, Ar and Ar ' are both 3, 5-dimethylphenyl, Ar and Ar ' are both 4- (tert-butyl) -phenyl, or one of Ar and Ar ' is 3, 5-dimethylphenyl and the other is 4- (tert-butyl) -phenyl. Other preferred options include one of Ar or Ar' being 3, 5-di-tert-butylphenyl and the other being 3, 5-dimethylphenyl or 4-tert-butylphenyl. These particular embodiments may be applied to all structures II-VIII described herein where technically feasible. In other words, in particular embodiments, R is selected¹、R^1’And each independent value of n is such that the C (4) or C (4') phenyl ring is a 3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl and/or 4- (tert-butyl) -phenyl group.

In one embodiment, at least one of the C (4) or C (4') phenyl rings is 3, 5-dimethylphenyl.

In one embodiment, at least one of the C (4) or C (4') phenyl rings is 4- (tert-butyl) -phenyl.

R²And R^2’Each is the same or different and is CH₂-R⁹Group, wherein R⁹Is H or straight or branched C₁-C₆Alkyl radicals (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl) or C_3-8Cycloalkyl (e.g. cyclohexyl) or C_6-10Aryl (preferably phenyl). Preferably, R²And R^2’Are identical and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C₁-C₄-alkyl groups, more preferably, R²And R^2’Are identical and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C₁-C₃-an alkyl group. Most preferably, R²And R^2’Are all methyl.

R³Is preferably-CH₂-. The subscript m is preferably 2 to 4, for example 3 (thus forming a 5-membered ring).

R⁵Preferably straight-chain or branched C₁-C₆-alkyl radical or C_6-20Aryl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably straight-chain C₁-C₄Alkyl radical, more preferably C₁-C₂Alkyl groups, most preferably methyl groups.

R⁶Is C (R)¹⁰)₃Group, wherein each R¹⁰Identical or different and being straight-chain or branched C₁-C₆-an alkyl group. Preferably, each R¹⁰Identical or different, R¹⁰Is straight-chain or branched C₁-C₄Alkyl radical, more preferably, R¹⁰Are the same and are C₁-C₂An alkyl group. Most preferably, R⁶Is a tert-butyl group, so that all R' s¹⁰Is methyl.

R⁷And R^7’Identical or different and is H or C which is linear or branched₁-C₆An alkyl radical, preferably H or a linear or branched C₁-C₄Alkyl radical, more preferably H or C₁-C₂An alkyl group. In some embodiments, R⁷Or R^7’One of them is H and the other is a straight or branched C₁-C₆An alkyl radical, preferably a linear or branched C₁-C₄Alkyl radical, more preferably C₁-C₂An alkyl group. Particularly preferably, R⁷And R^7’The same is true. Most preferably, R⁷And R^7’Are all H.

In a preferred embodiment, the present invention provides a complex of formula (II)

Wherein

M is Hf;

x is a sigma ligand, preferably each X is independently a hydrogen atom, a halogen atom, C_1-6Alkoxy radical, C_1-6An alkyl, phenyl or benzyl group;

l is an alkylene bridge or of the formula-SiR⁸ ₂A bridge of (a) wherein each R⁸Independently is C₁-C₆Alkyl radical, C_3-8Cycloalkyl or C₆-an aryl group;

each n is independently 1 or 2;

R¹and R^1’Each independently being the same or different and being a straight or branched C₁-C₆-an alkyl group, with the proviso that if four R's are present¹And R^1’All 4 of which cannot be tert-butyl at the same time;

R²and R^2’Are the same or different and are CH₂-R⁹Group, wherein R⁹Is H or straight or branched C_1-6-an alkyl group;

R⁵is straight-chain or branched C₁-C₆-an alkyl group; and

R⁶is C (R)¹⁰)₃Group, wherein R¹⁰Is straight-chain or branched C₁-C₆An alkyl group.

In another preferred embodiment, the present invention provides a complex of formula (III)

Wherein

M is Hf;

each X isSigma ligands, preferably each X is independently a hydrogen atom, a halogen atom, C_1-6Alkoxy radical, C_1-6An alkyl, phenyl or benzyl group;

l is-SiR⁸ ₂-, wherein each R⁸Is C₁-C₆-alkyl or C_3-8A cycloalkyl group;

each n is independently 1 or 2;

R⁵is straight-chain or branched C₁-C₆-an alkyl group; and

R⁶is C (R)¹⁰)₃Group, wherein R¹⁰Is straight-chain or branched C₁-C₆An alkyl group.

In another preferred embodiment, the present invention provides a complex of formula (IV)

Wherein

M is Hf;

each X is a hydrogen atom, a halogen atom, C_1-6Alkoxy radical, C_1-6An alkyl, phenyl or benzyl group;

l is-SiR⁸ ₂-, wherein each R⁸Is C_1-4Alkyl or C_5-6A cycloalkyl group;

each n is independently 1 or 2;

R⁵is straight chain or branchedC of the chain₁-C₆-an alkyl group; and

R⁶is C (R)¹⁰)₃Group, wherein R¹⁰Is straight-chain or branched C₁-C₆An alkyl group.

In another preferred embodiment, the present invention provides a complex of formula (V)

Wherein

M is Hf;

x is a hydrogen atom, a halogen atom, C_1-6Alkoxy radical, C_1-6An alkyl, phenyl or benzyl group;

l is-SiMe₂；

Each n is independently 1 or 2;

R⁵is straight-chain or branched C₁-C₄-an alkyl group; and

R⁶is C (R)¹⁰)₃Group, wherein R¹⁰Is straight-chain or branched C₁-C₄An alkyl group.

In another preferred embodiment, the present invention provides a complex of formula (VI)

Wherein

M is Hf;

x is a hydrogen atom, a halogen atom, C_1-6Alkoxy radical, C_1-6An alkyl, phenyl or benzyl group;

l is-SiMe₂；

Each n is independently 1 or 2;

R⁵is a straight chain C₁-C₄-alkyl groups, such as methyl; and

R⁶is a tert-butyl group.

In another preferred embodiment, the present invention provides a complex of formula (VII)

Wherein

M is Hf;

x is a hydrogen atom, a halogen atom, C_1-6Alkoxy radical, C_1-6Alkyl, phenyl or benzyl groups, especially chlorine;

l is-SiMe₂；

Each n is independently 1 or 2;

R¹and R^1’Each independently being the same or different and being a straight or branched C₁-C₄-an alkyl group, with the proviso that if four R's are present¹And R^1’All 4 of which cannot be tert-butyl at the same time;

R⁵is methyl; and

R⁶is a tert-butyl group.

In a preferred embodiment, the present invention provides a complex of formula (VIII)

Wherein

M is Hf;

x is Cl;

l is-SiMe₂；

Each n is independently 1 or 2;

R¹and R^1’Each independently being methyl or tert-butyl, provided that if four R's are present¹And R^1’All 4 of these radicals, which cannot be simultaneously tert-butyl,

R⁵is methyl; and

R⁶is a tert-butyl group.

In any of the formulae (I) to (VIII), it is preferred if the substituent in the 4-position on the indenyl or indacenyl ring is a 3, 5-dimethylphenyl or 4-tBu-phenyl group.

In any of the formulae (I) to (VIII), it is preferred if the substituent at the 4-position on one of the indenyl or indacenyl rings is a 3, 5-di-tert-butyl group, while the 3, 5-dimethylphenyl or 4-tBu-phenyl group with the 4-position on the other indenyl or indacenyl ring. In this structure, it is preferable if a di-tert-butylphenyl group is present on the indenyl ring.

In any one of formulae (I) to (VIII), if n ═ 2, two R' s¹The same groups are preferred.

In any one of formulae (I) to (VIII), if n ═ 2, two R' s^1’The same groups are preferred.

In any one of formulae (I) to (VIII), if n is 2, R¹Groups in the 3, 5-position are preferred.

In any one of formulae (I) to (VIII), if n is 2, R^1’Groups in the 3, 5-position are preferred.

In any one of formulae (I) to (VIII), if n ═ 1, R¹In the 4-position, this is preferred.

In any one of formulae (I) to (VIII), if n ═ 1, R^1’In the 4-position, this is preferred.

Particular complexes of the invention include:

rac-trans-dimethylsilanediyl [ 2-methyl-4- (4-tert-butylphenyl) -5,6, 7-trihydro-s-indacen-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylindenyl hafnium dichloride or hafnium dimethyl,

rac-trans-dimethylsilanediyl [ 2-isobutyl-4- (4-tert-butylphenyl) -5,6, 7-trihydro-s-indacen-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylindenyl hafnium dichloride or hafnium dimethyl,

rac-trans-dimethylsilanediyl [ 2-neopentyl-4- (4-tert-butylphenyl) -5,6, 7-trihydro-s-indacen-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylindenyl hafnium dichloride or hafnium dimethyl,

rac-trans-dimethylsilanediyl [ 2-benzyl-4- (4-tert-butylphenyl) -5,6, 7-trihydro-s-indacen-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylindenyl hafnium dichloride or hafnium dimethyl,

rac-trans-dimethylsilanediyl [ 2-cyclohexylmethyl-4- (4-tert-butylphenyl) -5,6, 7-trihydro-s-indacen-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylindenyl hafnium dichloride or hafnium dimethyl,

rac-trans-dimethylsilanediyl [ 2-methyl-4- (3, 5-dimethylphenyl) -5,6, 7-trihydro-s-indacen-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylindenyl hafnium dichloride or hafnium dimethyl,

rac-trans-dimethylsilanediyl [ 2-isobutyl-4- (3, 5-dimethylphenyl) -5,6, 7-trihydro-s-indacen-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylindenyl hafnium dichloride or hafnium dimethyl,

rac-trans-dimethylsilanediyl [ 2-neopentyl-4- (3, 5-dimethylphenyl) -5,6, 7-trihydro-s-indacen-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylindenyl hafnium dichloride or hafnium dimethyl,

rac-trans-dimethylsilanediyl [ 2-benzyl-4- (3, 5-dimethylphenyl) -5,6, 7-trihydro-s-indacen-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylindenyl hafnium dichloride or hafnium dimethyl,

rac-trans-dimethylsilanediyl [ 2-cyclohexylmethyl-4- (3, 5-dimethylphenyl) -5,6, 7-trihydro-s-indacen-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylindenyl hafnium dichloride or hafnium dimethyl,

rac-trans-dimethylsilanediyl [ 2-methyl-4- (4-tert-butylphenyl) -5,6, 7-trihydro-s-indacen-1-yl ] [ 2-methyl-4- (3, 5-di-tert-butylphenyl) -5-methoxy-6-tert-butylindenyl hafnium dichloride or hafnium dimethyl,

rac-trans-dimethylsilanediyl [ 2-methyl-4- (3, 5-di-tert-butylphenyl) -5,6, 7-trihydro-s-indacen-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylindenyl hafnium dichloride or hafnium dimethyl,

rac-trans-dimethylsilanediyl [ 2-methyl-4- (3, 5-dimethylphenyl) -5,6, 7-trihydro-s-indacen-1-yl ] [ 2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert-butylindenyl hafnium dichloride or hafnium dimethyl,

rac-trans-dimethylsilanediyl [ 2-methyl-4- (4-tert-butylphenyl) -5,6, 7-trihydro-s-indacen-1-yl ] [ 2-methyl-4- (3, 5-dimethylphenyl) -5-methoxy-6-tert-butylindenyl hafnium dichloride or hafnium dimethyl,

particularly preferred complexes are identified below under the designations MC-IE1 and MC-IE 2.

For the avoidance of doubt, any narrower definition of a substituent provided above may be combined with any other broader or narrower definition of any other substituent.

Throughout the disclosure above, where a narrower definition of a substituent is given, it is considered that this narrower definition is disclosed along with all broader and narrower definitions of other substituents in the application.

Synthesis of

The ligands required to form the metallocenes of the present invention may be synthesized by any method, and skilled organic chemistry experts will be able to devise various synthetic schemes to make the necessary ligand materials. WO2007/116034 discloses the necessary chemistry and is incorporated herein by reference. Synthetic schemes can also be found generally in WO2002/02576, WO2011/135004, WO2012/084961, WO2012/001052, WO2011/076780, and WO 2015/158790. The examples section also provides the skilled person with adequate guidance.

Intermediates

The present invention relates generally to hafnium complexes and catalysts thereof. According to the invention, the complex has a ligand of the formula (I

Preference is given to the formula (Ib'):

wherein the substituents are as defined above and the dotted lines indicate the double bond present between carbon 1 and carbon 2 or carbon 2 and carbon 3 of the indenyl ring and the double bond present between carbon 1 'and carbon 2' or carbon 2 'and carbon 3' of the indacenyl ring. Thus, it is understood that the molecule contains double bond isomers. Double bond isomers refer to compounds in which the double bond is located between the atoms in positions 2 and 3 of the bicyclic ring, rather than between the atoms in positions 1 and 2. More than one double bond isomer may be present in the sample. Preferred ligands are analogues of the above-mentioned complexes (II) to (VIII) in which HfX has been removed₂Coordinated and protons returned to the indenyl group.

Co-catalyst

In order to form the active catalytic species, it is generally necessary to use a promoter as is well known in the art. Typically, the cocatalyst comprises a compound of a group 13 metal, such as an organoaluminum compound. According to the present invention, a cocatalyst comprising two types of compounds of group 13 metals (i.e., an organoaluminum compound and a boron-based compound) is used in the present invention for activating a metallocene catalyst.

The olefin polymerization catalyst system of the present invention comprises (i) a complex as defined herein; and (ii) an alkylaluminum compound or a reaction product thereof, and (iii) a boron-based cocatalyst. Preferably, the aluminium-containing cocatalyst is an aluminoxane, such as MAO or an aluminoxane other than MAO, and the boron-containing cocatalyst is a borate. That is, the catalyst contains an Al-containing compound and a B-containing compound as a co-catalyst. The boron-containing promoter is preferably a borate.

Thus, borate promoters are used in the catalysts of the present invention along with Al-containing promoters.

The aluminoxane cocatalyst can be of one of the formulae (X):

wherein n is generally from 6 to 20 and R has the following meaning.

The aluminoxane is prepared by reacting an organoaluminum compound (e.g., of the formula AlR₃、AlR₂Y and Al₂R₃Y₃Those of (a) in which R may be, for example, C1-C10 alkyl, preferably C1-C5 alkyl, or C3-10 cycloalkyl, C7-C12-arylalkyl or alkylaryl and/or phenyl or naphthyl, in which Y may be hydrogen, halogen, preferably chlorine or bromine, or C1-C10 alkoxy, preferably methoxy or ethoxy. The resulting oxyaluminoxanes are generally not pure compounds but mixtures of oligomers of the formula (X).

The preferred aluminoxane is Methylaluminoxane (MAO). Since the aluminoxanes used as cocatalysts according to the present invention are not pure compounds, for their mode of preparation, the molar concentrations of the aluminoxane solutions are hereinafter based on their aluminum content.

However, it has surprisingly been found that in the case of heterogeneous catalysis, higher activity, higher melting temperature and higher molecular weight can be achieved in specific cases if a boron-based cocatalyst is also used as cocatalyst together with the aluminum cocatalyst, and if the metal M in the metallocene is hafnium.

Boron-based cocatalysts useful in the present invention include boron compounds, preferably containing borate anions, i.e., borate compounds. These compounds generally comprise an anion of the formula:

(Z)₄B^- (XI)

wherein Z is an optionally substituted phenyl derivative, said substituent being halo-C_1-6-alkyl or halo groups. A preferred choice is fluoro or trifluoromethyl. Most preferably, the phenyl group is perfluorinated. Such ionic cocatalysts preferably contain a non-coordinating anion, such as tetrakis (pentafluorophenyl) borate.

Suitable counterions are protonated amine derivatives or aniline derivatives or phosphorus ions. They may have the general formula (XII) or (XIII):

NQ₄ ⁺(XI) or PQ₄ ⁺ (XIII)

Wherein Q is independently H, C_1-6Alkyl radical, C_3-8Cycloalkyl, phenyl C_1-6-alkyl or optionally substituted phenyl. The optional substituent may be C_1-6-alkyl, halogen or nitro. There may be one or more such substituents. Thus, preferred substituted phenyl groups include para-substituted phenyl, preferably tolyl or dimethylphenyl.

It is preferred if at least one Q group is H, and therefore preferred compounds are those of the formula:

NHQ₃ ⁺(VI) or PHQ₃ ⁺ (XIV)

Preferred phenyl radicals-C_1-6-alkyl-groups include benzyl.

Thus, suitable counterions include: methylammonium, anilinium (anilinium), dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium, N-dimethylanilinium, trimethylammonium, triethylammonium, tri-N-butylammonium, methyldiphenylammonium, p-bromo-N, N-dimethylanilinium or p-nitro-N, N-dimethylanilinium, in particular dimethylammonium or N, N-dimethylanilinium. The use of pyridinium as the ion is another option.

Phosphorus ions of interest include triphenylphosphonium, triethylphosphonium, diphenylphosphonium, tris (methylphenyl) phosphonium and tris (dimethylphenyl) phosphonium.

A more preferred counterion is trityl (trityl) (CPh)₃ ⁺) Or the like, wherein the Ph group is functionalized to carry one or more alkyl groups. Thus, a highly preferred borate for use in the present invention comprises tetrakis (pentafluorophenyl) borate ion.

Preferred ionic compounds that may be used according to the present invention include:

tributylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (trifluoromethylphenyl) borate, tributylammonium tetrakis (4-fluorophenyl) borate, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate, N-dimethylbenzylammonium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N-di (propyl) ammonium tetrakis (pentafluorophenyl) borate, di (cyclohexyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, or ferrocenium tetrakis (pentafluorophenyl) borate.

Preference is given to triphenylcarbenium tetrakis (pentafluorophenyl) borate, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate, N-dimethylbenzylammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

It has surprisingly been found that certain boron promoters are particularly preferred. Therefore, the borate preferably used in the present invention contains trityl ion. Thus, the use of N, N-dimethylammonium tetrakis (pentafluorophenyl) borate and Ph is particularly recommended₃CB(PhF₅)₄And the like.

Suitable amounts of cocatalyst will be well known to the skilled person.

The molar ratio of boron to the metal ion of the metallocene may be in the range of 0.5:1mol/mol to 10:1mol/mol, preferably 1:1mol/mol to 10:1mol/mol, especially 1:1mol/mol to 5:1 mol/mol.

The molar ratio of Al in the aluminoxane to the metal ion of the metallocene may be in the range of 1:1mol/mol to 2000:1mol/mol, preferably 10:1mol/mol to 1000:1mol/mol, and more preferably 50:1mol/mol to 500:1 mol/mol.

Catalyst manufacture

As is well known in the art, the metallocene complexes of the present invention are used as catalysts for the polymerization of propylene in combination with suitable Al-containing and B-containing cocatalysts as defined above. Preferably, the polymerization of propylene is carried out in the condensed phase or in the gas phase.

The catalyst of the present invention may be used supported on an external support or support material. The particulate support material used is preferably an organic or inorganic material, for example silica, alumina or zirconia, or a mixed oxide, for example silica-alumina, in particular silica, alumina or silica-alumina. Preferably a silica support is used. The skilled person is aware of the steps required to support the metallocene catalyst.

It is particularly preferred that the support is a porous material so that the complex can be loaded into the pores of the support, for example using a method similar to that described in WO94/14856(Mobil), WO95/12622(Borealis) and WO 2006/097497. The particle size is not critical, but is preferably in the range of 5 μm to 200 μm, more preferably in the range of 20 μm to 80 μm. The use of such supports is conventional in the art.

In a preferred embodiment, no external support is used, but the catalyst is still present in the form of solid particles. Thus, no external support material is used, such as an inert organic or inorganic support, for example silica as described above.

To provide the catalyst of the invention in solid form without the use of an external carrier, it is preferred to use a liquid/liquid emulsion system. The process involves forming dispersed catalyst components (i) and (ii) in a solvent and solidifying the dispersed droplets to form solid particles.

In particular, the process involves preparing a solution of one or more catalyst components; dispersing the solution in a solvent to form an emulsion, wherein the one or more catalyst components are present in droplets of the dispersed phase; the catalyst components are immobilized in dispersed droplets in the absence of an external particulate porous support to form solid particles comprising the catalyst, and optionally recovering the particles.

The process enables the manufacture of active catalyst particles with improved morphology, for example with predetermined spherical, surface properties and particle size, and without the use of any added external porous support material, for example an inorganic oxide, for example silica. The term "preparing a solution of one or more catalyst components" means that the catalyst forming compounds can be combined in one solution that is dispersed in an immiscible solvent, or alternatively, for each portion of the catalyst forming compounds, at least two separate catalyst solutions can be prepared and then dispersed sequentially into the solvent.

In a preferred method of forming the catalyst, at least two separate solutions are prepared for each part or portion of the catalyst and then sequentially dispersed into immiscible solvents.

More preferably, a solution comprising the complex of the transition metal compound and the cocatalyst is combined with a solvent to form an emulsion, wherein the inert solvent forms a continuous liquid phase and the solution comprising the catalyst component forms a dispersed phase in the form of dispersed droplets (discontinuous phase). The droplets are then solidified to form solid catalyst particles, and the solid particles are separated from the liquid and optionally washed and/or dried. The solvent forming the continuous phase is immiscible with the catalyst solution at least under the conditions (e.g., temperature) used in the dispersing step.

The term "immiscible with the catalyst solution" means that the solvent (continuous phase) is completely immiscible or partially immiscible, i.e. not completely miscible with the dispersed phase solution.

Preferably, the solvent is inert with respect to the compounds of the catalyst system to be produced. The entire disclosure of the necessary methods can be found in WO03/051934, which is incorporated herein by reference.

The inert solvent must be chemically inert at least under the conditions (e.g., temperature) used in the dispersing step. Preferably, the solvent of the continuous phase does not contain any significant amount of catalyst-forming compounds dissolved therein. Thus, solid particles of catalyst are formed in the droplets by the compound originating from the dispersed phase (i.e. provided to the emulsion as a solution dispersed into the continuous phase).

The terms "fixed" and "cured" are used interchangeably herein for the same purpose, i.e., the formation of free-flowing solid catalyst particles in the absence of an external porous particle support (e.g., silica). Solidification thus takes place within the droplets. Said steps may be performed in various ways as disclosed in said WO 03/051934. Preferably, the curing is caused by an external stimulus (e.g., a change in temperature) to the emulsion system, thereby causing the curing. Thus, in said step, one or more catalyst components remain "fixed" within the formed solid particles. It is also possible that one or more catalyst components participate in the curing/fixing reaction.

Thus, solid, compositionally uniform particles having a predetermined particle size range can be obtained.

Further, the particle diameter of the catalyst particles of the present invention can be controlled by the size of the liquid droplets in the solution, and spherical particles having a uniform particle diameter distribution can be obtained.

The present invention is also industrially advantageous in that it enables the preparation of solid particles in a one-pot process. Continuous or semi-continuous processes may also be used to produce the catalyst.

Dispersed phase

The principle of preparing two-phase emulsion systems is known in the chemical art. Thus, in order to form a two-phase liquid system, at least in the dispersing step, the solution of the one or more catalyst components and the solvent used as the continuous liquid phase must be substantially immiscible. This can be achieved in a known manner, for example by selecting the temperatures of the two liquids and/or the dispersing/curing step accordingly.

A solvent may be used to form a solution of one or more catalyst components. The solvent is selected so as to dissolve the one or more catalyst components. The solvent may preferably be an organic solvent used in the art, including optionally substituted hydrocarbons, such as linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons, such as linear or cyclic alkanes, aromatic hydrocarbons and/or halogen-containing hydrocarbons.

Examples of aromatic hydrocarbons are toluene, benzene, ethylbenzene, propylbenzene, butylbenzene and xylenes. Toluene is the preferred solvent. The solution may comprise one or more solvents. Thus, such solvents may be used to facilitate emulsion formation and typically do not form part of the cured particles, but are removed with the continuous phase, e.g., after the curing step.

Alternatively, the solvent may participate in the solidification, for example, an inert hydrocarbon (wax) having a high melting point (e.g. above 40 ℃, suitably above 70 ℃, such as above 80 ℃ or above 90 ℃) may be used as the solvent for the dispersed phase to fix the catalyst compound within the formed droplets.

In another embodiment, the solvent is partially or completely composed of liquid monomers, such as liquid olefin monomers designed for polymerization in a "prepolymerization" fixing step.

Continuous phase

The solvent used to form the continuous liquid phase is a single solvent or a mixture of different solvents and may be immiscible with the solution of the catalyst components at least under the conditions (e.g., temperature) used in the dispersing step. Preferably, the solvent is inert with respect to the compound.

The term "inert with respect to the compound" means herein that the solvent of the continuous phase is chemically inert, i.e. does not chemically react with any of the components forming the catalyst. Thus, solid particles of catalyst are formed in the droplets by the compound originating from the dispersed phase (i.e. provided to the emulsion as a solution dispersed into the continuous phase).

Preferably the catalyst component used to form the solid catalyst will not be soluble in the solvent of the continuous liquid phase. Preferably, the catalyst component is substantially insoluble in the solvent forming the continuous phase.

The curing takes place substantially after the formation of the droplets, i.e. the curing takes place within the droplets, for example by causing a curing reaction between compounds present in the droplets. Furthermore, even if some curing agent is added separately to the system, it reacts in the droplet phase and the catalyst-forming components do not enter the continuous phase.

The term "emulsion" as used herein encompasses biphasic and multiphase systems.

In a preferred embodiment, the solvent forming the continuous phase is an inert solvent, including halogenated organic solvents or mixtures thereof, preferably fluorinated organic solvents, in particular semi-, highly or perfluorinated organic solvents and functionalized derivatives thereof. Examples of such solvents are semi-, highly-or perfluorinated hydrocarbons, such as alkanes, alkenes and cycloalkanes; ethers, such as perfluorinated ethers; and amines, particularly tertiary amines and functionalized derivatives thereof. Preferred are semi-, highly-or perfluorinated hydrocarbons, in particular perfluorinated hydrocarbons, such as C3-C30 (e.g. C4-C10) perfluorinated hydrocarbons. Specific examples of suitable perfluoroalkanes and perfluorocycloalkanes include perfluorohexane, perfluoroheptane, perfluorooctane, and perfluoro (methylcyclohexane). The semifluorinated hydrocarbons are in particular semifluorinated n-alkanes, such as perfluoroalkyl-alkanes.

"semi-fluorinated" hydrocarbons also include hydrocarbons in which blocks of-C-F and-C-H alternate. By "highly fluorinated" is meant that a majority of the-C-H units are replaced by-C-F units. "perfluorinated" means that all-C-H units have been replaced by-C-F units. See A.Enders and G.Maas in "Chemie in unser Zeit", 34.Jahrg.2000, Nr.6 and Pierandrea Lo nonstro in "Advances in Colloid and Interface Science", 56(1995) 245-.

Dispersing step

The emulsion may be formed by any means known in the art: the droplets are formed by mixing, for example by vigorously stirring the solution into the solvent forming the continuous phase, or by a mixing mill, or by ultrasound, or by using a solvent for preparing an emulsion by the so-called phase-change method, first a homogeneous system is formed, which is then converted into a two-phase system by changing the temperature of the system.

During the emulsion forming step and the curing step, the two-phase state is maintained, for example by suitable stirring.

In addition, it is preferred in a manner known in the artEmulsifiers/emulsion stabilizers are used to facilitate the formation and/or stabilization of the emulsion. For the above purpose, it is possible to use: for example surfactants, such as a class based on hydrocarbons (including polymeric hydrocarbons having a molecular weight of, for example, up to 10000 and optionally interrupted by one or more heteroatoms), preferably halogenated hydrocarbons, such as semifluorinated or highly fluorinated hydrocarbons optionally having functional groups, for example selected from-OH, -SH, NH₂、NR"₂、-COOH、-COONH₂Olefin oxide, -CR ═ CH₂Where R' is hydrogen or C1-C20 alkyl, C2-20-alkenyl or C2-20-alkynyl, oxo, cyclic ether and/or any reactive derivative of these groups, such as alkoxy or carboxylic acid alkyl ester groups, or semi-, highly or perfluorinated hydrocarbons, preferably with functionalized end groups, may be used. Surfactants may be added to the catalyst solution to form the dispersed phase of the emulsion to facilitate formation of the emulsion and stabilize the emulsion.

Alternatively, the emulsification and/or emulsion stabilization aid may also be formed by reacting a surfactant precursor bearing at least one functional group with a compound that reacts with the functional group and is present in the catalyst solution or solvent that forms the continuous phase. The reaction product obtained acts as the actual emulsification aid and/or stabilizer in the formed emulsion system.

Examples of surfactant precursors that can be used to form the reaction product include, for example, known surfactants bearing at least one functional group, for example selected from the group consisting of-OH, -SH, NH₂、NR"₂、-COOH、-COONH₂Olefin oxide, -CR ═ CH₂Wherein R' is hydrogen or C1-C20 alkyl, C2-20-alkenyl or C2-20-alkynyl, oxo, cyclic ether having 3 to 5 ring atoms and/or any reactive derivative of these groups, for example alkoxy or carboxylic acid alkyl ester groups; such as semi-, highly-or perfluorinated hydrocarbons bearing one or more of the above-mentioned functional groups. Preferably, the surfactant precursor has a terminal functional group as defined above.

The compound that reacts with such a surfactant precursor is preferably contained in the catalyst solution and may be an additional additive or one or more catalyst-forming compounds. Such compounds are, for example, compounds of group 13 (e.g. MAO and/or aluminum alkyl compounds and/or transition metal compounds).

If a surfactant precursor is used, it is preferred to react the surfactant precursor with the compounds of the catalyst solution prior to adding the transition metal compound. In one embodiment, for example, a highly fluorinated C1-n (suitably C4-30-or C5-15) alcohol (e.g., a highly fluorinated heptanol, octanol, or nonanol), oxide (e.g., propylene oxide), or acrylate is reacted with a co-catalyst to form the "actual" surfactant. Then, an additional amount of the cocatalyst and the transition metal compound are added to the solution, and the obtained solution is dispersed in a solvent forming a continuous phase. The "actual" surfactant solution may be prepared prior to the dispersing step or in the dispersion. If the solution is prepared prior to the dispersion step, the prepared "actual" surfactant solution and transition metal solution may be dispersed sequentially (e.g., surfactant solution first) into the immiscible solvent or combined together prior to the dispersion step.

Curing

The solidification of the one or more catalyst components in the dispersed droplets may be carried out in various ways, for example by causing or accelerating the formation of said solid catalyst-forming reaction products of the compounds present in the droplets. This may be achieved with or without an external stimulus (e.g., a change in temperature of the system), depending on the compound used and/or the desired cure rate.

In a particularly preferred embodiment, after the emulsion system has been formed, curing is carried out by subjecting the system to an external stimulus, for example a change in temperature. The temperature difference is, for example, from 5 ℃ to 100 ℃, e.g., from 10 ℃ to 100 ℃, or from 20 ℃ to 90 ℃, e.g., from 50 ℃ to 90 ℃.

The emulsion system can be subjected to rapid temperature changes to cause rapid solidification in the dispersion. The dispersed phase may be subjected to a transient (milliseconds to seconds) temperature change, for example, to achieve an instantaneous solidification of one or more components within the droplet. The appropriate temperature change required for the desired cure rate of the components (i.e. the increase or decrease in the temperature of the emulsion system) is not restricted to any particular range, but naturally depends on the emulsion system, i.e. on the compounds used and their concentration/ratio, and on the solvent used, and is selected accordingly. It will also be apparent that any technique may be used to provide sufficient heating or cooling effect to the dispersed system to cause the desired solidification.

In one embodiment, the heating effect or cooling effect (e.g. as described above) is obtained by bringing an emulsion system having a temperature into an inert receiving medium having a temperature that differs significantly, whereby said temperature change of the emulsion system is sufficient to cause a fast solidification of the droplets. The receiving medium may be gaseous (e.g., air), or a liquid, preferably a solvent, or a mixture of two or more solvents, wherein one or more of the catalyst components are immiscible and inert with respect to the catalyst components. For example, the receiving medium comprises the same immiscible solvent used as the continuous phase in the first emulsion forming step.

The solvent may be used alone or in admixture with other solvents (e.g., aliphatic or aromatic hydrocarbons, such as alkanes). Preferably, a fluorinated solvent is used as receiving medium, which may be the same as the continuous phase in the emulsion formation, e.g. a perfluorinated hydrocarbon.

Alternatively, the temperature difference may be achieved by stepwise heating of the emulsion system, e.g. up to 10 ℃ per minute, preferably from 0.5 ℃ to 6 ℃ per minute, more preferably from 1 ℃ to 5 ℃ per minute.

If a melt of, for example, a hydrocarbon solvent is used to form the dispersed phase, solidification of the droplets can be achieved by cooling the system using the temperature difference described above.

Preferably, the "single phase" change that can be used to form the emulsion can also be used to solidify the catalytically active content within the droplets of the emulsion system by again causing a temperature change in the dispersion, whereby the solvent used in the droplets becomes miscible with the continuous phase (preferably the fluorine-containing continuous phase as defined above), so that the droplets become devoid of solvent and the solidifying components remaining in the "droplets" start to solidify. Thus, the immiscibility can be adjusted with respect to the solvent and conditions (temperature) to control the curing step.

For example, miscibility of organic solvents and fluorine-containing solvents can be found in the literature and selected accordingly by the skilled person. The critical temperature required for the phase transition can also be obtained from the literature or can be determined using methods known in the art, such as Hildebrand-Scatchard-Theorie. Reference is also made to the above cited articles of a.orders and g. and Pierandrea Lo Nostro.

Thus, according to the invention, all or only a part of the droplets may be converted into a solid form. The size of the "solidified" droplets may be smaller or larger than the size of the original droplets, for example if the amount of monomer used for the prepolymerization is relatively large.

After the optional washing step, the recovered solid catalyst particles can be used in the polymerization process of propylene. Alternatively, the isolated and optionally washed solid particles may be dried to remove any solvent present in the particles prior to use in the polymerization step. The isolation and optional washing steps can be carried out in a known manner, for example by filtration, followed by washing of the solid with a suitable solvent.

The droplet shape of the particles may be substantially maintained. The particles formed may have an average size in the range 1 μm to 500 μm, for example 5 μm to 500 μm, advantageously 5 μm to 200 μm or 10 μm to 150 μm. Even an average size range of 5 μm to 60 μm is possible. The size may be selected according to the polymerization for which the catalyst is to be used. Advantageously, the particles are substantially spherical in shape, they have a low porosity and a low surface area.

The formation of the solution may be carried out at a temperature of from 0 ℃ to 100 ℃, for example from 20 ℃ to 80 ℃. The dispersing step may be carried out at-20 ℃ to 100 ℃, for example at about-10 ℃ to 70 ℃, for example at-5 ℃ to 30 ℃, for example at about 0 ℃.

An emulsifier as defined above may be added to the obtained dispersion to improve/stabilize droplet formation. The solidification of the catalyst component in the droplets is preferably carried out by increasing the temperature of the mixture, for example gradually from a temperature of 0 ℃ to 100 ℃, for example gradually to 60-90 ℃. For example in the range of 1 minute to 180 minutes, for example 1 to 90 minutes or 5 to 30 minutes, or with rapid heat exchange. The heating time depends on the size of the reactor.

During the curing step, preferably curing is carried out at about 60 ℃ to 100 ℃, preferably at about 75 to 95 ℃ (below the boiling point of the solvent), the solvent may preferably be removed, and the solid is optionally washed with a wash solution, which may be any solvent or solvent mixture, such as those defined above and/or used in the art, preferably a hydrocarbon, such as pentane, hexane or heptane, suitably heptane. The washed catalyst may be dried or may be slurried into an oil and used as a catalyst-oil slurry in the polymerization process.

All or part of the preparation steps may be carried out in a continuous manner. Reference is made to WO2006/069733, which describes the principle of a continuous or semi-continuous preparation method of solid catalyst types prepared via an emulsion/solidification method.

Catalyst off-line prepolymerization

As a disadvantage, the use of heterogeneous catalysts (also referred to as "self-supporting" catalysts) without an external support material may to some extent have a tendency to dissolve in the polymerization medium, i.e. some active catalyst components may leach out of the catalyst particles during slurry polymerization, thereby losing the original good morphology of the catalyst. These leached catalyst components are very active and may cause problems during the polymerization. Thus, the amount of leaching components should be minimized, i.e. all catalyst components should be kept in heterogeneous form.

Furthermore, due to the large amount of catalytically active species in the catalyst system, the self-supporting catalyst generates high temperatures at the start of the polymerization, which may lead to melting of the product material. Both of these effects, partial dissolution of the catalyst system and heat generation, can cause fouling, sheeting and deterioration of the morphology of the polymer material.

To minimize possible problems associated with high activity or leaching, the catalyst may be "prepolymerized" off-line prior to its use in the polymerization process.

It has to be noted in this connection that the off-line prepolymerization is part of the catalyst preparation process and is a step carried out after the formation of the solid catalyst. The catalyst off-line prepolymerization step is not part of the actual polymerization process configuration including a prepolymerization step. After the catalyst off-line prepolymerization step, the solid catalyst can be used for polymerization.

The "off-line prepolymerization" of the catalyst takes place after the solidification step of the liquid-liquid emulsion process. The pre-polymerisation may be carried out by known methods described in the art, for example as described in WO 2010/052263, WO 2010/052260 or WO 2010/052264. Preferred embodiments of this aspect of the invention are described herein.

As monomer in the off-line catalyst prepolymerization step, preferably an alpha-olefin is used. Preference is given to using C₂-C₁₀Olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, styrene and vinylcyclohexene. The most preferred alpha-olefins are ethylene and propylene, especially propylene.

The off-line catalyst prepolymerization can be carried out in the gas phase or in an inert diluent, typically an oil or a fluorinated hydrocarbon, preferably a fluorinated hydrocarbon or a mixture of fluorinated hydrocarbons. Perfluorinated hydrocarbons are preferably used. The melting point of such (per) fluorinated hydrocarbons is generally in the range of from 0 ℃ to 140 ℃, preferably in the range of from 30 ℃ to 120 ℃, for example from 50 ℃ to 110 ℃.

When the off-line prepolymerization of the catalyst is carried out in a fluorinated hydrocarbon, the temperature of the prepolymerization step is below 70 ℃, for example in the range-30 to 70 ℃, preferably 0 ℃ to 65 ℃, more preferably in the range 20 ℃ to 55 ℃. The pressure within the reaction vessel is preferably above atmospheric pressure to minimize the likelihood that air and/or moisture will eventually penetrate the catalyst vessel. Preferably, the pressure is in the range of at least 1 bar to 15 bar, preferably 2 bar to 10 bar. The reaction vessel is preferably maintained under an inert atmosphere, for example under nitrogen or argon or similar atmosphere.

The off-line prepolymerization is continued until the desired degree of prepolymerization, defined as the weight of the polymer matrix/weight of the solid catalyst before the prepolymerization step, is reached. The degree of preliminary polymerization is less than 25, preferably from 0.5 to 10.0, more preferably from 1.0 to 8.0, most preferably from 2.0 to 6.0.

The use of an off-line catalyst pre-polymerization step provides the advantage of minimizing catalyst component leaching and thus local overheating.

After off-line prepolymerization, the catalyst can be isolated and stored.

Polymerisation

The catalysts according to the invention are particularly suitable for forming propylene homopolymers and propylene copolymers, for example propylene copolymers with ethylene or C4 to C10 alpha-olefins and mixtures thereof, for example propylene random copolymers with ethylene, however, especially propylene homopolymers and propylene heterophasic copolymers.

The polymerization in the process of the present invention may be carried out in one or more (e.g. 1,2 or 3) polymerization reactors, e.g. a combination of a slurry reactor and at least one gas phase reactor, using conventional polymerization techniques (e.g. gas phase, slurry or bulk polymerization or combinations thereof). Heterophasic propylene polymers are usually produced in a reactor configuration comprising a slurry reactor and two gas phase reactors.

In the case of propylene polymerisation, the reaction temperature will typically be in the range 60 ℃ to 110 ℃ (e.g. 60 ℃ to 90 ℃) for a slurry reactor, the reactor pressure will typically be in the range 5 bar to 80 bar (e.g. 20 bar to 60 bar) and the residence time will typically be in the range 0.1 hour to 5 hours (e.g. 0.3 hour to 2 hours). Monomers are generally used as the reaction medium.

For gas phase reactors, the reaction temperature used will typically be in the range of 60 ℃ to 115 ℃ (e.g., 70 ℃ to 110 ℃), the reactor pressure will typically be in the range of 10 bar to 25 bar, and the residence time will typically be 0.5 hours to 8 hours (e.g., 0.5 hours to 4 hours). The gas used will be a monomer, optionally in admixture with a non-reactive gas such as nitrogen or propane. In addition to the actual polymerization step and reactor, the process may also comprise any other polymerization step, such as a prepolymerization step, as well as any other post-reactor treatment step known in the art.

Generally, the amount of catalyst used will depend on the nature of the catalyst, the type and conditions of the reactor, and the desired properties of the polymer product. As is well known in the art, hydrogen can be used to control the molecular weight of the polymer.

The metallocene catalysts of the present invention have good catalyst activity and are capable of providing polymers of high molecular weight Mw (as indicated by low melt flow rate) and high melting temperature.

The polymers obtained with the metallocenes of the invention have a normal particle morphology.

It is understood that the catalyst may be prepolymerized prior to the actual polymerization step, as is known in the art.

Polymer and method of making same

It is a feature of the present invention that the claimed catalyst is capable of forming high molecular weight polymers. These characteristics can be achieved at industrially relevant polymerization temperatures (e.g., 60 ℃ or higher). A preferred feature of the invention is that the catalyst of the invention is used to polymerize propylene at a temperature of at least 60 ℃, preferably at least 65 ℃, for example at least 70 ℃.

Polypropylene homopolymer

Depending on the use and the amount of hydrogen used as Mw regulator, the polypropylene homopolymer produced from the catalyst of the present invention can be produced with Mw (weight average molecular weight) values in the range of 40kg/mol to 2000kg/mol, preferably in the range of 50kg/mol to 1500 kg/mol. The catalysts of the present invention are capable of forming polypropylene homopolymers having a high melting point. In a preferred embodiment, the propylene homopolymer formed by the process of the present invention has a melting point of greater than 157 ℃, preferably greater than 158 ℃, or even 159 ℃ or higher.

Propylene-ethylene copolymer

Depending on the amount and/or use of the comonomer content and the amount of hydrogen used as Mw regulator, the propylene-ethylene copolymers prepared from the metallocenes of the present invention can be prepared with Mw values in the range of 40kg/mol to 2000kg/mol, preferably in the range of 50kg/mol to 1500 kg/mol.

It is known that for a given rubber, the co-polymerThe comonomer composition, tensile and impact properties of the heterophasic PP/EPR reactor blend (polypropylene/ethylene-propylene rubber) can be improved by increasing the molecular weight of the rubber phase. Typically, metallocene catalysts produce hPP with a relatively low hPP matrix T_mTypically below 157 ℃ or even well below 154 ℃. It is known that the higher T_mWhich contributes to the rigidity of the material.

The metallocene catalysts of the invention having Hf as the transition metal as defined in the claims produce EPR with higher molecular weight in the gas phase (as measured, iv (EPR))>2dL/g) and produces a homopolymer polypropylene matrix having a higher melting point, e.g. T_mAt least 157 ℃.

Catalysts based on these new metallocenes have very high activity and long lifetime, allowing the production of multi-reactor blend compositions. The relatively high molecular weight of the rubber phase allows the use of hydrogen to increase gas phase activity and fine tune blending properties.

The polymers produced from the catalysts of the present invention can be used in a variety of end-use articles, such as pipes, films (cast, blown or BOPP films, e.g., BOPP for capacitor films), fibers, molded articles (e.g., injection molded articles, blow molded articles, rotomolded articles), extrusion coatings, and the like.

The invention will now be illustrated with reference to the following non-limiting examples and figures.

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