WO2004087316A1

WO2004087316A1 - Transition metal catalysts and use thereof for homopolymerizing vinyl esters

Info

Publication number: WO2004087316A1
Application number: PCT/EP2004/003490
Authority: WO
Inventors: Jörg Ludwig SCHULTE; Jörg SCHOTTEK; Tim Dickner
Original assignee: Celanese Ventures Gmbh
Priority date: 2003-04-02
Filing date: 2004-04-02
Publication date: 2004-10-14
Also published as: DE10314993A1

Abstract

The invention relates to novel transition metal compounds, a method for the production thereof, the use thereof for polymerizing and copolymerizing vinyl esters, and the production of poly(vinyl alcohol) copolymers.

Description

TRANSITION METAL CATALYSTS AND THEIR USE FOR THE HOMOPOLYMERIZATION OF VINYL ESTERS

Transition metal catalysts, processes for their preparation and their use for the homo- and copolymerization of vinyl esters; Poly (vinyl esters), poly (vinyl alcohols); Poly (vinyl ester) copolymers, poly (vinyl alcohol) copolymers

The present invention relates to a process for the preparation of special transition metal compounds, new transition metal compounds and their use for the polymerization and copolymerization of vinyl esters and the production of poly (vinyl alcohol) copolymers.

Vinyl esters are olefinic compounds with the following basic structure.

Representatives of this class of compounds are, for example, vinyl acetate (R = CH ₃ ), benzoic acid vinyl ester (R = Ph), vinyl formate (R = H), vinyl propionate (R = C ₂ H ₅ ), pivalic acid vinyl ester (R = ffiu), vinyl hexanoate ( R = C ₅ Hn), vinyl laurate (R = CnH ₂₃ ). Polyvinyl esters are polymers accessible by olefinic polymerization from vinyl esters, of which the polyvinyl acetates have by far the greatest technical importance.

Polyvinyl acetate is an important thermoplastic polymer and is used, among other things, as an adhesive (component), paint raw material, for packaging films, for the coating of paper and food (sausage and cheese coatings), as an additive for concrete and as a raw material for the production of polyvinyl alcohols and polyvinyl acetals used (Römpp Lexikon Chemie - Version 2.0, Stuttgart / New

York: Georg Thieme Verlag 1999).

In the art, polyvinyl acetate is produced by free radical polymerizations, the polymerization being able to be carried out in solution, in bulk and in emulsion. Mainly serve as radical initiators Azoisobutyronitrile and dibenzoyl peroxide (AIBN / BPO). Since these radical polymerization proceed rapidly and uncontrollably, a stereodifferentiation is ruled out and control the molecular weight and molecular weight distribution very difficult (W. Daniels in. Kirk-Othmer encycl Chem Technol, ^3rd Ed 1983, 23, 817-... 847).

Because of the restriction to radical polymerization of vinyl acetate, it has not yet been possible to synthesize polyvinyl acetates in a stereospecific manner with a narrow molecular weight distribution. Polymers with special stereochemistry based on other monomers find their special

Properties, for example, applications as substitutes for more expensive polymers or more complicated polymer blends.

In contrast to free radical polymerization, the transition metal-catalyzed insertion polymerization enables so-called

Metallocene or post-metallocene synthesis of stereospecific polymers having a narrow molecular weight distribution (W. Kaminsky in Ullmann's Encyclopedia of Industrial Chemistry, 6 ^th Ed., 2002 Electronic Release, Wiley / VCH). This method has been used successfully for many mostly simple α-olefins. With this method, the use of polar monomers has hitherto been restricted to a few acrylates (WO0121670). However, the polymerization of vinyl acetate by a transition metal-catalyzed insertion polymerization with metallocenes or post-metallocenes has so far not been possible.

Polymerization of vinyl acetate has been described in the literature for a chromium complex with imido ligands (Kölling, L. Dissertation 2001, Bielefeld University, 79.), however an atactic polymer is obtained.

Surprisingly, it has now been found that the transition metal catalysts according to the invention can stereospecifically homo- and copolymerize vinyl acetate. The present invention relates to compounds of the formula I.

Formula I.

wherein:

M ^{1 is} a transition metal of the 5th to 8th group of the Periodic Table of the Elements, the oxidation state of which is not zero, in particular V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co, Rh, Ni or Pd , and Y ^{1 is} a bridging structural element between the donor atoms D ¹ and is a C ₂ -C 10 carbon bridge, which is defined by R ⁴ _e , and D ^{1 is} identical or different and a donor atom of the 15th to 16th Group of the Periodic Table of the Elements, in particular N, P, As, O, S, Se and Te, and R ^{1 are} identical or different and are a hydrogen atom, a Ci - C ₂ o-

Alkyl group, a C - C ₂ o-alkylaryl group, a C ₂ - C ₂ o-alkenyl group, C ₂

- C o-alkynyl group or a halogen-containing Ci - C ₂ o-alkyl group, a C ₇

- C ₂₀ alkylaryl group, a C ₂ - C ₂₀ alkenyl group, C ₂ - C ₂ o alkynyl group or a heteroatom-containing Ci - C ₂₀ alkyl group, a C ₇ - C ₂ o - alkylaryl group, a C ₂ - C ₂₀ - Alkenyl group, C ₂ - C ₂ o -alkynyl group, and R ^{2 are} identical or different and a hydrogen atom, a halogen atom, a Ci - C ₂ o -alkyl group, a C ₇ - C ₂₀ -alkylaryl group, a C ₂ - C ₂₀ - Alkenyl group, C ₂ - C ₂₀ alkynyl group or a halogen-containing Ci - C ₂₀ alkyl group, a C ₇ - C ₂ o alkylaryl group, a C ₂ - C ₂₀ alkenyl group, C ₂

- C ₂ o-alkynyl group or a hetero atom-containing Ci - C ₂ o-alkyl group, a C ₇ - C ₂ o alkylaryl group, a C ₂ - C ₂₀ alkenyl, C ₂ - C ₂₀ - alkynyl group, and R ³ are identical or different and are a hydrogen atom, a Ci - C ₂ o -

Alkyl group, a Cβ - C2o aryl group, a C ₇ - C ₂ o alkylaryl group, a C ₇ - C ₃ o arylalkyl group, a C ₂ - C ₂ o alkenyl group, C ₂ - C ₂ o -

Alkynyl group or a halogen-containing Ci - C ₂ o - alkyl group, a C ₆ - C20 aryl group, a C ₇ - C ₂ o alkylaryl group, a C - C ₃₀ arylalkyl group, a C ₂ - C ₂ o alkenyl group, C ₂ - C ₂ o -alkynyl group or a heteroatom-containing Ci - C ₂₀ - alkyl group, a C ₆ - C ₂ o -aryl group, a C - C ₂ o -alkylaryl group, a C - C ₃ o -arylalkyl group, a C ₂ - C ₂ o -

Alkenyl group, C ₂ - C ₂₀ alkynyl group, and R ^{4 are the} same or different and a hydrogen atom, a Ci - C ₂₀ -

Alkyl group, a C ₆ - C ₂ o aryl group, a C - C ₂₀ alkylaryl group, a C - C ₃ o arylalkyl group, a C ₂ - C ₂ o alkenyl group, C ₂ - C ₂ o alkynyl group or a halogen-containing group Ci - C ₂₀ - alkyl group, a Cβ - C20 -

Aryl group, a C ₇ - C ₂₀ alkylaryl group, a C ₇ - C ₃₀ arylalkyl group, a C ₂ - C ₂ o alkenyl group, C ₂ - C ₂ o alkynyl group or a heteroatom-containing C ₁ -C ₂₀ alkyl group, a CQ - C ₂ o aryl group, a C

- C ₂₀ alkylaryl group, a C ₇ - C ₃ o arylalkyl group, a C ₂ - C ₂₀ alkenyl group, C ₂ - C ₂₀ alkynyl group, where several R ⁴ radicals can form a mono- or polycyclic ring system with one another, and R ^{5 are the} same or different and represent a hydrogen atom, a Ci - C ₂ o -

Alkyl group, a C ₆ - C ₂ o aryl group, a C - C ₂₀ alkylaryl group, a C ₇ - C ₃₀ arylalkyl group, a C ₂ - C ₂ o alkenyl group, C ₂ - C ₂ o alkynyl group or a halogen-containing group Ci - C ₂ o - alkyl group, a C ₆ - C ₀ -

Aryl group, a C ₇ - C ₂₀ alkylaryl group, a C ₇ - C ₃ o arylalkyl group, a C ₂ - C ₂₀ alkenyl group, C ₂ - C ₂ o alkynyl group or a heteroatom-containing Ci - C ₂₀ alkyl group, a CQ - C ₂₀ aryl group, a C ₇

- C ₂ o alkylaryl group, a C ₇ - C ₂ o means alkynyl group, and b each are the same or different and are whole natural numbers of 1 - ₃ o C arylalkyl group, a C ₂ - C o - alkenyl, C ₂ to

2 and c are the same or different and an integer from 0 to

2 mean and are each the same or different and an integer from 0 to

2 mean, and are each the same or different and an integer from 2 to

20 and are each the same or different and an integer from 0 to

2 mean and

Illustrative but non-limiting examples of bridging structural elements D ¹ -γ ¹ (R ⁴ ) _e -D ¹ are:

M b II d

ιι j II k

M m II n

M o II p II q

Formula II a - r wherein: R ⁶ in formula IR corresponds to ⁴ and are identical or different and a hydrogen atom, a Ci - C ₂ o alkyl group, a CQ - C ₂ o aryl group, a C ₇ - C ₂ o alkylaryl group , a C ₇ - C ₃ o arylalkyl group, a C ₂ - C ₂ o alkenyl group, C ₂ - C ₂ o alkynyl group or a halogen-containing Ci - C ₂ o alkyl group, a C ₆ - C ₂ o aryl group, a C ₇ - C ₂ o alkylaryl group, a C - C ₃₀ arylalkyl group, a C ₂ - C ₂₀ alkenyl, C ₂ - C ₂₀ - alkynyl group or a heteroatom-containing Ci - C ₂₀ - alkyl group, a C ₆ - C ₂₀ Aryl group, a C - C ₂ o alkylaryl group, a C ₇ - C ₃ o arylalkyl group, a C ₂ - C ₂ o alkenyl group, C ₂ - C ₂₀ alkynyl group means, where several radicals R ⁶ can form a mono- or polycyclic ring system with each other, and are each the same or different and mean an integer from 0 to 20.

Transition metal compounds of the formula I or formula II are preferred in those

M ^{1 is} a transition metal of the 5th to 8th group of the Periodic Table of the Elements, the oxidation state of which is not zero, in particular V, Ta, Cr, Mo or W, and

D ^{1 is the} same or different and is a donor atom of the 15th to 16th group of the Periodic Table of the Elements, in particular N, P and S, and

Y ^{1 is} a bridging structural element between the two donor atoms D1, in particular formula II a - r, and

R ^{1 is the} same or different and is a hydrogen atom, a Ci-do-alkyl group, a C -Cn-alkylaryl group, a C ₂ -Cιo-alkenyl group, a C ₂ -Cιo-alkynyl group or a halogen-containing a Crdo-alkyl group, a C ₇ -Cn-alkylaryl group, a C ₂ -Cι ₀ -alkenyl group, a C ₂ -Cιo-alkynyl group or a heteroatom-containing one -C-C-ι ₀ -alkyl group, a C ₇ -Cn-alkylaryl group, a C ₂ -Cιo-alkenyl group, is a C ₂ -C ₀ alkynyl group, and

R ^{2 is the} same or different and is a hydrogen atom, chlorine, bromine, a Ci-C-io-alkyl group, a C ₇ -Cn alkylaryl group, a C ₂ -Cι ₀ alkenyl group, a C ₂ -Cι ₀ alkynyl group or one halogen-containing a CiC-io-alkyl group, a C ₇ -Cn-alkylaryl group, a C ₂ -Cι ₀ -alkenyl group, a C ₂ -Cι ₀ -alkynyl group or a heteroatom-containing a CiC-io-alkyl group, a C -Cn-alkylaryl group, is a C ₂ -C ₀ alkenyl group, a C ₂ -Cι ₀ alkynyl group, and

R ^{3 is the} same or different and is a hydrogen atom, a CiC-io-alkyl group, a Cß-Cio-aryl group, a C ₇ -Cιralkylaryl group, a C ₇ -Cn-

Arylalkyl group, a C ₂ -Cι ₀ alkenyl group, a C ₂ -Cιo alkynyl group or a halogen-containing a CiC-io-alkyl group, a C6-C ₁₀ aryl group, a C ₇ - Cn-alkylaryl group, a C -Cn-arylalkyl group , a C ₂ -Cιo alkenyl group, a C ₂ -Cιo alkynyl group or a heteroatom-containing one C-1-C10- Alkyl group, a C ₆ -Cιo-aryl group, a C ₇ -Cι rAlkylarylgruppe, a C ₇ - C 11 arylalkyl group, a C ₂ -Cιo alkenyl group, a C ₂ -Cι represents ₀ alkynyl group, and R ^{4 are} identical or are different and a hydrogen atom, a C ₁ -C ₁ alkyl group, a C ₆ -C 1o aryl group, a C ₇ -Cn alkylaryl group, a C ₇ -

Cn-arylalkyl group, a C ₂ -Cιo-alkenyl group, a C ₂ -Cιo-alkynyl group or a halogen-containing one CiCn-alkyl group, a C ₆ -Cι ₀ -aryl group, a C ₇ -Cn-alkylaryl group, a C ₇ -Cn- Arylalkyl group, a C ₂ -Cιo alkenyl group, a C ₂ -Cιo alkynyl group or a heteroatom-containing one CiCn-alkyl group, a C ₆ -Cι ₀ aryl group, a C ₇ -Cn alkylaryl group, a

C -Cι-arylalkyl group, a C ₂ -Cι ₀ alkenyl group, a C ₂ -C ιo alkynyl group, where several radicals R ⁴ can form a mono- or polycyclic ring system with one another, and R ^{5 is the} same or different and one Hydrogen atom, a CiC-io-alkyl group, a Cβ-Cio-aryl group, a C ₇ -Cιι alkylaryl group, a C ₇ -Cn-

Arylalkyl group, a C ₂ -Cι ₀ alkenyl group, a C ₂ -Cιo alkynyl group or a halogen-containing a CrCio alkyl group, a C ₆ -Cιo aryl group, a C ₇ - Cn alkylaryl group, a C -Cn arylalkyl group, one C ₂ -C 10 alkenyl group, a C ₂ -C ₀ alkynyl group or a hetero atom-containing one CICI O alkyl group, a C ₆ -C ₀ aryl group, a C ₇ -Cn alkylaryl group, a C ₇ -

Cn-arylalkyl group, a C ₂ -Cι ₀ alkenyl group, a C ₂ -Cιo alkynyl group, and R ^{6 is the} same or different and a hydrogen atom, a Cι -Cι ₀ alkyl group, a C ₆ -Cιo aryl group, a C7-Cn-alkylaryl group, a C ₇ -Cn-arylalkyl group, a C ₂ -Cιo-alkenyl group, a C ₂ -Cι ₀ -alkynyl group or a halogen-containing one CiC-io-alkyl group, a C ₆ -Cι ₀ -aryl group, a C ₇ - Cn alkylaryl group, a C ₇ -Cn arylalkyl group, a C ₂ -Cι ₀ alkenyl group, a C ₂ -Cιo alkynyl group or a heteroatom-containing C1-C-10-alkyl group, a C ₆ -Cι ₀ - aryl group, a C ₇ --CN alkylaryl group, a C - Cn-arylalkyl group, a C ₂ -Cιo alkenyl group, a C ₂ -Cιo alkynyl group, and b are the same or different and a whole natural number from 1 to 2 mean and c are the same or different and are an integer from 0 to

2 and d are the same or different and an integer from 0 to

2 and e are the same or different and an integer from 2 to

20 and f are the same or different and an integer from 0 to

2 and i are the same or different and are an integer from 0 to 24.

Compounds of the formula I in which

M ^{1 is} a transition metal of the 5th to 8th group of the Periodic Table of the Elements, the oxidation state of which is not zero, in particular Cr, Mo or W, and

D ^{1 is the} same or different and a donor atom of the 15th to 16th group of the

Periodic table of the elements, in particular N and P, and Y ¹ corresponds to the formulas Na, IIh, IM or m, and

R ^{1 is the} same or different and represents a hydrogen atom, methyl, ethyl, propyl, i-propyl, tert-butyl, n-butyl or benzyl, and

R ^{2 is the} same or different and is a hydrogen atom, chlorine, methyl, ethyl,

Propyl, i-propyl, tert-butyl, n-butyl or benzyl, and R ^{3 is the} same or different and is a hydrogen atom, methyl, ethyl, propyl, i-

Propyl, tert-butyl, n-butyl or benzyl, and R ^{4 is the} same or different and is a hydrogen atom, methyl, ethyl, propyl, i-

Propyl, tert-butyl, n-butyl, phenyl or benzyl means, with several radicals

R ⁴ can form a mono- or polycyclic ring system with one another, and R ^{5 is} identical or different and denotes a hydrogen atom, methyl, ethyl, propyl, i-propyl, tert-butyl, n-butyl or benzyl, and

R ^{6 is the} same or different and is a hydrogen atom, fluorine, chlorine, bromine, iodine,

Methyl. Is ethyl, propyl, i-propyl, tert-butyl, n-butyl, phenyl or benzyl, and b are each the same or different and mean 1 or 2, and c are the same or different and are an integer from 0 to

2 and d are the same or different and an integer from 0 to

2 and e are the same or different and an integer from 2 to

20 and f are the same or different and an integer from 0 to

2 and i are the same or different and an integer from 0 to

18 mean.

Illustrative but non-limiting examples of compounds of formula I are:

A further component of the invention are compounds in which the phenyl radical “Ph” is the same or different and can be, for example, tolyl or methoxyphenyl, a fluorinated phenyl or an oxyphenyl group or another substituted aromatic radical which may be substituted, as well as compounds in which the methyl radical "Me" is the same or different and can be, for example, an ethyl, propyl, i-propyl, tert-butyl, n-butyl or other alkyl group.

In the context of the present invention, C ₁ -C ₂ -alkyl group, particularly preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl understood, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl or cyclooctyl.

In the context of the present invention, a C ₂ -C ₂₀ alkenyl group, particularly preferably ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, octenyl or cyclooctenyl, is understood. In the context of the present invention, a C ₂ -C ₂ o -alkynyl group, particularly preferably ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl, is understood.

In the present invention, a C ₆ -C ₂ o-aryl group, particularly preferably benzylidene, o-methoxybenzylidene, 2,6-dimethylbenzylidene, phenyl, biphenyl, naphthyl, anthracenyl, triphenylenyl, [1, ^1, 3 ' , 1 "] Terphenyl-2 ^, -yl, binaphthyl or phenanthrenyl, understood.

In the context of the present invention, a C ₇ -C ₂ o-alkylaryl group, particularly preferably benzyl, ethylphenyl, propylphenyl, diphenylmethyl, triphenylmethyl or naphthalinylmethyl, is understood.

In the context of the present invention, a C ₇ -C ₃ o-arylalkyl group, particularly preferably o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di- i-propylphenyl, 2,6-di-t-butylphenyl, ot-butylphenyl, mt-butylphenyl, pt-butylphenyl, 2,4,6-triisopropylphenyl or 2,4,6-trimethylphenyl.

In the context of the present invention, a halogenated C1-C20-alkyl group means in particular a Ci-C ₂ o-fluoroalkyl group, particularly preferably trifluoromethyl, pentafluoroethyl or 2,2,2-trifluoroethyl.

In the context of the present invention, halogenated C6-C ₂ o

Aryl group, in particular _C6-C20 -Fluoraryl, more preferably pentafluorophenyl, 3,5-Bisthfluoromethylphenyl, Pentafluorobenzyliden, 3,5- Bistrifluoromethylbenzyliden, tetrafluorophenyl or Heptafluoronaphthyl,

In the context of the present invention, a C ₅ -C 20 heteroaryl, particularly preferably 2-pyridyl, 3-pyridyl, 4-pyridyl, quinolinyl, isoquinolinyl, acridinyl, benzoquinolinyl or benzoisoquinolinyl, C -C ₂ o-heterocycloalkyl, particularly preferably furyl , Benzofuryl, 2-pyrolidinyl, 2-indolyl, 3-indolyl, 2,3-dihydroindolyl, understood. In the context of the present invention, a hetero atom-containing C ₁ -C ₂ -alkyl group also contains C ₁ -C ₂ -alkoxy, particularly preferably methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy or t-butoxy understood.

In the context of the present invention, a heteroatom-containing Cβ-C ₂ o -aryl group also means C ₆ -C ₂ o -aryloxy, particularly preferably phenoxy, naphthoxy, biphenyloxy, anthracenyloxy, phenanthrenyloxy, 2,5-diisopropylphenyloxy or 2,5-dimethylphenyloxy ,

In the context of the present invention, a heteroatom-containing C ₇ -C ₃ arylalkyl group, particularly preferably toluenesulfonyl, or 2,4,6-trimethylphenylsulfonyl is understood.

The present invention also relates to a catalyst system which contains one or more chemical compounds of the formula I.

The metal complexes of formula I are also suitable as a component of catalyst systems for the production of polyvinyl esters by polymerization of, for. B. vinyl acetate in the presence of a catalyst having at least one

Contains cocatalyst and at least one metal complex.

The cocatalyst, which together with a transition metal complex of the formula I forms the catalyst system, contains at least one compound of the type of an aluminoxane or a Lewis acid or an ionic compound, which by

Reaction with an organometallic compound of the formula I converts this into a cationic compound. The cocatalysts which, together with one or more compounds of the formula I, form the catalyst system according to the invention are described in WO 0148034. The catalyst systems according to the invention, which consist of a compound of the formula

I and the cocatalysts described in WO 0148034 are also included in the present invention. Illustrative but not limiting examples of cocatalysts which together form one or more compounds of the formula I to form the catalyst system are: aluminoxanes, which are described, for example, in JACS 1 17 (1995), 6465-74 and Organometallics 13 (1994), 2957-69 or Lewis acids, which consist for example of organoboron or organoaluminium compounds, or ionic cocatalysts which contain, for example, a non-coordinating anion, or mixtures of at least one Lewis acid and at least one ionic compound, or borane or carborane compounds , or combinations of at least one amine and a support with organo-organic compounds as described in patent WO 99/40129, or compounds which result from the conversion of a boron compound with an organo-aluminum compound, or cocatalysts, which are described in EP-A-924223, DE-A-19622207, EP-A-601830, EP-A-8241 12, EP-A-8241 13, EP-A-81 1627, WO97 / 1 1775 and DE-A-19606 167 are described.

To prepare the catalyst system, at least one of the transition metal compounds of the formula I described above is brought into contact with at least one cocatalyst component in a suitable solvent, an adduct or a mixture preferably being obtained.

Preferred solvents for the preparation of the transition metal compound / cocatalyst mixture are hydrocarbons and hydrocarbon mixtures which are liquid at the selected reaction temperature and in which at least one of the individual components preferably dissolves. However, the solubility of individual components is not a requirement. Examples of suitable solvents include alkanes such as pentane, isopentane, hexane, heptane, octane, and nonane; Cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene, ethylbenzene and diethylbenzene. Toluene is very particularly preferred. The amounts of cocatalyst and transition metal compound used in the preparation of the catalyst system can be varied over a wide range. A molar ratio of cocatalyst to transition metal in the transition metal compounds of 1: 1 to 1000: 1 is preferably set, very particularly preferably a ratio of 1: 1 to 500: 1. If methylaluminoxane is used as cocatalyst, 30% are preferred toluene solutions used; the use of 10% solutions is also possible. Toluene is preferably used. The preactivation time is 1 minute to 200 hours. The preactivation can take place at room temperature (25 ° C). In individual cases, the use of higher temperatures can shorten the time required for preactivation and cause an additional increase in activity. In this case, a higher temperature means a range between 50 and 100 ^C C.

Another component of the invention is a process for the homo- and copolymerization of vinyl esters with catalyst systems which have been prepared in the manner described above and from at least one of the transition metal compounds of the formula I described above and at least one compound of the Lewis acid or ionic type Contains connection.

The synthesis of the compounds of formula I according to the invention can be carried out by the generally known method. An example is given below.

^S0C 'Cr0 ₂ CI _{2 /} BzMgCI

For this purpose, the diamine compound is reacted in the presence of imidazole using sulfuryl chloride to form the disulfurylamido compound. Then the ligand is reacted with the corresponding metal species and then reacted by a Grignard reagent to give a catalyst according to the invention.

The compounds according to the invention are suitable as catalysts for the preparation of polyvinyl esters.

Another component of the invention is therefore a process for the polymerization of vinyl esters using the catalyst according to the invention, polymerization being understood to mean both the homopolymerization of vinyl esters and the copolymerization of vinyl esters with other olefins. Examples of other olefins are 1-olefins having 2 to 20, preferably 2 to 10 carbon atoms, such as

Ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-decene, 4-methyl-1-pentene or 1 - octene, styrene, dienes such as 1, 3-butadiene, 1, 4-hexadiene, vinyl norbones and cyclic olefins such as norbornene, norbornadiene, ethylnorbomadiene, cyclopentadiene, tetracyclododecene or methylnorbornene, and polar monomers such as methyl acrylate, methyl methacrylate, acrylic acid, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate.

Vinyl acetate is preferably homopolymerized in the process according to the invention, or vinyl acetate is copolymerized with one or more 1-olefins having 2 to 8 carbon atoms, such as ethene, propene, styrene, norbornene, methyl acrylate, methyl methacrylate, acrylic acid or butadiene.

The polymerization is carried out at a temperature of from -20 to 300 ° C., preferably from 0 to 200 ° C., very particularly preferably at 20 to 100 ° C. The pressure is 0.5 to 2000 bar, preferably 1 to 64 bar. The polymerization can be carried out in solution, in bulk in suspension or in emulsion, continuously or batchwise, in one or more stages. Suitable solvents for the polymerization are, for example, aliphatic hydrocarbons such as pentane, hexane or the like or aromatic hydrocarbons such as benzene, toluene, xylenes and the like, or ethers such as diethyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, anisole, diphenyl ether and ethylphenyl ether, also halogenated solvents such as dichloromethane, trichloromethane, chlorobenzene, bromobenzene and the like, and also ethyl acetate, acetone, N, N-dimethylformamide, ethylene carbonate, methanol, ethanol, propanol, i-propanol or water. It can Mixtures of different solvents in different proportions can also be used according to the invention.

Furthermore, the catalysts of the invention can be used homogeneously and also heterogeneously supported. The carrier component of the catalyst according to the invention can be any organic or inorganic, inert solid, in particular a porous carrier such as talc, inorganic oxides and finely divided polymer powders (eg highly porous polyolefins such as polyethylene, polypropylene, polystyrenes, copolymers, or polar polymers such as polyurethanes, Polymethyl acrylates, polymethyl methacrylates, polyvinyl acetate,

Polyacrylonitrile, polyethylene glycol or copolymers).

Suitable inorganic oxides can be found in the II. VI. Main group of the periodic table and the II I. -VI. Subgroup of the Periodic Table of the Elements. Examples of preferred oxides as carriers include silicon dioxide, hydrotalcite,

Aluminum oxide, as well as mixed oxides of the elements calcium, aluminum, silicon, magnesium, titanium and corresponding oxide mixtures. Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxidic supports are, for example, MgO, ZrO ₂ , TiO ₂ or B ₂ O ₃ , to name just a few.

Another component of the invention are the polymers produced using the catalyst according to the invention. The polyvinyl acetate produced with catalyst 1 has an average molecular weight of 1300 g / mol and a dispersion index of 10.0. An examination of the glass temperature showed a T _g of -14 ° C. Due to the broad molecular weight distribution in conjunction with a higher isotacticity, the polymers are particularly suitable as paint or adhesive components or as plasticizers.

The invention is illustrated by the following example, which does not restrict the invention.

General information: The production and handling of the organometallic compounds was carried out in the absence of air and moisture under argon Shielding gas (Schlenk technology or glove box). All required solvents were flushed with argon before use and absoluteized using a molecular sieve.

Example 1: Polymerization of vinyl acetate with the catalyst 1 11 mg (32 μmol) of catalyst are placed in a heated flask under a protective gas

1 given and with 10 ml abs. Toluene added. Now add 1.85 mL freshly distilled vinyl acetate and stir for twelve hours at room temperature. The reaction is then stopped by adding 2 ml of acidic methanol and the mixture is concentrated to a residual volume of 1 ml. The polymer formed is precipitated by adding 20 ml of heptane and the supernatant solution is decanted off. The residue is dried in an oil pump vacuum. Yield: 310 mg (18%). ¹ H NMR (500 MHz, CDCI ₃ ): δ = 4.86 (bs, 1 H, CH), 2.01 (bt, 3H, COCH ₃ ), 1.75 (bd, 2H, CH ₂ ). ¹³ C-NMR (500 MHz, CDCI ₃ ): δ = 170.4 - 170.0 (C = O), 68.5 - 66.5 (CH), 40.5 - 38.5 (CH ₂ ), 21.1 - 20.8 (CH ₃ ).

Catalyst 1

Example 2: Polyvinyl acetate

The polyvinyl acetate produced with catalyst 1 has an average molecular weight of 1300 g / mol and a dispersion index of 10.0. An examination of the glass temperature showed a T _g of -14 ° C.

Claims

claims

1. Compounds of formula I.

Formula I.

wherein: M ^{1 is} a transition metal of the 5th to 8th group of the Periodic Table of the Elements, the oxidation state of which is not zero, in particular V, Nb, Ta, Cr,

Is Mo, W, Mn, Fe, Ru, Co, Rh, Ni or Pd, and

Y ^{1 is} a bridging structural element between the donor atoms D ¹ and is a C ₂ -C 10 carbon bridge, which is defined by R ⁴ _e , and

Periodic table of the elements is, in particular N, P, As, O, S, Se and Te, and

R ^{1 are the} same or different and represent a hydrogen atom, a Ci - C ₂ o

Alkyl group, a C ₇ - C ₂ o -alkylaryl group, a C ₂ - C ₂ o -alkenyl group, C ₂

- C ₂ o alkynyl group or a halogen-containing Ci - C ₂ o alkyl group, a C

- C ₂ o -alkylaryl group, a C ₂ - C ₂ o -alkenyl group, C ₂ - C ₂₀ -alkynyl group or a heteroatom-containing Ci - C ₂ o -alkyl group, a C ₇ - C ₂ o -alkylaryl group, a C ₂ - C ₂ o -alkenyl group, C ₂ -C ₂₀ -alkynyl group, and

R ^ are identical or different and are a hydrogen atom, a halogen atom, a Ci - C ₂ o -alkyl group, a C - C ₂ o -alkylaryl group, a C ₂ - C ₂₀ -alkenyl group, C ₂ - C ₂ o -alkynyl group or one halogen-containing Ci - C ₂₀ alkyl group, a C ₇ - C ₂₀ alkylaryl group, a C ₂ - C ₂ o alkenyl group, C ₂ - C ₂ o alkynyl group or a heteroatom-containing Ci - means alkynyl group, and - C ₂ o - alkyl group, a C ₇ - C ₂ o alkylaryl group, a C ₂ - C ₂ o alkenyl, C ₂ - C ₂ o

R ^{3 are the} same or different and are a hydrogen atom, a Ci - C20 alkyl group, a CQ - C20 aryl group, a C ₇ - C20 alkylaryl group, a

C - C ₃₀ arylalkyl group, a C2 - C ₂₀ alkenyl group, C ₂ - C ₂₀ alkynyl group or a halogen-containing Ci - C ₂₀ alkyl group, a C ₆ - C20 aryl group, a C - C ₂₀ alkylaryl group, a C - C ₃ o arylalkyl group, a C ₂ - C ₂₀ alkenyl, C ₂ - C 20 alkynyl group or a heteroatom-containing Ci - C ₂₀ - alkyl group, a C ₆ - C ₂ o aryl group, a C ₇

- C ₂ o -alkylaryl group, a C ₇ - C ₃ o -arylalkyl group, a C ₂ - C ₂ o -alkenyl group, C ₂ - C20 -alkynyl group, and

R ^{4 are the} same or different and represent a hydrogen atom, a Ci - C20 -

Alkyl group, a C ₆ - C 20 aryl group, a C ₇ - C ₂ o alkylaryl group, a C - C ₃ o arylalkyl group, a C ₂ - C ₂ o alkenyl group, C ₂ - C ₂ o -

Alkynyl group or a halogen-containing Ci - C20 alkyl group, a C ₆ - C ₂ o aryl group, a C - C ₂₀ alkylaryl group, a C - C ₃ o arylalkyl group, a C ₂ - C ₂₀ alkenyl group, C ₂ - C20 Alkynyl group or a heteroatom-containing Ci - C20 alkyl group, a CΘ - C ₂ o aryl group, a C - C20 alkylaryl group, a C ₇ - C ₃ o arylalkyl group, a C2 - C ₂ o -

Alkenyl group, C ₂ -C ₂₀ -alkynyl group, where several R ⁴ radicals can form a mono- or polycyclic ring system with one another, and R ^{5 are} identical or different and a hydrogen atom, a Ci - C ₂₀ -

Alkyl group, a C ₆ -C ₂₀ aryl group, a C - C ₂₀ alkylaryl group, a C ₇ - C ₃₀ arylalkyl group, a C ₂ - C ₂ o alkenyl group, C ₂ - C ₂ o -

Alkynyl group or a halogen-containing Ci - C20 alkyl group, a C ₆ - C ₂₀ aryl group, a C - C20 alkylaryl group, a C ₇ - C ₃ o arylalkyl group, a C2 - C ₂ o alkenyl group, C2 - C20 alkynyl group or a heteroatom-containing Ci - C ₂ o - alkyl group, a Cβ - C ₂ o aryl group, a C ₇ - C ₂₀ alkylaryl group, a C ₇ - C ₃ o arylalkyl group, a C - C ₂₀ -

Alkenyl group, C ₂ -C ₂₀ alkynyl group, and b are each the same or different and are an integer from 1 to 2, and c are the same or different and are an integer from 0 to

2 and d are the same or different and an integer from 0 to

2 and e are the same or different and an integer from 2 to

20 and f are the same or different and an integer from 0 to

2 mean and

2. A catalyst system containing at least one compound according to claim 1 and at least one cocatalyst.

3. Use of at least one compound according to claim 1 or at least one catalyst system according to claim 2 for the polymerization of vinyl esters.

4. A process for the preparation of vinyl esters, characterized in that at least one compound according to claim 1 or at least one catalyst system according to claim 2 is used.