DE10159385A1 - Process and catalyst for the preparation of polymers and / or copolymers of acrylic compounds and methacrylic compounds - Google Patents

Abstract

The invention relates to a catalyst complex and a method for producing polymers and/or copolymers of acrylic or methacrylic compounds using said catalyst complex. The inventive method comprises the following steps: polymerizing one or more polymerizable, monomeric compounds of the general formula (I) in the presence of a catalytic structure in an unpolar solvent for the catalytic compound at temperatures in the range of from 100 DEG C and the boiling point of the solvent, said catalytic structure being obtainable in situ from at least one organometallic rare earth (III) complex of the general formula (II) and at least one organometal compound of the general formula (IIIA), (IIIB), (IIIC) and/or (IIID), using at least one organometal compound of the general formula (IIIA), (IIIB), (IIIC) and/or (IIID) in a molar excess of greater than 2:1 based on the at least one organometallic rare earth (III) complex of the general formula (II). The groups R<sp>1</sp>, R<sp>2</sp>, Cp, Ln, R<sp>6</sp>, Met, R<sp>9</sp> and n are defined as in the description. The invention further relates to the polymers and copolymers obtained that have a high syndiotacticity and a narrow molecular weight distribution.

Description

Field of the invention

The invention relates to a process for the preparation of polymers and / or copolymers of acrylic compounds and of Methacrylic. Furthermore, the invention relates to a method for Preparation of a catalyst for a process for the preparation of Polymers and / or copolymers of acrylic compounds and of Methacrylic. In particular, the invention is directed to a Process for the preparation of polymers and / or copolymers with high syndiotacticity and narrow molecular weight distribution, at which one is very effective for novel lanthanoidocene complexes Polymerization or copolymerization of acrylic compounds and of Methacrylic compounds used.

State of the art

The control of stereoselectivity (syndiotactic or isotactic) and associated with this is the influence on the physical properties of Polymers of acrylic compounds is basically of great technical significance.

From Yasuda, H .; Tamai, H. Prog. Polym. Sci. 1993, 18, 1097; Yasuda, H .; Ihara, E. Macromol. Chem. Phys. 1995, 196, 2417; and Yasuda, H .; Ihara, E .; Hayakawa, T .; Kakehi, TJ Macromol. Symp. - Pure Appl. Chem. 1997, A34, 1929; It is known that organoanthanoid compounds very efficiently catalyze the "living polymerization" of alkyl methacrylic acid esters. The achiral bis (cyclopentadienyl) - rare earth metal complexes of the type [Cp * ₂ LnR] ₂ (Cp * = C ₅ (CH ₃ ) ₅ ; Ln = Sm, Y, Lu, R = CH ₃ , H) or Cp * ₂ LnCH ₃ (thf) give in high yields high molecular weight polymethyl methacrylate (PMMA, M _n > 400,000) with extremely narrow molecular weight distribution (M _w / M _n <1.05) and high syndiotacticity (polymerization temperature -95 ° C: rr = 95.3%; ° C: rr = 82.9%, 40 ° C: rr = 77.3%). These catalysts are extremely expensive in their preparation and handling and require to achieve the described good polymer properties technically not easily feasible low temperature conditions. Other achiral rare earth metal catalyst precursors have significantly lower polymerization activity and stereoselectivity (Habaue, S., Yoshikawa, M., Okamoto Y. Polym, J., 1995, 27, 986, Nakayama, Y., Shibahara, T .; Fukomoto, H Nakamura, A. Mashima, K. Macromolecules 1996, 29, 8014). The predominantly used bis (cyclopentadienyl) catalyst precursors [Cp * ₂ LnH] ₂ (Evans, WJ, Bloom, I, Hunter, WE, Atwood, JLJ Am Chem Chem 1983, 105, 1401), Cp * ₂ Ln (AlMe ₄ ) (Busch, MA; Harlow, R .; Watson, PA Inorg. Chim. Acta 1987, 140, 15) or Cp * ₂ LnCH ₃ (thf) (Evans, WJ; Chamberlain, L .; Ulibarm, TA;.. Ziller, JWJ Am Chem Soc 1988, 110, 6423) (Cp * = C ₅ (CH _{3) 5;.} Ln = Sm, Y, Lu), however, are available only in moderate to poor yields via multi-stage syntheses. The Katalyatorvorstufen must also be isolated before use in pure form, since the applied representation (salt metathesis reactions) favors the inclusion of alkali metal (M) components and at-complex formation. These alkali metal product contaminants can significantly influence the course of polymerization (syndiotactic or isotactic). In addition, the use of bis (cyclopentadienyl) catalysts with amide ligands is known, but they also have limited activity and selectivity (Mao, L., Shen, Q. Sun, J., J. Organomet. Chem. 1998, 566, 9-14). Yasuda et al. (Macromolecules, 1993, 26, 7134-7143) suggest that only lanthanoidocenes with sterically very demanding cyclopentadienyl ligands are capable of producing high syndiotacticities of the resulting polymers or copolymers in the polymerization of acrylates or methacrylates. The most common representative of the sterically very demanding cyclopentadienyl ligands, pentamethylcyclopentadiene (Cp *), however, is extremely expensive. For the development of a polymerization process on an industrially usable scale, this is a serious disadvantage.

task

Of great technical importance, it now appears, the synthesis of Catalyst precursors to improve and cheaper to design and this possibly together with the polymerization reaction in a kind "One-pot process" to combine.

In addition, the technology used polymerization called for the targeted control of molecular weight and in particular allow the molecular weight distribution. simultaneously should be compared to the corresponding polymerization Impurities of any kind should be as insensitive as possible, so that a time-consuming and costly cleaning of the used Components as far as possible is not necessary and one large-scale implementation of the method is possible.

In view of the prior art identified and discussed herein Technique of the present invention was the object of a efficient process for the preparation of polymers and / or To provide copolymers of acrylic compounds, which makes the use easily manufacturable and manageable Catalysts allowed.

Furthermore, it was an object of the present invention to provide a method for the preparation of polymers and / or copolymers of To specify acrylic compounds, which has a high control over the desired physical properties of the resulting polymers allows. In particular, unwanted side reactions it should be reduced and it should regulate the stereospecific Polymerization of acrylic compounds can be improved.

Among other things, the novel process is intended to enable, in particular, the production of polymer strands having a high syndiotacticity and a narrow molecular weight distribution M _w / M _n , preferably <1.5.

An object of the present invention is also to be seen therein Process for the preparation of polymers and / or copolymers to provide acrylic compounds which the polymerization and / or copolymerization of the broadest possible spectrum allowed monomeric compounds.

In addition, the method should be simple and inexpensive and be industrially executable. Furthermore, the method of the Invention under conditions of pressure, temperature and solvent be feasible, which simplifies a technical implementation shape.

It was therefore also the task, instead of the known and expensive Ligands to find new ligands and complexes that are inexpensive and are easily accessible and yet capable of being in one Polymerization or copolymerization the required high To provide syndiotacticities. It was also the task of a simple and to find cheap method for making the ligands. Further The task was to provide a method for the preparation of the complexes find and a polymerization or copolymerization with the develop new complexes.

solution

The task was solved by the provision of a new catalyst complex. The catalyst complex contains synthetically much simpler and cheaper to prepare ligands than the already known in the art Cp *. The new catalyst complex has good polymerization properties. The homopolymethyl methacrylate (PMMA) produced has a higher isotactic fraction at a higher polymerization temperature (+ 5 ° C.) than that prepared with [Cp ₂ Y (μ-Me)] ₂ (Yasuda et al., Macromolecules, 1993, 26, 7134 -7143) with comparable syndiotacticity. The preparation of block copolymers (MMA-co-nBuMA (nBuMA = n-butyl methacrylate) or MMA-co-EHMA (EHMA = 2-ethylhexyl methacrylate) succeeds easily with the new catalyst complex.

These and unspecified other tasks, however, for the One skilled in the art from the introductory discussion of the prior art According to the invention are, according to the invention by a catalyst and a method having the features of claim 1 and the following Claims solved. Advantageous modifications of the invention Catalyst complex and the method are in the claim 1 back claims. The claim of Product category protects this by the method according to the invention available polymer or copolymer.

In that, according to the present invention, in a process for the preparation of polymers and / or copolymers of acrylic compounds, one or more polymerizable, monomeric compounds of general formula (I)


wherein
R ^{1 is} hydrogen or (C ₁ -C ₂₀ ) -alkyl and
R ^{2 is} CSR ³ or COR ³ , where
R ^{3 is} OR ⁴ , SR ⁴ or NR ⁴ R ⁵ , where
R ⁴ and R ^5, independently of one another or different, are linear or branched alkyl, cycloalkyl or aryl groups having from 1 to 20 carbon atoms,
the alkyl, cycloalkyl or aryl groups optionally having one or more CC double bonds, C-C triple bonds, tertiary amino groups, carboxylalkyl groups, carboxycarbonylalkyl groups, N, N-dialkylated amide groups, N-arylated-N-alkylated amide groups, keto groups, epoxide groups, ether groups, Acetal groups, sulfonyl groups, sulfinyl groups, thioether groups, tertiary phosphine groups, alkyldialkoxysilyl groups, dialkylphosphonate groups, and trialkylphosphate groups,
polymerized in the presence of a catalytically active structure in a non-polar solvent for the catalytically active compound at temperatures in the range between -100 ° C and the boiling point of the solvent,
wherein the catalytically active structure is formed in situ from at least one organometallic rare earth metal (III) complex of the general formula (II)

Cp ₂ LnR ⁶ (II),

wherein
Cp denotes an unsubstituted or substituted cyclopentadienyl group,
Ln represents a rare earth element in the oxidation state +3, and
R ⁶ denotes an amide ligand capable of forming agostic interactions, the amide ligand having an Si atom,
and at least one organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) is obtainable

Met (R ⁹ ) ₃ (IIIA)

(R ⁹ -Al-O) _n (IIIB)

(R ⁹ -Al-O-) _n -Al (R ⁹ ) ₂ (IIIC)

Zn (R ⁹ ) ₂ (IIID),

wherein
Denotes Met Al or B,
R ^{9 is} a linear or branched alkyl radical, a cycloalkyl radical or an aromatic radical, where the cycloalkyl radical may be substituted by one or more alkyl groups, and
n represents an integer greater than or equal to 1,
wherein the at least one organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) in a molar excess of greater than or equal to 2: 1 based on the at least one organometallic rare earth metal (III) complex of general formula (II),
It is possible to provide a method which is not readily foreseeable and which enables the preparation of polymers and / or copolymers of acrylic compounds and / or methacrylic compounds in a simple and efficient manner.

In this case, the inventive method is largely insensitive against impurities in the solvent and / or in the monomer are included, so that their careful cleaning before the polymerization no longer absolutely necessary. This is especially because of that surprisingly because the hitherto known from the prior art Catalyst complexes extremely sensitive to the presence of Impurities react, for example, the sales, the Rate and selectivity of the polymerization. Therefore, to Implementation of the previously known polymerization a careful separation even of smallest amounts of impurities in usually indispensable. This procedure is in its outline in the German Patent Application No. 101 44 140.1 discloses.

At the same time can be achieved by the inventive method a number of other advantages. These include:
The spectrum of polymerizable monomers of the general formula (I) is surprisingly wide.
With regard to pressure, temperature and solvent, the implementation of the reaction is relatively unproblematic, even at moderate temperatures, acceptable results are still achieved under certain circumstances.
The invention allows excellent control over the desired physical properties of the resulting polymers.
The invention enables the achievement of polymer strands with high syndiotacticity.
The process of the invention is poor in side reactions.
The polymers or copolymers obtainable by the process according to the invention have a narrow molecular weight distribution, preferably <1.5.
The copolymers which can be prepared by the process according to the invention can be controlled well and reproducibly in their composition.
The organometallic rare earth metal (III) complexes to be used as catalyst precursors according to the invention, because of their synthetic route, ensure the freedom of alkali metal complexes.
The catalyst precursors to be used in the polymerization process according to the invention are accessible after simple synthesis routes.
The Cp ligands of the complex according to formula (II) used according to the invention are simple and inexpensive to synthesize.

According to the invention, acrylic compounds of the formula (I) polymerize. The inventive method allows the Polymerization of a type of monomer or the copolymerization of more as a type of monomer, whether in mixture or sequential. hereby become homopolymers, random copolymers or block copolymers accessible.

In the formula (I), R ^{1 is} hydrogen or a (C ₁ -C ₂₀ ) -alkyl, suitably a (C ₁ -C ₂₀ ) -alkyl, preferably a (C ₁ -C ₈ ) -alkyl, in particular a (C ₁ -C4) -alkyl. Most preferably, the process of the invention employs monomers wherein R ^{1 is} a methyl group.

R ² in the formula (I) represents CSR ³ or COR ³ , so that the compounds polymerizable according to the invention include acrylcarbonyl compounds and acrylic thiocarbonyl compounds. Particularly advantageously, R ² in the formula (I) COR ³ .

Here, R ^{3 is} OR ⁴ , SR ⁴ or NR ⁴ R ⁵ , preferably OR ⁴ or SR ⁴ , particularly preferably OR ⁴ .

R ⁴ and R ⁵ , independently of one another, are identical or different and represent linear or branched alkyl, cycloalkyl or aryl groups, each having 1 to 20 carbon atoms. They may optionally contain one or more CC double bonds, C 3 -C 3 triple bonds, tertiary amino groups, carboxylalkyl groups, carboxycarbonylalkyl groups, N, N-dialkylated amide groups, N-arylated-N-alkylated amide groups, keto groups, epoxide groups, ether groups, acetal groups, sulfonyl groups, Sulfinyl groups, thioether groups, tertiary phosphine groups, alkyldialkoxysilyl groups, dialkylphosphonate groups and trialkylphosphate groups. They include in particular alkyl, cycloalkyl, alkenyl, alkynyl, N, N-dialkylaminoalkyl, N-alkyl-N-arylaminoalkyl, carboxyalkyl, carboxycarbonylalkyl, alkylcarbonylalkyl, alkenylcycloalkyl, alkylcycloalkyl, alkoxyalkyl, 2 , 2-dialkyl-1,3-dioxolan-4-yl-alkyl, epoxyalkyl, dialkylphosphinoalkyl, alkylphosphitoalkyl, dialkylphosphatoalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkylthioalkyl, alkyldialkoxysilylalkyl, alkylaryl and aryl groups. The following compounds have proven to be particularly suitable:
Alkyl acrylates derived from saturated linear or branched alcohols, such as methyl acrylate, ethyl acrylate, isopropyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, n-decyl acrylate, isooctyl acrylate, amyl acrylate, Tetradecyl acrylate, 2-ethylhexyl acrylate, etc .;
Alkyl acrylates derived from unsaturated alcohols, such as. Oleyl acrylate, 2-propynyl acrylate, allyl acrylate, vinyl acrylate, etc .;
Amides of acrylic acid, such as N, N-bis (2-diethylaminoethyl) acrylamide, N-methyl-N-phenylacrylamide, N, N-diethylacrylamide, N, N-dimethylacrylamide;
Aminoalkyl acrylates such as tris (2-methacryloxyethyl) amine, 3-diethylaminopropyl acrylate;
Aryl acrylates, such as nonyl phenyl acrylate, benzyl acrylate, phenyl acrylate, where the aryl radicals may each be unsubstituted or up to four times substituted;
carbonyl-containing acrylates such as 2-carboxyethyl acrylate, carboxymethyl acrylate, N- (2-acryloyloxyethyl) -2-pyrrolidinone, N- (3-acryloyloxypropyl) -2-pyrrolidinone, N-acryloylmorpholine, acetonyl acrylate, N-acryloyl-2-pyrrolidinone;
Cycloalkyl acrylates such as 3-vinylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, bornyl acrylate, cyclopenta-2,4-dienyl acrylate, isobornyl acrylate, 1-methylcyclohexyl acrylate;
Glycol diacrylates such as 1,4-butanediol diacrylate, methylenediacrylate, 1,3-butanediol diacrylate, triethylene glycol diacrylate, 2,5-dimethyl-1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, 1,2-propanediol diacrylate, diethylene glycol diacrylate, ethylene glycol diacrylate;
Acrylates of ether alcohols, such as tetrahydrofurfuryl acrylate, vinyloxyethoxyethyl acrylate, methoxyethoxyethyl acrylate, 1-butoxypropyl acrylate, 1-methyl- (2-vinyloxy) ethyl acrylate, cyclohexyloxymethyl acrylate, methoxymethoxyethyl acrylate, benzyloxymethyl acrylate, furfuryl acrylate, 2-butoxyethyl acrylate, 2-ethoxyethoxymethyl acrylate, 2-ethoxyethyl acrylate, allyloxymethyl acrylate, 1- Ethoxybutyl acrylate, methoxymethyl acrylate, 1-ethoxyethyl acrylate, ethoxymethyl acrylate;
Acrylates of acetal alcohols, such as 2,2-dimethyl-1,3-dioxolan-4-yl methyl acrylate;
Oxiranyl acrylates such as 10,11-epoxyundecyl acrylate, 2,3-epoxycyclohexyl acrylate, 2,3-epoxybutyl acrylate, 3,4-epoxybutyl acrylate, glycidyl acrylate;
Phosphorus- and / or silicon-containing acrylates such as 2- (dibutylphosphono) ethyl acrylate, 2- (dimethylphosphato) propyl acrylate, methyldiethoxyacryloylethoxysilane, 2- (ethylenephosphito) propyl acrylate, dimethylphosphinoylacrylate, dimethylphosphonoethylacrylate, diethylacryloylphosphonate, diethylphosphatoethylacrylate, dipropylacryloylphosphate;
sulfur-containing acrylates such as ethylsulfinylethyl acrylate, ethylsulfonylethyl acrylate, methylsulfinylmethyl acrylate, bis (acryloyloxyethyl) sulfide;
Triacrylates, such as trimethyloylpropane triacrylate;
Alkyl methacrylates derived from saturated linear or branched alcohols, such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, n-decyl methacrylate, isooctyl methacrylate, amyl methacrylate, Tetradecyl methacrylate, 2-ethylhexyl methacrylate, etc .;
Alkyl methacrylates derived from unsaturated alcohols, such as. Oleyl methacrylate, 2-propynyl methacrylate, allyl methacrylate, vinyl methacrylate, etc .;
Amides of methacrylic acid such as N, N-bis (2-diethylaminoethyl) methacrylamide, N-methyl-N-phenylmethacrylamide, N, N-diethylmethacrylamide, N, N-dimethylmethacrylamide;
Aminoalkyl methacrylates such as tris (2-methacryloxyethyl) amine, 3-diethylaminopropyl methacrylate;
Aryl methacrylates, such as nonylphenyl methacrylate, benzyl methacrylate, phenyl methacrylate, where the aryl radicals may each be unsubstituted or up to four times substituted;
carbonyl-containing methacrylates such as 2-carboxyethyl methacrylate, carboxymethyl methacrylate, N- (2-methacryloyloxyethyl) -2-pyrrolidinone, N- (3-methacryloyloxypropyl) -2-pyrrolidinone, N-methacryloylmorpholine, acetonyl methacrylate, N-methacryloyl-2-pyrrolidinone;
Cycloalkyl methacrylates such as 3-vinylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, bornyl methacrylate, cyclopenta-2,4-dienyl methacrylate, isobornyl methacrylate, 1-methylcyclohexyl methacrylate;
Glycol dimethacrylates such as 1,4-butanediol dimethacrylate, methylene dimethacrylate, 1,3-butanediol dimethacrylate, triethylene glycol dimethacrylate, 2,5-dimethyl-1,6-hexanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,2-propanediol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate;
Methacrylates of ether alcohols, such as tetrahydrofurfuryl methacrylate, vinyloxyethoxyethyl methacrylate, methoxyethoxyethyl methacrylate, 1-butoxypropyl methacrylate, 1-methyl- (2-vinyloxy) ethyl methacrylate, cyclohexyloxymethyl methacrylate, methoxymethoxyethyl methacrylate, benzyloxymethyl methacrylate, furfuryl methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate, allyloxymethyl methacrylate, 1 Ethoxybutyl methacrylate, methoxymethyl methacrylate, 1-ethoxyethyl methacrylate, ethoxymethyl methacrylate;
Methacrylates of acetal alcohols, such as 2,2-dimethyl-1,3-dioxolan-4-yl-methyl methacrylate;
Oxiranyl methacrylates such as 10,11-epoxyundecyl methacrylate, 2,3-epoxycyclohexyl methacrylate, 2,3-epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate, glycidyl methacrylate;
Phosphorus- and / or silicon-containing methacrylates, such as 2- (dibutylphosphono) ethyl methacrylate, 2- (dimethylphosphato) propyl methacrylate, methyldiethoxymethacryloylethoxysilane, 2- (ethylenphosphito) propyl methacrylate, dimethylphosphinomethylmethacrylate, dimethylphosphonoethylmethacrylate, diethylmethacryloylphosphonate, diethylphosphatoethylmethacrylate, dipropylmethacryloylphosphate;
sulfur-containing methacrylates, such as ethylsulfinylethyl methacrylate, ethylsulfonylethyl methacrylate, methylsulfinylmethyl methacrylate, bis (methacryloyloxyethyl) sulfide; and
Trimethacrylates, such as trimethyloylpropane trimethacrylate.

Particular preference is given according to the invention to (C ₁ -C ₂₀ ) -alkyl, cycloalkyl, (C ₁ -C ₄ ) -alkyloxo- (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkylthio (C ₁ -) C ₄ ) -alkyl, alkylaryl and aryl, suitably (C ₁ -C ₈ ) -alkyl, (C ₃ -C ₅ ) -cycloalkyl or (C ₅ -C ₁₄ ) -aryl, in particular (C ₁ -C ₄ ) - alkyl. It has proved to be particularly advantageous that one uses compounds of general formula (I), wherein
R ^{1 is} (C ₁ -C ₄ ) -alkyl and R ^{2 is} COR ³ , where R ^{3 is} OR ⁴ and R ^{4 is} (C ₁ -C ₅ ) -alkyl.

Of particular interest are exoolefinic acrylic compounds, which are characterized in that R ¹ and R ⁴ are fused to a cyclic ester or amide, wherein 5-, 6- and 7-membered heterocycles are particularly preferred.

Of particular interest are also process modifications characterized by the use of compounds of general formula (I) wherein R ^{1 is} methyl and R ^{2 is} COR ³ , wherein R ^{3 is} OR ⁴ and R ^{4 is} (C ₁ -C ₄ ) Alkyl.

In addition, in the process according to the invention, the use of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, benzyl methacrylate, 1,1-diphenylmethyl methacrylate, triphenylmethyl methacrylate, methyl α-ethyl acrylate, ethyl α-ethyl acrylate and methyl α- propyl acrylate, in particular of methyl methacrylate (R ^{1 is} methyl and R ² for COOCH ₃ ) proved to be particularly advantageous.

In the above formula (I) as well as in the entire scope of the invention, the term "(C ₁ -C ₄ ) -alkyl" is an unbranched or branched hydrocarbon radical having one to four carbon atoms, such as. B. the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl-2-methylpropyl or tert-butyl radical to understand;
the term "(C ₁ -C ₈ ) -alkyl" the abovementioned alkyl radicals, and also, for example, the pentyl, 2-methylbutyl, 1,1-dimethylpropyl, hexyl, heptyl, octyl, iso-octyl or the 1,1,3,3-tetramethylbutyl radical;
the term "(C ₁ -C ₂₀ ) -alkyl" denotes the abovementioned alkyl radicals, and also, for example, the nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl or eicosyl radical;
the term "cycloalkyl" denotes a cyclic radical having 3 to 20 carbon atoms, preferably a (C ₃ -C ₈ ) -cycloalkyl radical, furthermore preferably a (C ₃ -C ₅ ) -cycloalkyl radical;
the term "(C ₃ -C ₅ ) -cycloalkyl" means the cyclopropyl, cyclobutyl or cyclopentyl group;
by the term "(C ₃ -C ₈ ) -cycloalkyl" the radicals mentioned above under "(C ₃ -C ₅ ) -cycloalkyl", as well as the cyclohexyl, cycloheptyl or cyclooctyl radical, but also bicyclic systems, such as, for example Norbornyl group or the bicyclo [2,2,2] octane residue;
by the term "alkylaryl" radicals such as diphenylmethyl or triphenylmethyl;
the term "(C ₁ -C ₄ ) -alkylthio (C ₁ -C ₄ ) -alkyl" for example methylthiomethyl, ethylthiomethyl, propylthiomethyl, 2-methylthioethyl, 2-ethylthioethyl or 3-methylthiopropyl;
the term "aryl" is an isocyclic aromatic radical having preferably 6 to 14, in particular 6 to 12, carbon atoms, such as, for example, phenyl, naphthyl or biphenyl, preferably phenyl;
the term "alkenyl" is an alkyl radical having at least one CC double bond, such as oleyl, allyl or vinyl;
the term "alkynyl" is an alkyl radical having at least one C-C triple bond, such as 2-propynyl;
by the term "N, N-dialkylaminoalkyl" radicals, such as N, N-diethylaminoethyl;
by the term "N-alkyl-N-arylaminoalkyl" radicals, such as N-methyl-N-phenyl;
the term "carboxyalkyl" means radicals such as carboxyethyl or carboxymethyl;
by the term "alkylcarbonylalkyl" radicals, such as acetonyl;
by the term "alkenylcycloalkyl" radicals, such as vinylcyclohexyl;
by the term "alkylcycloalkyl" radicals, such as trimethylcyclohexyl;
by the term "alkoxyalkyl" radicals, such as ethoxyethyl or butoxypropyl;
the term "2, 2-dialkyl-1,3-dioxolan-4-yl-alkyl" radicals, such as 2,2-dimethyl-1,3-dioxolan-4-ylmethyl;
the term "epoxyalkyl" refers to radicals such as 2,3-epoxybutyl or 10,11-epoxyundecyl;
by the term "dialkylphosphinoalkyl" radicals, such as dimethylphosphinomethyl;
the term "alkylphosphitoalkyl" refers to radicals such as diethylphosphitoethyl;
the term "dialkylphosphatoalkyl" refers to radicals such as diethylphosphatoethyl;
the term "alkylsulfinylalkyl" refers to radicals such as methylsulfinylmethyl;
the term "alkylsulfonyfalkyl" refers to radicals such as ethylsulfonylethyl;
the term "alkylthioalkyl" means radicals such as the methyl or the ethylthioethyl group;
under the term "alkyldialkoxysilylalkyl" radicals, such as methyldiethoxysilyl.

The compounds of formula (I) are according to the invention in Presence of a catalytically active structure implemented, d. H. oligomerized or polymerized. In this case, the catalytically active Structure in situ obtainable from at least one organometallic Rare earth metal (III) complex of general formula (II) and at least a metal organyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID).

The compounds of the formula (II) and (IIIA), (IIIB), (IIIC) and / or (IIID) can be understood as catalyst precursors. So it is to those compounds that are capable in the polymerization system to form catalytically active structures. The connections of the general formula (II) used in the present invention can be basically referred to as metallocene complexes which are preferably achiral.

Ln in the compounds of the formula (II) denotes a rare earth metal in the oxidation state +3. These include the metals of Lanthanide group with atomic numbers 57 to 71 in the Periodic table of elements as well as yttrium (Y, atomic number 39) and Scandium (Sc, atomic number 21). In detail, the name includes Ln in the formula (II) the metals La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, He, Tm, Yb, Lu as well as Y and Sc. Of these metals are for Complex compounds particularly useful in the process of the invention useful are lanthanum, cerium, neodymium, samarium, ytterbium, lutetium and Yttrium is particularly preferred. For certain compounds of the formula (II) are also yttrium, lanthanum, neodymium, samarium, ytterbium and lutetium of special interest. Especially useful results in the polymerization of compounds of formula (I), preferably of Methyl methacrylate (MMA) is obtained with lanthanum and yttrium as Ln.

In the formula (II), Cp is unsubstituted or substituted Cyclopentadienyl. The Cp residue is an electron donating ligand to the component Ln of the compound of the general formula (II) coordinated. The complex compounds of the formula (II) are essential two ligands Cp on.

Preferred substituents on the cyclopentadienyl include under Other silyl alkyl radicals having one to 20 carbon atoms, preferably one to eight carbons, aryl radicals having from five to 20 carbon atoms, preferably 6 carbon atoms, wherein a cyclopentadienyl ring up to may have five substituents.

Furthermore, the cyclopentadienyl radicals may carry one or more substituents of the formula (R ⁷ ).

Cp (R ⁷⁾ _n (IV)

The value of n in the formula (IV) may mean one, two or three.

R ⁷ can have the following meanings:

R ⁷ = Si (R ⁸ ) ₃ ,

where:
R ⁸ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, such as the methyl group, the ethyl group, the propyl group, the isopropyl group, the butyl group, the isobutyl group, the tert. Butyl group, the pentyl group or the hexyl group, wherein at least one R ⁸ must be unequal hydrogen. The methyl group is preferred.

As the ligand of formula (IV) is 1,3-bis (trimethylsilyl) cyclopentadiene particularly preferred.

In the polymerization reaction according to the invention, modifications are likewise advantageous in which a catalytically active structure is used which is obtainable from a mixture comprising at least one organometallic rare earth metal (III) complex in which the two cyclopentadienyl rings are bridged and represent a doubly negatively charged ligand , These ligands can be represented by the formula (IIA)

[(Cp) A (Cp)] LnR ⁶ (IIA),

wherein Cp, Ln and R ^{6 have} the abovementioned meaning and
A is a residue bridging the two Cp units.

The rest A is covalently bound to the two radicals Cp. the Fragment A thus plays the role of a spacer. To be favoured Fragments containing Si, Ge or C. Especially useful Fragments of Si or C.

For A, Si-based diols are particularly preferred. The corresponding radicals are readily available and give generally good results. Dialkylsilyl radicals wherein the alkyls have one to 20 carbon atoms are preferred. Very often achieved with the dimethylsilyl, diethylsilyl or Diisopropylsilylrest excellent results. Best results are given by A = (CH ₃ ) ₂ Si.

R ⁶ in the compound of the formula (II) or formula (IIA) denotes an amide ligand capable of forming agostic interactions. Here, the term "ligands capable of forming agostic interactions" is to be understood as meaning a ligand, radical or fragment which can saturate the metal center sterically or electronically additionally via a non-covalent, weak bond.

The radical R ⁶ may be capable of forming a mono- or diagostic interaction with the metal center. In the context of the invention, "monoagostic" interaction means such an interaction in which the ligand R ⁶ additionally interacts with the metal center via another ligand fragment, so to speak forming a bidentate ligand (η ² coordination), while under "diagostic" interaction such an interaction is understood, in which the ligand R ⁶ additionally interacts with the metal center via two further ligand fragments (R ⁶ as a tridentate ligand, η ³ coordination).

In particular, "SiH", "CH" and "SiCH _3" ligand fragments are capable of agostic interaction, and the same amide ligand can interact mono- or diagostically, depending on the nature of the cyclopentadienyl ligand backbone and the metal center (electronic and steric effects) For example, the [N (SiHMe ₂ ) ₂ ] ligand in (C ₅ Me ₄ H) ₂ -Y-N (SiHMe ₂ ) _{2 forms} a monoagostic interaction with the yttrium center, whereas in (C ₅ Me ₄ -SiMe ₂ -C ₅ Me ₄ ) ₂ -La-N (SiHMe ₂ ) _{2 is} diagostically bound.

In the process of the present invention, lanthanoidocenamide Complexes particularly preferred, the 1,3-bis (trimethylsilyl) cyclopentadiene Cyclopentadienyl ligands or two similarly substituted, not contain bridged cyclopentadienyl ligands, since these complexes are the highly syndiotactic polymerization of acrylic and methacrylic acid esters support.

R ⁶ radicals which are capable of carrying out the interaction required in the context of the invention include, inter alia, singly negatively charged radicals of the formula ^(-) NR ⁷ R ⁸ , where R ⁷ and R ⁸ independently of one another are identical or different (C ₁ -C ₂₀₎ ) Alkyl, cycloalkyl, (C ₁ -C ₄ ) alkylthio (C ₁ -C ₄ ) alkyl, alkylaryl or aryl. Preferably, R ⁷ and R ^{8 are} independently the same or different branched alkyl radicals having three to four carbon atoms, such as isopropyl, or dialkylsilyl radicals in which the alkyl radicals are the same or different from one to four carbon atoms, such as the dimethylsilyl or methylethylsilyl , Particularly expediently, the radicals R ⁷ and R ^{8 are} also different from one another, for example R ^{7 is} an isopropyl radical and R ^{8 is} a dimethylsilyl radical.

In this connection, it is also of great interest to use one or more compounds of the general formula (II) or (IIA) in which R ^{6 is} bis (dimethylsilyl) amide [ ^(-) N (SiHMe ₂ ) ₂ ], Isopropyldimethylsilylamide [ ^(-) N (iPr) (SiHMe ₂ )], diisopropylamide [ ^(-) N (iPr) ₂ ] or bis (methylsilyl) amide [ ^(-) N (SiH ₂ Me) ₂ ].

The compounds of general formula (II) are accessible according to the invention for new synthetic routes. For example, the complexes of formula (II) can be synthesized according to an amine elimination from free protonated ligand, typically a substituted cyclopentadienyl ligand of the formula [CpH] or [HCp-A-CpH], and a rare-earth amide (Equation 1).

Ln (NR _{2) 3} (L) _x 2 + CpH → Cp ₂ LnNR HNR ₂ + 2 ₂ + xL (1a)

Ln (NR _{2) 3} (L) _x + [HCp-A-CpH] → [Cp-A-Cp] ₂ + 2 LnNR HNR ₂ + xL) (1b)

This synthetic route according to the invention ensures the use of alkali metal complex (at-complex) free catalyst precursors.

Conventional lanthanidocene complexes were synthesized according to a salt metathesis reaction sequence (Equation 2),

LnCl ₃ + 2 MCp * → [Cp * ₂ LnCl (MCl)] + MCl (2a)

[Cp * ₂ LnCl (MCl)] + MCH (SiMe ₃ ) ₂ → Cp * ₂ LnCH (SiMe ₃ ) ₂ + 2 MCl (2b)

Cp * ₂ inch (SiMe _{3) 2} + H ₂ → [Cp * ₂ LnH] ₂ + CH ₂ (SiMe _{3) 2} (2c)

[Cp ₂ LnCl (MCl)] + MAlMe ₄ → Cp ₂ Ln (AlMe ₄ ) + 2 MCl (2d)

Cp ₂ Ln (AlMe ₄ ) + 2 THF → Cp ₂ LnCH ₃ (thf) + AlMe ₃ (thf) (2e)

wherein the presence of alkali metal components and their influence on the isotactic polymerization can not be excluded.

The beneficial in the process of the invention Lanthanidocen complexes can according to the reaction of the type Seltenerdamiden Ln [N (SiHMe _{2) 2] 3} (THF) _x (Ln = elements with atomic number 21, 39, 57-71, with x = 1: Ln = Sc, x = 2: Ln = Y, La, Ce-Lu) with protonated cyclopentadienyl ligands of the type [CpH] or of the bridged type [HCp-A-CpH] in toluene or mesitylene in an amine elimination reaction with high yields ( > 90%) (equation 1a, b). The complexes thus obtained can be used without further purification / isolation in the context of the present invention.

Ln (NR _{2) 3} (L) _x 2 + CpH → Cp ₂ LnNR HNR ₂ + 2 ₂ + xL (1a)

Ln (NR _{2) 3} (L) _x + [HCp-A-CpH] → [Cp-A-Cp] ₂ + 2 LnNR HNR ₂ + xL (1b)

This synthetic route ensures the use of alkali metal complex (at-complex) free catalyst precursors. The presence of alkali metal components and their influence on an isotactic course of polymerization can therefore be excluded. The amide ligands used are capable of forming agostic interactions with the rare earth metal centers. The ligand L represents a neutral weakly bound donor ligand. Examples of these are tetrahydrofuran (THF) and diethyl ether (OEt ₂ ). The preparation of the catalyst precursor preferably takes place at a temperature in the range of 0 to 200 ° C, without this being a limitation. Scheme 1 Synthesis of the ligand of the invention

In a similar way, the synthesis of trisubstituted Cydopentadiensysteme.

The ansa ligands of the type (Cp) A (Cp) can easily be obtained by replacing the monohalosilane in the second reaction step with a dihalosilane. Scheme 2 Synthesis of the Catalyst Complex of the Invention, Variant 1

Scheme 3 Synthesis of the Catalyst Complex of the Invention, Variant 2

The catalysts of the invention are according to Scheme 3 shown.

Explanation of the Abbreviations Used in the Schemes:

The Lanthanoidocenamid- complexes obtained according to Scheme 3 in high yields can be used either after isolation via recrystallization in pure form (spectroscopic and structural characterization) or directly as thus obtained toluene solution without further purification in the present invention. The possibly not completely converted educt compounds Ln [N (SiHMe ₂ ) ₂ ] ₃ (thf) _x and cyclopentadiene are polymerization-inactive. The amine liberated in the reaction is characterized by poor complexing behavior as a consequence of its steric demand and can therefore compete poorly with the monomer for the active site. They can be used directly in this "amide" form for polymerization.

In addition to the at least one organometallic rare earth metal (III) - Complex of the general formula (II) is used to prepare the According to the invention effective structure at least one Organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) required. The organometallic compound of the general Formula (IIIA) includes boron and aluminum alkyls, cycloalkyls and aryls.

The organometallic compound of the general formula (IIIB) and (IIIC) include alumoxanes, wherein the formula (IIIB) is the cyclic form and the Formula (IIIC) describes the linear form. The organometallic compound of the general formula (IIID) includes zinc alkyls, cycloalkyls and aryls.

Accordingly, Met denotes Al or B, preferably Al. The radical R ⁹ represents a linear or branched alkyl radical, a cycloalkyl radical or an aryl radical. Linear or branched alkyl radicals are particularly preferred according to the invention. R ⁹ preferably has 1 to 12, suitably 1 to 8, in particular 1 to 4, carbon atoms. In this case, methyl, ethyl, and iso-butyl groups have proven to be particularly useful. The index n is an integer greater than or equal to 1, preferably between 1 and 20.

In the context of the present invention, the at least one Organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) singly or as a mixture of several Organometallic compounds of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID).

According to the invention, the use of organometallic compounds of the general formula (IIA) is preferred. Particularly suitable Organometallic compound of the general formula (IIIA) Boron trimethyl, boron triethyl, boron tri-n-propyl, boron triisopropyl, borontri-n-butyl, Boron triisobutyl, aluminum trimethyl, aluminum triethyl, aluminum tri-n propyl, aluminum triisopropyl, aluminum tri-n-butyl and Aluminum triisobutyl, especially aluminum trimethyl, aluminum triethyl and aluminum triisobutyl.

In the context of the present invention, the at least one Organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) in a molar excess of greater than 2: 1, preferably greater than 4: 1, suitably greater than 6: 1, respectively based on the at least one organometallic Rare earth metal (III) complex of the general formula (II) used.

The catalytically active structure is generally in a concentration in the range of 10 ^-5 mol / l to 3 mol / l, preferably in the range of 10 ^-4 mol / l to 10 ^-1 mol / l and particularly preferably in the range of 10 ^{-. 3} mol / l to 10 ^-2 mol / l used, without this being a limitation. The corresponding details refer to the Ln contained in the catalytically active structure. From the ratio of catalytically active structure to monomer results in the molecular weight of the polymer, if the entire monomer is reacted. Preferably, this ratio is in the range of 10 ^-6 to 1 to 0.5 to 1, more preferably in the range of 10 ^-4 to 1 to 10 ^-2 to 1. Also at this point, the corresponding information refers to that in the catalytic effective structure contained Ln.

The process according to the invention preferably takes place in the presence a nonpolar solvent, conveniently in one homogeneous system. As a measure of the polarity of the solvent may serve the dielectric constant, which is preferably ≦ 4, preferably ≦ 3, and most preferably ≦ 2.5. This value is at 20 ° C determined, with the skilled person with respect to the measurement valuable References in Ullmanns Encyklopadie der technischen Chemie, 1966, volume II / 2, pages 455-479.

Particularly suitable solvents include Hydrocarbon solvents, in particular aromatic Solvents such as toluene, mesitylene, benzene, 1,2-xylene, 1,3-xylene and 1,4- Xylene, saturated hydrocarbons, such as cyclohexane, Heptane, octane, nonane, decane, dodecane, which are also branched can, mineral oils and synthetic oils. This toluene, Mesitylene, benzene, 1,2-xylene, 1,3-xylene and 1,4-xylene are particularly preferred.

According to the invention, the solvents can be used individually or as a mixture be used.

Mineral oils are known per se and commercially available. They are generally obtained from petroleum or crude oil by distillation and / or refining and, if appropriate, further purification and refining processes, the term "mineral oil" in particular falling to the relatively high-boiling fractions of crude oil or crude oil. In general, the boiling point of mineral oil is higher than 200 ° C, preferably higher than 300 ° C, at 5000 Pa. The production by smoldering of shale oil, coking of hard coal, distillation under exclusion of lignite and hydration of coal or lignite is also possible. To a small extent, mineral oils are also produced from raw materials of plant origin (eg from jojoba, rapeseed) or animal (eg claw oil) origin. Accordingly, mineral oils, depending on their origin, different proportions of aromatic, cyclic, branched and linear hydrocarbons to valuable information on mineral oils are found for example in Ullmann's Encyclopedia of Industrial Chemistry, ^5th Edition on CD-ROM, 1997, keyword "lubricants and related products" ,

Synthetic oils include organic esters, organic ethers, such as silicone oils, and synthetic hydrocarbons, in particular Polyolefins. They are usually slightly more expensive than the mineral oils but advantages in terms of their performance. To clarify still on the 5 API classes of base oil types (API: American Petroleum Institutes), these base oils being particularly can preferably be used as a solvent.

In the context of the present invention, the solvents are present and / or during the polymerization, preferably in an amount of 1 to 99 wt .-%, particularly preferably from 5 to 95 wt .-% and completely particularly preferably from 10 to 60 wt .-%, based on the Total weight of the mixture used.

The temperatures at which the polymerization reactions are carried out, are generally between -100 ° C or Freezing point and the boiling point of the solvent used. Preference is given to temperatures between -50 ° C and + 100 ° C, especially preferably between -40 ° C and + 50 ° C, even more preferably between -20 ° C and + 25 ° C.

The inventive method shows in comparison with conventional "living polymerization systems" a significantly reduced Sensitivity to contamination.

Nevertheless, it may be appropriate to the polymerization of the Invention under such conditions to perform a make unwanted demolition difficult. Particularly favorable is the Exclusion of moisture. Preferably, the Polymerization reaction under inert gas atmosphere (nitrogen and / or Argon).

• a) wird in einem Reaktor das unpolare Lösungsmittel und die mindestens eine Metallorganylverbindung der allgemeinen Formel (IIIA), (IIIB), (IIIC) und/oder (IIID) homogen gemischt
• b) der mindestens eine organometallische Seltenerdmetall(III)-Komplex der allgemeinen Formel (II) zugegeben und
• c) die eine oder mehrere Verbindung(en) der Formel (I), vorzugsweise ebenfalls in Mischung mit der mindestens einen Metallorganylverbindung der allgemeinen Formel (IIIA), (IIIB), (IIIC) und/oder (IIID), werden in Substanz oder als Lösung zur resultierenden Mischung aus Schritt (b) batchweise oder kontinuierlich zugeben.

Within the scope of a most preferred embodiment of the present invention

• a) is homogeneously mixed in a reactor, the non-polar solvent and the at least one organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID)
• b) the at least one organometallic rare earth metal (III) complex of the general formula (II) is added and
• c) the one or more compound (s) of the formula (I), preferably also in admixture with the at least one organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) are in substance or as a solution to the resulting mixture from step (b) batchwise or continuously.

The at least one organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) in such Amount one that the sum of the in step (a) and optionally in Step (b) used amounts of at least one Organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) has a molar excess of greater than 2: 1, preferably greater than 4: 1, suitably greater than 6: 1, respectively based on the amount of the at least one used in step (a) organometallic rare earth metal (III) complex of the general Formula (II) yields.

The polymerization reaction according to the invention is a "living" Polymerization and can thus for the production of block copolymers be used. The polymerization leads to the consumption of Monomers according to formula (I) and can by addition of Abbruchmittel be stopped early. The termination reaction can also for Labeling or functionalization of the polymers or Copolymers find use. Stopcases are protic, deuteric or tritiated substances, such as alcohols, preferably Methanol.

After completion of the polymerization by consumption of the monomer or by demolition, the product obtained can be further processed or isolated (precipitation, Abrotation and the like).

The invention also provides polymers or copolymers obtainable by the process of the invention, which are characterized by a high syndiotacticity, based on the ¹ H-NMR analysis of the α-CH ₃ groups. Preferably, the syndiotacticity rr> 40%, more preferably rr> 80% and most preferably rr> 96%.

The polymers and / or copolymers prepared in the context of the invention generally have a molecular weight in the range from 1000 to 1,000,000 g / mol, preferably in the range from 5. 10 ³ to 500. 10 ³ g / mol and more preferably in the range of 10. 10 ³ to 300. 10 ³ g / mol, without this being a restriction. These values are based on the weight average molecular weight of the polydisperse polymers in the composition.

The particular advantage of the process according to the invention is that polymers having a narrow molecular weight distribution can be prepared. Preferably, polymers and / or copolymers obtained by the process according to the invention have a polydispersity, given by M _w / M _n , in the range from 1 to <1.5, advantageously 1 to <1.4, preferably 1 to 1.3, more preferably 1 to <1.2 and particularly preferably 1.01 to <1.1, on.

Examples

The following examples are intended to illustrate the invention, but should be the invention should not be limited to the examples.

working methods

The molecular weight distributions were determined by SEC (instrument configuration: ThermoQuest equipped with SEC columns (10 ⁶ Å, 10 ⁵ Å, each 10 μm from Polymer Laboratories).) Helium Degassed THF was used as eluent Molecular weights were measured against polystyrene (Polymer Laboratories). The (triad) tacticities were calculated from ¹ H NMR spectra (FT, 500 MHz, ¹ H) taken at ambient temperature in CDCl ₃ , evaluating the α-CH ₃ signals and the monomer ratio was also determined NMR spectroscopy The DSC measurements were carried out under nitrogen at a rate of 10 K / min in the range 20-160 or 220 ° C (Mettler DSC 820 apparatus).

All work steps were under rigorous exclusion of Humidity in baked glassware using Schlenk, high vacuum and glove box techniques. The Solvents were purified by standard methods and dried over Na / K. Dried alloy; Monomers were stirred over calcium hydride and then distilled.

Synthesis of ligands

The ligand used in the present invention Bis (trimetylsilyl) cyclopentadiene was commercially obtained from Aldrich. However, the synthesis of the monosilyl as well as the bis (silyl) derivatives very easily by the deprotonation of freshly distilled cyclopentadiene with one or two equivalents of a suitable base (eg. Sodium hydride, butyl lithium, etc.) and subsequent reaction with the respective silyl halide possible, which is a significant advantage represents.

example 1 Synthesis of the new catalyst complex

2.258 g (10.73 mmol, 2.5 eq.) Of the ligand 1,3-bis (trimethylsilyl) cyclopentadiene were placed in a 100 ml round bottomed flask, about 50 ml of toluene and 2.705 g (4.29 mmol) of the Yttrium silylamide Y (bdsa) ₃ (thf) _{2 was} added and refluxed overnight (metal bath, about 125 ° C). After cooling, all volatiles were removed in vacuo. The brownish, slightly viscous residue was taken up in hexane, dried again (sample was then less "sticky") and finally recrystallized from hexane, whereby the compound is obtained in the form of colorless crystals (yields about 60%). Properties of the Novel Catalyst Complex ¹ H-NMR (500 MHz, C ₆ D ₆ , 25 ° C): δ = 6.82 [t, ⁴ J = 1.9 Hz, 2H, C ₅ H ₃ (SiMe ₃ ) ₂ ], 6 , 77 [d, ⁴ J = 1.9 Hz, 4H, C ₅ H ₃ (SiMe ₃ ) ₂ ], 3.77 [ψ-oct, ³ J _{H, H} ≍ ³ J _{Y, H} = 2.8 Hz, 2H, SiH (CH ₃ ) ₂ ], 0.23 (d, ³ J = 2.5 Hz, 12H, SiH (CH ₃ ) ₂ ], 0.20 [s, 36H, Si (CH ₃ ) ₃ ] ppm.
¹³ C- { ¹ H} NMR (125 MHz, C ₆ D ₆ , 25 ° C): δ = 123.41 [C ₅ H ₃ (SiMe ₃ ) ₂ ], 2.45 [SiH (CH ₃ ) ₂ ], 0.86 (Si (CH ₃ ) ₃ ] ppm (further resonances of the Cp ring presumably hidden under the residual solvent signal).

Examples 2-17 Preparation of methyl methacrylate homopolymers Examples 2 to 5 Variation of the amount of catalyst

In a glove box, add 18 ml of toluene to a cylindrical 20 ml Screw cap glass (∅ 2.7 cm) filled and with 4 equivalents Trimethylaluminium offset based on the amount of catalyst. To the thus obtained mixture is the amount indicated in Table 1 Catalyst complex, dissolved therein and the thus obtained Catalyst solution in the fridge of the glove box for a few hours -35 ° C tempered.

With intensive stirring by means of a magnetic stirrer, 2.0 ml (18.7 mmol, ρMMA = 0.936 g / ml, M = 100.12 g / mol) are likewise precooled methyl methacrylate (Röhm GmbH & Co. KG) to the cooled solution. quickly injected. Within a few minutes, the polymerization solution becomes viscous and partially solidifies into a gel. To ensure complete conversion, the batch is stirred for half an hour at -35 ° C and half an hour at room temperature. For workup, the product is dissolved in 150 ml of dichloromethane, the polymerization is stopped by addition of 100 ml of methanol and then the solvent is removed on a rotary evaporator in vacuo. The PMMA formed is obtained in quantitative yield as a white, powdery solid with a yield of> 99% of theory. Alternatively, in the case of flowable polymer solutions, the polymerization can also be stopped by stirring in 100 ml of methanol and the precipitated polymer can be filtered off. Table 1

Examples 6 to 17 Variation of temperature and AlMe ₃ amount

In a glove box, add 18 ml of toluene to a cylindrical 20 ml Screw cap glass (∅ 2.7 cm) filled and with a defined amount Trimethylaluminum, based on the amount of the catalyst complex (see Table 2). To the mixture thus obtained are 23.9 mg (37.4 μmol, 0.2 mol%, M = 640.17 g / mol) of the catalyst complex given, dissolved therein and the catalyst solution thus obtained for some Hours in the fridge the glove box to the specified Temperature tempered.

With vigorous stirring by means of a magnetic stirrer, 2.0 ml (18.7 mmol, ρMMA = 0.936 g / ml, M = 100.12 g / mol) of likewise pre-tempered methyl methacrylate (Rohm GmbH & Co. KG) are added to the cooled solution. quickly injected. Within a few minutes, the polymerization solution becomes viscous and partially solidifies into a gel. To ensure complete conversion, the mixture is stirred for half an hour at the indicated reaction temperature and for a further half hour at room temperature. The work-up is carried out as described in Example 2-5. Table 2

Examples 18-21 Preparation of (methyl methacrylate) - (n-butyl methacrylate) - block copolymers

In a glove box, add 18 ml of toluene to a cylindrical 20 ml Screw cap glass (∅ 2.7 cm) filled and with 4 equivalents Trimethylaluminium offset based on the amount of catalyst. To the thus obtained, 23.9 mg (37.4 μmol, 0.2 mol%, M = 640.17 g / mol) of the catalyst complex, dissolved therein and the catalyst solution thus obtained in the refrigerator for a few hours Glovebox tempered to -35 ° C.

With vigorous stirring by means of a magnetic stirrer, the volume indicated in Table 3, likewise precooled methyl methacrylate (from Röhm GmbH & Co. KG), is rapidly injected into the cooled solution. After a reaction time of 10 minutes, the volume of precooled n-butyl methacrylate (Röhm GmbH & Co. KG) given in Table 3 is injected. (In the case of the control experiment, Ex 18, the polymerization is stopped by the addition of methanol.) After stirring for a further 30 minutes at -35 ° C is stirred for another half an hour at room temperature. The work-up is carried out as described in Example 2-5. Table 3

Examples 22-24 Preparation of (methyl methacrylate) - (2-ethylhexyl methacrylate) - block copolymers

The preparation is carried out analogously as described for Examples 19-21. The results are summarized in Table 4. Table 4

Claims (30)

1. compounds of the formula II,

Cp ₂ LnR ⁶ (II),

where:
R ⁶ is an amide ligand capable of forming agostic interactions, the amide ligand having an Si atom,
Ln is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc
Cp is a compound of formula IV,

Cp (R ⁷⁾ _n (IV)

where the value for n in the formula (IV) can assume one, two or three and R ⁷ can have the following meanings:

R ⁷ = Si (R ⁸ ) ₃ ,

where:
R ⁸ independently represents either hydrogen or an alkyl group of 1 to 6 carbon atoms, at least one R ^{8 represents} an alkyl group. 2. compound of the formula II,

Cp ₂ LnR ⁶ (II),

where R ⁶ , R ⁷ , R ⁸ and Cp have the meanings given in claim 1 and
Ln means Y, La, Sm or Lu. 3. Compounds according to claim 1 or 2, characterized in that
R ^{8 is} the methyl group and n = 2. 4. Process for the preparation of polymers and / or copolymers of acrylic or methacrylic compounds, in which one or more polymerizable, monomeric compounds of the general formula (I)


wherein
R ^{1 is} hydrogen or (C ₁ -C ₂₀ ) -alkyl and
R ^{2 is} CSR ³ or COR ³ , where
R ^{3 is} OR ⁴ , SR ⁴ or NR ⁴ R ⁵ , where
R ⁴ and R ^5, independently of one another or different, are linear or branched alkyl, cycloalkyl or aryl groups having from 1 to 20 carbon atoms,
the alkyl, cycloalkyl or aryl groups optionally having one or more CC double bonds, C-C triple bonds, tertiary amino groups, carboxylalkyl groups, carboxycarbonylalkyl groups, N, N-dialkylated amide groups, N-arylated-N-alkylated amide groups, keto groups, epoxide groups, ether groups, Acetal groups, sulfonyl groups, sulfinyl groups, thioether groups, tertiary phosphine groups, alkyldialkoxysilyl groups, dialkylphosphonate groups, and trialkylphosphate groups,
polymerized in the presence of a catalytically active structure in a non-polar solvent for the catalytically active compound at temperatures in the range between -100 ° C and the boiling point of the solvent,
wherein the catalytically active structure is obtainable in situ from at least one organometallic rare earth metal (III) complex according to claim 1, and at least one organometallic compound of general formula (IIIA), (IIIB), (IIIC) and / or (IIID)

Met (R ⁹ ) ₃ (IIIA)

(R ⁹ -Al-O) _n (IIIB)

(R ⁹ -Al-O-) _n -Al (R ⁹ ) ₂ (IIIC)

Zn (R ⁹ ) ₂ (IIID),

wherein
Denotes Met Al or B,
R ^{9 is} a linear or branched alkyl radical, a cycloalkyl radical or an aromatic radical and
n represents an integer greater than or equal to 1,
wherein the at least one organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) in a molar excess of greater than or equal to 2: 1 based on the at least one organometallic rare earth metal (III) complex of the general formula (II) according to claim 1, 2 or 3. 5. Process for the preparation of polymers and / or copolymers of acrylic or methacrylic compounds, in which one or more polymerizable, monomeric compounds of the general formula (I)


wherein
R ^{1 is} hydrogen or (C ₁ -C ₂₀ ) -alkyl and
R ^{2 is} CSR ³ or COR ³ , where
R ^{3 is} OR ⁴ , SR ⁴ or NR ⁴ R ⁵ , where
R ⁴ and R ^5, independently of one another or different, are linear or branched alkyl, cycloalkyl or aryl groups having from 1 to 20 carbon atoms,
the alkyl, cycloalkyl or aryl groups optionally having one or more CC double bonds, C-C triple bonds, tertiary amino groups, carboxylalkyl groups, carboxycarbonylalkyl groups, N, N-dialkylated amide groups, N-arylated-N-alkylated amide groups, keto groups, epoxide groups, ether groups, Acetal groups, sulfonyl groups, sulfinyl groups, thioether groups, tertiary phosphine groups, alkyldialkoxysilyl groups, dialkylphosphonate groups, and trialkylphosphate groups,
polymerized in the presence of a catalytically active structure in a non-polar solvent for the catalytically active compound at temperatures in the range between -100 ° C and the boiling point of the solvent,
wherein the catalytically active structure is obtainable in situ from at least one organometallic rare earth metal (III) complex according to claim 2 and at least one organometallic compound of general formula (IIIA), (IIIB), (IIIC) and / or (IIID)

Met (R ⁹ ) ₃ (IIIA)

(R ⁹ -Al-O) _n (IIIB)

(R ⁹ -Al-O-) _n -Al (R ⁹ ) ₂ (IIIC)

Zn (R ⁹ ) ₂ (IIID),

wherein
Denotes Met Al or B,
R ^{9 is} a linear or branched alkyl radical, a cycloalkyl radical or an aromatic radical and
n represents an integer greater than or equal to 1,
wherein the at least one organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) in a molar excess of greater than or equal to 2: 1 based on the at least one organometallic rare earth metal (III) complex of the general formula (II) according to claim 1, 2 or 3. 6. The method according to claim 5, characterized in that the at least one organometallic compound of the general Formula (IIIA), (IIIB), (IIIC) and / or (IIID) in a molar excess of greater than 6: 1 based on the at least one organometallic A rare earth metal (III) complex of the general formula (II) according to claim 1 uses. 7. The method according to claim 5, characterized in that the at least one organometallic compound of the general Formula (IIIA), (IIIB), (IIIC) and / or (IIID) in a molar excess of greater than 6: 1 based on the at least one organometallic A rare earth metal (III) complex of the general formula (II) according to claim 2 uses. 8. The method according to claim 4 or 5, characterized in that one a) homogeneously mixing the non-polar solvent and the at least one organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) in a reactor, b) the at least one organometallic rare earth metal (III) - complex of the general formula (II) admits according to claim 1 and c) the one or more compound (s) of the formula (I), preferably also in admixture with the at least one organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID), in bulk or as Adding solution to the resulting mixture from step (b) batchwise or continuously, wherein the at least one organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) is employed in an amount such that the sum of the amounts used in step (a) and optionally in step (c) the at least one organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) has a molar excess of greater than 2: 1 relative to the amount of the at least one organometallic rare earth metal used in step (b) (III ) Complex of the general formula (II) according to claim 1. 9. The method according to claim 4, characterized in that
the at least one organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) is used in such an amount,
the sum of the amounts of the at least one organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) used in step (a) and optionally in step (b) has a molar excess of greater than or equal to 6: 1 based on the amount used in step (a) of the at least one organometallic rare earth metal (III) complex of the general formula (II). 10. The method according to one or more of the preceding claims, characterized in that
one uses compounds of general formula (I), wherein
R ^{1 is} (C ₁ -C ₄ ) -alkyl and
R ^{2 is} COR ³ , where
R ^{3 is} OR ⁴ and R ^{4 is} (C ₁ -C ₈ ) alkyl. 11. The method according to claim 8, characterized in that
one uses compounds of general formula (I), wherein
R ^{1 is} methyl and
R ^{2 is} COR ³ , where
R ^{3 is} OR ⁴ and R ^{4 is} (C ₁ -C ₄ ) alkyl. 12. The method according to claim 6, characterized in that compounds of the general formula (I) are used, wherein R ^{1 is} methyl and R ^{2 is} COOCH ₃ . 13. The method according to one or more of the preceding claims, characterized in that one uses a catalytically active structure which is obtainable from a mixture containing at least one organometallic rare earth metal (III) complex of the formula (IIA)

[(Cp) A (Cp)] LnR ⁶ (IIA),

wherein Cp, Ln and R ^{6 have} the meaning given in claim 1 and
A is a silyl radical bridging the two Cp units. 14. The method according to claim 9, characterized in that one uses a catalytically active structure, which consists of a Mixture containing at least one organometallic Rare earth metal (III) complex of the formula (IIA) is available, wherein A is a Dimethylsilyl radical is. 15. The method according to one or more of the preceding claims, characterized in that one uses a catalytically active structure which is obtainable from a mixture containing at least one organometallic rare earth metal (III) complex of the formula (II), wherein R ^{6 is} a mono-negatively charged Represents amide ligands. 16. The method according to claim 11, characterized in that one uses a catalytically active structure which is obtainable from a mixture containing at least one organometallic rare earth metal (III) complex of formula (II), wherein R ⁶ bis (dimethylsilyl) amide, isopropyldimethylsilylamide , or represents bis (methylsilyl) amide. 17. The method according to one or more of the preceding Claims, characterized in that one uses a catalytically active structure, which consists of a Mixture containing at least one organometallic Rare earth metal (III) complex of general formula (II) is obtainable, wherein Ln is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc is. 18. The method according to claim 16, characterized in that a catalytically active structure is used, which consists of a mixture containing at least one organometallic rare earth metal (III) - Complex of the general formula (II) is available, wherein Ln Y, LA, SM or Lu represents. 19. The method according to claim 17, characterized in that one uses a catalytically active structure, which consists of a Mixture containing at least one organometallic Rare earth metal (III) complex of general formula (II) is obtainable, where Ln is lanthanum or yttrium. 20. Method according to one or more of the preceding Claims, characterized in that one uses a catalytically active structure, which consists of a Mixture containing at least one organometallic Rare earth metal (III) complex of general formula (II) is obtainable, wherein Cp is 1,3-bis (trimethylsilyl) cyclopentadiene. 21. The method according to one or more of the preceding claims, characterized in that one uses a catalytically active structure which is obtainable from a mixture containing at least one organometallic compound of the general formula (IIIA), wherein R ^{7 is} a linear or branched alkyl radical. 22. Method according to one or more of the preceding Claims, characterized in that one uses a catalytically active structure, which consists of a Mixture containing at least one organometallic compound of general formula (IIIA) wherein Met is Al. 23. The method according to claim 18, characterized in that one uses a catalytically active structure, which consists of a Mixture containing trimethylaluminum, triethylaluminum and / or Triisobutylaluminum is available. 24. Method according to one or more of the preceding Claims, characterized in that one carries out the polymerization in a non-polar solvent. 25. The method according to claim 19, characterized in that the polymerization is carried out in toluene. 26. A polymer or copolymer obtainable by a process according to one or more of the preceding claims, characterized by a syndiotacticity of rr> 40%, based on the ¹ H-NMR analysis of the α-CH ₃ groups. 27. A polymer or copolymer according to claim 22, characterized by a polydispersity, which is given by M _w / M _n , in the range of 1 to <1.5. 28. Use of the polymer or copolymer according to claim 26 or claim 27 for the manufacture of PVC processing aids. 29. Use of the polymer or copolymer according to claim 26 or claim 27 for the preparation of PET processing aids. 30. Use of the polymer or copolymer according to claim 26 or claim 27 for the production of injection molded parts.