WO2003048176A1 - Catalyst for producing (co)polymers of (meth)acrylic 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 °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 R1, R2, Cp, Ln, R6, Met, R9 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

 CATALYST FOR PRODUCING (CO) POLYMERISATES OF (METH) ACRYLIC COMPOUNDS

Field of the Invention

The invention relates to a process for the preparation of polymers and / or copolymers of acrylic compounds and of methacrylic compounds. The invention further relates to a method for producing a catalyst for a method for producing polymers and / or copolymers of acrylic compounds and of methacrylic compounds. 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, in which novel lanthanoidocene complexes are very effectively used for the polymerization or copolymerization of acrylic compounds and methacrylic compounds.

State of the art

The control of the stereoselectivity (syndiotactic or isotactic) and the associated influencing of the physical properties of polymers from acrylic compounds is fundamentally of great technical importance.

From Yasuda, H .; Tamai, H. Prog. Polym. Be. 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 organolanthanoid 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 polymethyl methacrylate (PMMA, Mn> 400,000) with extremely narrow molecular weight distribution (Mw Mn <1.05) and high syndiotacticity (polymerization temperature -95 ° C: rr = 95.3%; 0 ° C: rr = 82.9%; 40 ° C: rr = 77.3 %). These catalysts are extremely complex to manufacture and handle and, in order to achieve the good polymer properties described, require low-temperature conditions that are not technically straightforward to achieve. 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 previously used bis (cyclopentadienyl) catalyst precursors [Cp * ₂ LnH] ₂ (Evans, WJ; Bloom, I .; Hunter, WE; Atwood, JLJ Am. Chem. Soc. 1983, 105, 1401), Cp * ₂ Ln (AIMe ₄ ) (Busch, MA; Harlow, R .; Watson, PA Inorg. Chim. Acta 1987, 140.15) or Cp * ₂ LnCH ₃ (thf) (Evans, WJ; Chamberlain, L; Ulibarri, TA ; Ziller, JWJ Am. Chem. Soc. 1988, 110, 6423) (Cp * = C ₅ (CH ₃ ) ₅ ; Ln = Sm, Y, Lu), however, can only be obtained in moderate to poor yields via multi-stage syntheses. The catalyst precursors must also be isolated in their pure form before use, since the method of preparation (salt metathesis reactions) favors the inclusion of alkali metal (M) components and at-complex formation. These alkali metal product impurities can have a decisive influence on the course of polymerization (syndiotactic or isotactic). In addition, the use of bis (cyclopentadienyl) catalysts with amide ligands is also known, but these 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 in the polymerization of acrylates or methacrylates have high syndiotacticities Are able to produce polymers or copolymers. However, the most common representative of the sterically very demanding cyclopentadienyl ligands, pentamethylcyclopentadiene (Cp *), is extremely expensive. This is a serious disadvantage for the development of a polymerization process on an industrially usable scale.

task

It now appears to be of great technical importance to improve the synthesis of the catalyst precursors and to make them less expensive, and possibly to combine them with the polymerization reaction in a type of "one-pot process".

In addition, the technology requires polymerization processes that allow the targeted control of the molecular weight and in particular the molecular weight distribution. At the same time, the corresponding polymerization processes should be as insensitive as possible to impurities of any kind, so that a time-consuming and costly cleaning of the components to be used is, if possible, not necessary and large-scale implementation of the process is made possible.

In view of the prior art identified and discussed herein, the object of the present invention was to provide an efficient process for the preparation of polymers and / or copolymers of acrylic compounds, which permits the use of catalysts which are easy to prepare and handle.

Furthermore, it was an object of the present invention to provide a process for the preparation of polymers and / or copolymers of acrylic compounds which has high control over the desired physical properties of the resulting polymers allows. In particular, undesired side reactions are to be reduced and the regulation of the stereospecific polymerization of acrylic compounds is to be improved.

Among other things, the new method should, in particular, enable the production of polymer strands with a high syndiotacticity and a narrow molecular weight distribution M _w / M _n , preferably <1.5.

It is also an object of the present invention to provide a process for the preparation of polymers and / or copolymers of acrylic compounds which allows the polymerization and / or copolymerization of the broadest possible range of monomeric compounds.

In addition, the method should be simple, inexpensive and can be carried out on an industrial scale. Furthermore, the process of the invention should be able to be carried out under conditions of pressure, temperature and solvent which make technical implementation easier.

There was also the task, instead of the known and expensive ligands, of finding new ligands and complexes which are inexpensive and easily accessible and which are nevertheless capable of delivering the required high syndiotacticities in a polymerization or copolymerization process. A further task was to find a simple and inexpensive process for the preparation of the ligands. Furthermore, the task was to find a process for the preparation of the complexes and to develop a polymerization or copolymerization process with the 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 produce ligands than the Cp * already known in the prior art. The new catalyst complex has good polymerization properties. The homo-polymethyl methacrylate (PMMA) produced has a lower isotactic content at a higher polymerization temperature (+ 5 ° C.) than that produced with [Cp ₂ Y (μ-Me)] ₂ (Yasuda et al., Macromolecules, 1993, 26, 7134 - 7143) with comparable syndiotacticity. Block copolymers (MMA-co-nBuMA (nBuMA = n-butyl methacrylate) or MMA-co-EHMA (EHMA = 2-ethylhexyl methacrylate) can be easily produced with the new catalyst complex.

These and other unspecified tasks, which, however, are readily apparent to the person skilled in the art from the introductory discussion of the prior art, are achieved according to the invention by a catalyst and a method having the features of claim 1 and the following claims. Appropriate modifications of the catalyst complex according to the invention and of the process are protected in the claims which refer back to claim 1. The claim of the product category protects the polymer or copolymer obtainable by the process according to the invention.

The fact 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 the general formula (I)

wherein

R ^{1 is} hydrogen or (-CC ₂₀ ) alkyl and

R ^{2 stands} for CSR ³ or COR ³ , where

R ^{3 is} OR ⁴ , SR ⁴ or NR ⁴ R ⁵ , where

R ⁴ and R ^{5 are} independently the same or different 1 to 20

Linear or branched carbon atoms

Are alkyl, cycloalkyl or aryl groups,

where the alkyl, cycloalkyl or aryl groups optionally one or more CC double bonds, CC triple bonds, tertiary amino groups, carboxylalkyl groups, carboxycarbonylalkyl groups, N, N-dialkylated amide groups, N-arylated-N-alkylated amide groups, keto groups, epoxy groups, ether groups, May contain acetal groups, sulfonyl groups, sulfinyl groups, thioether groups, tertiary phosphine groups, alkyl dialkoxysilyl groups, dialkyl phosphonate groups and trialkyl phosphate 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 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 metal in the +3 oxidation state, and

R ⁶ denotes an amide ligand capable of forming agostic interactions, the amide ligand being a

Has Si atom,

and at least one metal organyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) is available

Met (R ⁹ ) ₃ (IIIA)

(R ⁹ -AI-O) _n (IIIB)

(R ⁹ -AI-O-) _n -AI (R ⁹ ) ₂ (IIIC)

Zn (R ⁹ ) ₂ (IIID), wherein

Designated Met AI or B,

R ^{9 represents} a linear or branched alkyl radical, a cycloalkyl radical or an aromatic radical, where the cycloalkyl radical can 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 the general formula (II),

it is possible to provide a process 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.

The process according to the invention is largely insensitive to impurities which are present in the solvent and / or in the monomer, so that their careful cleaning before the polymerization is no longer absolutely necessary. This is particularly surprising because the catalyst complexes known to date from the prior art are extremely sensitive to the presence of impurities, for example the conversion, the rate and the selectivity of the polymerization decrease. Therefore, careful removal of even the smallest amounts of impurities is generally essential to carry out the previously known polymerization processes. The main features of this method are disclosed in German Patent Application No. 101 44 140.1.

At the same time, a number of further advantages can be achieved by the method according to the invention. 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; acceptable results are still achieved under certain circumstances even at moderate temperatures. • 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 according to 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 organometail rare earth metal (III) complexes to be used according to the invention as catalyst precursors ensure the freedom from alkali metal complexes due to their synthesis route.

• The catalyst stages to be used in the polymerization process according to the invention are accessible by simple synthesis routes.

• The Cp ligands of the complex of formula (II) used according to the invention are simple and inexpensive to synthesize.

According to the invention, acrylic compounds of the formula (I) can be polymerized. The method according to the invention allows the polymerization of one type of monomer or the copolymerization of more than one type of monomer, be it in a mixture or sequentially. This makes homopolymers, statistical (random) copolymers or block copolymers accessible. In formula (I), R ^{1 is} hydrogen or a (-C ₂₀ ) alkyl, advantageously a (C ₂₀ ) alkyl, preferably a (C ₈ ) alkyl, in particular a (C 1 -C ₈ ) alkyl. Monomers in which R ^{1 is} a methyl group are most preferably used in the process of the invention.

R ² in formula (I) stands for CSR ³ or COR ³ , so that the compounds polymerizable according to the invention include acrylic carbonyl compounds and acrylic thiocarbonyl compounds. R ² in the formula (I) is particularly advantageously COR ³ .

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

R ⁴ and R ⁵ in turn independently of one another are identical or different for linear or branched alkyl, cycloalkyl or aryl groups, each having 1 to 20 carbon atoms. They can optionally contain one or more CC double bonds, CC triple bonds, tertiary amino groups, carboxylalkyl groups, carboxycarbonylalkyl groups, N, N-dialkylated amide groups, N-arylated- N-alkylated amide groups, keto groups, epoxy groups, ether groups, acetal groups, sulfonyl groups, Contain sulfinyl groups, thioether groups, tertiary phosphine groups, alkyl dialkoxysilyl groups, dialkyl phosphonate groups and trialkyl phosphate 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-octyl acrylate, n-octyl acrylate, n-acrylate, Tetradecyl acrylate, 2-ethylhexyl acrylate, etc .;

Alkyl acrylates derived from unsaturated alcohols, such as. B. Olyl 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;

Amino alkyl acrylates such as tris (2-methacryloxyethyl) amine, 3-diethylaminopropyl acrylate;

Aryl acrylates, such as nonylphenyl acrylate, benzyl acrylate, phenyl acrylate, where the aryl radicals can in each case 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, acetonylacrylate, 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, methylene diacrylate, 1, 3-butanediol diacrylate, triethylene glycol diacrylate, 2,5-dimethyl-1, 6-hexanediol diacrylate, 1, 10-decanediol diacrylate, 1, 2-propanediol diacrylate diacrylate, diethylene glycol;

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, benzylethymethyl acrylate, benzyloxymethyl acrylate, 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) propylacrylate, dimethylphosphinoyl acrylate, diethylphosphonophonophylacrylate, dietl; 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, n-decyl methacrylate, n-decyl methacrylate, n-decyl methacrylate, Tetradecyl methacrylate, 2-ethylhexyl methacrylate, etc .;

Alkyl methacrylates derived from unsaturated alcohols, such as. B. 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-phenyl methacrylamide, N, N-diethyl methacrylamide, N, N-dimethyl methacrylamide;

Aminoalkyl methacrylates such as tris (2-methacryloxyethyl) amine, 3-diethylaminopropyl methacrylate;

Aryl methacrylates, such as nonylphenyl methacrylate, benzyl methacrylate, phenyl methacrylate, it being possible for the aryl radicals to be unsubstituted or substituted up to four times; 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, bomyl 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, ethylenedimethacrylate;

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, ethoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy 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- (ethylenephosphito) propyl methacrylate, dimethylphosphinomethyl methacrylate,

Dimethylphosphonoethyl methacrylate, diethyl methacryloyl phosphonate, diethyl phosphatoethyl methacrylate, dipropyl methacryloyl phosphate; sulfur-containing methacrylates, such as ethylsulfinylethyl methacrylate, ethylsulfonylethyl methacrylate, methylsulfinylmethyl methacrylate, bis (methacryloyloxyethyl) sulfide; and

Trimethacrylates such as trimethyloylpropane trimethacrylate.

According to the invention, particular preference is given to (-C ₂₀ ) alkyl, cycloalkyl, (C 1 -C ₄ ) alkyloxo (C 1 -C ₄ ) alkyl, (CC ₄ ) alkylthio (C 1 -C ₄ ) alkyl, alkylaryl and Aryl, expediently (CrC ₈ ) alkyl, (C ₃ -C ₈ ) cycloalkyl or (C ₆ -Cι ₄ ) aryl, in particular (Cι-C) alkyl. It has proven to be very particularly advantageous to use compounds of the general formula (I) in which

R ^{1 is} (-C ₄ ) alkyl and R ^{2 is} COR ³ , where R ^{3 are} OR ⁴ and R ^{4 are} (-C ₈ ) 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, 5, 6 and 7-membered heterocycles being particularly preferred. Also of particular interest are process modifications which are characterized in that compounds of the general formula (I) are used in which R ^{1 is} methyl and R ^{2 is} COR ³ , where R ^{3 is} OR ⁴ and R ⁴ (dC ₄ ) alkyl are.

In addition, 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-acrylate has been used in the process according to the invention. propyl acrylate, in particular methyl methacrylate (R ^{1 is} methyl and R ² for COOCH ₃ ) has been found to be particularly advantageous.

In the above formula (I) and also in the entire scope of the invention, the term "(-C ₄ ) alkyl" is an unbranched or branched hydrocarbon radical having one to four carbon atoms, such as, for example, methyl, ethyl or propyl - To understand isopropyl, 1-butyl, 2-butyl-2-methylpropyl or tert-butyl radical;

under the expression "(-CC ₈ ) alkyl" the aforementioned alkyl radicals, and for example the pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, hexyl, heptyl, octyl, iso-octyl or the 1,1,3,3-tetramethylbutyl residue;

under the expression "(C ₁ -C ₂ o) alkyl" the abovementioned alkyl radicals, and for example the nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl or eicosyl radical;

under the expression "cycloalkyl" a cyclic radical having 3 to 20 carbon atoms, preferably a (C ₃ -C ₈ ) cycloalkyl radical, more preferably a (C ₃ -C ₅ ) cycloalkyl radical;

under the expression "(C ₃ -C ₅ ) cycloalkyl" the cyclopropyl, cyclobutyl or cyclopentyl group; under the expression "(C ₃ -Cδ) cycloalkyl" the radicals mentioned above under "(C ₃ -C ₅ ) cycloalkyl", and the cyclohexyl, cycloheptyl or cyclooctyl radical, but also bicyclic systems, such as, for example Norbornyl group or the bicyclo [2,2,2] octane radical;

under the term "alkylaryl" radicals such as diphenylmethyl or triphenylmethyl;

under the expression ,, (-C-C4) 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” means an alkyl radical with at least one C — C double bond, such as oleyl, allyl or vinyl;

under the term "alkynyl" an alkyl radical with at least one C-C triple bond, such as 2-propynyl;

under the expression "N, N-dialkylaminoalkyl" radicals, such as N, N-diethylaminoethyl;

under the expression "N-alkyl-N-arylaminoalkyl" radicals, such as N-methyl-N-phenyl;

under the term "carboxyalkyl" radicals, such as carboxyethyl or carboxymethyl;

under the term "alkylcarbonylalkyl" radicals, such as acetonyl;

under the term "alkenylcycloalkyl" radicals, such as vinylcyclohexyl;

under the term "alkylcycloalkyl" radicals, such as trimethylcyclohexyl; under the term "alkoxyalkyl" radicals, such as ethoxyethyl or butoxypropyl;

under the expression "2,2-DialkyM, 3-dioxolan-4-yl-alkyl" radicals, such as 2,2-dimethyl-1, 3-dioxolan-4-yl-methyl;

under the term "epoxyalkyl" radicals, such as 2,3-epoxybutyl or 10,11-epoxyundecyl;

under the term "dialkylphosphinoalkyl" radicals, such as dimethylphosphinomethyl;

under the term "alkylphosphitoalkyl" radicals, such as diethylphosphitoethyl;

under the term "dialkylphosphatoalkyl" radicals, such as diethylphosphatoethyl;

under the term "alkylsulfinylalkyl" radicals, such as methylsulfinylmethyl;

under the term "alkylsulfonylalkyl" radicals, such as ethylsulfonylethyl;

under the term "alkylthioalkyl" radicals, such as the methyl or the ethylthioethyl group;

under the term "alkyldialkoxysilylalkyl" radicals, such as methyldiethoxysilyl;

According to the invention, the compounds of the formula (I) are reacted in the presence of a catalytically active structure, ie oligomerized or polymerized. The catalytically active structure is obtainable in situ from at least one organometallic rare earth metal (III) complex of the general formula (II) and at least one metal organanyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID). The compounds of the formulas (II) and (IIIA), (IIIB), (IIIC) and / or (IIID) can be understood as catalyst precursors. These are compounds which are capable of forming catalytically active structures in the polymerization system. The compounds of the general formula (II) which are used in the present invention can in principle be referred to as metallocene complexes, which are preferably achiral.

In the compounds of the formula (II), Ln denotes a rare earth metal in the +3 oxidation state. These include the metals of the lanthanide group with atomic numbers 57 to 71 in the periodic table of the elements as well as yttrium (Y, atomic number 39) and scandium (Sc, atomic number 21). Specifically, the designation Ln in the formula (II) includes the metals La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y and Sc. Of these metals, lanthanum, cerium, neodymium, samarium, ytterbium, lutetium and yttrium are particularly preferred for complex compounds which are particularly useful for the process of the invention. Yttrium, lanthanum, neodymium, samarium, ytterbium and lutetium are also of particular interest for certain compounds of the formula (II). Very particularly useful results in the polymerization of compounds of the formula (I), preferably methyl methacrylate (MMA), are achieved with lanthanum and yttrium as Ln.

In the formula (II), Cp represents an unsubstituted or a substituted cyclopentadienyl group. The Cp radical is coordinated as an electron-donating ligand to the component Ln of the compound of the general formula (II). The complex compounds of formula (II) essentially have two ligands Cp.

Preferred substituents on the cyclopentadienyl radical include, inter alia, silyl alkyl radicals having one to 20 carbon atoms, preferably one to eight carbons, aryl radicals having five to 20 carbon atoms, preferably 6 carbon atoms, where a cyclopentadienyl ring can have up to five substituents.

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

Cp (R ⁷ ) _n (IV)

The value for n in formula (IV) can 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, at least one R ⁸ must be different hydrogen. The methyl group is preferred. 1,3-bis (trimethylsilyl) cyclopentadiene is particularly preferred as the ligand of the formula (IV).

In the polymerization reaction according to the invention, such modifications are also advantageous in which a catalytically active structure is used which can be obtained from a mixture comprising at least one organometallic rare earth metal (III) complex, in which the two cyclopentadienyl rings are bridged and represent a double-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 meaning given above and A is a radical bridging the two Cp units.

The residue A is covalently bound to the two residues Cp. Fragment A therefore has the role of a spacer. Fragments containing Si, Ge or C are preferred. Fragments of Si or C are particularly useful.

Particularly preferred for A are diyls based on Si. The corresponding residues are readily available and generally give good results. Dialkylsilyl radicals in which the alkyls have one to 20 carbon atoms are preferred. Excellent results are very often achieved with the dimethylsilyl, diethylsilyl or diisopropylsilyl radical. A = (CH ₃ ) ₂ Si gives the best results.

R ⁶ in the compound of the formula (II) or formula (IIA) denotes an amide ligand capable of forming agostic interactions. The term “ligands capable of forming agostic interactions” is to be understood here as a ligand, residue or fragment which can also coordinate the metal center sterically or electronically via a non-covalent, weak bond.

The radical R ⁶ can be capable of forming a mono- or diagostic interaction with the metal center. For the purposes of the invention, “monoagostic” interaction here means an interaction in which the ligand R ⁶ additionally interacts with the metal center via a further ligand fragment, so to speak forms a bidentate ligand (η ² coordination), while “diagostic” interaction such an interaction is understood in which the ligand R ⁶ additionally via two further ligand fragments interacts with the metal center (R ⁶ as a tridentate ligand, η ³ coordination).

"SiH", "CH" and "SiCH3" ligand fragments are particularly capable of agostic interaction. Depending on the type of cyclopentadienyl ligand framework and the metal center (electronic and steric effects), the same amide ligand can interact mono- or diagostically. So z. For example, the [N (SiHMe2) 2] ligand in (CδMe4H) 2-Y- N (SiHMe2) 2 exhibits a monoagostic interaction with the yttrium center, while in (C5Me4-SiMe2-C5Me4) 2 -La-N (SiHMe2) 2 is bound diagostically.

In the process of the present invention, lanthanoidocenamide complexes are particularly preferred which contain 1,3-bis (trimethylsilyl) cyclopentadiene cyclopentadienyl ligands or two similarly substituted, non-bridged cyclopentadienyl ligands, since these complexes support the highly syndiotactic polymerization of acrylic and methacrylic acid esters.

Residues R ⁶ , which are able to perform the interaction required in the context of the invention, include, among others, simply negatively charged residues of the formula ^(") NR ⁷ R ⁸ , in which R ⁷ and R ⁸ independently of one another are identical or different (-C ₂ O ) -Alkyl, cycloalkyl, (dC ₄ ) -alkylthio- (CrC ₄ ) -alkyl, alkylaryl or aryl, R ⁷ and R ⁸ are preferably independently of one another identical or differently branched alkyl radicals having three to four carbon atoms, such as isopropyl, or Dialkylsilyl radicals in which the alkyl radicals have one to four carbon atoms, the same or different from one another, such as the dimethylsilyl or also the methylethylsilyl radical The radicals R ⁷ and R ^{8 are} also particularly advantageous from one another, for example R ⁷ an isopropyl radical and R ⁸ a dimethylsilyl radical , It is also of great interest here that one or more compounds of the general formula (II) or (IIA) are used, in which R ⁶ bis (dimethylsilyl) amide [ ^(') N (SiHMe ₂ ) ₂ ], Isopropyldimethylsilylamide [ ^(") N (iPr) (SiHMe ₂ )] _I diisopropylamide [ ^Θ N (iPr) ₂ ] or bis (methylsilyl) amide [ ^(") N (SiH ₂ Me) 2].

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

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

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

This synthesis 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),

LnCl3 + 2 MCp ^* → [Cp ^* ₂ LnCI (MCI)] + MCI (2a)

[Cp ₂ LnCI (MCI)] + MCH (SiMe ₃ ) ₂ - Cp ^* ₂ LnCH (SiMe ₃ ) ₂ + 2 MCI (2b)

Cp ^* ₂ LnCH (SiMe ₃ ) ₂ + H2 - [Cp ^* ₂ LnH] ₂ + CH ₂ (SiMe ₃ ) ₂ (2c)

[Cp ₂ LnCI (MCI)] + MAIMe ₄ → Cp ₂ Ln (AIMe4) + 2 MCI (2d)

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

the presence of alkali metal components and their influence on the isotactic course of polymerization cannot be excluded. The lanthanidocene complexes useful in the process of the invention can, according to the reaction of rare earth damides of the type Ln [N (SiHMe2) 2] 3 (thf) χ (Ln = elements with the 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%) can be obtained (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 ₂ + 2 HNR ₂ + xL (1a)

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

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 consequently be excluded. The amide ligands used are capable of forming agostic interactions with the rare earth centers. Ligand L is a neutral, weakly bound donor ligand. Examples include tetrahydrofuran (THF) and diethyl ether (OEt2). The representation of the catalyst / stage preferably takes place at a temperature in the range from 0 to 200 ° C., without this being intended to impose a restriction. Scheme 1

Synthesis of the ligand according to the invention:

The synthesis of trisubstituted is also possible in an analogous manner

Cydopentadiensysteme.

The type (Cp) A (Cp) ansa ligands can easily be replaced by the

Monohalosilane can be obtained in the second reaction step by a dihalosilane.

Scheme 2

Synthesis of the catalyst complex according to the invention, variant 1:

+ 2 eq. Na [Cp (SiMe ₃ ) ₂ ]

YCI ₃ (THF) ₃₅ - - ^2S - -

³¹ '"THF, refl., 2.5 h

Scheme 3

Synthesis of the catalyst complex according to the invention, variant 2:

The catalysts of the invention are shown in Scheme 3.

Explanation of the abbreviations used in the diagrams:

The lanthanoidocenamide complexes obtained according to Scheme 3 in high yields can either be used after isolation by recrystallization in the purest form (spectroscopic and structural characterization) or directly as the toluene solution thus obtained without further purification in the context of the present invention. The possibly incompletely converted reactant compounds Ln [N (SiHMe2) 2] 3 (thf) χ and cyclopentadiene are polymerization-inactive. The amine liberated in the reaction is characterized by poor complexation behavior owing to its steric nature and can therefore compete poorly with the monomer for the active center. They can be used for polymerization directly in this "amidic" form.

In addition to the at least one organometallic rare earth metal (III) complex of the general formula (II), at least one metal organanyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) is required to produce the structure which is effective according to the invention. The metal organyl compound of the general formula (IIIA) includes boron and aluminum alkyls, cycloalkyls and aryls. The metal organyl compound of the general formula (IIIB) and (IIIC) comprise alumoxanes, the formula (IIIB) describing the cyclic form and the formula (IIIC) the linear form. The metal organyl compound of the general formula (IIID) includes zinc alkyls, cycloalkyls and aryls.

Accordingly, Met denotes AI or B, preferably AI. The R ⁹ radical 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, advantageously 1 to 8, in particular 1 to 4, carbon atoms. Methyl, ethyl and isobutyl 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 metal organyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) can be used individually or as a mixture of several metal organanyl compounds of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) can be used.

According to the invention, the use of metal organyl compounds of the general formula (IIIA) is preferred. Particularly suitable metal organyl compounds of the general formula (IIIA) include boron trimethyl, boron triethyl, boron tri-n-propyl, boron triisopropyl, boron tri-n-butyl, boron triisobutyl, aluminum trimethyl, aluminum triethyl, aluminum tri-n-propyl, aluminum triisopropyl, aluminum tri-n-butyl and aluminum triisobutyl in particular aluminum trimethyl, aluminum triethyl and aluminum triisobutyl.

In the context of the present invention, the at least one metal organyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) is advantageously larger in a molar excess of greater than 2: 1, preferably greater than 4: 1 than 6: 1, each 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 from 10 ^'5 mol / l to 3 mol / l, preferably in the range from 10 ^"4 mol / l to 10 ^{" 1} mol / l and particularly preferably in the range from 10 ^{" 3} mol / l to 10 ^"2 mol / l are used without any limitation. The corresponding information relates to the Ln contained in the catalytically active structure. The molecular weight of the polymer results from the ratio of catalytically active structure to monomer if the entire monomer is reacted. This ratio is preferably in the range from 10 ^"6 to 1 to 0.5 to 1, particularly preferably in the range from 10 ^{" 4} to 1 to 10 ^"2 to 1. Here too, the corresponding information relates to that in the catalytic The structure according to the invention preferably takes place in the presence of a non-polar solvent, expediently in a homogeneous system. The dielectric constant, which is preferably <4, preferably <3 and very particularly preferably <2, can serve as a measure of the polarity of the solvent. 5. This value is determined at 20 ° C., the person skilled in the art finding valuable information regarding the measurement in Ulimanns Encyklopadie der Technische Chemie, 1966, Volume II / 2, pages 455 to 479.

Particularly suitable solvents include hydrocarbon solvents, especially 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 , Dodecan, which can also be branched, mineral oils and synthetic oils. 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 and as a mixture.

Mineral oils are known per se and are commercially available. They are generally obtained from petroleum or crude oil by distillation and / or refining and, if appropriate, further purification and upgrading processes, the term mineral oil in particular referring to the higher-boiling proportions of the crude or petroleum. In general, the boiling point of mineral oil is higher than 200 ° C, preferably higher than 300 ° C, at 5000 Pa. It is also possible to produce by smoldering shale oil, coking hard coal, distilling with the exclusion of air from brown coal and hydrogenating hard coal or brown coal. To a small extent, mineral oils are also made from raw materials of vegetable (e.g. jojoba, rapeseed) or animal (e.g. claw oil) origin. Accordingly, mineral oils have different proportions of aromatic, cyclic, branched and linear hydrocarbons depending on their origin. Valuable information on mineral oils can be found, for example, in Ulimann's Encyclopedia of Industrial Chemistry, 5 ^th Edition on CD-ROM, 1997, keyword "lubricants and related products".

Synthetic oils include organic esters, organic ethers such as silicone oils, and synthetic hydrocarbons, especially polyolefins. They are usually somewhat more expensive than mineral oils, but have advantages in terms of their performance. For clarification, reference should be made to the 5 API classes of the base oil types (API: American Petroleum Institute), whereby these base oils can be used particularly preferably as solvents.

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

The temperatures at which the polymerization reactions are carried out are generally between -100 ° C. or the solidification point and the boiling point of the solvent used. Temperatures between -50 ° C and +100 ° C are preferred, particularly preferably between -40 ° C and +50 ° C, even more preferably between - 20 ° C and +25 ° C.

In comparison with conventional “living polymerization systems”, the process according to the invention shows a significantly reduced sensitivity to impurities.

Nevertheless, it may be appropriate to carry out the polymerization reaction of the invention under conditions which make undesired termination difficult. The exclusion of moisture is particularly favorable. The polymerization reaction is preferably carried out under an inert gas atmosphere (nitrogen and / or argon).

In the context of a very particularly preferred embodiment of the present invention

(a) the non-polar solvent and the at least one metal organyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) are mixed homogeneously in a reactor

(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 likewise in a mixture with the at least one metal organyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID), are in substance or as a solution to add the resulting mixture from step (b) batchwise or continuously.

The at least one metal organyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) is used in an amount such that the sum of those used in step (a) and optionally in step (b) Amounts of the at least one organometallic compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) a molar excess of greater than 2: 1, preferably greater than 4: 1, advantageously greater than 6: 1, each based on the amount of at least one organometallic rare earth metal (III) complex of the general formula (II) used in step (a).

The polymerization reaction according to the invention is a "living" polymerization and can thus be used for the production of block copolymers. The polymerization leads to the consumption of the monomers of the formula (I) and can be stopped early by adding terminating agents. The termination reaction can also be used for labeling or Functionalization of the polymers or copolymers are used, and demolition agents are protic, deuteric or tritiated substances, such as alcohols, preferably methanol.

After the end of the polymerization by consumption of the monomer or by termination, the product obtained can be processed further or isolated (precipitation, rotation and the like).

The invention also relates to polymers or copolymers which can be obtained by the process of the invention and which are distinguished by a high

Syndiotacticity based on the ¹ H-NMR analysis of the α-CH3 groups, distinguished. The syndiotacticity is preferably rr> 40%, particularly preferably rr> 80% and very particularly preferably rr> 96%.

The polymers and / or copolymers produced in the context of the invention generally have a molecular weight in the range from 1,000 to 1,000,000 g / mol, preferably in the range from 5 * 10 ³ to 500 * 10 ³ g / mol and particularly preferably in the range from 10 * 10 ³ to 300 * 10 ³ g / mol, without any limitation. 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 with a narrow molecular weight distribution can be produced. Polymers and / or copolymers obtained by the process according to the invention preferably have a polydispersity, which is given by M _w / M _n , in the range from 1 to <1.5, suitably 1 to <1.4, preferably 1 to 1, 3, particularly preferably 1 to <1, 2 and particularly preferably 1, 01 to <1, 1.

Examples

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

Working methods:

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

All work steps were carried out with rigorous exclusion of air humidity in heated glass devices using Schlenk, high vacuum and glovebox techniques. The solvents were cleaned using standard methods and dried over Na / K alloy; Monomers were stirred over calcium hydride and then distilled.

Synthesis of the ligands

The ligand bis (trimetylsilyl) cyclopentadiene used in the present invention was obtained commercially from Aldrich. However, the synthesis of the monosilyl and bis (silyl) derivatives is very easy by deprotonating freshly distilled cyclopentadiene with one or two equivalents of a suitable base (e.g. sodium hydride, butyllithium, etc.) and then reacting it with the respective silyl halide , which is a major advantage.

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 bottom flask, approx. 50 ml toluene and 2.705 g (4.29 mmol) of the yttrium Silylamids Y (bdsa) ₃ (thf) ₂ added and refluxed overnight (metal bath, approx. 125 ° C). After cooling, all became volatile Components removed in a vacuum. 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 approx. 60%).

Properties of the new 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 r ₃ (SiMe ₃ ) ₂ ], 6.77 [d , ⁴ J = 1.9 Hz, 4H, Csr ^ SiMe ^], 3.77 [ψ-oct, ³ J _H , _H « ³ , _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 (Cry ₃ ) ₃ ] ppm.

¹³ C- { ¹ H} -NMR (125 MHz, C ₆ D ₆ , 25 ° C): 5 = 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 signal of the solvent).

Examples 2-17

Manufacture of methyl methacrylate homopolymers

Examples 2 to 5: Variation of the amount of catalyst

In a glove box, 18 ml of toluene are filled into a cylindrical 20 ml screw-top glass jar (02.7 cm) and mixed with 4 equivalents of trimethyl aluminum based on the amount of catalyst. The amount of the catalyst complex given in Table 1 is added to the mixture thus obtained, dissolved therein and the catalyst solution thus obtained is heated to -35 ° C. in the refrigerator of the glove box for a few hours.

With intensive stirring using a magnetic stirrer, 2.0 ml (18.7 mmol, pMMA = 0.936 g / ml, M = 100.12 g / mol) likewise precooled methyl methacrylate (from Röhm GmbH & Co. KG) are added to the cooled solution. injected quickly. The polymerization solution becomes viscous within a few minutes and partially solidifies into a gel. to To ensure complete conversion, the batch is stirred for half an hour at -35 ° C. and for half an hour at room temperature. For working up, the product is dissolved in 150 ml of dichloromethane, the polymerization is stopped by adding 100 ml of methanol, and the solvent is then removed in vacuo on a rotary evaporator. The PMMA formed is obtained in quantitative yield as a white, powdery solid with a yield> 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 AIMe ₃ amount

In a glove box, 18 ml of toluene are poured into a cylindrical 20 ml screw-top glass jar (0 2.7 cm) and a defined amount of trimethyl aluminum, based on the amount of the catalyst complex (see Table 2), is added. 23.9 mg (37.4 μmol, 0.2 mol%, M = 640.17 g / mol) of the catalyst complex are added to the mixture thus obtained, dissolved therein and the catalyst solution thus obtained is left in the refrigerator of the glove box for a few hours tempered to the specified temperature.

With intensive stirring using a magnetic stirrer, 2.0 ml (18.7 mmol, pMMA = 0.936 g / ml, M = 100.12 g / mol) likewise preheated methyl methacrylate (from Röhm GmbH & Co. KG) are added to the cooled solution. injected quickly. Within a few minutes the Polymerization solution viscous and partially solidifies to a gel. To ensure complete conversion, the batch is stirred for half an hour at the specified reaction temperature and for a further half hour at room temperature. Working up is carried out as described in Example 2-5. Table 2.

Tacticity [%]

Example T AIMe ₃ educ. Λ MM _n syn. het. iso. Tg

[° C] l ^e q-] [%] [g / mol] [° C]

6 -35 2> 99 126,100 1, 17 76.5 22 1, 5

7 -35 4> 99 134,150 1, 18 76.5 22.5 1 121

8 -35 6> 99 115,500 1, 19 76.5 22.5 1 116

9 -15 2> 99 133,850 1, 31 75.5 23 1, 5 105

10 -15 4> 99 131,450 1, 30 76.5 22.5 1 110

11 -15 6> 99 133,450 1.33 75.5 23 1, 5 107

12 5 2 80 127.150 1, 51 74.5 24 1, 5 127

13 5 4 78 112.950 1, 42 74 24.5 1, 5 114

14 5 6 81 108.200 1, 48 75 23.5 1, 5 115

15 25 2 59 93,600 1, 44 74 24.5 1, 5 117

16 25 4 60 91,250 1, 48 73.5 25 1, 5 111

17 25 6 60 92,300 1, 47 74 24 2 113

Examples 18-21

Production of (methyl methacrylate) - (n-butyl methacrylate) -

block copolymers

In a glove box, 18 ml of toluene are placed in a cylindrical 20 ml

Screw cap glass (02.7 cm) filled and with 4 equivalents

Trimethylaluminum based on the amount of catalyst added. 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 for a few hours in the refrigerator

Glovebox tempered to -35 ° C.

With intensive stirring using a magnetic stirrer, the volume given in Table 3 is also added to the cooled solution Pre-cooled methyl methacrylate (Röhm GmbH & Co. KG) quickly injected. After a reaction time of 10 minutes, the volume of precooled n-butyl methacrylate (from Röhm GmbH & Co. KG) given in Table 3 is injected. (In the case of the control experiment, Example 18, the polymerization is terminated by adding methanol.) After stirring for a further 30 minutes at -35 ° C., stirring is continued for half an hour at room temperature. Working up is carried out as described in Example 2-5. VV v

Table 3.

E.g. MMA nBMA educ. M _w MM _n mol% MMA mol%

[Ml]

[ml] [%] [g / mol] is (theor.) nBMA is (theor.)

18 2 -> 99 117,900 1, 08 100 (100) -

19 2 1 191,650 1, 17 76.7 (74.8) 23.3 (25.2) 20 2 2 301,850 1, 28 60.3 (59.8) 39.7 (40.2) 21 1 1, 5

156,300 1.10 50.1 (49.8) 49.9 (50.2)

Examples 22-24

Production of (methyl methacrylate) - (2-ethylhexyl methacrylate) -

block copolymers

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

Table 4.

Claims

claims

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 means 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 take 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 having 1 to 6 carbon atoms, at least one R ^{8 representing} an alkyl group.

2. compound of 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)

* γ ^R2 (i),

Rl wherein

R ^{1 is} hydrogen or (-CC ₂ o) alkyl and

R ^{2 stands} for CSR ³ or COR ³ , where

R ^{3 is} OR ⁴ , SR ⁴ or NR R ⁵ , where

R ⁴ and R ^{5 are} independently the same or different 1 to 20 Are linear or branched alkyl, cycloalkyl or aryl groups containing carbon atoms,

where the alkyl, cycloalkyl or aryl groups optionally one or more CC double bonds, CC triple bonds, tertiary amino groups, carboxylalkyl groups, carboxycarbonylalkyl groups, N, N-dialkylated amide groups, N-arylated-N-alkylated amide groups, keto groups, epoxy groups, ether groups, May contain acetal groups, sulfonyl groups, sulfinyl groups, thioether groups, tertiary phosphine groups, alkyl dialkoxysilyl groups, dialkyl phosphonate groups and trialkyl phosphate 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 metal organanyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID)

Met (R ⁹ ) ₃ (IIIA)

(R ⁹ -AI-O) _n (IIIB)

(R ⁹ -AI-O-) _n -AI (R ⁹ ) ₂ (IIIC)

Zn (R ⁹ ) ₂ (IIID),

wherein Designated Met AI or B,

R ^{9 is} a linear or branched alkyl radical, one

Denotes 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 (-CC ₂₀ ) alkyl and

R ^{2 stands} for CSR ³ or COR ³ , where

R ^{3 is} OR ⁴ , SR ⁴ or NR ⁴ R ⁵ , where

R ⁴ and R ^{5 are} independently the same or different 1 to 20

Linear or branched alkyl having carbon atoms,

Are cycloalkyl or aryl groups,

where the alkyl, cycloalkyl or aryl groups optionally one or more CC double bonds, CC triple bonds, tertiary amino groups, carboxylalkyl groups, carboxycarbonylalkyl groups, N, N-dialkylated amide groups, N-arylated-N-alkylated amide groups, keto groups, epoxy groups, ether groups, acetal groups, sulfonyl groups, sulfinyl groups, thioether groups, tertiary phosphine groups, alkyldialkoxyskylphosphonyl 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 metal organanyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID)

Met (R ⁹ ) ₃ (IIIA)

(R ⁹ -AI-O) _n (IIIB)

(R ⁹ -AI-O-) _n -AI (R ⁹ ) ₂ (IIIC)

Zn (R ⁹ ) ₂ (IIID), wherein

Designated Met AI or B,

R ^{9 is} a linear or branched alkyl radical, one

Denotes 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 metal organanyl 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 rare earth metal (III) complex of the general formula (II) according to claim 1.

7. The method according to claim 5,

characterized in that

the at least one metal organanyl 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 rare earth metal (III) complex of the general formula (II) according to claim 2.

8. The method according to claim 4 or 5, characterized in that one

(a) the non-polar solvent and the at least one metal organyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) are mixed homogeneously in a reactor,

(b) adding the at least one organometallic rare earth metal (III) complex of the general formula (II) according to claim 1 and

(c) the one or more compound (s) of the formula (I), preferably likewise in a mixture with the at least one metal organyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID), in substance or as a solution to the resulting mixture from step (b) is added batchwise or continuously, the at least one metal organyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) being used in such an amount that the sum the amounts of the at least one metal organyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) used in step (a) and if appropriate in step (c) a molar excess of greater than 2: 1, based on the amount of at least one organometallic rare earth metal (III) complex of the general formula (II) according to claim 1 used in step (b).

9. The method according to claim 4,

characterized in that

the at least one metal organyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) is used in such an amount that the sum of the amounts used in step (a) and optionally in step (b) of the at least one metal organyl compound of the general formula (IIIA), (IIIB), (IIIC) and / or (IIID) a molar excess of greater than or equal to 6: 1, based on the amount of the at least one organometallic rare earth metal used in step (a) ( III) complex of the general formula (II).

10. The method according to one or more of the preceding claims,

characterized in that

compounds of the general formula (I) are used, in which

R ^{1 means} (dC ₄ ) alkyl and

R ^{2 stands} for COR ³ , where

R ³ OR ⁴ and R ^{4 are} (-C ₈ ) alkyl.

11. The method according to claim 8,

characterized in that

compounds of the general formula (I) are used, in which

R ^{1 is} methyl and

R ^{2 stands} for COR ³ , where

R ^{3 are} OR ⁴ and R ⁴ (dC ₄ ) alkyl.

12. The method according to claim 6, characterized in that

compounds of the general formula (I) are used in which 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 can be obtained from a mixture comprising 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

a catalytically active structure is used which can be obtained from a mixture comprising at least one organometallic rare earth metal (III) complex of the formula (IIA) in which A is a dimethylsilyl radical.

15. The method according to one or more of the preceding claims, characterized in that

one uses a catalytically active structure which can be obtained from a mixture comprising at least one organometallic rare earth metal (HI) complex of the formula (II), in which R ^{6 represents} a single-negatively charged amide ligand.

16. The method according to claim 11,

characterized in that

one uses a catalytically active structure which is obtainable from a mixture comprising at least one organometallic rare earth metal (III) complex of the formula (II) in which R ^{6 represents} bis (dimethylsilyl) amide, isopropyldimethylsilylamide or bis (methylsilyl) amide.

17. The method according to one or more of the preceding claims,

characterized in that

a catalytically active structure is used which can be obtained from a mixture comprising at least one organometallic rare earth metal (III) complex of the general formula (II), in which Ln La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc.

18. The method according to claim 16,

characterized in that one / 048176

47

uses a catalytically active structure which can be obtained from a mixture comprising at least one organometallic rare earth metal (III) complex of the general formula (II) in which Ln represents Y, LA, SM or Lu.

19. The method according to claim 17,

characterized in that

a catalytically active structure is used which can be obtained from a mixture comprising at least one organometallic rare earth metal (III) complex of the general formula (II) in which Ln is lanthanum or yttrium.

20. The method according to one or more of the preceding claims,

characterized in that

a catalytically active structure is used which can be obtained from a mixture comprising at least one organometallic rare earth metal (III) complex of the general formula (II), in which Cp is 1,3-bis (trimethylsilyl) cyclopentadiene.

21. The method according to one or more of the preceding claims,

characterized in that

a catalytically active structure is used which can be obtained from a mixture comprising at least one metal organyl compound of the general formula (IIIA), in which R ^{7 is} a linear or branched alkyl radical.

22. The method according to one or more of the preceding claims,

characterized in that

one uses a catalytically active structure which can be obtained from a mixture comprising at least one metal organyl compound of the general formula (IIIA), in which Met is Al.

23. The method according to claim 18,

characterized in that

one uses a catalytically active structure which is obtainable from a mixture comprising trimethyl aluminum, triethyl aluminum and / or triisobutyl aluminum.

24. The method according to one or more of the preceding claims,

characterized in that

the polymerization is carried out in a non-polar solvent.

25. The method according to claim 19,

characterized in that

the polymerization is carried out in toluene.

26. 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-CH3 groups.

27. The polymer or copolymer according to claim 22,

marked by

a polydispersity, which is given by M _w / M ", in the range from 1 to <1.5.

28. Use of the polymer or copolymer according to claim 26 or claim 27 for the production of PVC processing aids.

29. Use of the polymer or copolymer according to claim 26 or claim 27 for the production 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.