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WO2003048176A1 - Catalyseur pour preparer des (co)polymeres de composes (meth)acryliques - Google Patents

Catalyseur pour preparer des (co)polymeres de composes (meth)acryliques Download PDF

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Publication number
WO2003048176A1
WO2003048176A1 PCT/EP2002/012309 EP0212309W WO03048176A1 WO 2003048176 A1 WO2003048176 A1 WO 2003048176A1 EP 0212309 W EP0212309 W EP 0212309W WO 03048176 A1 WO03048176 A1 WO 03048176A1
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general formula
groups
complex
iiia
rare earth
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Hans GÖRLITZER
Dorothea Staschik
Alfons Kress
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Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes

Definitions

  • 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.
  • 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.
  • the technology requires polymerization processes that allow the targeted control of the molecular weight and in particular the molecular weight distribution.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ( ⁇ -Me)] 2 (Yasuda et al., Macromolecules, 1993, 26, 7134 - 7143) with comparable syndiotacticity.
  • R 1 is hydrogen or (-CC 20 ) alkyl
  • 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
  • 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,
  • Cp denotes an unsubstituted or substituted cyclopentadienyl group
  • Ln represents a rare earth metal in the +3 oxidation state
  • R 6 denotes an amide ligand capable of forming agostic interactions, the amide ligand being a
  • 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,
  • 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.
  • the invention enables the achievement of polymer strands with high syndiotacticity.
  • the polymers or copolymers obtainable by the process according to the invention have a narrow molecular weight distribution, preferably ⁇ 1.5.
  • copolymers which can be prepared by the process according to the invention can be controlled well and reproducibly in their composition.
  • 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.
  • 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.
  • 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 .
  • 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.
  • 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-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;
  • 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-
  • 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 methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy methoxy me
  • 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,
  • Trimethacrylates such as trimethyloylpropane trimethacrylate.
  • 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.
  • 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.
  • 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.
  • methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, benzyl methacrylate, 1, 1-diphenylmethyl methacrylate, triphenylmethyl methacrylate, methyl- ⁇ -ethyl acrylate, ethyl- ⁇ -ethyl acrylate and methyl ⁇ -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.
  • (-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;
  • (-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;
  • (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;
  • 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;
  • alkylaryl radicals such as diphenylmethyl or triphenylmethyl
  • (-C-C4) alkylthio- (C 1 -C 4 ) alkyl "for example methylthiomethyl, ethylthiomethyl, propylthiomethyl, 2-methylthioethyl, 2-ethylthioethyl or 3-methylthiopropyl;
  • 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;
  • alkenyl means an alkyl radical with at least one C — C double bond, such as oleyl, allyl or vinyl;
  • alkynyl an alkyl radical with at least one C-C triple bond, such as 2-propynyl
  • N, N-dialkylaminoalkyl radicals such as N, N-diethylaminoethyl
  • N-alkyl-N-arylaminoalkyl such as N-methyl-N-phenyl
  • alkylcarbonylalkyl such as acetonyl
  • alkenylcycloalkyl radicals, such as vinylcyclohexyl
  • alkylcycloalkyl such as trimethylcyclohexyl
  • alkoxyalkyl such as ethoxyethyl or butoxypropyl
  • epoxyalkyl radicals such as 2,3-epoxybutyl or 10,11-epoxyundecyl
  • dialkylphosphinoalkyl radicals such as dimethylphosphinomethyl
  • alkylphosphitoalkyl radicals such as diethylphosphitoethyl
  • dialkylphosphatoalkyl radicals such as diethylphosphatoethyl
  • alkylsulfinylalkyl radicals, such as methylsulfinylmethyl
  • alkylsulfonylalkyl radicals, such as ethylsulfonylethyl
  • alkylthioalkyl such as the methyl or the ethylthioethyl group
  • alkyldialkoxysilylalkyl radicals, such as methyldiethoxysilyl
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • cyclopentadienyl radicals can carry one or more substituents of the formula (R 7 ).
  • 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).
  • a catalytically active structure 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.
  • 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.
  • 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.
  • 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.
  • “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 ( ⁇ 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, ⁇ 3 coordination).
  • SiH "CH” and “SiCH3" ligand fragments are particularly capable of agostic interaction.
  • the same amide ligand can interact mono- or diagostically. So z.
  • the [N (SiHMe2) 2] ligand in (C ⁇ Me4H) 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.
  • 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
  • the compounds of the general formula (II) are accessible according to new synthetic routes.
  • 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).
  • This synthesis route according to the invention ensures the use of alkali metal complex (at complex) free catalyst precursors.
  • the complexes thus obtained can be used without further purification / isolation in the context of the present invention.
  • Monohalosilane can be obtained in the second reaction step by a dihalosilane.
  • 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) ⁇ 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.
  • 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.
  • 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.
  • 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.
  • metal organyl compounds of the general formula (IIIA) are 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.
  • 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.
  • 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.
  • 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
  • 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.
  • vegetable e.g. jojoba, rapeseed
  • animal e.g. claw oil
  • 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.
  • 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.
  • the process according to the invention shows a significantly reduced sensitivity to impurities.
  • the polymerization reaction of the invention may be carried out 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).
  • step (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.
  • 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 ⁇ -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.
  • 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.
  • the molecular weight distributions were determined via SEC (device configuration: ThermoQuest equipped with SEC columns (10 6 ⁇ , 10 5 ⁇ ; each 10 ⁇ m 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 ⁇ -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).
  • the ligand bis (trimetylsilyl) cyclopentadiene used in the present invention was obtained commercially from Aldrich.
  • a suitable base e.g. sodium hydride, butyllithium, etc.
  • 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.
  • the polymerization can also be stopped by stirring in 100 ml of methanol and the precipitated polymer can be filtered off.
  • Trimethylaluminum based on the amount of catalyst added 23.9 mg (37.4 ⁇ mol, 0.2 mol%,

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un complexe catalytique et un procédé pour préparer des polymères et/ou des copolymères de composés acryliques ou méthacryliques au moyen de ce complexe catalytique. Selon ce procédé, on fait polymériser un ou plusieurs composés monomères polymérisables de formule (I) en présence d'une structure à effet catalytique dans un solvant non polaire pour le composé à effet catalytique à des températures allant de 100 DEG C au point d'ébullition du solvant. La structure à effet catalytique in situ est constituée d'au moins un complexe organométallique de métal des terres rares (III) de formule (II) Cp2LnR6 et d'au moins un composé organométallique de formule (IIIA), (IIIB), (IIIC) et/ou (IIID) : Met(R9)3 (IIIA), (R9-AI-O)n (IIIB), (R9-AI-O)n-AI(R9)2 (IIIC), Zn(R9)2 (IIID). Selon l'invention, le composé organométallique de formule (IIIA), (IIIB), (IIIC) et/ou (IIID) est utilisé avec un excès molaire supérieur à 2:1, relativement au complexe organométallique de métal des terres rares (III) de formule (II), les restes R1, R2, Cp, Ln, R6, Met, R9 et n ayant la signification indiquée dans la description. La présente invention porte également sur les polymères et copolymères ainsi obtenus, lesquels ont une syndiotacticité élevée et une répartition du poids moléculaire étroite.
PCT/EP2002/012309 2001-12-04 2002-11-05 Catalyseur pour preparer des (co)polymeres de composes (meth)acryliques Ceased WO2003048176A1 (fr)

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DE2001159385 DE10159385A1 (de) 2001-12-04 2001-12-04 Verfahren und Katalysator zur Herstellung von Polymerisaten und/oder Copolymerisaten von Acrylverbindungen und von Methacrylverbindungen
DE10159385.6 2001-12-04

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WO2018086730A1 (fr) * 2016-11-08 2018-05-17 Merck Patent Gmbh Complexes métalliques contenant des ligands de cyclopentadiényle
CN109906228A (zh) * 2016-11-08 2019-06-18 默克专利有限公司 包含环戊二烯基配体的金属配合物
JP2020502044A (ja) * 2016-11-08 2020-01-23 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ シクロペンタジエニル配位子を含む金属錯体
JP7026683B2 (ja) 2016-11-08 2022-02-28 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング シクロペンタジエニル配位子を含む金属錯体
US11312730B2 (en) * 2016-11-08 2022-04-26 Merck Patent Gmbh Metal complexes containing cyclopentadienyl ligands
JP2022070966A (ja) * 2016-11-08 2022-05-13 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング シクロペンタジエニル配位子を含む金属錯体
JP7385687B2 (ja) 2016-11-08 2023-11-22 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング シクロペンタジエニル配位子を含む金属錯体
JP2024023276A (ja) * 2016-11-08 2024-02-21 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング シクロペンタジエニル配位子を含む金属錯体
IL266352B1 (en) * 2016-11-08 2024-11-01 Merck Patent Gmbh Metal complexes containing cyclopentadienyl ligands
IL266352B2 (en) * 2016-11-08 2025-03-01 Merck Patent Gmbh Metal complexes containing cyclopentadienyl ligands
US12286449B2 (en) 2016-11-08 2025-04-29 Merck Patent Gmbh Metal complexes containing cyclopentadienyl ligands
JP7702465B2 (ja) 2016-11-08 2025-07-03 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング シクロペンタジエニル配位子を含む金属錯体

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