WO2003022897A1 - Verfahren zur herstellung von polymerisaten und copolymerisaten von acrylverbindungen - Google Patents
Verfahren zur herstellung von polymerisaten und copolymerisaten von acrylverbindungen Download PDFInfo
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- WO2003022897A1 WO2003022897A1 PCT/EP2002/009151 EP0209151W WO03022897A1 WO 2003022897 A1 WO2003022897 A1 WO 2003022897A1 EP 0209151 W EP0209151 W EP 0209151W WO 03022897 A1 WO03022897 A1 WO 03022897A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
Definitions
- the invention relates to a process for the preparation of polymers
- Copolymers of acrylic compounds are directed to a process for the preparation of polymers and 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.
- 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.
- alkali metal product impurities can have a decisive influence on the course of the polymerization (syndiotactic or isotactic) (EP-A-0 462 588; Japanese Offenlegungsschrift Hei 7-292047, November 7, 1996).
- 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). It now appears to be of great technical importance to improve the synthesis of the catalyst precursors and possibly to combine them together with the polymerization reaction in a type of "one-pot process”.
- 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 copolymers of acrylic compounds To provide, which allows the use of easily manufactured and manageable catalysts.
- the new process should and in particular the production of polymer strands with high syndiotacticity and a tight
- the method should be simple, inexpensive and can be carried out on an industrial scale. It 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 not necessary if possible. 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.
- R 1 is hydrogen or (C r C 20 ) alkyl
- 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 of one another, identical or different, linear or branched alkyl, cycloalkyl or aryl groups having 1 to 20 carbon atoms,
- 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, alkyl dialkoxysilyl groups, dialkylphosphonate groups and trialkylphosphate groups,
- Cp denotes an unsubstituted or substituted cyclopentadienyl group
- Ln represents a rare earth metal in the +3 oxidation state
- R ö one capable of developing agostic interactions
- R 9 represents a linear or branched alkyl radical, a cycloalkyl radical or an aromatic radical and n represents an integer greater than or equal to 1,
- Impurities contained in the solvent and / or in the monomer so that their careful cleaning before 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 indispensable for carrying out the polymerization processes known to date.
- 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.
- the organometallic rare earth (Ji ⁇ ) complexes to be used as catalyst precursors according to the invention ensure the freedom from alkali metal complexes due to their synthetic route. •
- the catalyst precursors 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 r C 20 ) alkyl, advantageously a (CC 20 ) alkyl, preferably a (CC 8 ) alkyl, in particular a 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 aciylthiocarbonyl 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 have 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, sulfonyl groups, sulfonyl groups, sulfonyl groups, sulfonyl groups Contain thioether groups, tertiary phosphine groups, alkyl dialkoxysilyl groups, dialkyl phosphonate groups and trialkyl phosphate groups.
- the following compounds have proven to be particularly suitable:
- Alkyl acrylates which are 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-hexyl 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, isobomylacrylate, 1-methylcyclohexyl acrylate;
- Glycol diacrylates such as 1,4-butanediol diacrylate, methylene diacrylate, 1,3-butanediol diacrylate, triethylene glycol diacrylate, 2,5-dimethyl-l, 6-hexanediol diacrylate, 1,10-decanediol diacrylate, 1, 2-propanediol diacrylate, diethylene glycol;
- Acrylates of ether alcohols such as tetrahydrofurfuryl acrylate, vinyloxyethoxyethyl acylate, methoxyethoxyethyl acrylate, 1-butoxypropyl acylate, 1-methyl- (2-vinyloxy) ethyl acrylate, cyclohexyloxymethyl acrylate, methoxymethoxyethyl acrylate, benzyloxymethylacrylate, furfurylacrylate, 2-butoxyethyl acrylate, 2-ethoxyethoxymethyl acrylate, 2-ethoxyethyl acrylate, allyloxymethyl 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-
- 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, 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-phenylmethacrylamide, N, N-diethylmethac ⁇ ylamide, N, N-dimethylmethacrylamide;
- Aminoalkyl methacrylates such as tris (2-methacryloxyethyl) amine, 3-diethylaminopropyl methacrylate;
- Ayl 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, Ca-boxymethyl methacrylate, N- (2-methacryloyloxyethyl) -2-pyrrolidinone, N- (3-methacryloyloxypropyl) -2-pyrrolidinone, N-methacryloylmo holin, acetonyl methacrylate, N-methacryloyl-2-pyrrolidinone ; Cycloalkyl methacrylates, such as 3-vinylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, bornyl methacrylate, cyclopenta-2,4-dieny
- Glycol dimethacrylates such as 1,4-butanediol dimethacrylate, methylene dimethacrylate, 1,3-butanediol dimethacrylate, triethylene glycol dimethacrylate, 2,5-dimethyl-l, 6-hexanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,2-propanediol dimethacrylate, diethylene glycol acrylate;
- Methacrylates of ether alcohols such as tetrahyclrofurfuryl methacrylate,
- Methacylates 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, dimethylphosphinomethylphosphate phosphate, dimethylphosphonoethyl methacrylate phosphate, diethyl methacrylate, sulfur-containing methacrylates, such as ethylsulfmylethyl methacrylate, ethylsulfonylethyl me
- R 1 is (C r C 4 ) alkyl and R 2 is COR 3 , where R 3 is OR 4 and R 4 are (C r 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.
- methyl methacrylate, ethyl methacrylate, isopropyl methyl acrylate, n-butyl methacrylate, t-butyl methacrylate, benzyl methacrylate, 1,1-diphenylmethyl methacrylate, triphenylmethyl methacrylate, methyl- ⁇ -ethyl acrylate, ethyl- ⁇ -ethyl acrylate has been used in the process according to the invention
- Methyl propyl acrylate, in particular methyl methacrylate (R 1 is methyl and R 2 is COOCH 3 ) has been found to be particularly advantageous.
- (C 1 -C 4 ) -alky 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;
- (C r C 8 ) alkyl the abovementioned alkyl radicals, and for example the pentyl, 2-methylbutyl, 1,1-dimethylpropyl, hexyl, heptyl, octyl or the 1, 1, 3,3-tetramethylbutyl residue;
- alkyl radicals 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
- 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 radicals such as N-methyl-N-phenyl
- alkylcarbonylalkyl such as acetonyl
- alkenylcycloalkyl radicals, such as vinylcyclohexyl
- alkylcycloalkyl radicals, such as trimethylcyclohexyl
- alkoxyalkyl such as ethoxyethyl or butoxypropyl
- 2,2-dialkyl-1,3-dioxolan-4-yl-alkyl radicals such as 2,2-dimethyl-1,3-dioxolan-4-yl-methyl
- epoxyalkyl radicals such as 2,3-epoxybutyl or 10,11-epoxyundecyl
- dialkylphosphinoalkyl radicals such as dimethylphosphinomethyl
- alkylphosphitoalkyl radicals such as diethylphosphitoethyl
- dialkylphosphatoalkyl such as diethylphosphatoethyl
- alkylsulfinylalkyl 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 formula (I) are reacted according to the invention in the presence of a catalytically active structure, i.e. oligomerized or polymerized.
- a catalytically active structure i.e. 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), (UIC) and / or (IHD).
- the compounds of the formulas (II) and (IIIA), (RISS), (UIC) and / or (IHD) 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 (U) 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).
- Particularly useful results in the polymerization of Compounds of formula (I), preferably methyl methacrylate (MMA), are obtained 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 alkyl radicals having one to 20 carbon atoms, preferably one to eight
- Cp should be mentioned by way of example: 2-ethylcyclopentadien-1-yl, 2-methylcyclopentadien-l-yl, 2,3,4,5-tetamethylcyclopentadien-1-yl, pentamethylcyclopentadienyl. Of these, 2,3, 4, 5-tetramethylcyclopentadien-1-yl and pentamethylcyclopentadienyl are particularly preferred.
- a catalytically active structure which can be obtained from a mixture comprising at least one organometallic rare earth metal ( ⁇ i) complex in which the two cyclopentadienyl rings are bridged and represent a double-negatively charged ligand ,
- ⁇ i organometallic rare earth metal
- ligands can be represented by the formula (ILA)
- A (CH 3 ) 2 Si gives the best results.
- (Cp) A (Cp) radical include bis (2-methylcyclopentadien-l-yl) methyl, bis (2-methylcyclopentadien-l-yl) ethyl, 2,3-bis (2-methylcyclopentadien-1 -yl) propyl, bis (2-methylcyclopentadien-1-yl) dimethylsilyl, bis (2,3,4,5-tetramethylcyclopentadien-l-yl) methyl, bis (2,3,4,5-tetramethylcyclopentadien-l-yl ) ethyl, bis (2,3,4,5-tetramethylcyclopentadien-l-yl) dimethylsilyl and the like.
- R ⁇ in the compound of the formula (II) or formula (ILA) denotes an amide ligand capable of developing agostic interactions.
- ligands capable of developing 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 rest R s can form a mono- or diagostic
- “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 under “Diagostic” interaction is understood to mean an interaction in which the ligand R 6 additionally interacts with the metal center via two further ligand fragments (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 (C5Me4H) 2-YN (SiHMe2) 2 exhibits a monoagostic interaction with the yttrium center, while it is diagostically bound in (CsMe4-SiMe2-C5Me4) 2 -La-N (SiHMe2) 2 is.
- lanthanoidocenamide complexes are particularly preferred which contain either a highly substituted bridged cyclopentadienyl ligand or two highly substituted non-bridged cyclopentadienyl ligands because these complexes support the highly syndiotactic polymerization of acrylic acid esters.
- highly substituted bridged cyclopentadienyl ligands refer to cyclopentadienyl ligands which, in addition to the bridge, have at least 3, preferably 4, further substituents other than hydrogen per cyclopentadienyl ring.
- the highly substituted, non-bridged cyclopentadienyl ligands have at least 4, preferably 5, substituents other than hydrogen per cyclopentadienyl ring.
- Residues R 6 which are able to perform the interaction required in the context of the invention, include, among others, single-negatively charged residues of the formula ° NR 7 R 8 , in which R 7 and R ⁇ independently of one another are identical or different (C r C 20 ) -Alkyl, cycloalkyl, (CC 4 ) -alkylthio- (C r C 4 ) - alkyl, alkylaryl or aryl.
- R 7 and R 8 are preferably, independently of one another, identical or different branched alkyl radicals having three to four carbon atoms, such as isopropyl, or dialkylsilyl radicals in which the alkyl radicals have one or four carbon atoms, identical or different from one another, such as dimethylsilyl or else Methylethylsilylrest.
- the radicals R 7 and R 8 are also particularly advantageously different from one another, for example R 7 is an isopropyl radical and R 8 is a dimethylsilyl radical.
- the compounds of the general formula (EL) 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 lanthanidocene complexes useful in the process of the invention can be according to the reaction of rare earth damides of the type
- the lanthanoidocenamide complexes obtained according to scheme 1 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) x 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 (HIA), (IIIB), (IIIC) and / or (HID) is required to produce the structure which is active according to the invention.
- the metal organyl compound of the general formula (ILIA) includes boron and aluminum alkyls, cycloalkyls and aryls.
- the metal organyl compound of the general formula (IÜB) and (IIIC) include alumoxanes, the formula (IIIB) describing the cyclic form and the formula (UIC) the linear form.
- the metal organyl compound of the general formula (IHD) 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 used according to the invention particularly preferred. 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.
- Metallorganyl compound of the general formula (IIIA), (UIB), (IIIC) and / or (HID) can be used individually or as a mixture of several metal organyl compounds of the general formula (HIA), (Hffi), ( ⁇ iC) and / or (IHD).
- metal organyl compounds of the general formula (HIA) is preferred.
- Particularly suitable metal organyl compounds of the general formula (HIA) are particularly suitable.
- Metallorganyl compounds of the general formula (IHA) include boron trimethyl, boron triethyl, boron tri-n-propyl, boron trisisopropyl, boron tri-n-butyl, boron triisobutyl, aluminum trimethyl, aluminum triethyl, aluminum tri-n-propyl, aluminum triisopropyl, aluminum tri-n-butyl and aluminum triisobutyl , Aluminum triethyl and aluminum triisobutyl.
- the at least one metal organyl compound of the general formula (IHA), (H1B), (HIC) and / or (HID) is advantageously larger in a molar excess of greater than 4: 1, preferably greater than 5: 1 than 6: 1, in particular greater than 8: 1, very particularly preferably greater than 10: 1, in each case based on the at least one organometallic rare earth metal (HI) complex of the general formula (II).
- the catalytically active structure is generally used in a concentration in the range from 10 "5 mol / 1 to 3 mol / 1, preferably in the range from 10 " 4 mol / 1 to 10 "1 mol / 1 and particularly preferably in the range from 10 " 3 mol / 1 to 10 "2 mol / 1 are used, without this being intended to impose any restriction.
- the corresponding information relates to the Ln contained in the catalytically active structure.
- the ratio of catalytically active structure to monomer gives the molecular weight of the Polymers if all of the monomer is reacted. This ratio is preferably in the range from 10 " ⁇ to 1 to 0.5 to 1, particularly preferably in the range from 10 "4 to 1 to 10 " 2 to 1.
- the corresponding information relates to the Ln contained in the catalytically active structure.
- the process according to the invention preferably takes place in the presence of a non-polar solvent in a homogeneous system.
- the dielectric constant which is preferably ⁇ 4, preferably ⁇ 3 and very particularly preferably ⁇ 2.5, can serve as a measure of the polarity of the solvent. This value is determined at 20 ° C., the person skilled in the art finding valuable information regarding the measurement in Ullmanns Encyklopadie der Technische Chemie, 1966, Volume H / 2, pages 455 to 479.
- Particularly suitable solvents include hydrocarbon solvents, in particular aromatic solvents, such as toluene, mesitylene, benzene, 1,2-xylene, 1,3-xylene and 1,4-xylene, saturated hydrocarbons, such as cyclohexane, heptane, octane, nonane, decane, Dodecane, which can also be branched, mineral oils and synthetic oils.
- aromatic solvents such as toluene, mesitylene, benzene, 1,2-xylene, 1,3-xylene and 1,4-xylene
- saturated hydrocarbons such as cyclohexane, heptane, octane, nonane, decane, Dodecane, which 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.
- the solvents
- Mineral oils are known per se and are commercially available. They are generally obtained from crude oil or crude oil by distillation and / or refining and, if appropriate, further purification and upgrading processes, the term mineral oil particularly including the higher-boiling fractions of crude or petroleum. In general, the boiling point of mineral oil is higher than 200 ° C, preferably higher than 300 ° C, at 5000 Pa. Production by smoldering shale oil, coking coal, distillation under
- 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 aiOmatic, cyclic, branched and linear, depending on their origin Hydrocarbons. 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 andrelatedproducts".
- 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 1 to 99% by weight, particularly preferably 5 to 95% by weight and very particularly preferably 10 to 60% by weight. %, based on the total weight of the mixture used.
- the temperatures at which the polymerization reactions are carried out are generally between -100 ° C. or the solidification point and the boiling point of the solvent used. Temperatures between -50 ° C and +100 ° C are preferred, particularly preferably between -30 ° C and +50 ° C, even more preferably between 0 ° C and +25 ° C.
- the process according to the invention shows a significantly reduced sensitivity to impurities in comparison with conventional “living polymerization systems”. It places far fewer demands on the purity of the components to be used, in particular of the solvent and the monomer, so that the otherwise necessary cleaning steps are no longer absolutely necessary. For example, carrying out the polymerization using industrial solvents and technically pure monomers also leads to very good results.
- 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 carried out under an inert gas atmosphere (nitrogen and / or argon).
- the nonpolar solvent and the at least one metal organyl compound of the general formula (IHA), (HIB), (HIC) and / or (HID) are mixed homogeneously in a reactor (b) the at least one organometallic rare earth metal ( ⁇ i) 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 (IHA) , (HIB), ( ⁇ iC) and / or (IHD) are added in bulk or as a solution to the resulting mixture from step (b) batchwise or continuously.
- the at least one metal organyl compound of the general formula ( ⁇ iA), (IHB), (IHC) and / or ( ⁇ iD) is used in such an amount that the sum of those used in step (a) and optionally in step (b) Amounts of the at least one metal organyl compound of the general formula (HIA), (HIB), (HIC) and / or (IHD) have a molar excess of greater than 4: 1, preferably greater than 5: 1, advantageously greater than 6: 1, in particular greater than 8: 1, very particularly preferably greater than 10: 1, in each case based on the amount of the at least one organometallic rare earth metal (IH) complex of the general formula (H) used in step (a).
- IH organometallic rare earth metal
- 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 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 are distinguished by a high syndiotacticity, based on the 1 H-NMR analysis of the -CH3 groups.
- 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 1, in the range from 1 to ⁇ 1.5, advantageously 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 (ThermoQuest device configuration 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 calibrated against polystyrene (Polymer Laboratories) The (triad) tacticities were calculated from iH-NMR spectra (FT; 500 MHz; 1H), recorded at ambient temperature in CDCI3, with evaluation of the ⁇ -CH3 signals. The DSC measurements were carried out under nitrogen with a heating rate of 1 OK / min in the range 20-160 or 220 ° C carried out (device Mettler DSC 820).
- the lanthanoidocenamide complex was characterized by IR spectra, NMR and mass spectrometry, elemental analysis and single-crystal X-ray structure analysis.
- Polymerization was stopped by adding 100 ml of methanol and then the solvent was removed on a rotary evaporator in vacuo.
- 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.
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP02762449A EP1427763A1 (de) | 2001-09-07 | 2002-08-16 | Verfahren zur herstellung von polymerisaten und copolymerisaten von acrylverbindungen |
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DE10144140.1 | 2001-09-07 | ||
DE2001144140 DE10144140A1 (de) | 2001-09-07 | 2001-09-07 | Verfahren zur Herstellung von Polymerisaten und Copolymerisaten von Acrylverbindungen |
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WO2003022897A1 true WO2003022897A1 (de) | 2003-03-20 |
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PCT/EP2002/009151 WO2003022897A1 (de) | 2001-09-07 | 2002-08-16 | Verfahren zur herstellung von polymerisaten und copolymerisaten von acrylverbindungen |
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EP (1) | EP1427763A1 (de) |
DE (1) | DE10144140A1 (de) |
WO (1) | WO2003022897A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN115260367A (zh) * | 2022-08-26 | 2022-11-01 | 中国科学院长春应用化学研究所 | 稀土金属配合物在乙烯和1,3-丁二烯制备乙烯/丁二烯共聚物过程中的应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0442476A2 (de) * | 1990-02-14 | 1991-08-21 | Showa Denko Kabushiki Kaisha | Verfahren zur Herstellung eines Polymers oder Copolymers eines Esters einer ungesättigten Karbonsäure |
US5527751A (en) * | 1993-06-29 | 1996-06-18 | Maruzen Petrochemical Co., Ltd. | Polymerization catalyst and method for producing polyolefin or olefin block copolymer using the same |
-
2001
- 2001-09-07 DE DE2001144140 patent/DE10144140A1/de not_active Ceased
-
2002
- 2002-08-16 WO PCT/EP2002/009151 patent/WO2003022897A1/de not_active Application Discontinuation
- 2002-08-16 EP EP02762449A patent/EP1427763A1/de not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0442476A2 (de) * | 1990-02-14 | 1991-08-21 | Showa Denko Kabushiki Kaisha | Verfahren zur Herstellung eines Polymers oder Copolymers eines Esters einer ungesättigten Karbonsäure |
US5527751A (en) * | 1993-06-29 | 1996-06-18 | Maruzen Petrochemical Co., Ltd. | Polymerization catalyst and method for producing polyolefin or olefin block copolymer using the same |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115260367A (zh) * | 2022-08-26 | 2022-11-01 | 中国科学院长春应用化学研究所 | 稀土金属配合物在乙烯和1,3-丁二烯制备乙烯/丁二烯共聚物过程中的应用 |
CN115260367B (zh) * | 2022-08-26 | 2023-10-10 | 中国科学院长春应用化学研究所 | 稀土金属配合物在乙烯和1,3-丁二烯制备乙烯/丁二烯共聚物过程中的应用 |
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DE10144140A1 (de) | 2003-03-27 |
EP1427763A1 (de) | 2004-06-16 |
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