EP1237942A1 - Verfahren zur (co)polymerisation von polaren und unpolaren monomeren - Google Patents
Verfahren zur (co)polymerisation von polaren und unpolaren monomerenInfo
- Publication number
- EP1237942A1 EP1237942A1 EP00977581A EP00977581A EP1237942A1 EP 1237942 A1 EP1237942 A1 EP 1237942A1 EP 00977581 A EP00977581 A EP 00977581A EP 00977581 A EP00977581 A EP 00977581A EP 1237942 A1 EP1237942 A1 EP 1237942A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- aryl
- monomers
- carbon atoms
- transition metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
-
- 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
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
Definitions
- the present invention relates to a process for the transition metal-catalyzed preparation of polymers having a syndiotactic or predominantly syndiotactic structure from vinylaromatic monomers and a process for the production of block copolymers from vinylaromatic monomers and olefinically unsaturated polar monomers.
- the invention further relates to the block copolymers obtained by the process mentioned and to their use as impact modifiers in the production of fibers, films or moldings.
- the invention relates to fibers, films or moldings containing the aforementioned block copolymers.
- Transition metal complexes based on rare earth metals have recently been increasingly investigated for their suitability as catalysts for the coordinative polymerization of nonpolar or polar olefinically unsaturated monomers (cf. H. Yasuda, E. Ihara, Bull. Chem. Soc. Jpn., 1997 , 70, pp. 1745 to 1767).
- metal complexes with one or two metal centers are used, and satisfactory results can often only be achieved if a suitable cocatalyst is used.
- the polymerization of styrene succeeds in the presence of a catalyst mixture consisting of complexes of the formula Sm (0-i-Pr) 3 or Nd (acac) 3 and aluminum trialkyl compounds.
- it was also possible to polymerize styrene with monometallic samarium and lanthanum complexes without being dependent on a cocatalyst only atactic polystyrene was likewise obtained.
- Syndiotactic polystyrene ie those with a rr triad fraction> 70%, is suitable for use due to its good mechanical properties and its thermal stability
- the present invention was therefore based on the object of providing a preparatively simple block copolymerization process for the production of block copolymers from vinylaromatic and polar monomer units.
- M scandium, yttrium, lanthanum or a lanthanoid metal
- R is hydrogen, halogen, Ci to C 20 alkyl, C 3 - to -C 0 cycloalkyl, C ⁇ - to Cis-aryl or C 3 - to C 3 rj-organosilyl, two adjacent radicals R optionally being a 4 to Form 18 saturated or unsaturated cyclic or heterocyclic groups,
- R is hydrogen, C ⁇ ⁇ to C 2 o-alkyl, C 3 - to Cio-cycloalkyl,
- Metal hydride complexes (I) in which the substituents and indices have the following meaning are preferably used:
- L tetrahydrofuran, 2, 5-dialkyltetrahydrofuran, dioxane, dialkyl ether, acetonitrile, triarylphosphine or halogenated triarylphosphine.
- the central metals M scandium, yttrium, lanthanum or lanthanide metal such as cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium are suitable (see also textbook of inorganic chemistry, Hollemann-Wiberg, de Gruyter, Berlin, 1985, p. 59). Yttrium, lanthanum, lutetium and ytterbium are preferably used, particularly preferably terbium and erbium as the central metal M.
- R radicals for example by Halogen such as fluorine, chlorine or bromine, linear or branched C ⁇ ⁇ to C rj alkyl, preferably C ⁇ ⁇ to C ⁇ 0 alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, C 3 - to C ⁇ o ⁇ cycloalkyl, preferably C 3 - to C 7 cycloalkyl, such as cyclopropyl or cyclohexyl, or C ⁇ ⁇ to C ⁇ s-aryl, preferably ⁇ to C ⁇ o-aryl, such as phenyl or
- Suitable aryl substituents include, for example, C 6 to C 6 alkyl such as methyl or i-propyl or C 6 to C 6 aryl substituted with halogen such as fluorine, chlorine or bromine, preferably C 6 to C 6 aryl.
- Two adjacent radicals R can also together form a saturated or unsaturated cyclic or heterocyclic group containing 4 to 18, preferably 4 to 15 carbon atoms. This includes, for example, condensed aryl units. Accordingly, indenyl, fluorenyl or benzindenyl systems are also suitable monoanionic ⁇ 5 -bound cyclic ligands.
- R * can independently of one another C ⁇ ⁇ to C ⁇ o-alkyl, preferably C ⁇ ⁇ to C 7 alkyl, for example methyl, ethyl or i-propyl, C 3 - bis
- C ⁇ o-cycloalkyl preferably C 3 - to C -cycloalkyl, for example cyclopropyl or cyclohexyl, C ⁇ - to C ⁇ o ⁇ aryl, preferably phenyl, or alkylaryl with 1 to 4 carbon atoms in the alkyl and 6 to 10 carbon atoms in the aryl part , for example benzyl.
- radicals R in a compound (I) can both agree and have different meanings.
- ⁇ 5 -bonded ligands among the aforementioned compounds those are particularly suitable which are derived from cyclopentadienyl, tetra-C ⁇ - to Ce-alkylcyclopentadienyl, indenyl, fluorenyl or benzindenyl, the three the latter ligands can also be substituted one or more times with C ⁇ ⁇ to C ⁇ alkyl groups.
- Preferred radicals bearing the substituent Z are cyclopentadienyl, tetra-C - to C 4 -alkylcyclopentadienyl, indenyl, benzindenyl and 1- to 3-fold C ⁇ ⁇ to C 4 -alkyl-substituted indenyl or benzindenyl.
- Cyclopentadienyl, tetramethylcyclopentadienyl or indenyl, in particular tetramethylcyclopentadienyl is particularly preferably used.
- complexes (I) which have identical ⁇ 5 -bound ligands. However, these ligands can also differ from one another in their ring system as such and / or in their ring substitution pattern.
- Suitable radicals Z are bivalent structural units based on monatomic bridge members, the free valences of which may be saturated by organic radicals R '.
- Suitable bridge bridges are, for example, the silyl- (-SiR ' 2 -), alkyl- (-CR' 2 -), Germanyl- (-GeR ' 2 -), stannyl- (-SnR' 2 -), boranyl- ( -BR'-) or the oxo group (-0-).
- Z naturally does not necessarily have to be in the form of two identical structural units.
- the two-part bridge segments are in particular the systems -SiR '-SiR' 2 -, -SiR '-CR' 2 -,
- the radicals R ' can be C ⁇ ⁇ to C rj-alkyl, preferably C ⁇ _ to C ⁇ o-alkyl, for example methyl, ethyl or i-propyl, C 3 - to C ⁇ rj-cycloalkyl, preferably C 3 - to C 7 -cycloalkyl, for example cyclohexyl, C ⁇ , - to C ⁇ s-aryl, preferably C 6 ⁇ to C ⁇ rj-aryl, especially phenyl, or alkylaryl with 1 to 10 carbon atoms in the alkyl and 6 to 10 carbon atoms in the aryl part, for example benzyl.
- the Z radicals are Di-C ⁇ - bis
- C -alkyl-substituted silyl groups such as dimethylsilyl, diethylsilyl or di-i-propylsilyl are particularly preferred.
- the unit X includes, for example, the oxo (-0-), thio- (-S-), amido ((-NR "-) or the phosphido group (-PR" -). These groups are usually connected to the metal center M via an ⁇ x bond. Furthermore, X can also represent a neutral two-electron donor such as -OR ", -SR", -NR " 2 or -PR". The latter radicals X mostly have a coordinative link to the metal center M via a free pair of electrons. X preferably represents an oxo or thio group, particularly preferably an amido unit.
- R "in the radicals -NR" -, -PR "-, -OR", -SR ", -NR” or -PR " 2 are generally hydrogen, C ⁇ ⁇ to C 20 alkyl, C 3 - to C ⁇ o ⁇ cycloalkyl, C 6 - to C ⁇ s-aryl , Alkylaryl with 1 to 10 carbon atoms in the alkyl and 6 to 10 carbon atoms in the aryl part or C 3 - to C 30 organosilyl.
- radicals R "are sterically demanding groups such as C 3 - to C 10 -alkyl groups , for example i-propyl or t-butyl, the C ⁇ - to C ⁇ rj aryl group such as phenyl or substituted phenyl, and the alkylaryl group with 1 to 6 C atoms in the alkyl and 6 to 10 C atoms in the aryl part, for example benzyl , X -N (t-butyl-) or -N (1,1-dimethyl-propyl) is used particularly frequently as the unit X.
- groups such as C 3 - to C 10 -alkyl groups , for example i-propyl or t-butyl, the C ⁇ - to C ⁇ rj aryl group such as phenyl or substituted phenyl, and the alkylaryl group with 1 to 6 C atoms in the alkyl and 6 to 10 C atoms in the aryl part, for example benz
- Residuals R '''in include linear and branched alkyl residues. These can also be substituted one or more times with inert functional groups such as fluorine, nitro or nitrile.
- C 3 to C 20 / in particular C 4 to C 10 alkyl radicals are preferably used, linear alkyl radicals being particularly preferred.
- alkyl radicals examples include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-hexadecyl and n- eicosyl.
- N-Hexyl is particularly suitable as the radical R '''.
- the radicals R '''in a compound (I) can have identical or different meanings. Identical radicals R '''are usually present in a compound (I).
- the radical R ''' is connected, preferably via the carbon atom located at the chain end of the alkyl radical, to the two metal centers of the binuclear metal complex via ⁇ bonds.
- the ligands and radicals R, R ', R'',R''', L, Z and X as well as the central metal M and the ⁇ each occurring two or more times in a complex 5 -bound ligand system in a compound (I) both agree and assume different meanings.
- the ligands, the radicals and the central metals M agree in their respective meanings.
- the polymerization-active transition metal compounds (I) used in the processes according to the invention are either coordinatively unsaturated at all p metal centers or at least one metal center of the complex, ie the metal centers are present in the transition metal compound as so-called 16-electron species (the ligand coordination point L remains implemented).
- Preferred transition metal compounds (I) are those in which the ligand coordination point L remains unoccupied at all or at almost all metal centers.
- the inventive Driving naturally also include catalyst systems in which the aforementioned different transition metal compounds are present side by side.
- bi- or higher-nuclear metal complexes may also be present, in which all metal centers are coordinatively saturated with ligands L.
- L represents a low molecular weight organic Lewis base, i.e. a compound which has a two-electron donor.
- the ligand L in these cases is, for example, tetrahydrofuran, 2, 5-dialkyltetrahydrofuran such as 2, 5-dimethyltetrahydrofuran, dioxane, dialkyl ethers such as diethyl ether or diethyl ether, acetonitrile, triarylphosphine, especially tri - phenylphosphine, or partially or perhalogenated triarylphosphine such as tris (p-fluorophenyl) phosphine or tris (pentafluorophenylphosphine).
- Preferred metal alkyl complexes are, for example, [Y ( ⁇ 5 : ⁇ 1 -CsMe 4 SiMe 2 NCMe 3 ) ( ⁇ -R "')] 2, [Tb ( ⁇ 5 : ⁇ 1 -C 5 Me 4 SiMe 2 NCMe 3 ) ( ⁇ -R '")] and [Sc ( ⁇ 5 : ⁇ 1 -C 5 Me 4 SiMe 2 NCMe 3 ) ( ⁇ -R''')] 2 with R '''in the meaning of i-butyl and / or i-propyl, preferably n-butyl, n-octyl and / or n-decyl and the complex [Cp * Y (OC 6 H 3 -2, 6-t-Bu 2 )] 2 ( ⁇ ⁇ H) ( ⁇ - R ''') with R'''' meaning ethyl, i-propyl, i-butyl or n-hexyl
- a ligand L for example in the form of a low molecular weight neutral Lewis base
- n 1 for all p metal centers of (I)
- Usually, 50-60% of the coordinatively bound ligand L can be removed at a vacuum of 5 ⁇ 10 -3 mmHg for one hour, as a result of which the starting complex described is converted into the polymerization-active compounds (I).
- Any mixtures of transition metal compounds (I) can also be used, in which complexes with one, more or p unsaturated metal centers next to each other.
- it is harmless to the success of the processes according to the invention if, in addition to the polymerization-active transition metal compounds (I), there are also those in which all p metal centers are coordinatively saturated by electron donor ligands L.
- the latter compounds do not take part in the reaction, they can be used to generate the active catalyst species, if necessary, by briefly applying a vacuum, even during the polymerization process. In this way it is possible, even during the course of the polymerization, to influence the polymerization activity in a simple manner by increasing the concentration of active polymerization catalyst without the need for external catalyst addition.
- 1-olefins in particular C 3 - to C o ⁇ 1-olefins.
- 1-Hexene, 1-octene, 1-decene or mixtures thereof are preferably used.
- With two equivalents of 1-olefin, based on the binuclear starting transition metal compound it is usually possible to achieve quantitative conversion in about 2-24 hours at room temperature.
- the transition metal compounds mentioned above can also be prepared at higher temperatures, for example at 60 ° C. and above, without the polymerization of 1-olefins being ascertained.
- the compounds (Ia) regularly have C 1l symmetry.
- the binuclear bishydride-bridged transition metal compounds (Ib) are generally obtained by hydrogenating treatment of mononuclear metal complexes of the general formula (II)
- n 0 or 1 and the other substituents and indices have the general or preferred meaning already described above.
- the desired metal complex is usually obtained in high yield, optionally in the form of an isomer mixture.
- the binuclear complexes (Ib) are prepared in inert solvents, for example a low molecular weight aliphatic hydrocarbon such as n-pentane, n-hexane or cyclohexane, an aromatic hydrocarbon such as benzene, toluene or xylene or a halogenated hydrocarbon such as dichloromethane or Chloroform performed. Aliphatic hydrocarbons such as n-pentane and n-hexane are preferably used.
- Complexes of the general formula (I) are thermally very stable and show no CH activation or H / D exchange with divergent solvents even at 50 ° C.
- Mononuclear complexes of the general formula (II) can be problem-free, for example starting from compounds of the type Y [CH 2 - n (SiMe 3 ) ⁇ + n ] 3 (Ha), by reaction with compounds such as [C 5 R ( H) (SiR ' 2 -XH)] (Ilb), e.g.
- the defined metal complex (I) according to the invention can be used both as such and in the form of any mixture of compounds covered by the general formula (I) as a catalyst for the polymerization of vinylaromatic monomers or for the copolymerization of vinylaromatic with polar monomers, in particular of polar olefinically unsaturated monomers are used.
- all mononuclear or polynuclear aromatic compounds which have one or more vinyl groups are suitable as vinylaromatic monomers.
- the aromatic ring systems of these compounds can also be heteroaryl and contain, for example, one or more heteroatoms such as O, S and / or N as ring atoms.
- the ring systems can be substituted with any functional groups.
- Preferred vinyl aromatic compounds are those which are mono- or dinuclear unsubstituted or with alkyl groups or halogen atoms represent substituted aromatic or heteroaromatic ring systems of 5 to 10 ring atoms, with 0, 1, 2 or 3 heteroatoms, the preferred heteroatom is nitrogen.
- Suitable heteroaromatic vinyl compounds are, for example, 2-vinylpyridine or 4-vinylpyridine.
- Suitable polynuclear vinyl aromatic compounds are 4-vinylbiphenyl or 4-vinylnaphthalene.
- Particularly suitable vinyl aromatic monomers are compounds of the general formula (III)
- R 1 is hydrogen, C ⁇ -to C ⁇ -alkyl or a halogen atom and R 2 is C ⁇ ⁇ to Cs-alkyl or a halogen atom and k assumes the value 0, 1, 2 or 3.
- Particularly suitable as vinyl aromatic monomers (III) are styrene, ⁇ -methylstyrene, o-, m-, p-methylstyrene, p-ethylstyrene, 3-vinyl-o-xylene, 4-vinyl-o-xylene, 2-vinyl-m -xylene, 4-vinyl-m-xylene, 5-vinyl-m-xylene,
- Polar olefinically unsaturated monomers for the purposes of the invention include vinyl cyanides such as acrylonitrile or methacrylonitrile, in particular acrylonitrile, and also acrylic acid and the C ⁇ ⁇ to C 2 o-alkyl and ⁇ ⁇ to C ⁇ s aryl esters of acrylic acid, also methacrylic acid and the C ⁇ ⁇ to Crj -Alkyl- and C ß - to C ⁇ s aryl esters of methacrylic acid or mixtures thereof.
- vinyl cyanides such as acrylonitrile or methacrylonitrile, in particular acrylonitrile
- acrylic acid and the C ⁇ ⁇ to C 2 o-alkyl and ⁇ ⁇ to C ⁇ s aryl esters of acrylic acid also methacrylic acid and the C ⁇ ⁇ to Crj -Alkyl- and C ß - to C ⁇ s aryl esters of methacrylic acid or mixtures thereof.
- acrylates are methyl, ethyl, propyl, n-butyl, t-butyl, 2-ethylhexyl, glycidyl and phenyl acrylate, as methacrylates methyl, ethyl, propyl, n-butyl, t-butyl, 2-ethylhexyl, glycidyl and phenyl methacrylate.
- Acrylic nitrile, n-butyl, t-butyl, 2-ethylhexyl and glycidyl acrylate and mixtures thereof are particularly preferred as polar monomers.
- t-butyl acrylate is used.
- nonpolar ⁇ -olefinically unsaturated monomers which are not vinylaromatic monomers to the vinylaromatic monomers or to sequence these ⁇ -olefins sequentially with the vinylaromatic monomer units to form essentially nonpolar blocks - to let structure segments react.
- Suitable ⁇ -olefinic monomers are, for example, unsaturated hydrocarbons such as ethene, propene, 1-butene, i-butene, 1-pentene, 2-pentene, 1-hexene or any mixtures of the aforementioned olefins into consideration.
- the polymerization of vinyl aromatic monomer units and the block copolymerization of vinyl aromatic monomer units with polar olefinically unsaturated monomers in the presence of transition metal compounds of the general formula (I) can be carried out both in bulk and in solution. If polymerization is carried out in solution, aprotic solvents are preferred.
- aliphatic hydrocarbons such as pentane, hexane or cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene or ethylbenzene or halogenated hydrocarbons such as dichloromethane can be used.
- Aromatic hydrocarbons, in particular toluene are preferably used. Any mixtures of the abovementioned solvents are of course also suitable.
- one or more blocks of vinyl aromatic monomer units and possibly non-polar ⁇ -olefinic monomer compounds are first formed, whereupon one or more blocks of these components are polymerized by adding the polar olefinically unsaturated monomers.
- the entire process of block copolymer production can be carried out in bulk or only e.g. the production of the non-polar vinyl aromatic block segment.
- the initial concentration of the monomer added in each case is generally set to a value in the range from 0.001 to 10, preferably from 0.01 to 8, mol / l.
- the polymerization temperature can be varied over a wide range. A temperature in the range from -70 to 100 ° C., preferably below 80 ° C. and particularly preferably in the range from +10 to 60 ° C., is usually selected.
- the polymerization time for the processes according to the invention is generally in the range from 0.5 to 75 h. Average response times in the range of 1 to 50 h have proven successful.
- the polymerization reactions can be carried out at pressures in the range from 0.001 to 50 bar. Polymerization is usually carried out at pressures in the range from 0.5 to 10 bar, and even a polymerization carried out under normal pressure regularly gives a satisfactory result.
- the ratio of starting monomer to transition metal compound (I) is generally in the range 1: 1 to 10,000: 1, preferred Range from 5: 1 to 5000: 1 and especially in the range from 40: 1 to 5000: 1.
- the polymerization processes according to the invention are preferred under inert reaction conditions, i.e. in the absence of oxygen and moisture. If necessary, a protective gas such as argon or nitrogen can be used.
- the transition metal compound (I) to the vinylaromatic monomer or to a solution of the vinylaromatic monomer
- the complex compound (I) can also be introduced as such or in dissolved form.
- the polymerization or block copolymerization processes according to the invention generally do not require the addition of further coactivators or catalysts.
- metal alkyl complex (I) If in the presence of the metal alkyl complex (I) only vinyl aromatic monomer compounds and, if appropriate, further nonpolar olefinically unsaturated monomer units are reacted, polymers with a syndiotactic or largely syndiotactic structure are regularly obtained.
- the proportion of rr triads is preferably over 55%, particularly preferably over 62%. Polymers with a syndiotacticity of over 90% can also be obtained without further notice.
- molecular weights M n in the range from 3000 to 500,000 and preferably> 10,000 g / mol are accessible.
- the polydispersities (M w / M n ) achieved are generally below 3.0, but preferably assume values less than 2.0.
- the polymerization reactions are generally terminated by adding a protic compound, for example a low molecular weight alcohol such as methanol, ethanol or i-propanol, or by simply removing the solvent.
- a protic compound for example a low molecular weight alcohol such as methanol, ethanol or i-propanol
- the (co) polymer obtained is generally obtained as a solid and can be mechanically, e.g. be separated by filtration.
- the polymers and block copolymers obtained by the process described are suitable for the production of fibers, films and moldings.
- the block copolymers of vinylaromatic and polar block segments obtainable by the process according to the invention can be used, inter alia, as impact modifiers in thermoplastic polymers or in polymer blends. Furthermore, the block copolymers according to the invention can be used as compatibilizers in polymer mixtures of otherwise immiscible polymers. Block copolymers in which the vinyl aromatic block segment is syndiotactic or predominantly syndiotactic Structural units can be used, for example, for the compatibility of blend materials made of syndiotactic polystyrene and polyacrylates and / or polymethacrylates.
- the vinyl aromatic polymers obtained by the process according to the invention stand out just like those described
- Block copolymers from a very narrow molecular weight distribution Polydispersities less than 2.0 and 1.4 can be easily obtained.
- the molecular weights of the homo- and block copolymers produced were determined by means of quantitative 1 H-NMR spectroscopy by end group analysis and by means of gel permeation chromatography against polystyrene standards on columns from Shodex with tetrahydrofuran as eluent.
- Styrene was refluxed over calcium hydride for several hours, then distilled shortly before use. Toluene was refluxed in the presence of sodium, then distilled.
- Inert gas technology was used to manufacture the transition metal complexes.
- the reactions were carried out under argon.
- T g ⁇ glass transition temperature of the polystyrene block
- T g2 glass transition temperature of the poly-t-butyl acrylate block
- Ig served as the starting compound for the polymerization-active complex.
- Corresponding amounts of toluene were used instead of benzene.
- the time for the styrene polymerization was 16 h, that for the block copolymerization of t-butyl acrylate 5 min.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Graft Or Block Polymers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE19959252 | 1999-12-09 | ||
DE19959252A DE19959252A1 (de) | 1999-12-09 | 1999-12-09 | Verfahren zur (Co)polymerisation von polaren und unpolaren Monomeren |
PCT/EP2000/011811 WO2001042314A1 (de) | 1999-12-09 | 2000-11-27 | Verfahren zur (co)polymerisation von polaren und unpolaren monomeren |
Publications (1)
Publication Number | Publication Date |
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EP1237942A1 true EP1237942A1 (de) | 2002-09-11 |
Family
ID=7931910
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP00977581A Withdrawn EP1237942A1 (de) | 1999-12-09 | 2000-11-27 | Verfahren zur (co)polymerisation von polaren und unpolaren monomeren |
Country Status (5)
Country | Link |
---|---|
US (1) | US6599996B1 (de) |
EP (1) | EP1237942A1 (de) |
JP (1) | JP2004500450A (de) |
DE (1) | DE19959252A1 (de) |
WO (1) | WO2001042314A1 (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2852015B1 (fr) * | 2003-03-07 | 2007-06-22 | Composantes catalytiques a geometrie contrainte comprenant un ligant fluorenyle et basees sur des metaux du groupe iiib | |
US8071701B2 (en) * | 2005-12-16 | 2011-12-06 | Dow Global Technologies Llc | Polydentate heteroatom ligand containing metal complexes, catalysts and methods of making and using the same |
EP1834970B1 (de) * | 2006-03-15 | 2014-05-14 | Styrolution GmbH | Ein Verfahren zur Herstellung von Polyolefin-Polyvinylaromatischen-Blockcopolymeren |
CN100408626C (zh) * | 2006-07-17 | 2008-08-06 | 南京大学 | 聚苯乙烯在10℃至60℃的范围内加工方法 |
JP5820756B2 (ja) * | 2012-03-28 | 2015-11-24 | 出光興産株式会社 | 芳香族ビニル化合物重合体の製造方法 |
CN107709383B (zh) * | 2015-05-29 | 2021-03-30 | 陶氏环球技术有限责任公司 | 一种用于制造聚烯烃的方法 |
Family Cites Families (7)
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US5264527A (en) * | 1989-07-10 | 1993-11-23 | Elf Atochem S.A. | Acrylic triblock copolymers, their preparation and their application to the manufacture of elastomeric articles |
US5504169A (en) * | 1989-09-13 | 1996-04-02 | Exxon Chemical Patents Inc. | Process for producing amorphous poly-α-olefins with a monocyclopentadienyl transition metal catalyst system |
US5218064A (en) * | 1990-02-14 | 1993-06-08 | Showa Denko K.K. | Process for preparing narrow molecular weight distribution syndiotactic polymers or copolymers of unsaturated carboxylic acid esters |
US5563219A (en) | 1993-07-16 | 1996-10-08 | Mitsui Toatsu Chemicals, Inc. | Process for Preparing block copolymer of monoolefin |
US5464906A (en) | 1994-11-21 | 1995-11-07 | The Dow Chemical Company | Ethylene homopolymerization using group 3 metal complexes |
EP0889913B1 (de) | 1996-03-27 | 2003-07-02 | Dow Global Technologies Inc. | Allyl-enthaltende metallkomplexe, und verfahren zur polymerisation von olefinen |
DE19700305A1 (de) | 1997-01-09 | 1998-07-16 | Basf Ag | Verfahren zur Herstellung von Polymerisaten aus vinylaromatischen Verbindungen durch Dispersionspolymerisation |
-
1999
- 1999-12-09 DE DE19959252A patent/DE19959252A1/de not_active Withdrawn
-
2000
- 2000-11-27 US US10/130,820 patent/US6599996B1/en not_active Expired - Fee Related
- 2000-11-27 EP EP00977581A patent/EP1237942A1/de not_active Withdrawn
- 2000-11-27 JP JP2001543609A patent/JP2004500450A/ja not_active Withdrawn
- 2000-11-27 WO PCT/EP2000/011811 patent/WO2001042314A1/de not_active Application Discontinuation
Non-Patent Citations (1)
Title |
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See references of WO0142314A1 * |
Also Published As
Publication number | Publication date |
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DE19959252A1 (de) | 2001-06-13 |
US6599996B1 (en) | 2003-07-29 |
JP2004500450A (ja) | 2004-01-08 |
WO2001042314A1 (de) | 2001-06-14 |
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