WO1998025975A2 - Anionische polymerisation von acrylaten und methacrylaten - Google Patents
Anionische polymerisation von acrylaten und methacrylaten Download PDFInfo
- Publication number
- WO1998025975A2 WO1998025975A2 PCT/EP1997/006711 EP9706711W WO9825975A2 WO 1998025975 A2 WO1998025975 A2 WO 1998025975A2 EP 9706711 W EP9706711 W EP 9706711W WO 9825975 A2 WO9825975 A2 WO 9825975A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acrylate
- solvent
- methacrylate
- butyl
- styrene
- Prior art date
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
- 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
-
- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- 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 present invention relates to a process for the preparation of homo-, co- or block copolymers containing acrylates or methacrylates by means of anionic polymerization, and to the use of the reaction mixtures obtained for free-radical polymerization.
- EP-A 0 524 054 describes the polymerization of, for example, 2-ethylhexyl acrylate in the presence of lithium diphenylmethylide as the initiator and CH 3 (OCH 2 CH 2 ) 2 OLi as an additive.
- JP-A 2258808, JP-A 6306112 and JP-A 6093049 describe the polymerization of acrylates and methacrylates with the aid of lanthanoid metallocenes, such as (C 5 Me 5 ) 2 Sm (THF) 2 .
- anionic polymerization processes rely on the use of an inert solvent, including to prevent early chain termination.
- anionic polymerization tetrahydrofuran (THF), toluene or ethylbenzene or any mixtures of these components very often form a suitable reaction medium.
- THF tetrahydrofuran
- toluene or ethylbenzene or any mixtures of these components very often form a suitable reaction medium.
- a disadvantage of the use of the last-mentioned solvents, particularly also in the case of the anionic polymerization initiated by Samarocene is the increased gel formation which occurs above all at the end of the polymerization, which prevents unproblematic work-up and consequently also a transfer to production on an industrial scale. In addition, this phenomenon often leads to broad molecular weight distributions and incomplete monomer conversion.
- the present invention was therefore based on the object of developing a reaction medium for anionic polymerization which does not have the disadvantages mentioned and which, moreover, independently of the initiator system used and of the approach, delivers large, reproducibly good polymerization results. Accordingly, a process for the preparation of reaction mixtures comprising homo-, co- or block copolymers, and of homo-, co- and block copolymers containing acrylates or methacrylates or acrylates and methacrylates by means of anionic polymerization has been found, in which as a solvent or as solvent components olefinically unsaturated compounds are used which are not an acrylate or methacrylate derivative. In a preferred embodiment, vinyl aromatic compounds are used as the solvent or solvent component.
- R a , R b independently of one another, hydrogen, Ci to -C 4 alkyl in straight-chain and branched form, also substituted, such as methyl, ethyl, i-propyl, n-propyl, i-butyl, n-butyl, t-butyl , C 6 - to -C 4 aryl, also mono- or polysubstituted, such as phenyl or tolyl, C 3 - to C 7 -cycloalkyl, also substituted, such as cyclopropyl, cyclopentyl or cyclohexyl, C - to Cio-alkenyl, such as Vinyl, allyl, butenyl or butadienyl, and
- R c , R d independently of one another, hydrogen, Ci to -C 4 alkyl in straight-chain and branched form, also substituted, such as methyl, ethyl, i-propyl, n-propyl, i-butyl, n-butyl, t-butyl , C 6 - to C 4 substituted aryl, also one or more times, such as phenyl or tolyl, C 3 - to C -cycloalkyl, also be substituted, such as cyclopropyl, cyclopentyl or cyclohexyl, C 2 - to C ⁇ 0 alkenyl, like vinyl, allyl,
- Suitable olefinically unsaturated compounds are ethylene, propylene, 1-butene, 2-butene, butadiene, 1,4-hexadiene, 1,5-hexadiene or 1-octene.
- the radicals R a , R b or R c , R d and the radicals R a , R c or R b , R d can each form an unsaturated carbo- or heterocycle, such as cyclopentene, cyclohexene, cyclopropylidene, cyclopentylidene or fulvene .
- Particularly suitable solvents or solvent components for the process according to the invention are vinyl styrene, ⁇ -methyl styrene, o-, m-, p-methyl styrene or any mixtures of the vinyl aromatic compounds mentioned.
- Styrene, but also butadiene and ethene are preferably used as solvent or as solvent component, styrene is particularly preferred.
- vinyl aromatic compounds or the unsaturated compounds according to claim 1 form a component of a solvent system, the proportion of this component, based on the total amount of solvent, is preferably in the range from 5 to 99% by volume.
- solvent constituents for example, tetrahydrofuran, diethyl ether, dirthhoxyethane, toluene,
- Ethylbenzene, cyclohexane or any mixture of the solvents mentioned can be used.
- Suitable solvent systems are e.g. Styrene / tetrahydrofuran, styrene / toluene or styrene / tetrahydrofuran / ethylbenzene.
- Both homopolymers and copolymers or block copolymers of vinyl monomers with polar groups are accessible with the process according to the invention.
- Homo-, co- and block copolymers containing acrylates or methacrylates are preferably produced.
- Copolymers consisting of acrylates or methacrylates or from a mixture of acrylates and methacrylates can be produced.
- both two-block and multi-block copolymers consisting of acrylates and / or methacrylates are accessible, e.g. n-Butyl acrylate / 2-ethyl - hexyl acrylate or methyl methacrylate / 2-ethyl hexyl acrylate block copolymers.
- Homopolymers, copolymers and block copolymers for the purposes of the present invention are not only the isolated polymers, but also the reaction mixtures obtained by means of anionic polymerization, including homopolymers, copolymers or block copolymers.
- Suitable acrylate monomer units are, for example, C 1 -C 2 -alkyl acrylates.
- Ci- are preferred to C ⁇ 0 -, more preferably Ci to C 8 alkyl acrylates used.
- the alkyl radicals can be both linear and branched or form a ring or contain ether groups or amino groups and can be partially or completely substituted with halogen atoms.
- acrylates with an olefinically unsaturated ester unit such as dihydrodicyclopentadienyl acrylate, allyl acrylate, 3- or 4-vinylbenzyl acrylate, 2-A1-lyloxyethyl acrylate or those with aromatic groups, such as phenyl acrylate or 2-phenoxyethyl acrylate or vinylaromatic groups.
- Methyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dihydrodicyclopentadienyl acrylate and allyl acrylate, in particular 2-ethylhexyl acrylate are preferred.
- Suitable methacrylate monomer units include Alkyl methacrylates with 1 to 20 C atoms, preferably 1 to 10, in particular 1 to 8 C atoms in the ester group.
- the alkyl radicals can be both linear and branched or form a ring and can be partially or completely substituted with halogen atoms or contain ether or amino groups.
- methacrylates with an olefinically unsaturated ester unit such as dihydrodicyclopentadienyl methacrylate, allyl methacrylate, 3- or 4-vinylbenzyl methacrylate, 2-allyloxymethacrylate or those with aromatic ester radicals, such as phenyl or 2-phenoxyethyl or with vinyl aromatic ester radicals.
- methyl methacrylate, 2-ethyl-hexyl methacrylate and allyl methacrylate are preferred.
- acrylates and methacrylates mentioned can each be used individually for the preparation of homopolymers and in any combination for the production of copolymers and block copolymers.
- acrylonitrile, methacrylonitrile, acrylamides and methacrylamides can also be considered as further monomer units for the production of copolymers and block copolymers containing acrylates and / or methacrylates.
- those are preferred which are composed of 2-ethylhexyl acrylate and methyl methacrylate, n-butyl acrylate, t-butyl acrylate, dihydrodicyclopentadienyl acrylate, 3- or 4-vinylbenzyl acrylate, 2-allyloxyethyl acrylate or allyl acrylate, and in particular-2-ethyl acrylate .
- block copolymers preference is given to those which are composed of 2-ethylhexyl acrylate and methyl methacrylate, n-butyl acrylate, t-butyl acrylate, dihydrodicyclopentadienyl acrylate, 3- or 4-vinylbenzyl methacrylate, 2-allyloxymethacrylate or allyl acrylate and in particular methyl 2-acrylate and in particular methyl 2-acrylate, and in particular methyl 2-acrylate, and in particular methyl 2-acrylate, and in particular methyl 2-acrylate, and in particular methyl 2-acrylate, and in particular methyl 2-acrylate, and in particular methyl 2-acrylate, and in particular 2-acrylate, and in particular 2-acrylate, and in particular 2-acrylate, and in particular 2-acrylate, and in particular 2-acrylate, and in particular 2-acrylate, and in particular 2-acrylate, and in particular 2-acrylate, and in particular 2-acrylate, and in particular 2-acrylate, and in particular 2-acrylate, and in particular 2-acrylate
- the method according to the invention can be used for the anionic
- An initiator system consisting of an organometallic, preferably alkali-organic compound or a mixture of different organometallic compounds as starter and a metal alcoholate, in particular an alkali alcoholate, has proven to be suitable as a chelating additive.
- an initiator composition can be found in EP-A 0 524 054 with preferred mentioning of diphenylmethyl-lithium as starter and the lithium salt of CH 3 (OCHCH 2 ) OH as additive, and also in EP 0 668 297, in which in addition to the already mentioned initiator system bimetallic alkoxyalkoxides are highlighted.
- anionic initiator system for the process according to the invention is based on
- R 1 and R 2 each independently of one another, and R 4 as the alkyl group methyl, ethyl, i- or n-propyl or i-, n- or t-butyl; as cycloalkyl group cyclopropyl, pentyl or hexyl; as alkylaryl group benzyl; can be phenyl as aromatic group, pyridyl as heteroaromatic group,
- R 3 is, for example, a methylene, ethylene, n, i-propylene, ethoxyethyl or phenylene unit,
- R 5 and R 6 independently of one another, as the aryl group phenyl; as alkylaryl group benzyl; can represent methyl, ethyl, i- or n-propyl or i-, n- or t-butyl as the alkyl group and
- M, Z 1 and Z 2 independently of one another, mean metal cations selected from the group of alkali metals, in particular lithium, and
- alkali metal alcoholates falling under the general formulas (i) and (ii) are the lithium salts of 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-diisopropylaminoethanol, l- (dimethylamino) -2-propanol, 2-dibutylaminoethanol, 2 , 2 '- (n-Butyl - imino) bisethanol, 1, 1' - (methylimino) bis-2-propanol, 2- [2- (dimethylamino) ethoxy] ethanol, 2-diphenylaminoethanol, 2- (ethyl - phenylamino) ethanol, 2- [ethyl- (3-methylphenyl) a ino] ethanol, 3- (ethylamino) -4-methylphenol, 3-diethylaminophenol, 2,2'- (phenylimino) bisethanol and 2,2 '- [(3-methylphenyl) imino] isethanol.
- the lithium salts of 2-dimethylaminoethanol and 1, 1 '- (methylimino) bis-2-propanol are particularly preferred.
- the alkali metal alcoholates can be obtained from the corresponding amino alcohols by base treatment by customary processes. For example, 2-dimethylaminolithium ethoxide is prepared by deprotonating 2-dimethylaminoethanol at 0 ° C. using s-butyllithium.
- alkyl or alkylarylalkali metal compounds can be used as anionic metal alkyl starter compounds for the process according to the invention, the alkyl radical preferably having 1 to 10, particularly preferably 1 to 6, C atoms.
- the alkylaryl compounds preferably have a Ci - to Cio alkyl group and a C 6 - to -C 4 aryl group, particularly preferred aryl radical is phenyl or substituted phenyl.
- Suitable alkylaryl compounds are, for example, alkali compounds derived from styrene, ⁇ -methylstyrene or 1,1-diphenylethene, which are obtained by reaction with, for example, n-butyllithium, s-butyllithium or t-butyllithium.
- alkylaryl and alkylalkali compounds n-butyllithium, s-butyllithium, t-butyllithium, diphenylmethyllithium, sodium, potassium, 1-phenylhexyllithium, 1,1-diphenylhexyllithium.
- alkali amides, alkali ester enolates or alkali ketoenolates can be used as anionic starter compounds. Preferred among these are: lithium diisopropylamide, lithium ethyl isobutyrate and the lithium enolate of diisopropyl ketone.
- one or more solvent components are preferably used as the solvent in addition to styrene.
- Inert nonpolar and polar solvents are preferably used as further components. These include aromatic hydrocarbons, such as toluene, benzene, xylene or ethylbenzene, and aliphatic hydrocarbons, such as cyclohexane, hexane, pentane or tetrahydrofuran. Mixtures of non-polar solvent components, such as mixtures of toluene with ethylbenzene, and mixtures of non-polar and polar solvents, such as mixtures of ethylbenzene and tetrahydrofuran, can also be used as the solvent component.
- aromatic hydrocarbons such as toluene, benzene, xylene or ethylbenzene
- aliphatic hydrocarbons such as cyclohexane, hexane, pentane or tetrahydrofuran.
- non-polar solvent components such as mixtures of toluene with
- the proportion of styrene in the total amount of solvent is in the range from 10 to 100% by volume, preferably in the range from 20 to 99% by volume and particularly preferably in the range from 30 to 95% by volume when the anionic polymerization is started with alkali or alkaline earth metal alkylene.
- the solvent component used in addition to the vinylaromatic compound preferably consists of nonpolar solvents or of solvent mixtures consisting of essentially nonpolar and, in addition, polar constituents.
- a mixture of ethylbenzene and tetrahydrofuran can be used as the solvent component, which has a mixing ratio in the range from 55:45 to 99: 1, preferably in the range from 80:20 to 95: 5.
- the processes according to the invention in the presence of an anionic initiator can be used both in a batch and in a continuous process.
- the components of the initiator composition, the solvent and the monomers can be mixed together in a different order.
- all of the starter components can be introduced and the solvent and monomer can then be added.
- the components of the initiator system can be added to the monomer solution either in separate solutions - simultaneously or in succession, the metal organyl compound being introduced regularly - or as a mixture prepared in an inert solvent or solvent system.
- the monomer solution is preferably added to the initiator system.
- the amount of monomers can be added all at once, in stages or continuously.
- the monomer solution and the initiator solution are mixed in a mixing nozzle with a small volume under turbulent flow conditions and then passed through a tube with a narrow cross section, which can be equipped with static mixers (e.g. SMX mixer from Sulzer).
- static mixers e.g. SMX mixer from Sulzer.
- the flow rate should be so high that a relatively uniform residence time is observed.
- a second monomer can be added in a further, downstream mixing nozzle.
- the reaction can be carried out, for example, at a temperature in the range from -78 ° C. to + 100 ° C. A temperature range from -55 ° C to + 80 ° C is preferred.
- the reaction temperature can either be kept constant or increased in a controlled manner. To achieve high molecular weights M n and narrow molecular weight distributions are not detrimental if the reaction mixture heats up within a short time as a result of the reaction enthalpy released.
- the polymerization reaction is terminated by adding a protic substance such as an alcohol (e.g. methanol, ethanol or i-propanol), an acid (e.g. acetic acid, formic acid or hydrochloric acid), water or a mixture of these compounds.
- a protic substance such as an alcohol (e.g. methanol, ethanol or i-propanol), an acid (e.g. acetic acid, formic acid or hydrochloric acid), water or a mixture of these compounds.
- the reaction mixture can be worked up in a manner known per se.
- the polymers obtained can be precipitated, for example, by adding a suitable amount of a lower alcohol or water.
- the solvent or solvent system can also be separated off by distillation.
- the polymers obtainable by means of an anionic initiator system by the process according to the invention generally have molecular weights M n in the range from 5,000 to 2,000,000 g / mol, preferably in the range from 5,000 to 500,000 g / mol and particularly preferably in the range from 5,000 to 250,000 g / mol .
- the molecular weight distribution M w / M n is generally in the range from 1.05 to 3.5. The incorporation of, for example, vinyl aromatic compounds into the polymer chains is not observed, regardless of the polymerization conditions or the amount of vinyl aromatic compound chosen.
- the anionic polymerization is carried out with the aid of metallocene complexes.
- Lanthanide metallocene complexes are preferably used, and very particular preference is given to metallocene complexes of samarium, ytterbium or europium, in particular samarium, in which the metal is formally positively charged twice or three times.
- the metallocene complexes can have one or two metallocene ligands.
- C 5 to C 50 cyclopentadienyl structural units are preferred as metallocene ligands.
- Examples include cyclopentadienyl derivatives substituted one to five times with organic to C 20 to C 20 carbon or organic to C 3 to C 3 o -silicon radicals.
- radicals can be C 1 to C 10 alkyl, C 5 to C 7 cycloalkyl, C 6 to C 5 aryl or aralkyl, where appropriate two adjacent radicals together for 4 can have up to 15 C atoms having saturated or unsaturated cyclic groups, or SiR 3 with R in the meaning of Ci to Cio alkyl, C 3 to C 10 cycloalkyl or C 6 to C 5 aryl.
- cyclopentadienyl pentamethylcyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, 4-butylcyclopentadienyl, trimethylsilylcyclopentadienyl and (ethyl) (tetramethyl) cyclopentadienyl.
- Indenyl, fluorenyl and benzindenyl may be mentioned as multinuclear derivatives with a cyclopentadienyl structural unit.
- cyclopentadienyl structural units which form a sterically demanding metallocene ligand are preferred.
- Pentamethylcyclopentydienyl is particularly preferred.
- the two free coordination sites on the lanthanoid (II) metalocene with double cyclopentadienyl complex ligands are saturated, for example, by weakly coordinating Lewis bases such as tetrahydrofuran, diethyl ether, dimethoxyethane or acetonitrile. Tetrahydrofuran is preferably used.
- Samarium has proven to be a suitable lanthanide metal, which in the preferred complexes is generally formally positively charged twice or three times.
- a metallocene initiator for the anionic polymerization of, in particular, acrylates and methacrylates is, for example, bis (pentamethylcyclopentadienyl) samarium (II) - bis (tetrahydrofran) [(C 5 Me 5 ) 2 Sm (THF) 2 ], its preparation and Characterization can be found, for example, in WJ Evans, I. Bloom, WE Hunter, JL Atwood, J. Am. Chem. Soc. 1981, 193, pp. 6507-6508.
- Suitable formally triply positively charged metallocene complexes are also those of the general formula (II)
- R 12 and R 13 are Ci to Cio alkyl, C ⁇ - to C-aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,
- R 7 to R 11 are hydrogen, Ci to Cio alkyl,
- 5- to 7-membered cycloalkyl which in turn can carry a Ci to Cio-alkyl as a substituent, C 6 - to Cis-aryl or arylalkyl, optionally also two adjacent radicals together for 4 to 15 C-atoms having saturated or unsaturated can be cyclic groups or Si (R 14 ) 3 with
- R 14 Ci to Cio alkyl, C 3 to Cio cycloalkyl or C 6 to Cis aryl,
- Ris to R 19 hydrogen, C ⁇ ⁇ to Cio-alkyl,
- 5- to 7-membered cycloalkyl which in turn can carry a C 1 -C 1 -alkyl group as a substituent, is C 6 - to C 5 -aryl or arylalkyl, and where appropriate also two adjacent radicals together for 4 to 15 C atoms containing saturated or unsaturated cyclic groups, or Si (R 20 ) with
- Ci to Cio-alkyl C 6 - to -C 5 aryl or C 3 - to Cio-cycloalkyl.
- Such complex compounds can be synthesized by methods known per se. Examples of corresponding production processes are described, inter alia, in the Journal of Organometallic Chemistry, 1993, 450, pp. 121-124. Mixtures of different metal complexes can also be used.
- olefinically unsaturated compounds can be used as solvents or solvent components for the inventive method for anionic polymerization using lanthanide metallocenes, which are not an acrylate or
- methacrylate derivative include, for example, olefinically unsaturated compounds which fall under the general formula (I) already described.
- Vinyl aromatic compounds, in particular styrene, are preferably used as solvents.
- the solvents which are suitable for the process according to the invention can be used as such or in a mixture with further inert solvents. However, it has proven to be advantageous to use at least small amounts of a further solvent component, primarily for reasons of the solubility of the metallocene initiator. In principle, the solvents and solvent systems already described above are suitable for this. Tetrahydrofuran, for example, has proven to be suitable.
- the proportion of this component in the total amount of solvent is preferably in the range from 0.1 to 95, particularly preferably in the range from 0.5 to 50 and in particular in the range from 0.5 to 20% by volume.
- the metallocene initiator, the solvent or the solvent components and the monomers can be mixed with one another in the most varied of orders.
- the metallocene initiator can be introduced, optionally dissolved in a suitable solvent, e.g. Tetrahydrofuran, and the solvent and monomer are then added.
- the monomer building block (s) and the solvent or solvent system are preferably initially introduced and then mixed with a metallocene initiator solution.
- the reaction can be carried out, for example, at a temperature in the range from -30 to + 80 ° C. A temperature range from -20 to + 50 ° C is preferably used.
- the reaction temperature can be kept constant or increased in a controlled manner. To achieve high molecular weights M n and narrow molecular weight distributions, it is not detrimental if the reaction mixture warmed up within a short time due to the released enthalpy of reaction.
- Suitable aluminum organyls are, for example, trialkyl and triaryl aluminum compounds and aluminum organyls with alkyl and aryl radicals or hydride radicals, for example diisobutyl aluminum hydride. Mixtures of these compounds are also suitable.
- Trialkyl aluminum compounds, in particular triethyl aluminum and triisobutyl aluminum, are preferably used. In principle, however, easily hydrolyzable compounds are suitable which do not react with the monomer units and solvents. These are added to the monomer and solvent components before the metallocene initiator is added.
- the polymerization reaction can be terminated by adding a protic substance, as described above for anionic initiator systems.
- a protic substance as described above for anionic initiator systems.
- Mixtures of methanol and acetic acid e.g. in a ratio in the range from 100: 1 to 1: 100, preferably from 10: 1 to 1:10.
- the polymers obtained using the metallocene initiator are generally worked up as described for the anionic polymerization initiated by metal organyls.
- reaction mixtures obtained by the process according to the invention can be subjected directly to a radical-initiated polymerization.
- the process according to the invention is distinguished on the one hand by the fact that complete or almost complete conversions are achieved.
- the anionic Polymerization in ether solvents completely suppressed gel formation that regularly occurred.
- homo-, co- and block copolymers of acrylates and / or methacrylates can be prepared in a controlled manner.
- the subsequent radical polymerization of the reaction mixture makes it possible, for example, to obtain acrylate-containing and methacrylate-containing styrene polymers and styrene copolymers in a simple manner while saving the conventional solvents.
- the block copolymers obtainable by the process according to the invention can be used as a blend component for the production of thermoplastic molding compositions.
- Two- or multiblock copolymers are preferably used in which at least one block has a glass transition temperature (T g ) less than 0 ° C., preferably less than -20 ° C., particularly preferably less than -45 ° C., and at least one block has a glass transition temperature greater than 30 ° C, preferably greater than 70 ° C, particularly preferably greater than 100 ° C.
- Suitable three-block copolymers are e.g. Poly [methyl methacrylate-b-2-ethylhexyl acrylate -b-methyl methacrylate], poly [methyl methacrylate-b-n-butyl acrylate-b-methyl methacrylate] or Pol [2-ethylhexyl acrylate-b-methyl methacrylate-b-2-ethylhexyl acrylate].
- the individual blocks can also be constructed from copolymers with a statistical composition.
- An example is: poly [methyl methacrylate-b- (methyl methacrylate-lat-co-2-ethylhexyl acrylate) -b-methyl methacrylate].
- the proportion of the block or blocks with a T g value less than 0 ° C. in the total block copolymer is generally in the range from 1 to 99% by weight, preferably in the range from 10 to 90% by weight, particularly preferably a range from 20 to 80% by weight.
- these block copolymers can be used as a blend component in their production.
- Such blends can be manufactured, for example with polycarbonates, poly carbonate ASA molding compositions, for example Terblend ® S (BASF AG), polyesters, especially polyethylene terephthalate and polybutylene terephthalate (Ultradur ®, BASF AG), polyester-ASA molding compositions, especially polybutylene terephthalate-ASA Molding compounds (Ultrablend ® S, BASF AG), Polyamides (e.g.
- Ultramid ® BASF AG
- polyphenylene ethers polyphenylene ether (styrene / butadiene copolymer) blend
- polyether sulfones Ultrason ® E, BASF AG
- polysulfones Ultrason ® S, BASF AG
- polyoxymethylenes e.g. Ultraform ® , BASF AG
- polyvinyl chlorides polyvinyl chloride /
- Acrylate graft copolymers e.g. Vinidur ® , BASF AG
- polystyrenes or impact-modified polystyrenes as described in DE-A 29 46 761 and DE-A 17 70 392
- ABS molding compounds acrylonitrile / butadiene / styrene polymers, for example Terluran ® , BASF AG
- styrene - acrylonitrile copolymers e.g. Luran ® , BASF AG
- acrylonitrile / styrene / acrylic ester polymers e.g. Luran ® S, BASF AG
- polymethyl methacrylate molding compounds e.g.
- Impact-modified polyalkyl methacrylate molding compositions are also those according to WO 97/08241, which are composed, for example, of a hard methyl methacrylate polymer, a hard styrene / acrylonitrile polymer and a soft graft copolymer, consisting of a first graft shell made of vinylaromatic and alkyl methacrylate and a second graft shell consisting essentially of Assemble (meth) acrylates on a rubber.
- the proportion of the block copolymers described in the thermoplastic molding composition is usually in the range from 1 to 90% by weight, preferably in the range from 2 to 80% by weight.
- the block copolymers can generally be mixed into the molding compositions listed by processes known per se, such as e.g. by mixing in dry, cold form, followed by melting and mixing together in the extruder.
- Films, fibers and moldings can be produced in a conventional manner from the thermoplastic molding compositions obtained.
- the number and weight average molecular weights M n and M w were determined by means of gel permeation chromatography (GPC) in tetrahydrofuran at 35 ° C. relative to a narrowly distributed polymethyl methacrylate Standard determined. The detection was carried out with a refractive index (RI) detector Waters 410.
- GPC gel permeation chromatography
- the content of residual monomer in the reaction mixture was determined by means of 5 gas chromatography (GC) on an HP 5890 gas chromatograph.
- a capillary column, DB1 (30 ⁇ m) was used under the following conditions: split 1:50; Injection block 250 ° C; Detector (FID) 250 ° C; Oven temperature 5 min at 60 ° C, then 15 ° C / min to 250 ° C.
- Dioxane was used as the internal standard.
- the monomeric acrylates and methacrylates were cleaned using a nitrogen purge, aluminum oxide and calcium hydride and then distilled in vacuo.
- Styrene was purified by introducing nitrogen and bearings over alumina beads.
- a low-pulsation, preparative HPLC pump of the Dynamax SD1 type from Rainin was used to deliver the initiator, additive and monomer solution.
- the monomer solution of 100 ml of 2-ethylhexyl acrylate (EHA) and 300 ml of styrene (flow of 17 ml / min) and the initiator solution (flow of 45 50 ml / min) were fed via HPLC pumps at -50 ° C to a mixing nozzle and through a 15 long pipe with an inner diameter of 1.17 mm (average residence time approx. 14 sec).
- a glass transition temperature T g of -55 ° C. was determined for the copolymer obtained by means of DSC analysis (heating rate: 20 ° C./min.).
- Example 10 Analogously to Example 7, copolymers with 2-ethylhexyl acrylate as the main monomer component and allyl methacrylate (Ex. 8) or 2-allyloxyethyl acrylate (6.6 instead of 10% by weight) (Ex. 9) as the second component were produced.
- Example 10 in deviation from Example 7, the amount of dihydrodicyclopentadienyl acrylate was chosen so that 7.5% by weight was incorporated into the copolymer (see also Table 1).
- the polymer was precipitated in 500 ml of methanol with 1 ml of 2N aqueous hydrochloric acid, filtered off and dried at 50 ° C. in a vacuum drying cabinet for 24 h. 5.4 g of a white, free-flowing powder were obtained, which corresponds to a yield of 100%, based on EHA and MMA. No signals of aromatic protons could be detected by i H NMR spectroscopy.
- Example 14 5 Block copolymerization of 2-ethylhexyl acrylate with methyl methacrylate at 0 ° C
- the polymerization was terminated by adding 20 ml of a methanol / acetic acid mixture (10/1). After precipitation of the polymer 30 in 8 l of methanol with 150 ml of 2N HCl, washing with methanol and drying at 60 ° C. in vacuo, 111 g of white powder were isolated (100% yield).
- AMA allyl methacrylate
- DCPA dihydrodicyclopentadienyl acrylate
- AOEA 2-allyloxyethyl acrylate
- LA lauryl acrylate
- MMA methyl methacrylate 25 t >
- thermoplastic molding compositions and the block copolymers were extruded at a kneader temperature of 250 ° C. and a kneading time of 8 minutes.
- the ground extrudate was transferred to test specimens by means of injection molding. More detailed information on the composition of the molding compositions and block copolymers used and on the properties of the test specimens obtained can be found in Tables 2 and 3.
- SAN styrene-acrylonitrile copolymer
- AN acrylonitrile
- EHA 2-ethylhexyl acrylate
- MMA methyl methacrylate b) proportion of the SAN molding composition in the impact-modified molding composition c) determined by means of gel permeation chromatography on a polymethyl methacrylate standard d) produced analogously to Example 13 e) proportion of the block copolymer in the impact-modified molding composition
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97954344A EP0944654B1 (de) | 1996-12-10 | 1997-12-01 | Anionische polymerisation von acrylaten und methacrylaten |
JP52616398A JP2001505943A (ja) | 1996-12-10 | 1997-12-01 | アクリラートおよびメタクリラートの陰イオン重合方法 |
DE59706702T DE59706702D1 (de) | 1996-12-10 | 1997-12-01 | Anionische polymerisation von acrylaten und methacrylaten |
US09/319,598 US6262213B1 (en) | 1996-12-10 | 1997-12-01 | Anionic polymerization of acrylates and methacrylates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19651299.9 | 1996-12-10 | ||
DE19651299A DE19651299A1 (de) | 1996-12-10 | 1996-12-10 | Anionische Polymerisation von Acrylaten und Methacrylaten |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1998025975A2 true WO1998025975A2 (de) | 1998-06-18 |
WO1998025975A3 WO1998025975A3 (de) | 1998-08-20 |
Family
ID=7814238
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1997/006711 WO1998025975A2 (de) | 1996-12-10 | 1997-12-01 | Anionische polymerisation von acrylaten und methacrylaten |
Country Status (7)
Country | Link |
---|---|
US (1) | US6262213B1 (de) |
EP (1) | EP0944654B1 (de) |
JP (1) | JP2001505943A (de) |
KR (1) | KR20000057461A (de) |
DE (2) | DE19651299A1 (de) |
ES (1) | ES2174335T3 (de) |
WO (1) | WO1998025975A2 (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4573967B2 (ja) * | 1999-08-24 | 2010-11-04 | 株式会社クラレ | アニオン重合方法および該重合方法による重合体の製造方法 |
JP4549508B2 (ja) * | 1999-09-20 | 2010-09-22 | 株式会社クラレ | メタクリル酸エステル又はアクリル酸エステルの重合方法 |
JP4549507B2 (ja) * | 2000-09-19 | 2010-09-22 | 株式会社クラレ | メタクリル酸エステル又はアクリル酸エステルの重合方法 |
JP5184769B2 (ja) * | 2005-09-06 | 2013-04-17 | 日本曹達株式会社 | 活性水素を含有するモノマーを用いた重合体の製造方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2131111A5 (en) * | 1971-03-31 | 1972-11-10 | Inst Francais Du Petrole | Heat stable polymethacrylates - prepd in olefin soln and useful in lubricants |
EP0524054B1 (de) * | 1991-07-19 | 1997-03-05 | Elf Atochem S.A. | Polymerisation von (Meth)Acrylmonomere |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2750145B2 (ja) | 1989-03-31 | 1998-05-13 | 出光興産株式会社 | ビニル系重合体の製造方法 |
JPH0693049A (ja) | 1992-09-09 | 1994-04-05 | Mitsubishi Petrochem Co Ltd | メタクリル系ランダム共重合体およびその製造方法 |
JPH06306112A (ja) | 1993-04-23 | 1994-11-01 | Mitsubishi Kasei Corp | エチレン−極性モノマーブロック共重合体の製造方法 |
US5548043A (en) * | 1994-11-30 | 1996-08-20 | Xerox Corporation | Processes for producing bimodal toner resins |
-
1996
- 1996-12-10 DE DE19651299A patent/DE19651299A1/de not_active Withdrawn
-
1997
- 1997-12-01 JP JP52616398A patent/JP2001505943A/ja active Pending
- 1997-12-01 US US09/319,598 patent/US6262213B1/en not_active Expired - Fee Related
- 1997-12-01 EP EP97954344A patent/EP0944654B1/de not_active Expired - Lifetime
- 1997-12-01 WO PCT/EP1997/006711 patent/WO1998025975A2/de not_active Application Discontinuation
- 1997-12-01 ES ES97954344T patent/ES2174335T3/es not_active Expired - Lifetime
- 1997-12-01 KR KR1019990705102A patent/KR20000057461A/ko not_active Application Discontinuation
- 1997-12-01 DE DE59706702T patent/DE59706702D1/de not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2131111A5 (en) * | 1971-03-31 | 1972-11-10 | Inst Francais Du Petrole | Heat stable polymethacrylates - prepd in olefin soln and useful in lubricants |
EP0524054B1 (de) * | 1991-07-19 | 1997-03-05 | Elf Atochem S.A. | Polymerisation von (Meth)Acrylmonomere |
Also Published As
Publication number | Publication date |
---|---|
US6262213B1 (en) | 2001-07-17 |
KR20000057461A (ko) | 2000-09-15 |
WO1998025975A3 (de) | 1998-08-20 |
JP2001505943A (ja) | 2001-05-08 |
DE19651299A1 (de) | 1998-06-18 |
EP0944654A2 (de) | 1999-09-29 |
ES2174335T3 (es) | 2002-11-01 |
DE59706702D1 (de) | 2002-04-25 |
EP0944654B1 (de) | 2002-03-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE60019419T2 (de) | Verfahren zur herstellung von polymeren durch eine kontrollierte radikalischpolymerisation mit halogenierten xanthaten | |
DE60121970T2 (de) | Verfahren zur herstellung von pfropfcopolymeren und daraus hergestellte zusammensetzungen | |
EP0245647B2 (de) | Polymethacrylat-Formmasse mit hoher Wärmeformbeständigkeit und hoher thermischer Stabilität | |
DE69813492T2 (de) | Verfahren zur kontrollierten Radikalpolymerisation mit Verwendung geringer Mengen eines stabilen Freien Radikalen | |
DE112006000410B4 (de) | Pfropf-Copolymer und Verfahren zum Herstellen desselben | |
WO2004016668A1 (de) | Verwendung von blockcopolymeren als dispergiermittel für wässrige feststoff-suspensionen | |
DE60028477T2 (de) | Anionisches Polymerisationsverfahren und Verfahren zur Herstellung eines Polymers durch das anionische Polymerisationsverfahren | |
EP1334133B1 (de) | Verfahren zur kontinuierlichen herstellung von polymerzusammensetzungen sowie verwendung | |
EP0944654B1 (de) | Anionische polymerisation von acrylaten und methacrylaten | |
DE1720530A1 (de) | Verfahren zur Herstellung von Polymerisationsprodukten | |
DE2948152A1 (de) | Copolymeres mit peroxybindungen in seinem molekuel und verfahren zu dessen herstellung | |
EP0941256B1 (de) | Verfahren zur herstellung von polyalkyl(meth)acrylaten | |
DE3048881C2 (de) | Verfahren zur Herstellung einer nicht-wäßrigen, flüssigen Polymerdispersion aus polymeren Peroxiden | |
EP0001782B1 (de) | Verfahren zur Herstellung von Pfropfmischpolymerisaten | |
WO2013030261A1 (de) | Herstellung von polymeren durch kontrollierte radikalische polymerisation | |
WO1999042501A2 (de) | Verfahren zur herstellung von polymeren aus n-vinylverbindungen | |
WO2001098373A1 (de) | Verfahren zur herstellung eines polymeren umsetzungsprodukts | |
EP0944656B1 (de) | Verfahren zur herstellung kautschukmodifizierter formmassen | |
DE19959252A1 (de) | Verfahren zur (Co)polymerisation von polaren und unpolaren Monomeren | |
DE1296802B (de) | Thermoplastische Formmassen | |
WO2000035963A1 (de) | Verfahren zur lebenden freien radikalischen polymerisation | |
EP1155046A1 (de) | Verfahren zur lebenden freien radikalischen polymerisation | |
DE69926373T2 (de) | Polymerisationsverfahren | |
EP0980873B1 (de) | Binucleare Metallhydridkomplexe und deren Verwendung als Katalysatoren für die (Co)polymerisation von polaren Monomeren | |
EP0429453B1 (de) | Diisopropylbenzol-bisperneoalkanoate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): BR CN JP KR MX US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
AK | Designated states |
Kind code of ref document: A3 Designated state(s): BR CN JP KR MX US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A3 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1997954344 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 1998 526163 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/1999/005253 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09319598 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1019997005102 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 1997954344 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1019997005102 Country of ref document: KR |
|
WWG | Wipo information: grant in national office |
Ref document number: 1997954344 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1019997005102 Country of ref document: KR |