EP1117713A1 - Procede de polymerisation de diolefines conjuguees (dienes), au moyen de catalyseurs aux terres rares, en presence de solvants vinyliques aromatiques - Google Patents

Procede de polymerisation de diolefines conjuguees (dienes), au moyen de catalyseurs aux terres rares, en presence de solvants vinyliques aromatiques

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Publication number
EP1117713A1
EP1117713A1 EP99934601A EP99934601A EP1117713A1 EP 1117713 A1 EP1117713 A1 EP 1117713A1 EP 99934601 A EP99934601 A EP 99934601A EP 99934601 A EP99934601 A EP 99934601A EP 1117713 A1 EP1117713 A1 EP 1117713A1
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EP
European Patent Office
Prior art keywords
iii
compounds
neodymium
rare earth
earth metals
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EP99934601A
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German (de)
English (en)
Inventor
Heike Windisch
Werner Obrecht
Gisbert Michels
Norbert Steinhauser
Thomas Schnieder
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Bayer AG
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Bayer AG
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Publication of EP1117713A1 publication Critical patent/EP1117713A1/fr
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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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated

Definitions

  • the present invention relates to a process for the polymerization of conjugated diolefins in the presence of rare earth catalysts and in the presence of aromatic vinyl compounds.
  • a disadvantage of the polymerization processes carried out today for the production of poly-diolefins, such as BR, IR or SBR is the time-consuming work-up of the polymer solution to isolate the polymers, for example by stripping with
  • a further disadvantage particularly if the polymerized diolefins are to be further processed as impact modifiers for plastic applications, is that the polymeric diolefins obtained first have to be dissolved again in a new solvent, for example styrene, in order then to e.g. to be processed into acrylonitrile-butadiene-styrene copolymer (ABS) or high-impact polystyrene (HIPS).
  • ABS acrylonitrile-butadiene-styrene copolymer
  • HIPS high-impact polystyrene
  • US 3299178 describes a catalyst system based on TiCL / iodine / Al (iso-Bu) 3 for the polymerization of butadiene in styrene to form homogeneous polymer. butadiene claimed. With the same catalyst system, Harwart et al. in Plaste and Kautschuk, 24/8 (1977) 540 describes the copolymerization of butadiene and styrene and the suitability of the catalyst for the production of polystyrene.
  • US 5096970 and EP 304088 describe a process for the preparation of polybutadiene in styrene using catalysts based on neodymphosphonates, organic aluminum compounds such as di (isobutyl) aluminum hydride (DIBAH) and based on a halogen-containing Lewis acid such as Ethylaluminum sesquichloride, described, in which butadiene is converted into styrene without further addition of inert solvents to a 1,4-cis-polybutadiene.
  • DIBAH di (isobutyl) aluminum hydride
  • a halogen-containing Lewis acid such as Ethylaluminum sesquichloride
  • the polymerization was stopped at a monomer conversion of butadiene of about 25%, or by increasing the monomer conversion of butadiene to about 36% by a high butadiene concentration of about 55% by weight, so that the majority of the used In both cases, butadiene must be separated off by distillation before the styrenic rubber solution is used for impact modification.
  • SBR Styrene-butadiene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene (SBR) are formed which, based on the butadiene units, allow only a slight control of the microstructure. It is not possible with anionic
  • Initiators to produce a high cis-containing SBR in which the 1, 4-cis content over Is 40%.
  • By adding modifiers only the proportion of 1,2- or 1,4-trans units can be increased, the 1,2-content in particular leading to an increase in the glass transition temperature of the polymer.
  • This fact is disadvantageous above all because SBR is formed in this process, which results in a further increase in the glass transition temperature with increasing styrene content compared to homopolymeric polybutadiene (BR).
  • BR homopolymeric polybutadiene
  • a high glass transition temperature of the rubber has a disadvantageous effect on the low-temperature toughness of the material, so that rubbers with low glass transition temperatures are preferred.
  • a disadvantage of these catalysts in addition to the presence of inert solvents, is that the catalyst activity drops from less than 5 mol% to less than 10 g of polymer / mmol of catalyst h, even with a small amount of styrene, and that the 1,4-cis content of the polymer increases with increasing Styrene content decreases significantly.
  • ABS the rubber is used in a matrix of acrylonitrile-styrene copolymers (SAN).
  • SAN acrylonitrile-styrene copolymers
  • the SAN matrix is incompatible with polystyrene. If, in addition to the rubber, homopolymers of the solvent, such as polystyrene, are formed in the polymerization of the diolefins in vinylaromatic solvents, the incompatibility of the SAN matrix with the polymerized vinylaromatics leads to a significant deterioration in the material properties of the ABS in the production of ABS.
  • the present invention therefore relates to a process for copolymerizing conjugated dienes with vinylaromatic compounds, which is characterized in that the polymerization of the conjugated dienes in the presence of catalysts consists of
  • Component (a) :( c) is in the range from 1: 0.1 to 1000, component (a) of the catalyst in amounts of 1 ⁇ mol to 10 nmol, based on 100 g of the conjugated diolefins used, and the aromatic vinyl compound in Quantities from 50 g to 2000 g, based on 100 g of the conjugated diolefins used, are used.
  • conjugated diolefins e.g. 1,3-butadiene, 1,3-isoprene, 2,3-dimethylbutadiene, 2,4-hexadiene, 1,3-pentadiene and / or 2-methyl-1,3-pentadiene can be used.
  • the amount of unsaturated compounds which can be copolymerized with the conjugated diolefins depends on the intended use of the desired copolymers and can easily be determined by appropriate preliminary tests. It is usually 0.1 to 80 mol%, before adds 0.1 to 50 mol%, particularly preferably 0.1 to 30 mol%, based on the diolefin.
  • the molar ratio of components (a) :( b) :( c) in the catalyst used is in the range from 1: 0.1 to 1.9: 3 to 500, particularly preferably 1: 0.2 to
  • the molar ratio of component (a) :( c) is preferably in the range from 1: 3 to 500, in particular 1: 5 to 100.
  • Suitable compounds of the rare earth metals are, in particular, those which are selected from
  • Oxygen or nitrogen donor compound
  • the compounds of the rare earth metals are based in particular on the elements with atomic numbers 21, 39 and 57 to 71.
  • Lanthanum, praseodymium or neodymium or a mixture of elements of the rare earth metals, which contains at least one of the elements lanthanum, praseodymium or, are preferably used as rare earth metals Contains neodymium to at least 10 wt .-%.
  • Lanthanum or neodymium, which in turn, are very particularly preferably used as rare earth metals can be mixed with other rare earth metals.
  • the proportion of lanthanum and / or neodymium in such a mixture is particularly preferably at least 30% by weight.
  • Suitable alcoholates, phosphonates, phosphinates and carboxylates of the rare earth metals or as complex compounds of the rare earth metals with diketones are, in particular, those in which the organic group contained in the compounds in particular straight-chain or branched alkyl radicals having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms , contains, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, isopropyl, isobutyl, tert-butyl, 2-ethylhexyl, neo-pentyl, neo-octyl, neo-decyl or neo-dodecyl.
  • Rare earth alcoholates e.g. called:
  • phosphinates and rare earth phosphates e.g. called: neodymium (III) -dibutylphosphonate, neodymium (III) -dipentylphosphonate, neodymium (III) -dihexylphosphonate, neodymium (III) -diheptylphosphonate, neodymium (III) -dioctyl-phosphonate, neodymium (III) -dinonylphymonate, III) didodecylphosphonate,
  • Suitable carboxylates of rare earth metals are:
  • lanthanum (III) acetylacetonate lanthanum (III) acetylacetonate, praseodymium (III) acetylacetonate and neodymium (III) acetyl acetonate, preferably neodymium (III) acetylacetonate.
  • Examples of addition compounds of the halides of rare earth metals with an oxygen or nitrogen donor compound are: lanthanum (III) chloride with tributyl phosphate, lanthanum (III) chloride with tetrahydrofuran,
  • Neodymium versatate, neodymium octanoate and / or neodymium naphthenate are very particularly preferably used as compounds of the rare earth metals.
  • the above-mentioned compounds of rare earth metals can be used both individually and in a mixture with one another.
  • the most favorable mixing ratio can easily be determined by appropriate preliminary tests.
  • R 1 to R 9 are the same or different or are optionally linked to one another or are condensed on the cyclopentadiene of the formula (I), (II) or (III), and for hydrogen, a C r to C 30 alkyl group, a C 6 - to C, 0 -aryl group, a C 7 - to C 40 -alkylaryl group and a C 3 - to C 30 -silyl group, where the alkyl groups can be either saturated or mono- or polyunsaturated and heteroatoms such as oxygen , Nitrogen or halides.
  • the radicals can be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, methylphenyl, cyclohexyl, benzyl, trimethylsilyl or trifluoromethyl.
  • cyclopentadienes examples include the unsubstituted cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, n-butylcyclopentadiene, tert-butylcyclopentadiene, vinylcyclopentadiene, benzylcyclopentadiene, phenylcyclopentadiene, trimethylsilylcyclopentadiene, 2-methadylophenadiene, 2-methadylophenadiene, 2-methadadylophenadiene, 2-methadadylophenadiene, 2-methadadylophenadiene, 2-methadadylophenadiene, 2-methadadylophenadiene, 2-methadadylophenadiene Dimethylcyclopentadiene, trimethylcyclopentadiene, tetramethylcyclopentadiene,
  • the cyclopentadienes can also be used individually or in a mixture with one another.
  • Suitable organoaluminum compounds are, in particular, alumoxanes and / or aluminum organyl compounds.
  • Aluminum-oxygen compounds which, as is known to the person skilled in the art, are obtained as alumoxanes and are obtained by contacting organoaluminum compounds with condensing components, such as water, and the non-cyclic or cyclic compounds of the formula (-Al (R) Represent 0-) n , where R can be the same or different and for a linear or branched alkyl group is 1 to 10 carbon atoms, which may also contain heteroatoms, such as oxygen or nitrogen.
  • R represents methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-octyl or iso-octyl, particularly preferably methyl, ethyl or iso-butyl.
  • alumoxanes are: methylalumoxane, ethylalumoxane and isobutylalumoxane, preferably methylalumoxane and isobutylalumoxane.
  • R can be the same or different and for a Ci-Ci Q aryl group and one
  • alkyl groups can either be saturated or monounsaturated and can contain heteroatoms, such as oxygen or nitrogen,
  • X represents a hydrogen, an alcoholate, phenolate or amide
  • d represents a number from 0 to 2.
  • organoaluminum compounds of the formula can in particular be used: trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-iso-propyl aluminum, tri-n-butyl aluminum, tri-iso-butyl aluminum, tripentyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum, di-, di-ethyl aluminum -butyl aluminum hydride, di-iso-butyl aluminum hydride, diethyl aluminum butanolate, diethyl aluminum methylidene (dimethyl) amine and diethyl aluminum imethylidene (methyl) ether, preferably trimethyl aluminum, triethyl aluminum, tri-iso-butyl aluminum and di-iso-butyl aluminum.
  • the organoaluminum compounds can in turn be used individually or as a mixture with one another. It is also possible to add a further component (d) to the catalyst components (a) to (c).
  • This component (d) can be a conjugated diene, which is, for example, the same diene that is later to be polymerized with the catalyst. Butadiene and / or isoprene are preferably used.
  • the amount of (d) is preferably 1 to 1000 mol, based on 1 mol of component (a), particularly preferably 1 to 100 mol. 1 to 50 mol, based on 1 mol of component (a), of (d) are very particularly preferably used.
  • the catalysts are used in amounts of preferably 10 ⁇ mol to 5 mmol of component (a), particularly preferably 20 ⁇ m to 1 mmol of component (a), based on 100 g of the monomers.
  • the process according to the invention is carried out in the presence of aromatic vinyl compounds, in particular in the presence of styrene, ⁇ -methylstyrene, ⁇ -methylstyrene dimer, p-methylstyrene, divinylbenzene and / or other alkylstyrenes with 2 to 6 carbon atoms.
  • Atoms in the alkyl radical such as ethylbenzene, carried out.
  • the polymerization according to the invention is very particularly preferably carried out in the presence of styrene, ⁇ -methylstyrene, ⁇ -methylstyrene dimer and / or p-methylstyrene as solvent.
  • the solvents can be used individually or in a mixture; the most favorable mixture ratio can be easily determined by means of appropriate preliminary tests.
  • the amount of aromatic vinyl compounds used is preferably 30 to 1000 g, very particularly preferably 50 to 500 g, based on 100 g of the monomers used.
  • the process according to the invention is preferred at temperatures from -20 to
  • the process according to the invention can be carried out without pressure or at elevated pressure (0.1 to 12 bar).
  • the process according to the invention can be carried out continuously or batchwise, preferably in a continuous manner.
  • the solvent used in the process according to the invention need not be distilled off, but can remain in the reaction mixture.
  • aliphatic or aromatic solvents such as benzene, toluene, dimethylbenzene, ethylbenzene, hexane, heptane or octane, and / or polar solvents, such as ketones, ethers or esters, which are usually used as solvents and / or diluents for the polymerization of the vinyl aromatic solvent can be used.
  • the process according to the invention is particularly economical and environmentally friendly, since the solvent used can be polymerized in a subsequent step, the polymer contained in the solvent being used to modify thermoplastics (e.g. to increase the impact strength).
  • composition and thus the properties of the polymers obtained can be varied very widely by the process according to the invention.
  • the type of substitution of the cyclopentadiene used has an influence on the copolymerization parameters, particularly with regard to the diolefins and vinyl aromatic solvents used.
  • the vinyl aromatic content in the resulting polymer can be affected by varying the catalyst composition.
  • the advantage of low molecular weight polymers is that even with a high content of the polymers, the solution viscosity remains as desired low and the solutions can thus be easily transported and processed.
  • diolefins in vinylaromatic solvents copolymers of diolefins and vinylaromatics which, in contrast to the anionic initiators, have a high content of 1,4-cis double bonds, based on the diolefin content, and which continue to have a high catalyst activity and high conversion of diolefins used simple control of the microstructure, ie the content of lateral 1,2- and 1,4-cis units, the polymer composition and the molecular weight, enable.
  • the polymerizations were carried out in the absence of air and moisture under argon.
  • the isolation of the polymers from the styrenic solution described in individual examples was carried out only for the purpose of characterizing the polymers obtained.
  • the polymers can of course also be stored in the styrenic solution without insulation and processed further accordingly.
  • styrene used as solvent for the diolefin polymerization was stirred under argon for 24 h over CaH 2 at 25 ° C. and distilled off under reduced pressure at 25 ° C. (Examples 1 to 16).
  • the styrene was dried over molecular sieve 4A (Baylith) for 2 days and the polymerization was carried out in the presence of the stabilizer (bis (tert-butyl) benzate catechol, 15 ppm) (Examples 17 to 19).
  • the styrene content in the polymer is determined by means of NMR-NMR spectroscopy, the selectivity of the polybutadiene (1,4-cis, 1,4-trans and 1,2-content) is determined by means of IR spectroscopy, the determination the solution viscosity in a 5% by weight solution of the polymer in styrene using an Ubelohde viscometer at 25 ° C., the determination of the glass transition temperature T to ⁇ using DSC and the
  • the polymerization was carried out in a 0.5-1 bottle, which was provided with a crown cap with an integrated septum.
  • the specified amount of liquid butadiene was added to the styrene under argon and the specified amounts of a 1 molar solution of tri (isobutyl) aluminum in toluene (TIBA) as scavenger and the aged catalyst solution were then added using a syringe.
  • TIBA tri (isobutyl) aluminum in toluene
  • BKF bis [(3-hydroxy) (2,4-di-tert-butyl) (6-methyl) phenyl] methane
  • the catalyst aging was carried out analogously to Examples 1 to 5.
  • the polymerization was carried out in a 6-1 glass pot which was equipped with an anchor stirrer, a reflux condenser, connected to a cryostat with a temperature of -30 ° C., a double jacket, connected to a thermostat, an internal thermometer, a septum and an argon connection . Under argon, 292 g of liquid butadiene were added to 1050 ml of styrene at 25 ° C. and then 68.8 ml of the aged catalyst solution were added. The polymerization was carried out at 50 ° C. and stopped after 3 hours by adding 20 ml of acetone with 2 g of BKF.
  • the solids content of the polymer solution was 34%.
  • the polymer has the following composition: 29.0 mol% styrene, 71.0 mol% butadiene (with 54% 1,4-cis, 41% 1,4-trans, 5% 1,2 units), the viscosity (5% by weight in styrene) is 15.3 mPa-s, the glass temperature is -86 ° C.
  • Example 7-10
  • the polymerization was carried out according to Examples 1 to 5, with various aluminum compounds being used as scavengers.
  • the batch sizes, reaction conditions and the properties of the polymer obtained are given in Table 2.
  • the polymerization was carried out in a 6-1 glass pot using an anchor stirrer
  • the polymerization was carried out in a 40-1 steel reactor with anchor stirrer (50 rpm). At room temperature, a solution of trimethylaluminum in hexane was added to a solution of butadiene in styrene as a scavenger, the reaction solution was heated to 50 ° C. within 45 minutes and the appropriate amount of catalyst solution was added. The reaction temperature was kept at 50 ° C. during the polymerization. After the reaction time had elapsed, the polymer solution was transferred to a second reactor (80 l reactor, anchor stirrer, 50 rpm) within 15 min and the polymerization was carried out by adding 3410 g of butanone
  • the polymerization was carried out in a 0.5-1 bottle, which was provided with a crown cap with an integrated septum. Under argon, the specified amount of liquid butadiene was added to the initially introduced styrene and a further component ( ⁇ -methylstyrene, divinylbenzene or isoprene) via a cannula and the specified amounts of the aged catalyst solution were then added using a syringe.
  • the temperature was adjusted by a water bath.
  • the polymer was isolated by precipitating the polymer solution in methanol / BKF and dried for one day in a vacuum drying cabinet at 60 ° C.
  • the batch sizes, reaction conditions and the properties of the polymer obtained are given in Table 5.

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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)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)

Abstract

Des dioléfines, éventuellement en combinaison avec d'autres composés insaturés pouvant être copolymérisés avec les dioléfines, sont polymérisées en effectuant la polymérisation des dioléfines en présence de catalyseurs à base de composés des terres rares, de cyclopentadiènes et de composés organo-aluminiques, en présence de composés vinyliques aromatiques utilisés comme solvants, à des températures de -30 à +100 DEG C. Le procédé selon l'invention permet de fabriquer de manière simple, des solutions de copolymères, par exemple de copolymères styrol-butadiène, à teneurs variées en styrol, ainsi qu'à teneurs variées, par rapport à la dioléfine, en motifs 1,2 et cis dans des composés vinyliques aromatiques, pouvant être ultérieurement traités pour obtenir de l'ABS ou de l'HIPS.
EP99934601A 1998-07-18 1999-07-07 Procede de polymerisation de diolefines conjuguees (dienes), au moyen de catalyseurs aux terres rares, en presence de solvants vinyliques aromatiques Withdrawn EP1117713A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19832446A DE19832446A1 (de) 1998-07-18 1998-07-18 Verfahren zur Polymerisation von konjugierten Diolefinen (Dienen) mit Katalysatoren der Seltenen Erden in Gegenwart vinylaromatischer Lösungsmittel
DE19832446 1998-07-18
PCT/EP1999/004741 WO2000004066A1 (fr) 1998-07-18 1999-07-07 Procede de polymerisation de diolefines conjuguees (dienes), au moyen de catalyseurs aux terres rares, en presence de solvants vinyliques aromatiques

Publications (1)

Publication Number Publication Date
EP1117713A1 true EP1117713A1 (fr) 2001-07-25

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EP99934601A Withdrawn EP1117713A1 (fr) 1998-07-18 1999-07-07 Procede de polymerisation de diolefines conjuguees (dienes), au moyen de catalyseurs aux terres rares, en presence de solvants vinyliques aromatiques

Country Status (11)

Country Link
EP (1) EP1117713A1 (fr)
JP (1) JP2002520457A (fr)
KR (1) KR20010071951A (fr)
CN (1) CN1309674A (fr)
AU (1) AU5032599A (fr)
CA (1) CA2337423A1 (fr)
DE (1) DE19832446A1 (fr)
HK (1) HK1039952A1 (fr)
RU (1) RU2001104876A (fr)
TW (1) TW546312B (fr)
WO (1) WO2000004066A1 (fr)

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JP6630138B2 (ja) * 2015-12-01 2020-01-15 株式会社ブリヂストン 共重合体の製造方法、共重合体、ゴム組成物、及びゴム製品
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KR102106806B1 (ko) * 2018-02-09 2020-05-06 주식회사 엘지화학 공액디엔계 중합체 제조방법 및 공액디엔계 중합체 제조장치
CN109467661B (zh) * 2018-11-05 2020-06-16 大连理工大学 功能化苯乙烯类热塑性弹性体及其制备方法
CN109824811A (zh) * 2018-12-08 2019-05-31 濮阳班德路化学有限公司 一种α-甲基苯乙稀液体树脂的制备方法
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WO2000004066A1 (fr) 2000-01-27
HK1039952A1 (zh) 2002-05-17
KR20010071951A (ko) 2001-07-31
TW546312B (en) 2003-08-11
CN1309674A (zh) 2001-08-22
CA2337423A1 (fr) 2000-01-27
JP2002520457A (ja) 2002-07-09
RU2001104876A (ru) 2003-08-27
AU5032599A (en) 2000-02-07
DE19832446A1 (de) 2000-01-27

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