WO2014075901A1 - Procédé de production de polybutadiène - Google Patents

Procédé de production de polybutadiène Download PDF

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Publication number
WO2014075901A1
WO2014075901A1 PCT/EP2013/072484 EP2013072484W WO2014075901A1 WO 2014075901 A1 WO2014075901 A1 WO 2014075901A1 EP 2013072484 W EP2013072484 W EP 2013072484W WO 2014075901 A1 WO2014075901 A1 WO 2014075901A1
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range
polymerization
tubular reactor
polybutadiene
reactor
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PCT/EP2013/072484
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German (de)
English (en)
Inventor
Julien Couet
Jürgen Erwin LANG
Markus Schwarz
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Evonik Oil Additives Gmbh
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Publication of WO2014075901A1 publication Critical patent/WO2014075901A1/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
    • C08F36/06—Butadiene

Definitions

  • the present invention relates to a process for producing polybutadiene.
  • Polymers with a relatively low molecular weight and architecture are needed for a variety of applications. These polymers include in particular polybutadienes, which polymers may have a relatively low molecular weight. For the production of polymers with a very low
  • Polydispersity index is usually carried out an anionic polymerization, which is relatively expensive.
  • this polymerization process is often carried out as a batch process, as described, for example, by Chang et al., Fundamental Modeling in Anionic Polymerization Processes, J. Appl. Polym. Sci., Vol. 39, 2395-2417 (1990).
  • Chang et al. Fundamental Modeling in Anionic Polymerization Processes, J. Appl. Polym. Sci., Vol. 39, 2395-2417 (1990).
  • only processes under laboratory conditions are described, which were carried out at great expense.
  • the data show that the molecular weight distribution of the resulting polymers produced is subject to very large fluctuations, without any explicit reason being given.
  • polymers having a polydispersity index of 1.08 are obtained, with other polymers having a polydispersity index of 1.33 in an almost identical process. Accordingly, the stated statements are not suitable for the production of a product with precisely defined properties in large quantities. This is especially true due to the large fluctuations in the
  • the process should be able to be carried out in a very reproducible manner, the process also having to solve the tasks set out above, even under industrial conditions.
  • the present invention accordingly provides a process for the preparation of polybutadiene, which is characterized in that butadiene in a tubular reactor having an interface of at least 200 m 2 / m 3 using a
  • a solvent mixture comprising at least one non-polar and at least one polar solvent is anionically polymerized, wherein the obtained polybutadiene
  • polybutadiene having a defined structure and a very low polydispersity index can be obtained by the process according to the invention.
  • the degree of vinylation of the polybutadiene can be adjusted relatively accurately by the method.
  • the implementation of the method is particularly simple and inexpensive.
  • the process can be carried out very reproducibly and under industrial conditions, with products having very small deviations in the important properties, such as degree of vinylation, polydispersity and molecular weight.
  • the inventive method is used for the production of polybutadiene, wherein the polybutadiene has a weight average molecular weight M w in the range of 1000 to 20,000 g / mol and a polydispersity index PDI less than or equal to 1 .5.
  • the polybutadiene obtained has a vinylation degree of at least 10%.
  • the weight average molecular weight M w of the polybutadiene may preferably be in the range from 1000 to 15000 g / mol, preferably in the range from 1500 to 10000 g / mol.
  • the polydispersity index PDI is defined as the ratio of the weight average of the
  • the polydispersity index PDI is less than or equal to 1 .2, more preferably less than or equal to 1 .1, wherein the polydispersity index PDI should be as small as possible, so that the lower limit results from the technical possibilities.
  • GPC Gel permeation chromatography
  • butadiene in the polymerization, butadiene can be incorporated in the form of a 1, 2-linkage or 1, 4-linkage in the polymer, wherein in a 1, 2-linkage, a vinyl group is obtained, whereas in a 1, 4 linkage in the Main chain of the polymer integrated double bond is formed.
  • the degree of vinylation can be determined by means of nuclear magnetic resonance.
  • the process is used to produce polybutadiene, with 1,3-butadiene being anionically polymerized for this purpose.
  • Butadiene has the CAS no. 106-99-0.
  • polystyrene resin In addition to 1,3 butadiene, further monomers can be copolymerized, the polymer preferably being at least 50% by weight, preferably at least 65% by weight, more preferably at least 80% by weight and especially preferably at least 95% by weight. %, is composed of monomer units which are derived from 1,3 butadiene, based on the weight of the monomer used to prepare the polymer.
  • the content of butadiene in the polymerization composition is preferably 1 to 90% by weight, preferably 10 to 80% by weight, more preferably 20 to 70% by weight, and especially preferably 30 to 60% by weight.
  • the polymerization is carried out using an anionic polymerization initiator.
  • a mono- or bifunctional initiator can be used, whose general form is given in EP 749987 A.
  • alkyl or aryl metal compounds having different radicals R straight-chain or branched alkyl chains and substituted or unsubstituted aryl radicals
  • a metal M from the series of alkali or alkaline earth metals are used.
  • Examples of monofunctional initiators are sec-butyllithium, n-butyllithium, fluorenyllithium, alpha-methylstyryllithium, 1,1-diphenylhexyllithium (DPHLi), diphenymethyllithium or sodium or potassium and 1,1-diphenyl-3-methylpentyllithium.
  • Examples of bifunctional initiators are 1, 1, 4,4-tetraphenyl-1,4-dilithium butane, 1,1,4,4-tetraphenyl-1,4-dibium butane.
  • known precursors can be used as bifunctional initiators. Examples include: naphthalene lithium, naphthalene sodium, naphthalene potassium and their homologs.
  • the initiator used may preferably be a lithium compound, preferably butyllithium, particularly preferably n-butyllithium.
  • a mixer with known devices, for example slot-type interdigital micromixers (SIMM), Crawler mixers, microroil reactors, T-shaped micromixer or tubular reactors are suitable, which may preferably have corresponding internals.
  • SIMM slot-type interdigital micromixers
  • Crawler mixers Crawler mixers
  • microroil reactors T-shaped micromixer or tubular reactors
  • T-shaped micromixer or tubular reactors which may preferably have corresponding internals.
  • a micromixer can be used for this purpose.
  • the term "micromixer” is known in the art, this being understood to mean mixers which have relatively small channels with one
  • the educt streams are combined via very small microchannels. In the microchannels mostly laminar and highly symmetrical multiphase flows are to be found, which have a high order between the phases. This leads to extremely short diffusion times and improved mixing of the reactants.
  • micromixers are disclosed inter alia in EP 913 187 B1, filed on 07.10.1998 at the European Patent Office with the application number EP98402490.1, this document being incorporated by reference into the present specification for purposes of disclosure.
  • the mixer preferably the micromixer, can be configured in a component with the tubular reactor, so that the tubular reactor can comprise as an integral component a mixer, for example one or more static mixing elements. Furthermore, it can be provided that the mixer represents a component independent of the tubular reactor. According to a preferred embodiment, the mixer may preferably be tempered independently of the part of the tubular reactor in which the polymerization takes place.
  • an anionic polymerization is carried out using a solvent mixture comprising at least one non-polar and at least one polar solvent.
  • the mixture of a nonpolar and a polar solvent may have a dielectric constant in the range of 1 to 60 ⁇ m "1 , more preferably in the range of 1 to 5 ⁇ m " 1 .
  • the nonpolar solvent has a dielectric constant in the range from 1 to 4 ⁇ m "1 , particularly preferably in the range from 1.5 to 3 ⁇ m " 1 .
  • the polar solvent has a dielectric constant in the range from 4.5 to 200 .mu.m.sup.- 1 , particularly preferably in the range from 5 to 90 .mu.m.sup.- 1 .
  • the dielectric constant can be measured at a temperature of 20 ° C and a frequency of 50 Hz.
  • Another criterion for determining the solvent mixture can be determined by the
  • the non-polar solvent may have an E T (30) value in the range of 29 to 33 kcal / mol, more preferably in the range of 30 to 32 kcal / mol, measured according to the above literature at a temperature of 25 ° C and a Pressure of 1 bar.
  • the polar solvent has an E T (30) value in the range from 34 to 50 kcal / mol, particularly preferably in the range from 35 to 45 kcal / mol, measured according to the above literature at a temperature of 25 ° C and a pressure of 1 bar.
  • non-polar solvent can exhibit solubility parameters according to Hansen, which lie in the following ranges:
  • H d (dispersing fraction) in the range of 13 to 20 MPa 0'5 , preferably in the range of 14 to 19.0 MPa 0 5 ;
  • H p (polar fraction) in the range of 0 to 3 MPa 0 5 , preferably in the range of 0 to 2.5 MPa 0 5 and
  • H h hydrogen bonding contribution in the range from 0 to 3 MPa 0 5 , preferably in the range from 0 to 2.5 MPa 0 5 .
  • the polar solvent can have solubility parameters according to Hansen, which lie in the following ranges: H d (dispersing fraction) in the range of 13 to 20 MPa 0'5 , preferably in the range of 14 to 19.0 MPa 0 5 ;
  • Hp polar fraction in the range of 2.5 to 10 MPa 0 5 , preferably in the range of 2.9 to 9 MPa 0 5 and
  • Hansen Solubility Parameters A user's handbook, Second Edition. Boca Raton, Fla: CRC Press, ISBN 978-0-8493-7248-3. Furthermore, these parameters can be calculated from the structure of the solvent, using software (HSPiP: Hansen
  • the non-polar solvent used may preferably be a hydrocarbon, preferably an alkane or cycloalkane having 5 to 10 carbon atoms, more preferably hexane, heptane or cyclohexane and especially preferably cyclohexane.
  • a heteroaliphatic solvent is used as the polar solvent.
  • Preferred heteroaliphatic solvents include, but are not limited to, tertiary amines, of which tetramethylethylenediamine (TMEDA) or pentamethyldiethylenetriamine (PMDETA) are preferred.
  • preferred heteroaliphatic solvents include ethers, of which diethyl ether or tetrahydrofuran (THF) can preferably be used. Of these, tetrahydrofuran (TH F) is particularly preferred.
  • a mixture comprising at least one polar and at least one nonpolar solvent is used.
  • both the non-polar and the polar solvent as a mixture of different
  • a solvent composition comprising cyclohexane as a non-polar solvent and tetrahydrofuran (THF) as a polar solvent. Due to the proportion of polar solvent, the degree of vinylation of the polybutadiene can be adjusted, with high proportions of a polar solvent leading to a high degree of vinylation. It can furthermore be provided that the weight ratio of nonpolar solvent to polar solvent is in the range from 5: 1 to 30: 1, particularly preferably in the range from 10: 1 to 20: 1.
  • the molar ratio of polar solvent to initiator in the range of 0.25: 1 to 30: 1, preferably in the range of 0.5: 1 to 20: 1, more preferably in the range of 0.75: 1 to 10: 1, and more preferably in the range from 1: 1 to 5: 1.
  • educts which have a very high purity.
  • the educts in particular the butadiene used and the solvents used, preferably have at most 20 ppm, preferably at most 15 ppm, more preferably at most 10 ppm, of impurities, in particular water, by weight and measured in accordance with DIN 51 777, Part 1.
  • the polymerization may, for example, at a temperature in the range of 10 ° C to 120 ° C, preferably in the range of 20 ° C to 100 ° C, more preferably in the range of 25 ° C to 90 ° C and especially preferably in the range of 45 ° C to 80 ° C, to be performed.
  • a temperature in the range of 10 ° C to 120 ° C, preferably in the range of 20 ° C to 100 ° C, more preferably in the range of 25 ° C to 90 ° C and especially preferably in the range of 45 ° C to 80 ° C, to be performed.
  • the proportion of vinyl groups can be reduced so that the degree of vinylation can be adjusted via the polymerization temperature and the proportion of nonpolar solvent in the solvent mixture.
  • the pressure at which polymerization takes place is not subject to any specific conditions.
  • the pressure is chosen so that the butadiene is present as a liquid, but below supercritical conditions.
  • Surprising advantages can be achieved at a pressure (absolute) in the range from 1 to 100 bar, particularly preferably in the range from 2 to 50 bar and particularly preferably in the range from 5 to 20 bar.
  • the polymerization is carried out with a residence time in the range from 10 seconds to 20 minutes, particularly preferably in the range from 30 seconds to 10 minutes and particularly preferably in the range from 1 minute to 5 minutes.
  • Monomer solution have a lower temperature than the polymerization solution at a conversion of greater than 10%.
  • Polymerization solution to the temperature which is measured at a conversion of about 20%.
  • the degree of conversion refers to the molar fraction of polymerized butadiene, based on the total amount of butadiene before the beginning of the polymerization.
  • the mixing may preferably be carried out at a temperature in the range of -40 ° C to 100 ° C, preferably in the range of -20 ° C to 60 ° C, more preferably in the range of -10 ° C to 40 ° C, and especially preferably in Range of -5 ° C to 30 ° C, to be performed.
  • the temperature difference between the mixing temperature and the polymerization temperature is preferably at least 1 ° C., preferably at least 10 ° C. and especially preferably at least 15 ° C., this temperature difference particularly preferably in the range from 1 to 60 ° C., particularly preferably in the range from 5 to 50 ° C, more preferably in the range of 10 to 40 ° C and especially preferably in the range of 15 to 30 ° C.
  • this measure the polydispersity index can be reduced. Furthermore, it can thereby be achieved that the set by the choice of initiator share
  • the polymerization of the butadiene is carried out in a tubular reactor with an interface of at least 200 m 2 / m 3 , preferably at least 500 m 2 / m 3 , preferably at least 1000 m 2 / m 3 , more preferably at least 2000 m 2 / m 3 and especially preferred at least 3000 m 2 / m 3 .
  • a tubular reactor is understood to mean a reactor in which continuously introduced a starting material composition and a product composition can be discharged.
  • the tubular reactor may comprise static mixing elements.
  • the tubular reactor can be constructed from several reactor units.
  • a preferred tubular reactor is designed so that the reaction composition undergoes the lowest possible backmixing during the reaction in the flow direction, so that a tubular reactor generally comprises no mobile mixing elements.
  • a unit of a reactor is understood as meaning an element of a multi-element reactor, each element representing an area or reaction space for the said reaction. That Reactor units of a multi-element reactor in the sense of the present invention
  • Invention are in particular stainless steel or quartz glass capillaries, stainless steel tubes or well-dimensioned stainless steel reactors, such as pre-reactors, tubes in
  • Microtube bundle heat exchanger reactors as well as converted areas in the form of integrated block reactors.
  • the inner walls of the reactor elements may be coated, for example with a ceramic layer, a layer of metal oxides, such as Al 2 O 3 , Ti0 2 , Si0 2 , Zr0 2 , zeolites, silicates, to name just a few, but also organic
  • one or more multi-element reactors may be used as the tubular reactor, which in turn are based on at least 2 to 1,000,000 reactor units, including all intervening natural numbers, preferably from 3 to 10,000, especially from 4 to 1000 reactor units.
  • the reactor or reaction space of at least one reactor unit preferably has a semicircular, semi-oval, round, oval, triangular, square, rectangular or trapezoidal cross-section perpendicular to the flow direction.
  • Such a cross section preferably has a cross-sectional area of 75 ⁇ m 2 to 75 cm 2 . Particularly preferred are cross-sectional areas with 0.7 to 120 mm 2 and all numerically intervening numerical values.
  • the tubular reactor may preferably have a cross-sectional area in the range of 0.5 mm 2 to 10 mm 2 , preferably in the range of 1 mm 2 to 5 mm 2 and more preferably in the range of 2 mm 2 to 3 mm 2 .
  • a diameter of greater than or equal to 30 ⁇ m to less than 15 mm, in particular 150 ⁇ m to 10 mm is preferred.
  • Square cross-sectional areas preferably have edge lengths of greater than or equal to 30 ⁇ m to less than 15 mm, preferably 0.1 to 12 mm.
  • reactor units with differently shaped cross-sectional areas can be present in a multielement reactor of a plant which can be used according to the invention.
  • the structure length in a reactor unit i. from entry of the reaction or product stream into the reactor unit up to the outlet, preferably 5 cm to 500 m, including all numerically intervening numerical values, particularly preferably greater than or equal to 15 cm to 100 m, very particularly preferably 20 cm to 50 m,
  • reactor units are preferred whose respective reaction volume (also referred to as reactor volume, i.e. the product of cross-sectional area and structure length) is 0.01 ml to 100 L, including all numerically intervening numerical values. This is particularly preferred
  • Reactor volume of a reactor unit of a plant usable according to the invention 0.05 mL to 10 L, most preferably 1 mL to 5 L, most preferably 3 mL to 2 L, in particular 5 mL to 500 mL.
  • a multielement reactor can be based on at least one, preferably at least two, parallel-connected stainless steel capillaries, or on at least one, preferably at least two quartz glass capillaries connected in parallel, or on at least one, preferably at least two plastic capillaries connected in parallel, or at least one tube bundle heat exchanger reactor or at least one integrated block reactor.
  • reaction space facing surface of a Stainless steel capillary or a multi-element reactor with a polymer layer, for example a fluorine-containing layer, including Teflon, or a ceramic layer, preferably an optionally porous Si0 2 -, Ti0 2 - or Al 2 0 3 layer be equipped.
  • a polymer layer for example a fluorine-containing layer, including Teflon, or a ceramic layer, preferably an optionally porous Si0 2 -, Ti0 2 - or Al 2 0 3 layer be equipped.
  • an integrated block reactor as described, for example, as a heatable block reactor constructed from defined metal plates (also referred to below as a plane)
  • the heat of reaction liberated during the reaction can advantageously be achieved via the relative heat of reaction
  • Reactor volume large surface of the reactor inner walls and - if provided - to dissipate a heat transfer medium.
  • Pipe reactors preferably multi-element reactors, a significant increase in the space-time yield of fast, heat-melting conversions possible. This is made possible by a faster mixing of the educts, a higher average concentration level of the educts than in the batch process, ie no limitation by educt depletion, and / or an increase in temperature, which can usually cause an additional acceleration of the reaction.
  • the present invention allows in
  • tubular or capillary-like reaction spaces seen in the flow direction may have a straight course, wherein the cross-sectional area or other
  • the reaction spaces seen in the flow direction can have indentations or widening.
  • the indentations or widenings are designed so that a mixture is made possible transversely to the flow direction, without any significant mixing in the flow direction.
  • This can surprisingly improve the polydispersity index.
  • the ratio of the highest flow velocity to the lowest flow velocity in the tubular reactor during the polymerization is at most 1, preferably at most 0.1 and particularly preferably at most 0.04.
  • the pressure fluctuations in the tube reactor with an interface of at least 200 m 2 / m 3 are at most 5%, preferably at most 1% and particularly preferably at most 0.5%, in each case based on the mean pressure.
  • the polymerization can be terminated with a terminating agent, wherein the terminating agent is preferably a heteroaliphatic and / or
  • heterocyclic compound more preferably an epoxide, especially preferred
  • the method comprises the following steps: (a) preparation of an initiator solution;
  • step (d) polymerizing the mixture obtained in step (c) in a tubular reactor having an interface of at least 200 m 2 / m 3 ;
  • FIG. 1 Flow diagram for an apparatus for carrying out chemical reactions by the method according to the invention.
  • FIG. 1 shows a very schematic representation of a flow chart.
  • a reservoir 1 for a monomer solution comprising monomer and solvent from a reservoir 1 for a monomer solution comprising monomer and solvent, and an initiator solution comprising initiator and solvent are passed from a reservoir 2 into a micromixer 3.
  • the composition obtained is passed into a tubular reactor 4, in which the polymerization takes place.
  • the micromixer 3 and the tubular reactor 4 may be embodied in one component, but the micromixer 3 may preferably be tempered independently of the tubular reactor 4.
  • a termination reaction is preferably carried out by adding a terminating agent.
  • the polymerized composition can be introduced into a further reactor 5, in which in addition from a reservoir 6, a corresponding starting material is introduced.
  • the terminated polymer can be worked up accordingly, this being done after the removal point 7.
  • the invention will be explained in more detail by the examples, without this being a restriction. Experimental part
  • an initiator solution comprising 20 ml of tetrahydrofuran and 10 ml of n-butyllithium 1.6 M in n-hexane was prepared. Furthermore, a monomer composition was prepared containing 320 ml of cyclohexane and 126 g of 1, 3 butadiene. The proportion of
  • Impurities in the monomer composition was at most 15 ppm as measured by Karl Fischer titration (for solvent). For this purpose, the
  • Monomer composition purified by Activated Alumina and molecular sieve 4 ⁇ .
  • the microreactor comprised a feed line for the initiator solution and a feed line for the monomer composition, wherein the tube diameter of both feed lines was about 0.8 mm.
  • the two supply lines combined in the mixing area, the two
  • the effluent had a diameter of 1 .8 mm, the effluent forming the tube reactor and showing an interface of 2300 m 2 / m 3 .
  • the tube reactor had a length of 1.66 m, wherein in the front, immediately following the leads to a temperature of 0 ° C was cooled, whereas the temperature in the subsequent region, which had a length of 1 .6 m, 45 ° C. ,
  • the residence time was about 80 s, wherein the polymerization was carried out at a pressure of 7 bar.
  • the degree of vinylation (VG) was determined according to NMR, the

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne un procédé de production de polybutadiène dans lequel du butadiène est polymérisé en conditions anioniques dans un réacteur tubulaire ayant une surface limite d'au moins 200 m2/m3 en utilisant un mélange de solvants comprenant au moins un solvant apolaire et au moins un solvant polaire. Le polybutadiène obtenu a une masse moléculaire moyenne en poids Mw dans la plage de 1000 à 20000 g/mol et un indice de polydispersité PDI inférieur ou égal à 1,5.
PCT/EP2013/072484 2012-11-15 2013-10-28 Procédé de production de polybutadiène WO2014075901A1 (fr)

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EP12192719.8 2012-11-15

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017097702A1 (fr) * 2015-12-08 2017-06-15 Evonik Oil Additives Gmbh Procédé de préparation de polyoléfines hydroxylées
EP3378877A1 (fr) 2017-02-28 2018-09-26 Evonik Oil Additives GmbH Polybutadiènes hydrogénés utiles en tant qu'additifs de lubrification

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3356763A (en) * 1962-04-09 1967-12-05 Phillips Petroleum Co Continuous process for producing block copolymers of dienes and vinyl aromatic hydrocarbons
US4346193A (en) * 1981-05-04 1982-08-24 Atlantic Richfield Company Continuous process for making star-block copolymers
DE4327495A1 (de) * 1993-08-16 1995-02-23 Basf Ag Verfahren zur Herstellung von anionisch polymerisierbaren Vinylverbindungen
US5587423A (en) * 1992-10-14 1996-12-24 Basf Aktiengesellschaft Preparation of block copolymers by ionic polymerization
DE19721400A1 (de) * 1997-05-22 1998-11-26 Basf Ag Verfahren zur Herstellung von Dienpolymerisatlösungen in vinylaromatischen Monomeren
US5955537A (en) * 1998-02-13 1999-09-21 The Goodyear Tire & Rubber Company Continuous polymerization process

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3356763A (en) * 1962-04-09 1967-12-05 Phillips Petroleum Co Continuous process for producing block copolymers of dienes and vinyl aromatic hydrocarbons
US4346193A (en) * 1981-05-04 1982-08-24 Atlantic Richfield Company Continuous process for making star-block copolymers
US5587423A (en) * 1992-10-14 1996-12-24 Basf Aktiengesellschaft Preparation of block copolymers by ionic polymerization
DE4327495A1 (de) * 1993-08-16 1995-02-23 Basf Ag Verfahren zur Herstellung von anionisch polymerisierbaren Vinylverbindungen
DE19721400A1 (de) * 1997-05-22 1998-11-26 Basf Ag Verfahren zur Herstellung von Dienpolymerisatlösungen in vinylaromatischen Monomeren
US5955537A (en) * 1998-02-13 1999-09-21 The Goodyear Tire & Rubber Company Continuous polymerization process

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017097702A1 (fr) * 2015-12-08 2017-06-15 Evonik Oil Additives Gmbh Procédé de préparation de polyoléfines hydroxylées
EP3378877A1 (fr) 2017-02-28 2018-09-26 Evonik Oil Additives GmbH Polybutadiènes hydrogénés utiles en tant qu'additifs de lubrification
US10787623B2 (en) 2017-02-28 2020-09-29 Evonik Operations Gmbh Hydrogenated polybutadienes useful as lubricant additives

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