WO2007113196A1 - Procede de fabrication d'homopolymeres d'isobutene de masse moleculaire elevee par polymerisation dans un appareil presentant des proprietes de melange et de promotion - Google Patents

Procede de fabrication d'homopolymeres d'isobutene de masse moleculaire elevee par polymerisation dans un appareil presentant des proprietes de melange et de promotion Download PDF

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Publication number
WO2007113196A1
WO2007113196A1 PCT/EP2007/053005 EP2007053005W WO2007113196A1 WO 2007113196 A1 WO2007113196 A1 WO 2007113196A1 EP 2007053005 W EP2007053005 W EP 2007053005W WO 2007113196 A1 WO2007113196 A1 WO 2007113196A1
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WO
WIPO (PCT)
Prior art keywords
polymerization
isobutene
inert solvent
degassing
molecular weight
Prior art date
Application number
PCT/EP2007/053005
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German (de)
English (en)
Inventor
Thomas Wettling
Uwe Rachwalsky
Marco-Christian Volland
Werner Bochnitschek
Roland Kunklel
Markus JÄGGI
Pierre-Alain Fleury
Original Assignee
Basf Se
List Holding Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Publication of WO2007113196A1 publication Critical patent/WO2007113196A1/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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/08—Butenes
    • C08F110/10—Isobutene

Definitions

  • the present invention relates to an improved process for the preparation of isobutene homopolymers having a weight-average molecular weight M w of from 75,000 to 10,000,000 by polymerization of isobutene or isobutene-containing monomer mixtures in the liquid phase in the presence of one or more Lewis acids as polymerization catalysts and an inert solvent.
  • a common process for the preparation of higher molecular weight polyisobutenes is the so-called "BASF belt process", in which liquid isobutene with boron trifluoride as a polymerization catalyst and a high excess of liquid ethene on an endless steel strip of 50 to 60 cm wide leads, which is designed trough-shaped by a suitable guide and is located in a gas-tight, cylindrical housing.
  • BASF belt process liquid isobutene with boron trifluoride as a polymerization catalyst and a high excess of liquid ethene on an endless steel strip of 50 to 60 cm wide leads, which is designed trough-shaped by a suitable guide and is located in a gas-tight, cylindrical housing.
  • the vaporized ethene is collected, purified and recycled.
  • the resulting polyisobutenes are freed from adhering ethene and residual monomers by degassing.
  • the type of polymerization leads to a virtually complete isobutene conversion.
  • the polymerization temperature may vary due to the boiling-cooling, i. be controlled simply and safely by forming large vapor passages.
  • a disadvantage of the BASF strip process is that due to lack of movement of the reaction mixture on the belt no mixing and thus no product surface renewal takes place, which can adversely affect the product properties.
  • Exxon slurry process Another common method for producing higher molecular weight polyisobutenes is the "Exxon slurry process" in which the polymerization is carried out at -80 to -85 ° C. in a stirred tank equipped with a cooling jacket which is charged with liquid ethene is carried out.
  • the catalyst system used is anhydrous aluminum chloride in methyl chloride.
  • the polymer precipitates as a slurry consisting of small droplets, which flows over an intermediate vessel into a degassing vessel.
  • the slurry is treated with steam and hot water so that the volatiles (essentially unreacted isobutene and methyl chloride) can be removed and sent for reprocessing.
  • the remaining aqueous slurry of Polymerisatteil- is worked up by removing catalyst residues, solvent residues and Isobutenresten.
  • the BASF belt process and the Exxon Breeding process are, for example, in
  • WO 02/090391 generally discloses the use of two-shaft kneading reactors for carrying out polymerization reactions in which a solvent is added only in a second stage, when the viscosity of the reaction mixture has already markedly increased due to the advanced polymerization.
  • a solvent for example, methyl methacrylate in the presence of diethyl ether as a solvent and the initiator "Perkadox 16", which is based on di- (4-tert-butyl-cyclohexyl) peroxydicarbonate, in a temperature range of +5 to +60 ° C polymerized.
  • the object of the present invention was to provide an easy to carry out, efficient and economical process for the preparation of higher molecular weight isobutene homopolymers, in particular those having a weight-average molecular weight M w of 75,000 to 10,000,000, which on the one hand a safe Kon- trolle deep polymerization and on the other hand allows intensive mixing of the reaction mixture.
  • the object has been achieved by a process for the preparation of isobutene homopolymers having a weight-average molecular weight M w of from 75,000 to
  • isobutene homopolymers are understood to mean those polymers which, based on the polymer, are composed of at least 98 mol%, preferably at least 99 mol%, of isobutene.
  • isobutene or the isobutene-containing monomer mixture as a monomer to be polymerized is suitable as an isobutene source in particular pure isobutene, which is usually at most 0.5 vol .-% of residual impurities such as 1-butene, 2-butenes , Butane, water and / or C 1 to C 4 alkanols.
  • isobutene-containing technical C4 hydrocarbon streams for example C4 raffinates, C4 cuts from isobutane dehydrogenation, C4 cuts from steam crackers and FCC crackers (fluid catalysed cracking), insofar as they are largely derived from 1, 3-butadiene contained therein are liberated.
  • Suitable technical C4 hydrocarbon streams generally contain less than 500 ppm, preferably less than 200 ppm, butadiene.
  • the isobutene from such technical C4 hydrocarbon streams polymerized here largely selectively to the desired isobutene homopolymer, without appreciable amounts of other C4 monomers are incorporated into the polymer chain.
  • the isobutene concentration in the stated C4 hydrocarbon streams is in the range from 40 to 60% by weight.
  • the process according to the invention can also be operated with isobutene-containing C4 hydrocarbon streams which contain less isobutene, for example only 10 to 20% by weight.
  • the isobutene-containing mono-mersgemisch may contain small amounts of contaminants such as water, carboxylic acids or mineral acids, without there being any critical yield or selectivity losses. It is expedient to avoid an accumulation of these impurities by removing such pollutants from the isobutene-containing monomer mixture, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.
  • the polymerization catalysts used are heterogeneous or, in particular, homogeneous catalysts from the Lewis acid class.
  • Lewis acids are electron-deficient compounds at their central atom and derive their catalytic properties from them Activity ago.
  • these Lewis acids are compounds of elements of the 3rd main group of the Periodic Table, that is, boron, aluminum, indium, gallium and thallium.
  • halides in particular chlorides, of tin, of titanium, of antimony or of iron.
  • Such Lewis acids are often referred to as Friedel-Crafts catalysts.
  • boron and aluminum compounds for example anhydrous aluminum chloride, boron trichloride, boron trifluoride, boron tribromide, boron triiodide and in particular boron trihalide complexes with activators such as boron trifluoride etherates, e.g. Boron trifluoride diethyl etherate, or boron trifluoride-alcohol complexes. If boron halides, in particular boron trifluoride, are used, it is advisable to use the additional activators in the complexes mentioned.
  • a particularly preferred activator for boron trifluoride is here an alcohol, in particular a C 1 to C 4 alkanol, e.g. Methanol, ethanol, isopropanol, isobutanol or sec-butanol.
  • the amount of polymerization catalyst to be used depends essentially on the type of catalyst and on the reaction conditions, in particular the reaction temperature and the desired molecular weight of the polymer. It can be determined by means of fewer random tests for the respective reaction system.
  • the polymerization catalyst is used in amounts of 0.0001 to 1 wt .-%, in particular 0.0005 to 0.1 wt .-%, especially 0.001 to 0.01 wt .-%, each based on isobutene used ,
  • the isobutene homopolymers prepared by the process according to the invention preferably have a weight-average molecular weight M w of from 100,000 to 8,000,000, in particular from 150,000 to 6,000,000, especially from 250,000 to 4,000,000.
  • the polymerization in the context of the present invention at temperatures below -60 ° C at a pressure of 10 mbar to 50 bar or preferably below -60 ° C at a pressure of 500 mbar to 5 bar or even more preferably below -60 ° C at a pressure of 800 mbar to
  • the polymerization apparatus is operated at or near the ambient pressure (normal pressure).
  • a slight negative pressure may provide benefits for some of the possible inert solvents.
  • higher pressures generally bring no additional advantages.
  • the optimum pressure also depends on the boiling point of the inert solvent used.
  • the controlled low polymerization temperatures have an advantageous effect on the product properties.
  • the generally necessary low polymerization temperatures are preferably generated and controlled by the fact that the inert solvent acts as an internal coolant due to the boiling cooling caused by evaporation in the polymerization apparatus.
  • solvents are, in particular, hydrocarbons or halogenated, in particular chlorinated or fluorinated, hydrocarbons each having 1 to 3 carbon atoms, for example methane, ethane, propane, methyl chloride, methyl fluoride, difluoromethane or ethene (ethylene).
  • Ethene with a boiling point of -104 ° C at atmospheric pressure is particularly preferred.
  • ethene contains an olefinic double bond, it is completely inert in the inventive polymerization of isobutene or isobutene-containing monomer mixtures. Furthermore, as is generally the case when working at low temperatures, it is generally advisable to use additional jacket cooling with double jacket construction with the same or a different cooling medium than in the case of the internal boiling-air cooling described above.
  • the weight ratio of isobutene or isobutene-containing monomer mixture to inert solvent in the polymerization apparatus is generally 1: 0.1 to 1:20, in particular 1: 0.5 to 1:10.
  • At least 50%, in particular at least 75%, especially at least 95%, of the total inert solvent to be fed into the polymerization apparatus is added before or at the beginning of the polymerization.
  • Particularly preferred is the complete addition of the inert solvent before or at the start of polymerization in the polymerization apparatus together with the monomers to be polymerized and the polymerization catalyst. Contrary to the prejudice built up in WO 02/090391 that the presence of solvent makes a reaction slower and therefore that it can be done without solvent in the first phase, the complete or partial addition of solvent described above achieves good results from the beginning Successes.
  • the substances supplied to the polymerization appliance is advantageous to distribute the substances supplied to the polymerization appliance to at least two separate streams, one of which contains the monomers to be polymerized and a second the preactivated or non-activated catalyst .
  • a portion of the inert solvent which then preferably less than 50%, in particular less than 25%, especially less than 5% of the total amount to be fed into the polymerization of inert solvent is to meter in the already polymerized reaction.
  • the simultaneous mixing and conveying properties having polymerization works usually continuously.
  • the amount of reaction material discharged by the conveying action in a certain direction at the outlet of the apparatus is replaced at the inlet or at the inlet by the corresponding amount of starting materials and solvent.
  • Such apparatus are usually constructed substantially cylindrical or tubular, have inside mixing and conveying devices and normally have a length to diameter ratio of at least 2: 1, in particular from 2: 1 to 30: 1, especially 5: 1 to 10: 1.
  • the polymerization apparatus is a single-shaft or multi-shaft kneading reactor. Particularly preferred are single-shaft or twin-shaft kneading reactors. Also, three- and multi-shaft kneading reactors, which are structurally complex, can be used successfully.
  • kneading reactors are meant here continuously operating apparatus, usually such apparatuses are also referred to as mixing kneaders, extruders or screw machines.
  • the waves can work in the same direction or in opposite directions.
  • the waves in single and multi-shaft kneading reactors are normally filled with stirring elements. If possible, the stirring elements of the shafts should be arranged in such a way that thorough mixing, conveying action and, in addition, the best possible cleaning of the reactor interior and the other shaft (s) is ensured. This is especially necessary to ensure smooth continuous operation.
  • the speeds of rotation of the waves are usually in the range of 20 to 150, in particular 40 to 120, especially 60 to 90 revolutions per minute.
  • the waves may be formed as worm shafts, whose gears are engaged with each other and whose inner shaft diameter is preferably constant over the entire length.
  • Preferred building material for the described kneading reactors are steels or stainless steels.
  • Isobutene or isobutene-containing monomer mixtures can be controlled by means of catalysts based on Lewis acids controlled by boiling heat, polymerized efficiently and economically to specification-compliant products.
  • the described polymerization reactor is preferably operated in such a way that its degree of liquid filling - with a preferably continuous mode of operation in the stationary state - is 30 to 90%, in particular 35 to 70%, especially 45 to 60% of the apparatus volume, i. the internal volume of the polymerization apparatus is. This ensures that a sufficiently large gas space is available for the buffering of evaporating internal coolant or, in other words, a sufficiently large surface area for the liquid / gas phase transition.
  • the average residence time of the polymerization mixture in the polymerization apparatus described is generally less than 100 minutes, in particular less than 60 minutes, especially 3 to 30 minutes.
  • the product is freed after successful or largely successful polymerization in a downstream apparatus with conveying properties by degassing residues of the inert solvent and / or unreacted monomers and / or other undesirable components in the product.
  • a downstream equipment can be used, for example, a continuous screw machine or an extruder with one or more waves. In multi-wave machines, they can work equally or in opposite directions. The speeds of rotation of the waves are generally in the range of 50 to 500, in particular 150 to 350 revolutions per minute. These appliances are usually self-cleaning.
  • the ratio of length to diameter of the degassing apparatus described, which are usually constructed substantially cylindrical or tubular, is usually 10: 1 to 60: 1, in particular 20: 1 to 40: 1.
  • this downstream apparatus with conveying properties used for degassing is an extruder with at least two shafts, in particular with two shafts, and with a plurality of different temperature-controlled degassing zones.
  • this extruder is a self-cleaning, co-rotating twin-screw extruder.
  • the number of degassing zones which generally operate in stages, is determined; it is usually 1 to 8, in particular 2 to 6.
  • Each degassing zone expediently has at least one degassing dome.
  • the degassing pressure is expediently reduced in stages in the direction of product conveyance. For example, a typical pressure profile starts at 4000 mbar and ends in the vacuum range at, for example, 50 mbar.
  • the degassing temperature in the said degassing zones is generally raised stepwise in the direction of product delivery.
  • a typical temperature profile starts at + 20 ° C, especially at + 50 ° C, and ends at, for example, + 230 ° C, especially + 200 ° C.
  • a thermally induced unwanted degradation (depolymerization) of the polymer chains can already occur.
  • the residual concentrations of inert solvent and unreacted monomers and optionally other undesirable components in the product can be up to less than 5000 ppm by weight, in particular less than 500 ppm by weight, especially less than 100 wt. -ppm humiliate.
  • the weight-average molecular weight M w of the product after carrying out the degassing described is generally less than 10% lower than the weight-average molecular weight M w of the product at the outlet of the polymerisation apparatus.
  • the downstream degassing apparatus described is usually connected to the polymerization apparatus, in which a partial degassing of the product may have already taken place due to the boiling-cooling effect, usually by means of a discharge apparatus.
  • the discharge apparatus may be a discharge screw or a discharge extruder.
  • the discharge apparatus is usually self-cleaning as well. It can be single-wave or the same or opposite directions designed Centerwellig. A self-cleaning, co-rotating twin-screw extruder is preferred.
  • the discharge apparatus is normally operated at the same low temperature as the polymerization apparatus, for this purpose the discharge extruder is expediently provided with a jacket jacket with double jacket construction, which is generally operated with the same coolant as the jacket cooling of the polymerization apparatus.
  • the arrangement of the polymerization apparatus, the discharge apparatus and the degassing apparatus is expediently chosen such that the lowest possible dead volumes occur during joint operation.
  • a preferred arrangement of the three apparatuses provides that the polymerization apparatus is parallel to the degassing apparatus and both are connected by the horizontally extending at right angles thereto discharge apparatus, wherein the inlet of the discharge is connected to the bottom outlet of the polymerization and the outlet of the discharge is connected to the input housing of the degassing apparatus.
  • the inlet housing of the degassing apparatus is usually located between the backward degassing zone and the degassing zones in the conveying direction.
  • the inert solvent released during the polymerization of the isobutene or of the isobutene-containing monomer mixtures and / or the subsequent work-up as inert gas may conveniently again be liquefied, if appropriate after a purification step, and recycled to the polymerization apparatus.
  • the crude product Due to the staggered arrangement of the two stirrer shafts in the kneading reactor, the crude product was moved to its outlet and by means of the connected jacket-cooled and operated at a speed of 65 revolutions per minute counter-rotating twin-screw discharge to run at a speed of 300 revolutions per minute degassing extruder with 6 degassing zones ( Type ZSK 70 from Coperion). At the inlet housing of the degassing extruder, the crude product had a temperature of -85 ° C.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé de fabrication d'homopolymères d'isobutène ayant une masse moléculaire moyenne pondérée Mw comprise entre 75 000 et 10 000 000 par polymérisation d'isobutène ou de mélanges de monomères contenant de l'isobutène en phase liquide en présence d'un ou de plusieurs acides de Lewis en tant que catalyseurs de polymérisation et un solvant inerte, la polymérisation étant réalisée dans un appareil possédant à la fois des propriétés de mélange et de promotion.
PCT/EP2007/053005 2006-04-05 2007-03-29 Procede de fabrication d'homopolymeres d'isobutene de masse moleculaire elevee par polymerisation dans un appareil presentant des proprietes de melange et de promotion WO2007113196A1 (fr)

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EP06112239.6 2006-04-05
EP06112239 2006-04-05

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WO2007113196A1 true WO2007113196A1 (fr) 2007-10-11

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130217847A1 (en) * 2012-02-17 2013-08-22 Thomas Wettling Process for preparing higher molecular weight polyisobutylene
KR20140122757A (ko) * 2012-02-17 2014-10-20 바스프 에스이 고분자량 폴리이소부틸렌의 제조 방법
WO2015010943A1 (fr) * 2013-07-25 2015-01-29 Basf Se Procédé de production d'homopolymères d'isobutène de poids moléculaires élevés

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2435229A (en) * 1944-06-23 1948-02-03 Jasco Inc Kneader polymerization process for olefins
US4714747A (en) * 1985-06-17 1987-12-22 Enichem Elastomeri S.P.A. Manufacture of butyl rubber
WO2002090391A1 (fr) * 2001-05-09 2002-11-14 List Ag Procede permettant d'effectuer des reactions de polymerisation
DE10361638A1 (de) * 2003-12-30 2005-08-04 Basf Ag Herstellung hochreaktiver Polyisobutene mit niedrigem Fluorgehalt unter Verwendung eines Moderators
WO2007006556A1 (fr) * 2005-07-12 2007-01-18 Basf Aktiengesellschaft Procede de production de polyisobutene de haute qualite

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2435229A (en) * 1944-06-23 1948-02-03 Jasco Inc Kneader polymerization process for olefins
US4714747A (en) * 1985-06-17 1987-12-22 Enichem Elastomeri S.P.A. Manufacture of butyl rubber
WO2002090391A1 (fr) * 2001-05-09 2002-11-14 List Ag Procede permettant d'effectuer des reactions de polymerisation
DE10361638A1 (de) * 2003-12-30 2005-08-04 Basf Ag Herstellung hochreaktiver Polyisobutene mit niedrigem Fluorgehalt unter Verwendung eines Moderators
WO2007006556A1 (fr) * 2005-07-12 2007-01-18 Basf Aktiengesellschaft Procede de production de polyisobutene de haute qualite

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130217847A1 (en) * 2012-02-17 2013-08-22 Thomas Wettling Process for preparing higher molecular weight polyisobutylene
KR20140122757A (ko) * 2012-02-17 2014-10-20 바스프 에스이 고분자량 폴리이소부틸렌의 제조 방법
US9963521B2 (en) * 2012-02-17 2018-05-08 Basf Se Process for preparing higher molecular weight polyisobutylene
KR101974337B1 (ko) 2012-02-17 2019-05-02 바스프 에스이 고분자량 폴리이소부틸렌의 제조 방법
WO2015010943A1 (fr) * 2013-07-25 2015-01-29 Basf Se Procédé de production d'homopolymères d'isobutène de poids moléculaires élevés

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