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
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/04—Monomers containing three or four carbon atoms
  • C08F10/08—Butenes
  • C08F10/10—Isobutene

Definitions

• the present invention relates to an improved process for preparing isobutene homopolymers having a weight-average molecular weight of from 75,000 to 10,000,000 by polymerization of isobutene in the liquid phase in an inert solvent in the presence of a Lewis acid-based polymerization catalyst. Efficient and specification-specific production processes of higher molecular weight polyisobutenes usually require very low polymerization temperatures.
• 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.
• a temperature of -104 ° C is established.
• the heat of polymerization is thereby completely dissipated.
• 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 be due to the boiling-cooling, i. be controlled simply and safely by forming large vapor passages.
• it is a disadvantage of the BASF strip process that due to the lack of movement of the reaction mixture on the strip, there is no adequate mixing of the reaction mixture and thus no product surface renewal, which may adversely affect the product properties.
• Boiling of the reaction mixture come when overheated areas and ethenreiche cold areas contact each other, which then leads to contamination of the reactor wall by entrainment of polymerizing reaction mixture.
• Another disadvantage is that the inhomogeneous temperature distribution causes an undesirable broadening of the molecular weight distribution of the polymer, which is associated with unfavorable product properties.
• Another disadvantage of the BASF belt process is that the steel strip is subject to wear and thus causes high maintenance costs.
• Another common method for the preparation of higher molecular weight polyisobutenes is the "Oxy-slurry process" in which the polymerization is carried out at -80 to -85 ° C. in a cooling jacket provided with cooling jacket which is charged with liquid ethene
• anhydrous aluminum chloride in methylene chloride is used, and as a result of very vigorous stirring, the polymer precipitates as a slurry consisting of small droplets, which flows via an intermediate vessel into a degassing vessel, where the slurry is steamed and treated with hot water so that the volatiles (substantially unreacted isobutene and methyl chloride) can be removed and subjected to reprocessing
• the remaining aqueous slurry of polymer particles is worked up by removing catalyst residues, solvent residues and isobutene residues.
• the object of the present invention was to provide an easy to carry out, efficient and economical process for the preparation of high molecular weight isobutene homopolymers, which allows a safe control of the polymerization with regard to the product parameters to be adjusted such as molecular weight, polydispersity and residual monomer content and an easily aufreininigendes and easy to handle, before In particular, a non-adhesive product before work-up supplies.
• the polymerization should be carried out in a conventional closed reactor and in the disperse phase in a non-miscible fluid or homogeneously mixed in a miscible fluid, i. in a suitable solvent or diluent.
• Aluminum trichloride has the disadvantage that, as a non-volatile catalyst, it hinders the subsequent purification of the polyisobutene. Reaction accelerators or chain length regulators are not used.
• the object of the present invention has been achieved by a process for producing isobutene homopolymers having a weight-average molecular weight of from 75,000 to 10,000,000 by polymerizing isobutene in the liquid phase in an inert solvent in the presence of a Lewis acid-based polymerization catalyst is characterized in that in a polymerization reactor simultaneously
• the polymerization is carried out at temperatures of -80 ° C to -190 ° C, (b) as inert solvent one or more d- to Cs-hydrocarbons or one or more halogenated d- to Cs-hydrocarbons or a mixture thereof used and
• an ethylenically saturated hydrocarbon compound containing at least one oxygen atom and no abstractable proton and / or (e) carrying out the polymerization in the presence of at least one chain length regulator containing at least one tertiary olefinic carbon atom.
• 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.
• the isobutene source is in particular pure isobutene, which generally contains at most 0.5% by volume of residual impurities such as 1-butene, 2 Butenes, 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 significant amounts of other C4 monomers are incorporated into the polymer chain.
• the isobutene concentration in said C4 hydrocarbon commercial streams is in the range of 40 to 60 weight percent.
• the process according to the invention can also be operated with isobutene-containing C 4 hydrocarbon streams which contain less isobutene, for example only 10 to 20% by weight.
• the isobutene-containing monomer mixture may contain small amounts of contaminants such as water, carboxylic acids or mineral acids, without resulting in 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 according to measure (c) to be used as a polymerization catalyst Lewis acid complexes based on iron halides, aluminum trihalides or aluminum alkylalkylhalogeniden and used as a polymerization catalyst Lewis acids in combination with organic sulfonic acids as initiators are described in detail in WO 2012/072643 A2 , which is hereby incorporated by reference.
• the said iron halide, aluminum trihalide and aluminum alkyl halide complexes contain, in addition to the Lewis acid, a donor in the form of an organic compound having at least one ether function or one carboxylic ester function.
• the said combination of Lewis acids, in particular boron trifluoride, iron halides, aluminum trihalides or Aluminiumalkylhalogeniden, with organic sulfonic acids as initiators contain at least one organic sulfonic acid of the general formula Z-SO3H, in which Z is a Ci-C2o-alkyl radical, Ci-C2o Haloalkyl, Cs-Cs-cycloalkyl, C6-C20-aryl or C7-C20-aralkyl; a typical such organic sulfonic acid is methanesulfonic acid.
• a complex of boron trifluoride and a proton source is preferably used as the polymerization catalyst.
• proton sources which the function of an activator or moderator in the catalyst complex are suitable, especially ethers, in particular C 1 to C 4 dialkyl ethers such as diethyl ether, and alcohols, in particular low molecular weight monohydric aliphatic alcohols.
• the polymerization catalyst used is a complex of boron trifluoride and a C 1 to C 3 alkanol, for example. Methanol, ethanol, n-propanol or isopropanol. It can be used as proton source and mixtures of said ethers and / or alcohols.
• the boron trifluoride and the proton source can be premixed and already added as an action ready complex in the polymerization reactor.
• the boron trifluoride gaseous, liquid or dissolved in an inert solvent or diluent, for example in an inert solvent according to measure (b)] and the proton source may also be supplied separately to the polymerization medium.
• 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 in amounts of 0.0001 to 1 wt .-%, in particular 0.0005 to 0.5 wt .-%, especially 0.001 to 0.1 wt .-%, each based on the Lewis acid Component or boron trifluoride portion in the catalyst complex and on isobutene used.
• the proton source can be used in substoichiometric, stoichiometric or superstoichiometric amounts in relation to boron trifluoride.
• Typical molar ratios of proton source to boron trifluoride are in the range of 0.3: 1 to 3: 1, in particular 0.5: 1 to 2: 1, especially 0.7: 1 to 1, 3: 1 (in each case based on 1 Proton equivalent of the proton source).
• the amount of proton source according to measure (c) can also influence the adjustment of the molecular weight of the isobutene homopolymer to be achieved and with the targeted adjustment of its molecular weight serve.
• the isobutene homopolymers prepared by the process according to the invention preferably have a weight-average molecular weight (M w ) of from 150,000 to 8,000,000, in particular from 250,000 to 6,000,000, especially from 400,000 to 5,000,000.
• M w weight-average molecular weight
• M n number average molecular weight (determined by gel permeation chromatography) of from 25,000 to 2,000,000, particularly preferably from 45,000 to 1,500,000, in particular from 55,000 to 1,000,000, especially from 65,000 to 750,000.
• the polymerization process according to the invention is carried out in the liquid polymerization medium at temperatures of -80.degree. C. to -190.degree.
• temperatures near the lower limit of the above temperature range and at -130 ° C to -190 ° C, especially at less than -160 ° C to -185 ° C, especially at - 165 ° C to -180 ° C, in a typical procedure at -168 ° C to -173 ° C.
• the process is carried out at temperatures of -100 ° C to -150 ° C, preferably at -105 ° C to -147 ° C, especially at -1 10 ° C to -140 ° C, in particular at -1 15 ° C to -135 ° C, in a typical procedure at -120 ° C to -130 ° C, by.
• the controlled low polymerization temperatures have an advantageous effect on the product properties.
• the temperature setting during the precooling of the starting materials used, in particular the isobutene may also influence the course of the polymerization and the results obtained;
• the isobutene to be used is usually cooled to temperatures of from -70.degree. C. to -140.degree. C., in particular to -70.degree. C. to -100.degree.
• the cooling of the reaction medium to the above-mentioned temperatures is advantageously carried out by external cooling.
• the polymerization medium is brought to the required cryogenic temperature by means of a separate cooling circuit and kept there during the polymerization.
• the separated cooling circuit which is structurally usually implemented as an outer cooling jacket to the polymerization, is usually operated with liquid nitrogen or liquefied air as a coolant.
• the polymerization is generally carried out at a pressure of 500 mbar to 5 bar, in particular at a pressure of 800 mbar to 2 bar.
• the polymerization reactor is operated at or near the ambient pressure (normal pressure).
• a slight overpressure may provide benefits for some of the possible inert solvents.
• a procedure of polymerization with overpressure is possible in principle, bring higher pressures, especially those above 5 bar, in general, no additional advantages.
• certain inert solvents or mixtures of such inert solvents are used in the liquid polymerization medium.
• inert solvents are understood to mean not only fluids in which isobutene dissolves homogeneously in the liquid phase, but also fluids with which isobutene is immiscible and is present in dispersed form.
• Suitable inert solvents are suitable for a C 1 to C 8 hydrocarbons, preferably C 1 to C 8 hydrocarbons, in particular C 2 to C 4 hydrocarbons, which are usually saturated or simply ethylenically unsaturated and are generally linear or slightly branched structure.
• C 1 to C 8 hydrocarbons preferably C 1 to C 8 hydrocarbons, in particular C 2 to C 4 hydrocarbons, which are usually saturated or simply ethylenically unsaturated and are generally linear or slightly branched structure.
• they must not polymerize themselves under the reaction conditions of the present invention; they usually have only primary and / or secondary olefinic carbon atoms.
• C to Cs-hydrocarbons are methane, ethane, ethene, propane, propene, n-butane, isobutane, n-pentane, 2-methylbutane, 2,3-dimethylbutane, 2-methylpentane, 3-methylpene tan, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2-methyl-hexane, 3-methylhexane, 3-ethyl-2-methylpentane, 2,2-dimethylhexane, 2,3-dimethylhexane, 3,3-dimethylhexane, 4-methylheptane, 2,2,3-trimethylpentane and 3-methylheptane.
• halogenated C 1 to C 5 hydrocarbons preferably halogenated C 1 to C 8 hydrocarbons, in particular fluorinated and / or chlorinated C 1 to C 8 or C 1 -hydrocarbons, such as methyl chloride, methyl fluoride, difluoromethane, dichloromethane , Fluoroethane, 1-fluoropropane, 1, 1, 1, 2,3,3,3-
• Hydrocarbons or mixtures of one or more d- to Cs or d- to Cs- hydrocarbons and one or more halogenated C to d or Cs or Cs hydrocarbons are used.
• the measure used as measure (b) as the inert solvent is ethane, ethene, propane, propene, n-butane, isobutane or a mixture thereof.
• the measure used as measure (b) as the inert solvent is 1,1,1,3,3,3,3-heptafluoropropane, octafluoropropane or a mixture thereof.
• the weight ratio of isobutene to the inert solvents according to measure (b) in the polymerization reactor is generally 1: 0.1 to 1:50, preferably 1: 0.1 to 1:40, especially 0.1: 1 to 1: 20, in particular 1: 0.5 to 1: 10.
• the polymerization is carried out in the presence of one or more reaction accelerators.
• a reaction accelerator is a compound which, under the chosen polymerization conditions, influences and thus controls the catalytic activity of the boron trifluoride in the desired manner.
• Such reaction accelerators are saturated hydrocarbon compounds which contain at least one oxygen atom, preferably as an ether oxygen atom or as part of a carbonyl function.
• the polymerization is carried out as measure (d) in the presence of at least one reaction accelerator selected from ketones, aldehydes, ethers, acetals and hemiacetals.
• reaction accelerators are low molecular weight compounds having 1 to 40, in particular 1 to 16, especially 1 to 8 carbon atoms; their structure can be open-chain or cyclic; they may be aliphatic, aromatic or heteroaromatic in nature.
• Typical representatives of such reaction accelerators are ketones such as acetone, butanone, cyclohexanone, acetophenone or benzophenone, aldehydes such as formaldehyde, trioxane, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, cyclohexylaldehyde or glyoxal, dialkyl ethers such as dimethyl ether, diethyl ether or di-n butyl ethers, cyclic ethers such as tetrahydrofuran or dioxane, as well as acetals and hemiacetals, which are prepared by reacting the abovementioned ketones and aldehydes with alcohols such as methanol, ethanol, n-propanol, isopropanol. nol, n-butanol, isobutanol, sec-butan
• reaction accelerators may most advantageously be used together with one or more medium-molecular weight alcohols, in particular monohydric aliphatic, cycloaliphatic or araliphatic alcohols, especially C 4 -C 10 -alcohols, eg. n-butanol, isobutanol, sec-butanol, tert. Butanol, n-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, n-decanol, 2-propylheptanol, cyclohexanol or benzyl alcohol.
• medium-molecular weight alcohols in particular monohydric aliphatic, cycloaliphatic or araliphatic alcohols, especially C 4 -C 10 -alcohols, eg. n-butanol, isobutanol, sec-butanol, tert. Butanol,
• such medium molecular weight alcohols act similarly to the low molecular weight alcohols used as proton source according to measures (c) as activators or moderators in the catalyst complex, but usually with a weaker activating effect; on the other hand, they act as solvents for the reaction accelerators.
• aldehydes or ketones are used as reaction accelerators, the abovementioned medium molecular weight alcohols as well as some of the low molecular weight alcohols mentioned can form with these acetals or hemiacetals or ketals (ketone acetals) which likewise act as reaction accelerators.
• formaldehyde as a reaction accelerator, a corresponding alcoholic solution, for.
• the reaction accelerator itself is normally used in amounts of from 0.0001 to 1% by weight, preferably from 0.0003 to 0.75% by weight, in particular from 0.0005 to 0.5% by weight, in particular from 0.001 to 0, 1 wt .-%, each based on isobutene used.
• the polymerization is carried out in the presence of at least one chain length regulator which normally represents an ethylenically unsaturated system and contains one or more tertiary olefinic carbon atoms, optionally in addition to one or more primary and / or secondary olefinic carbon atoms.
• chain length regulators are mono- or polyethylenically unsaturated hydrocarbons having 5 to 30, in particular 5 to 20, especially 5 to 16 carbon atoms; their structure can be open-chain or cyclic.
• Typical representatives of such chain length regulators are isoprene (2-methyl-1,3-butadiene), 2-methyl-2-butene, diisobutene, triisobutene, tetraisobutene and 1-methylcyclohexene.
• the polymerization is carried out as measure (e) in the presence of isoprene and / or diisobutene as chain length regulators.
• Diisobutene (isooctene) is usually understood to mean the mixture of isomers of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene; Of course, the individually used isomers 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene also act as chain length regulators according to measure (e).
• the amount of chain length regulators used according to the invention allows the molecular weight of the isobutene homopolymers produced to be adjusted in a simple manner: the higher the amount of chain length regulators, the lower the molecular weight generally becomes.
• the chain length regulator controls Usually, the molecular weight is replaced by the fact that sooner or later it will be incorporated into the polymer chain, leading to chain termination at this point.
• the chain length regulator is normally used in amounts of from 0.0001 to 2% by weight, in particular from 0.0005 to 1% by weight, in particular from 0.001 to 0.5% by weight, based in each case on isobutene used.
• the process according to the invention for the preparation of isobutene homopolymers can be carried out batchwise or continuously.
• the polymerization conditions for the process according to the invention are chosen such that the isobutene used in the polymerization onsreaktor with a conversion of at least 90%, in particular of at least 95%, especially of at least 99%, to isobutene homopolymers having a weight average molecular weight of 75,000 to 10,000,000 is implemented.
• an advantageous embodiment of the inventive method is that in a separate vessel, the starting material isobutene or an isobutene-containing hydrocarbon mixture together with the proton source, in particular a C 1 to C 3 alkanol, and together with one or more reaction accelerators, in particular selected from Ketonen, aldehydes, ethers, acetals and hemiacetals, and / or one or more chain length regulators, in particular selected from isoprene and diisobutene, premixed and in the polymerization reactor to the cooled to the polymerization temperature inert solvent containing the boron trifluoride. It is also particularly advantageous to cool this mixture before it is added to the polymerization reactor.
• the proton source in particular a C 1 to C 3 alkanol
• reaction accelerators in particular selected from Ketonen, aldehydes, ethers, acetals and hemiacetals
• chain length regulators in particular selected from isoprene and diisobut
• This isobutene-containing mixture is added to the polymerization reactor so that the desired polymerization temperature can be kept constant by the external cooling.
• a rapid and complete mixing of the isobutene in the continuous phase is crucial for an effective temperature control and thus for the success of the process.
• Evaporating nitrogen from the external cooling can then either be re-liquefied in a closed circuit or - without having to carry out a cleaning - be conducted into the environment. With renewed liquefaction of the recirculated nitrogen stream, the low temperature of the vaporized nitrogen can be used advantageously and thus recovered.
• Dispensing with the feedback the cold energy of the gaseous nitrogen for other cooling purposes, for. B. for the cooling of the degassed end product can be used.
• liquid nitrogen or liquefied air when working in the range of a polymerization temperature of -100 ° C to -150 ° C, other external coolants can also be used, for example based on halogenated hydrocarbons.
• the workup of the isobutene homopolymers produced in the process according to the invention with a weight-average molecular weight of 75,000 to 10,000,000 is usually carried out by discharging the product from the polymerization reactor and - optionally after a suitable pretreatment - by thermal purification of the product.
• the discharge takes place advantageously at the lowest possible temperatures.
• the discharge from the reactor can be carried out, for example, by means of a mechanical discharge device such as a discharge screw.
• the isobutene homopolymers produced in the polymerization reactor are discharged from the polymerization reactor at temperatures of less than -80 ° C.
• the thermal cleaning after discharge of the product from the polymerization reactor is advantageously carried out in the industrial scale of the inventive method by using one or more extruders.
• the isobutene homopolymers are heated to temperatures of more than 80 ° C., in particular more than 100 ° C.
• the inner surface is renewed again and again for better degassing of the volatile constituents in the product, such as residual monomers and solvents.
• the degassing and the purification of the product can be facilitated by applying a vacuum, in particular one works for this purpose at a pressure of less than 700 mbar, in particular less than 200 mbar, especially less than 100 mbar.
• the waves can work in the same direction or in opposite directions.
• the waves in single and multiple-shaft extruders are normally occupied by kneading and / or conveying elements. These appliances are usually self-cleaning.
• the speeds of rotation of the waves are generally in the range of 10 to 500, in particular 15 to 350 revolutions per minute.
• the waves may be formed as worm shafts, whose gears are engaged with each other and whose inner shaft diameter preferably via the entire length is constant.
• Preferred building materials for the described extruders are steels or stainless steels.
• an inert gas for example nitrogen, is introduced into one or more segments of the extruder in order to promote the degassing process.
• the process according to the invention has the advantage that the isobutene homopolymers produced have only a low solubility in the solvents used (hydrocarbons and / or halogenated hydrocarbons) - and this applies to a greater extent at low temperatures - and thus largely precipitates as a solid.
• This precipitated solid has no tendency to stick at the low temperatures used, so that the crude product can be easily discharged and further processed, since in the region of collection of the product from the reactor in the workup at any point temperatures above the glass transition temperature of the polymer.
• the following examples are intended to illustrate the present invention without limiting it.
• a 1 liter 3-necked flask with mechanical stirrer, dry nitrogen gaseous inert gas inlet tube, a temperature control thermocouple, and a coolable dropping funnel was placed after inerting with the aid of liquid nitrogen (in a half-shell dewar flask placed around the flask). 100 ° C pre-cooled. Subsequently, 300 ml of liquid propane were placed in the flask under nitrogen atmosphere and 0.1 g of gaseous boron trifluoride was introduced.
• the desired polymerization temperature T could be easily adjusted.
• 94.0 g (1.68 mol) of liquid isobutene were added to the dropping funnel cooled with dry ice (about -78 ° C.) or liquid nitrogen (about -130 ° C.).
• the respectively below indicated amounts of methanol, isobutanol, formaldehyde (which had been freshly produced from paraformaldehyde and was present dissolved in the methanol / isobutanol mixture) and diisobutene were metered in and mixed with the isobutene in the dropping funnel.
• the desired reaction temperature T was kept constant during the entire dripping time by raising or lowering the dewar vessel by means of a lifting platform and adding liquid nitrogen. After the entire dropping funnel contents had dripped in, the contents of the flask were allowed to thaw, the solvent propane (boiling point: -42 ° C) evaporating. The crude product which had become tacky at room temperature was then removed and freed from the remaining solvent by heating in a drying oven (temperature: 160 ° C. at 30 mbar, duration: 2 h). Thereafter, the analytical data of the obtained isobutene homopolymer could be determined.
• Amount of methanol 0.15 ml 0.15 ml 0.15 ml 0.15 ml 0.15 ml 0.15 ml 0.15 ml amount isobutanol 0.05 ml 0.05 ml 0.50 ml 0.50 ml 0.05 ml 0, 05 ml amount of formaldehyde 0.05 g 0.05 g 0.05 g 0.50 g 0.50 g amount of diisobutene 0.01 ml 0.01 ml 0.01 ml 0.01 ml 0.01

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