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WO1999007753A1 - Proceed de preparation de polyisobutene reactif exempt d'halogene - Google Patents

Proceed de preparation de polyisobutene reactif exempt d'halogene Download PDF

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Publication number
WO1999007753A1
WO1999007753A1 PCT/EP1998/004632 EP9804632W WO9907753A1 WO 1999007753 A1 WO1999007753 A1 WO 1999007753A1 EP 9804632 W EP9804632 W EP 9804632W WO 9907753 A1 WO9907753 A1 WO 9907753A1
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WO
WIPO (PCT)
Prior art keywords
isobutene
polyisobutene
molecular weight
polymerization
catalyst
Prior art date
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Ceased
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PCT/EP1998/004632
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German (de)
English (en)
Inventor
Christoph Sigwart
Thomas Narbeshuber
Heiko Arnold
Manfred Barl
Rolf Hartmuth Fischer
Eugen Gehrer
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BASF SE
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BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to AU87324/98A priority Critical patent/AU8732498A/en
Publication of WO1999007753A1 publication Critical patent/WO1999007753A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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 a process for the preparation of free of charge, reactive polyisobutene with a content of terminal double bonds of more than 50 mol% and an average molecular weight M n of 500 to 5000 daltons by the cationic polymerization of isobutene or isobutene-containing hydrocarbon mixtures in liquid Phase in the presence of molybdato heteropolyacids.
  • Isobutene polymerization forms an inseparable mixture of polyisobutenes with different positions of the double bond in the individual polyisobutenes.
  • ß-olefinic a statistical mixture of polyisobutenes with ⁇ -olefinic, ie terminal, ⁇ -olefinic and double bonds located further inside the polyisobutene molecule is formed.
  • the content of terminal double bonds in a polyisobutene product produced by a specific production process and the content of ⁇ -olefinic double bonds are stated in mol%.
  • Polyisobutenes with molecular weights of up to 100,000 daltons are known.
  • reactive polyisobutene with molecular weights of usually 500 to 5000 daltons has a high content of terminal vinylidene groups, preferably of more than 15 50 mol%.
  • These reactive polyisobutenes as insects for the production of lubricant and Kraf tstoff -Additi - ven as they are described for example in DE-A 27 02 604 is used.
  • polyisobutene is first reacted with maleic anhydride. In this case, preferably 20 to react the terminal double bonds of the vinylidene type, whereas double bonds that are located further inside of the macro ⁇ molecule, depending on the position in the molecule to a lesser extent or even not respond.
  • polyisobutene-maleic anhydride adducts formed are then converted into the corresponding additives by reaction with 25 specific amines.
  • a high proportion of terminal double bonds is therefore absolutely necessary for polyisobutenes, which are used as starting materials for the additives mentioned above.
  • Polyisobutene with a high content of terminal double bonds is also preferably used here, but ß-olefinic polyisobutenes are also hydroforylated to the desired product in the hydroformylation with cobalt catalysts owing to their double bond isomerization activity.
  • a disadvantage of these homogeneously catalyzed processes is that the Lewis acid catalysts used are corrosive and there is a risk that halogenated, polymeric by-products are formed in addition to the desired reactive polyisobutene, which are practically inseparable from the PIB and adversely affect the product and processing properties of the PIB.
  • the separation of the homogeneous catalyst in these methods is usually carried out by quenching with a nucleophile, whereby the catalyst is destroyed, and subsequent separation of the PIB Extrak ⁇ tive from the quench mixture.
  • WO 94/28036 relates inter alia to the production of polyisobutene using heterogeneous Lewis acid-like catalysts.
  • insoluble salts of elements from III., IV., V. and VI. preferably their halides, sulfates, perchlorates, trifluoromethanesulfonates, nitrates and fluorosulfonates.
  • halogenice of these elements are used as catalysts for the isobutene polymerization.
  • An indication of the properties of the polyisobutene obtained in these examples is given neither with regard to the molecular weight nor with regard to the content of terminal double bonds.
  • the reaction medium is mixed with methanoic ammonia solution, as a result of which the catalysts in question are destroyed or at least inactivated to a considerable extent.
  • US Pat. No. 5,326,920 relates to a process for isobutene polymerization, 5 in which an oxidic support material, preferably silicon dioxide, which has been activated with a metal chloride, preferably an aluminum chloride, attached to it, is used as the heterogeneous catalyst.
  • an Si0 -AlCl catalyst is particularly preferably used in which 0 A1C1 groups are anchored to the Si0 2 support via oxygen bridges.
  • a disadvantage of this process is that the polyisobutene products obtained have an extremely broad molecular weight distribution D 8-14, their content of terminal double bonds ⁇ is low and its chlorine content in the ppm range.
  • heterogeneous catalysts containing zirconium dioxide and molybdenum oxide are used for the production of isobutene oligomers having a molecular weight of less than 300 daltons 5.
  • Aluminum fluoride can also be added to these catalysts to increase their activity.
  • isobutene-containing C 4 cut composition: 46% isobutene, 28% 1-butene, 8% 2-butenes, 12% n-butane, 5% isobutane, 1% 1, 3 -Butadiene
  • 35 NL-A 7 002 055 relates to a process for the preparation of isobutene oligomers in the gas phase with a tin oxide / molybdenum oxide on a silicon dioxide catalyst. This gives a mixture of dimers, trimers and tetramers of isobutene.
  • EP-A 535 516 relates to a catalyst for the production of ethylene polymers which contains chromium trioxide on a special SiO 2 carrier material.
  • a teaching on the production of reactive, low molecular weight polyisobutene is not given in this document.
  • DE-A 19528942 relates to a process for the production of low molecular weight, reactive and halogen-free polyisobutene, in which a support material doped with various promoters made from an oxygen-containing compound of zirconium is used as the catalyst.
  • CA 738019 describes a process for isobutene polymerization, in which supported heteropolyacid catalysts are brought into contact with isobutene at 20-200 ° C. and catalyst loads of 1 to 40 h -1 .
  • a process for the production of triisobutene by isobutene is brought into contact - Polymerization is described at 40 to 140 ° C., in which heteropolyacids applied as carrier materials on essentially alkali-free gels are used as catalysts
  • the formation of the isobutene trimers desired according to the teaching of this patent can be promoted by low reaction temperatures, at higher temperatures
  • the isobutene polymerization is carried out exclusively in the gas phase and the isobutene trimers obtained are mainly composed of 2, 2, 6, 6-tetramethyl-4-methyleneheptane and 2, 2, 4, 6, 6-penta - methyl - 3-heptene
  • the products obtained by this process have only a low molecular weight (dimers 112, trimers
  • JP-A 14538/1982 describes a process for the preparation of isobutene oligomers by selective isobutene oligomerization in the presence of n-butene on dehydrated heteropolyacids and / or heteropolyacid salts at temperatures ⁇ 120 ° C.
  • Isobutene oligomers are mainly understood to mean isobutene dimers with small amounts of isobutene trimers and the isobutene polymerization is carried out exclusively under conditions in which the starting materials are in the gas phase. There is no teaching in the publication of the production of reactive, higher molecular weight polyisobutene with terminal double bonds in the present case.
  • JP-A 102825/1982 discloses processes for the preparation of isobutylene di- and t ⁇ meren on tungsten heteropolyacids. Although these heteropolyacids are calcined at 250-400 ° C., de oligomerization is carried out at temperatures from 50 to 5150 ° C., in particular at 100 ° C. 140 ° C., ie always in the gas phase. A lowering of the temperature is referred to as WANTED Unwanted, since a reduction in the yield of the Select Required di- and Tr mers at temperatures below 50 ° C was obser ⁇ tet. Accordingly, no teaching is given for the production of reactive, high molecular weight polyisobutene at low temperature in the liquid phase.
  • the present invention was also based on the problem, a process for the preparation of halogen-free, reactive polyisobutene with a content of terminal double ends of less than 50 mol%, in particular a content of terminal non- ⁇ -olefinic double bonds of more than 80 mol -% and to find an average molecular weight of 500 to 5000 daltons with the aid of a heterogeneous catalyst, which is not the aforementioned
  • the heteropolyacids to be used according to the invention contain tungsten or preferably molybdenum as the essential element, partial substitution by vanadium being possible.
  • vanadium the preferred atomic ratios are V: Mo 1: 6 to 1: 12.
  • the central atoms are phosphorus, silicon, arsenic, germanium, boron, titanium, cerium, thorium, manganese, nickel, tellurium, iodine, cobalt, Chromium, iron, gallium, vanadium, piatm, beryllium and zinc. Phosphorus and silicon are preferred.
  • the preferred ratio of molybdenum or tungsten atoms to the respective central atom is 2.5: 1 to 12: 1, preferably 11: 1 to 12: 1.
  • Do ⁇ ecamolybdatocer (IV) acidic H g CeMo 12 0d 2 * n H 2 0
  • Dodecamolybdatoarsen (V) acidic H ⁇ As ⁇ 2 0 42 * n H 2 0
  • hexamolybdatochrome (III) acidic H 3 CrM ⁇ 6 ⁇ 4 H 6 * n H 2 0
  • Hexamolybdatonickel (II) acidic H 4 N ⁇ Mo 6 0 24 H 6 * 5 H 2 0
  • Octadecamolybdatod ⁇ arsen (V) acid H 6 s 2 M ⁇ aOs 2 * 25 H 2 0
  • Nonamoiybdatomangan (IV) acid HgMnMogO ⁇ * n H 2 0
  • Dodecamolybdatophosphoric acid and dodecamolybdatosilicic acid are preferably used.
  • heteropolyacids are known compounds and can be prepared using known methods, for example using the methods of Brauer (editor): Handbuch der Praparativen Anorganischen Chemie, Volume III, Enke, Stuttgart, 1981 or the methods of Top. Curr. Chem. 76, 1 (1978). Preparation methods which do not require the use of organic solvents and are instead carried out in aqueous solution are particularly preferred.
  • the heteropolyacids thus produced are generally in hydrated form and are freed of the co-ordinatively bound water contained therein before they are used.
  • the dehydration can advantageously be thermal, for example by the Makromol process. Chem. 190, 929 (1989).
  • Another possibility for dehydrating the heteropolyacids, depending on the heteropolyacid used, is to dissolve the heteropolyacid in an organic solvent, for example in a dialkyl ether or alcohol, to displace the water with the organic solvent from its coordinative bond with the heteropolyacid and to azeotropically with it Distilled off solvent.
  • Anhydrous heteropolyacids produced by these methods are generally subsequently calcined at temperatures of 250 to 500 ° C., preferably 280 to 400 ° C. Depending on the temperature and the selected pressure, the calcination is usually between one hour and 24 hours.
  • the catalysts thus obtained can be used directly in the process according to the invention.
  • the heteropolyacid catalysts can also be used supported.
  • the heteropolyacid is applied to a carrier material which is inert under the reaction conditions, such as activated carbon, silicon dioxide, titanium dioxide or zirconium dioxide, by methods known per se, for example by soaking the carrier material in question with a solution of the heteropolyacid in a solvent, preferably water, and then at temperatures of 100 to 250 ° C, preferably 130 to 250 ° C under reduced pressure until water is no longer detectable in the catalyst.
  • a solvent preferably water
  • anhydrous heteropolyacids are subsequently at temperatures of 250 to 500 ° C preferably 280 to 400 C calcined C.
  • the catalysts to be used according to the invention are expediently shaped or comminuted to give shaped articles, such as tablets, spheres, cylinders, rings or spirals, or comminuted into chippings before being used, and are preferably used in this form in a fixed bed arrangement in the reactor, or they become powder marry and in this form, e.g. used as suspension catalysts.
  • the catalysts to be used according to the invention can be stored practically without restriction, especially with the exclusion of moisture. Catalysts which have become moist are advantageously dried at atmospheric pressure or under reduced pressure before they are used, at atmospheric pressure generally at temperatures above 150 ° C., preferably at 180 to 250 ° C., at reduced pressure even at lower temperatures.
  • Both pure isobutene and isobutene-containing hydrocarbon mixtures, such as C 4 raffinate or isobutane / isobutene mixtures from isobutane dehydrogenation, can be used as starting material in the process according to the invention.
  • C 4 raffinate is a mixture of carbon and 5 hydrogen mixtures which are removed from the C 4 section of steam crackers or FCC crackers (FCC: Fluid Catalyzed.)
  • FCC Fluid Catalyzed.
  • the process according to the invention can be carried out discontinuously or continuously at temperatures of generally from -40 ° C. to + 10 ° C., preferably from -30 to + 10 ° C. and particularly preferably from -20 ° C.
  • cascades can be used in the continuous operation of the process.
  • tubular reactors or tubular reactor cascades operated in sump or trickle mode can advantageously be used in the continuous operation of the process according to the invention.
  • Typical catalyst loads are 10 kg isobutene / kg cat. * H to 0.1 kg / kg * h, preferably 7 to 0.2 kg / kg * h, especially before -
  • typical residence times are 0.05 to 30 h, preferably 0.1 to 20 h, particularly preferably 0.2 to 10 h.
  • the isobutene polymerization can be carried out in the presence or absence of preferably non-polar, halogen-free solvents, preferably hydrocarbons.
  • the hydrocarbons additionally contained therein, in addition to the isobutene act as solvents or diluents.
  • Butanes, pentanes, hexanes, heptanes and octanes, which can be linear or branched, are preferred.
  • Butanes, pentanes and hexanes are particularly preferred. Since the isobutene polymerization is exothermic, it can be advantageous to equip the reactors used with devices for internal or external cooling. 45
  • the desired average molecular weight M n of the polyisobutene can be set by varying the reaction parameters, in particular by varying the temperature, residence time and catalyst load. 5
  • the average molecular weight M n is generally adjusted by varying the amount of catalyst used, the reaction time and the reaction temperature. Depending on the amount of catalyst used, the reaction time is generally from 0.01 to
  • the catalyst is generally obtained in an amount of 0.1 to 50% by weight, preferably 0.5 to 20% by weight and particularly preferably 1 to 15 10% by weight to the weight of the isobutene contained in the starting material used.
  • the average molecular weight M n is adjusted accordingly, but instead of the amount of catalyst used, the reaction parameters of catalyst loading and residence time are varied. 25th
  • the isolation of the polyisobutene from the polymerization mixture generally has no special procedural features and, if a suspended catalyst is used after it has been separated off, for example by filtration, centrifugation or decanting, can be carried out by distillation, expediently initially volatile constituents of the polymerization mixture, such as Unreacted isobutene, hydrocarbons contained in the starting material or added as a solvent, are distilled off and then higher-boiling by-products, for example low-molecular weight isobutene oligomers, are separated off from the polyisobutene by distillation.
  • the process according to the invention enables the production of reactive, halogen-free polyisobutene of an average molecular weight
  • the catalyst was made and used in the form of powder.
  • the contents of the catalyst in Mo and P were determined by means of X-ray fluorescence analysis (Lit. R. Bock: Methods of Analytical Chemistry; Volume 2: Detection and Determination Methods Part 1, Verlag Chemie, Weinheim 1980).
  • the number average molecular weight M n also referred to herein as the average molecular weight M n , was determined using
  • GPC Gel permeation chromatography
  • the content of ⁇ and ⁇ olefin 0 can be determined.
  • Deuterated chloroform (CDC1 3 ) was used as the solvent and tetramethylsilane as the internal standard.

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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 préparation de polyisobutène réactif exempt d'halogène, contenant plus de 50 % en mole de liaisons doubles terminales et présentant un poids moléculaire moyen Mn compris entre 500 et 5000 Dalton, par polymérisation d'isobutène ou de mélanges hydrocarbures en phase liquide contenant de l'isobutène. Ce procédé se caractérise en ce que la polymérisation s'effectue à une température comprise entre -40 et + 10 DEG C, en présence d'un hétéropolyacide molybdique ou wolframique.
PCT/EP1998/004632 1997-08-07 1998-07-23 Proceed de preparation de polyisobutene reactif exempt d'halogene Ceased WO1999007753A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU87324/98A AU8732498A (en) 1997-08-07 1998-07-23 Process for preparing halogen-free, reactive polyisobutylene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19734176.4 1997-08-07
DE1997134176 DE19734176A1 (de) 1997-08-07 1997-08-07 Verfahren zur Herstellung von halogenfreiem, reaktivem Polyisobuten

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WO1999007753A1 true WO1999007753A1 (fr) 1999-02-18

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DE (1) DE19734176A1 (fr)
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9034998B2 (en) 2011-12-16 2015-05-19 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US9156924B2 (en) 2013-03-12 2015-10-13 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US9631038B2 (en) 2013-10-11 2017-04-25 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US9771442B2 (en) 2015-05-13 2017-09-26 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US10047174B1 (en) 2017-06-28 2018-08-14 Infineum International Limited Polymerization initiating system and method to produce highly reactive olefin functional polymers
US10167352B1 (en) 2017-06-28 2019-01-01 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US10174138B1 (en) 2018-01-25 2019-01-08 University Of Massachusetts Method for forming highly reactive olefin functional polymers
US10829573B1 (en) 2019-05-21 2020-11-10 Infineum International Limited Method for forming highly reactive olefin functional polymers

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19834593A1 (de) 1998-07-31 2000-02-03 Basf Ag Verfahren zur Herstellung von halogenfreiem, reaktivem Polyisobuten
US6346585B1 (en) * 1999-06-24 2002-02-12 The Lubrizol Corporation Ammonium heteropolyacid catalized polymerization of olefins
US9498772B2 (en) * 2013-11-26 2016-11-22 Saudi Arabian Oil Company Unsupported metal substituted heteropolyacid catalysts for dimerization and/or oligomerization of olefins

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB847065A (en) * 1958-04-28 1960-09-07 Bataafsche Petroleum Process for the selective polymerisation of isobutylene
GB847784A (en) * 1958-04-28 1960-09-14 Bataafsche Petroleum Improvements in or relating to catalysts containing a hetero-polyacid
JPS5714538A (en) * 1980-07-01 1982-01-25 Asahi Chem Ind Co Ltd Production of isobutylene oligomer
JPS57102825A (en) * 1980-12-19 1982-06-26 Nippon Oil & Fats Co Ltd Preparation of isobutylene oligomer
DE19528942A1 (de) * 1995-08-07 1997-02-13 Basf Ag Verfahren zur Herstellung von halogenfreiem, reaktivem Polyisobuten
EP0825205A1 (fr) * 1996-08-23 1998-02-25 The Lubrizol Corporation Polymérisation d'oléfins utilisant un catalyseur à base d'un hétéropolyacide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB847065A (en) * 1958-04-28 1960-09-07 Bataafsche Petroleum Process for the selective polymerisation of isobutylene
GB847784A (en) * 1958-04-28 1960-09-14 Bataafsche Petroleum Improvements in or relating to catalysts containing a hetero-polyacid
JPS5714538A (en) * 1980-07-01 1982-01-25 Asahi Chem Ind Co Ltd Production of isobutylene oligomer
JPS57102825A (en) * 1980-12-19 1982-06-26 Nippon Oil & Fats Co Ltd Preparation of isobutylene oligomer
DE19528942A1 (de) * 1995-08-07 1997-02-13 Basf Ag Verfahren zur Herstellung von halogenfreiem, reaktivem Polyisobuten
EP0825205A1 (fr) * 1996-08-23 1998-02-25 The Lubrizol Corporation Polymérisation d'oléfins utilisant un catalyseur à base d'un hétéropolyacide

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8209, Derwent World Patents Index; AN 82-16839e *
DATABASE WPI Week 8231, Derwent World Patents Index; AN 82-64753e *
PATENT ABSTRACTS OF JAPAN vol. 006, no. 078 (C - 102) 15 May 1982 (1982-05-15) *
PATENT ABSTRACTS OF JAPAN vol. 006, no. 191 (C - 127) 30 September 1982 (1982-09-30) *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9034998B2 (en) 2011-12-16 2015-05-19 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US9156924B2 (en) 2013-03-12 2015-10-13 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US9631038B2 (en) 2013-10-11 2017-04-25 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US9771442B2 (en) 2015-05-13 2017-09-26 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US10047174B1 (en) 2017-06-28 2018-08-14 Infineum International Limited Polymerization initiating system and method to produce highly reactive olefin functional polymers
US10167352B1 (en) 2017-06-28 2019-01-01 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US10174138B1 (en) 2018-01-25 2019-01-08 University Of Massachusetts Method for forming highly reactive olefin functional polymers
US10829573B1 (en) 2019-05-21 2020-11-10 Infineum International Limited Method for forming highly reactive olefin functional polymers

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Publication number Publication date
DE19734176A1 (de) 1999-02-11
AU8732498A (en) 1999-03-01

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