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WO2023152033A1 - Polyisobutène moléculaire moyen avec une certaine distribution d'isomères à double liaison - Google Patents

Polyisobutène moléculaire moyen avec une certaine distribution d'isomères à double liaison Download PDF

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Publication number
WO2023152033A1
WO2023152033A1 PCT/EP2023/052636 EP2023052636W WO2023152033A1 WO 2023152033 A1 WO2023152033 A1 WO 2023152033A1 EP 2023052636 W EP2023052636 W EP 2023052636W WO 2023152033 A1 WO2023152033 A1 WO 2023152033A1
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Prior art keywords
isomer
sum
content
medium molecular
polyisobutene
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Inventor
Paul Lederhose
Bernard Pierre
Markus Brym
Thomas Wettling
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BASF SE
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BASF SE
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Priority to CN202380021191.7A priority Critical patent/CN118679193A/zh
Priority to EP23702482.3A priority patent/EP4476272A1/fr
Priority to JP2024547514A priority patent/JP2025506490A/ja
Priority to US18/836,033 priority patent/US20250179224A1/en
Priority to KR1020247030254A priority patent/KR20240144399A/ko
Priority to CA3251435A priority patent/CA3251435A1/fr
Priority to EP23703473.1A priority patent/EP4476273A1/fr
Priority to JP2024547540A priority patent/JP2025505724A/ja
Priority to CN202380021195.5A priority patent/CN118679194A/zh
Priority to CA3251428A priority patent/CA3251428A1/fr
Priority to US18/835,972 priority patent/US20250145742A1/en
Priority to KR1020247026581A priority patent/KR20240144197A/ko
Priority to PCT/EP2023/053253 priority patent/WO2023152258A1/fr
Publication of WO2023152033A1 publication Critical patent/WO2023152033A1/fr
Anticipated expiration legal-status Critical
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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
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/48—Isomerisation; Cyclisation

Definitions

  • the present invention concerns mixtures of medium molecular polyisobutene with a numberaverage molecular weight M n of more than 10000 and up to 100000 g/mol with a distribution of isomers exhibiting a certain reactivity in thermal and/or photoreactions.
  • EP 807641 A further disadvantage of EP 807641 is the recycling process in which unreacted isobutene is recycled to the reaction with the help of hexane. Although under the distillation conditions not all of the unreacted monomer is removed furthermore hexane is introduced into the polymer. Since both isobutene as well as hexane are toxic, polymers comprising such contaminants are not suitable for certain applications.
  • a high content of alpha- and/or beta-double bonds is necessary for medium molecular polyisobutene in order to achieve a high reactivity in thermal reactions, e.g. against maleic acid anhydride, see e.g. WO 2017/216022 where a polyisobutene with a number-average molecular weight M n of 17000 g/mol and a content of alpha-double bond of 40% and of beta-double bonds of 47% is used in the examples.
  • alpha-double bonds are more reactive in thermal reactions than beta-double bonds.
  • the yield of a desired product is not only affected by the reactivity of the double bonds but also the distribution of the isomers carrying double bonds with different reactivity and the content of isomers bearing no double bond or a sterically hindered double bond which are not available for the reaction.
  • WO 2017/216022 is silent about further isomers in the polyisobutene and structural elements thereof. Especially the content of isomers reactive in other reactions than the reaction with maleic acid anhydride is not given or rendered obvious.
  • polyisobutene deployed in the photo oxygenation described has a degree of polymerisation of approximately 100 at most and, hence, is low molecular.
  • the reactivity of polyisobutene is a function of its molecular weight and the reactivity of low molecular weight polyisobutene cannot be transferred to medium molecular weight.
  • An exemplary thermal reaction is the thermal ene reaction of polyisobutene with maleic acid anhydride, as it is described in WO 2017/216022.
  • R tr 100% * [A] + 79% * ([C6] + [C8]) + 37% * ([B] + [C7]) + 11% * ([C1] + [C2]).
  • the reactivity of an alpha-vinylidene double bond in isomer (A) in a photo oxygenation is 37%
  • the reactivity of isomers (C6) and (C8) (see below) of polyisobutene with the same molecular weight is 21 %
  • the reactivity of isomers (B) bearing a beta-double bond and (C7) is 100%
  • the reactivity of isomers (C1) and (C2) is 95%.
  • a reactivity in photo oxygenations R po is defined as
  • the reactivity of the double bonds isomers in polyisobutene in the photo oxygenation is preferably determined as described in the following: A photochemical batch reactor, equipped with eighty-eight 405 nm LEDs is charged with 10.0 g polyisobutene (Mn approx. 17000 g/mol, commercially available e.g. as Oppanol B10 from BASF SE, Ludwigshafen), 2.5 mg tetra- phenylporphyrin and 66.5 g dichloromethane. Oxygen (1.5 Nl/h) is bubbled through the reaction mixture while it is irradiated at 20 °C. After 120 min the reaction is terminated. After evaporation of the solvent the reaction mixture is analysed by NMR spectroscopy.
  • tetra-substitued isomer (C4) is lowest in energy
  • another tetra-substitued isomer (C3) has an energy content of just 2.63 kJ/mol higher.
  • the isomer (A) with an alphadouble bond is 30.46 kJ/mol higher
  • the isomer (B) which is desired according to the present invention is even 33.98 kJ/mol higher (for the designation of the isomers see below).
  • the desired isomer (B) is highest in energy and, therefore, under thermodynamic control of the reaction conditions expected to be formed least in equilibrium.
  • reactivity of the different double bond isomers in polyisobutene depends on the molecular weight.
  • the reactivity of double bond isomers may be different in low, medium or high molecular weight polyisobutene.
  • WO 2017/216022 see e.g. Example 3, that under reaction conditions which lead to good yields of maleinated product for low molecular polyisobutene only minor amounts of product can be obtained if higher molecular weight polyisobutene is used.
  • higher molecular weight polyisobutene a much higher stochiometry of maleic acid anhydride, higher reaction temperatures and/or longer reaction times are necessary to achieve comparable yields.
  • medium molecular polyisobutene comprises a mixture of different isomers with a different position and configuration of the double bond: isomers (A) bearing an alpha-double bond, isomers (B) bearing a beta-double bond and polyisobutene isomers (C) other than (A) and (B), selected from the group consisting of in which PIB, PIB' and PIB" refer to appropriately shortened polymeric backbones of the polyisobutene.
  • the groups PIB, PIB' and respectively PIB" together with the explicitly shown substructures add up to a polyisobutene polymer with a numberaverage molecular weight M n of more than 10000 and up to 100000 g/mol.
  • the groups PIB, PIB' and respectively PIB" refer to a polyisobutene polymer shortened by the explicitly shown substructures.
  • PIB' -[-(H 3 C) 2 C-CH 2 -]n- and
  • PIB -[-(H 3 C) 2 C-CH 2 -]O-, wherein the polymer chain, especially of PIB and PIB', may be started on an appropriate initiator, see below, preferably may be connected to hydrogen, with m, n and o independently of another each being positive integers, with the proviso that the sum of m, n, and o plus the monomer units in the shown substructures match the degree of polymerisation of the medium molecular polyisobutene. In a copolymer some isobutene units may be replaced by other monomer units, e.g. 1-butene, cis or trans 2-butene, see below.
  • the mixtures of isomers of medium molecular polyisobutene comprise at least one of the isomers (C6) and (C8) in amounts necessary to fulfil the required reactivity in thermal reactions (R tr ) and/or photo oxygenations (R po ).
  • the present invention concerns a medium molecular polyisobutene containing composition in which the polyisobutene exhibits a reactivity in thermal reactions R tr of at least 50%.
  • the reactivity is mainly determined by the isomers (A), (C6), and (C8).
  • Isomers (B) and especially (C1) and (C2) contribute to the reactivity to a much lesser extent. Therefore, according to this embodiment the polyisobutene comprises isomer (A), at least one of (C6) and (C8) and preferably also isomer (B).
  • the minimum amount of isomer (A) in the composition is at least 0.1 %, preferably at least 0.25%, very preferably at least 0.5%.
  • the minimum amount of isomer (B) in the composition is at least 0.1 %, preferably at least 0.25%, very preferably at least 0.5%.
  • the minimum amount of isomers [(C6) and (C8)] (in sum) in the composition is at least 0.1 %, preferably at least 0.25%, very preferably at least 0.5%.
  • the content of the isomers is determined with the help of 1 H-NMR spectroscopy, the detection level is determined by the frequency used. Preferably 1 H-NMR spectroscopy at 700 MHz at 25 °C is used.
  • the isomers are part of a polymeric mixture with a molecular weight distribution the content of each single isomer in the mixture in weight% and mol% is the same.
  • medium molecular polyisobutenes compositions are further embodiments to this option of the present invention insofar they exhibit a reactivity in thermal reactions R tr of at least 50%:
  • - of isomer (B) is from 40% to 50%, and - of isomer [(C6)+(C8)] (in sum) is from 15% to 20%, wherein the sum [(A)+(B)+(C6)+(C8)] is not more than 100%.
  • the present invention concerns a medium molecular polyisobutene containing composition in which the polyisobutene exhibits a reactivity in photo oxygenations R po of at least 49%.
  • the reactivity is mainly determined by the isomers (B), (C1), (C2), and (A). Isomers (C6) and (C8) contribute to the reactivity to a much lesser extent. Therefore, according to this embodiment the polyisobutene comprises isomer (A), (B), and at least one of (C1) and (C2).
  • medium molecular polyisobutenes compositions are further embodiments to this option of the present invention insofar they exhibit a reactivity in photo oxygenations R po of at least 49%:
  • - of isomer (B) is from 50% to 60%, and - of isomer [(C6)+(C8)] (in sum) is from 10% to 15%, wherein the sum [(A)+(B)+(C6)+(C8)] is not more than 100%.
  • the present invention concerns a medium molecular polyisobutene containing composition in which the polyisobutene exhibits a reactivity in thermal reactions R tr of at least 40% and in photo oxygenations R po of at least 49%.
  • medium molecular polyisobutenes compositions are further embodiments to this option of the present invention insofar they exhibit a reactivity in thermal reactions R tr of at least 40% and in photo oxygenations R po of at least 49%:
  • - of isomer (A) is from 0.1% to 10%
  • - of isomer (B) is from 40% to 50%
  • - of isomer (B) is from 50% to 60%, and - of isomer [(C6)+(C8)] (in sum) is from 5% to 10%, wherein the sum [(A)+(B)+(C6)+(C8)] is not more than 100%.
  • the present invention concerns a medium molecular polyisobutene containing composition in which the polyisobutene exhibits a reactivity in thermal reactions R tr of not more than 40% and in photo oxygenation R po of not more than 49%.
  • Polyisobutene according to this embodiment has the advantage that is less reactive than polyisobutene according to the other embodiments and, therefore, is less susceptible to weathering and more stable against oxidation or thermal degradation. Therefore, composition comprising such polyisobutenes are especially useful in sealants, adhesives, coatings or roofings.
  • the following medium molecular polyisobutenes compositions are further embodiments to this option of the present invention insofar they exhibit a reactivity in thermal reactions R tr of not more than 40% and in photo oxygenation R po of not more than 49%:
  • - of isomer (B) is from 20% to 30%, and - of isomer [(C6)+(C8)] (in sum) is from 0.1% to 5%, wherein the sum [(A)+(B)+(C6)+(C8)] is not more than 100%.
  • a high thermal reactivity can also be achieved with medium molecular polyisobutene comprising
  • polyisobutene isomers (C1) + (C2) + (C7) selected from the group consisting of in which PI B' and PIB" refer to appropriately shortened polymeric backbones of the polyisobutene, wherein at least one of the isomers (C1), (C2), (C6), (C7), and (C8) is present, wherein the sum of (A), (B), (C1), (C2), and (C7) is at least 75 mol% and the sum of all isomers (A), (B), and (C) always adds up to 100 mol%.
  • polyisobutene isomers (C1) + (C2) + (C7) selected from the group consisting of in which PI B' and PIB" refer to appropriately shortened polymeric backbones of the polyisobutene, wherein at least one of the isomers (C1), (C2), (C6), (C7), and (C8) is present, wherein the sum of (A), (B), (C1)
  • At least one of the isomers (C6) and (C8) is present, more preferably both isomers (C6) and (C8).
  • At least one of the isomers (C1), (C2), and (C7) is present.
  • Such polyisobutene compositions and those with a high thermal reactivity can advantageously be used in reactions thermal chemical reactions, especially epoxidation, hydroformylation, and ene-reaction with maleic anhydride.
  • a high reactivity in photo oxygenations can also be achieved with medium molecular polyisobutene comprising - not more than 10 mol% (in sum) of at least one polyisobutene species selected from the group consisting of
  • polyisobutene isomers (C1) + (C2) + (C7), selected from the group consisting of in which PI B' and PIB" refer to appropriately shortened polymeric backbones of the polyisobutene, wherein at least one of the isomers (C1), (C2), (C6), (C7), and (C8) is present, wherein the sum of (A), (B), (C1), (C2), and (C7) is at least 75 mol% and the sum of all isomers (A), (B), and (C) always adds up to 100 mol%.
  • At least one of the isomers (C6) and (C8) is present, more preferably both isomers (C6) and (C8).
  • At least one of the isomers (C1), (C2), and (C7) is present.
  • Another subject matter of the present invention is a process for preparation of such compositions with an increased content of beta-double bonds, comprising the steps of
  • polyisobutene composition with a content of polyisobutene species (A) bearing an alpha-double bond of at least 30 mol%, preferably at least 40 mol%, more preferably at least 50 mol%, most preferably at least 60 mol% and especially at least 70 mol%,
  • the content of polyisobutene species (A) bearing an alpha-double bond in the starting material may even preferably be at least 75 mol%, more preferably at least 80 mol%, most preferably at least 85 mol% and especially at least 90 mol%,
  • compositions with an increased content of beta-double bonds in reactions to obtain further derivatives, preferably in oxidation reactions, more preferably in photo oxygenations.
  • isomers bearing a "beta-double bond” refers to polyisobutene isomers (B) with the sub-structure in which
  • PPB polymeric backbone of the polyisobutene except for the final incorporated isobutene unit.
  • isomers bearing an "alpha-double bond” refers to polyisobutene isomers (A) with the sub-structure
  • vinylidene double bonds are referred to as double bonds bearing two hydrogen substituents on the same carbon atom of the double bond, if not explicitly mentioned otherwise.
  • Such vinylidene double bonds may be terminal, such as in isomer (A), or internal, as in isomers (C6) or (C8).
  • Other polyisobutene isomers (C) may be in which PI B' and PIB" refer to appropriately shortened polymeric backbones of the polyisobutene.
  • PI B' and PIB refer to appropriately shortened polymeric backbones of the polyisobutene.
  • Such a shortened polymeric backbone, especially PIB comprises at least one isobutene unit in polymerised form.
  • the mixture may comprise other polyisobutene-derived species (D):
  • halogenated polyisobutenes (D1) may be found.
  • polyisobutenes (D2) may be found, which do not comprise any multiple bonds at all and are not halogenated.
  • isomers (C1) and (C2) also represent trisubstituted polyisobutene isomers with a betadouble bond they are distinguished from compound (B) since their reactivity in a photo oxygenation is different from compound (B): While compound (B) comprises six (nearly) equivalent hydrogen atoms on the two methyl groups in allylic position to the double bond which yield the same product on photo oxygenation, isomers (C1) and (C2) each comprise two different methyl groups which lead to different photo oxygenation products.
  • compound (B) in a photo oxygenation yields a more uniform reaction mixture, thus, compound (B) is preferred over compounds (C1) and (C2). It furthermore is assumed that compound (B) under reaction conditions of photo oxygenation appears to be less sterically hindered than isomers (C1) and (C2) which is a further advantage of polyisobutene compositions with a higher content of compound (B).
  • Isomers (C3), (C4), and (C5) together with their (E)- and (Z)-isomers (not shown) represent tetrasubstituted isomers. Although the tetrasubstituted isomers are highly reactive in photo oxygenation they are unwanted since they lead to complex reaction mixtures due to their number of different reaction sites in photo oxygenation.
  • Isomers (C6) and (C7) are isomers with an internal double bond, since the double bond is at least one isobutene unit in polymerised form apart from the end of the polymer backbone, although isomer (C7) is less reactive than (C6) due to its double bond in the polymer backbone. This, again, emphasises the role of an accessible double bond in polyisobutenes.
  • Isomers (C6) are advantageous since they are known to yield fuel and lubricant additive derivatives with better performance properties, as disclosed in US 9688791 B2.
  • isomer (C6) is advantageous for a higher reactivity especially in thermal reactions
  • isomer (C7) exhibits an advantage in photo reactions, especially photo oxygenations.
  • Isomer (C8) is the product of a methyl group rearrangement.
  • At least one of isomers (C1) and (C2) is present in the compositions according to the present invention, preferably both (C1) and (C2).
  • At least one of isomers (C6) and (C8) is present in the compositions according to the present invention, preferably both (C6) and (C8).
  • isomer (C7) is present in the compositions according to the present invention.
  • Such isomers independently of another are present in the compositions according to the present invention in amounts of at least 0.5 mol%, preferably at least 1 mol%.
  • the number-average molecular weight M n (determined by gel permeation chromatography) of the medium molecular polyisobutene according to the present invention is from 10000 to 100000, preferably from 11000 to 90000, more preferably from 12000 to 80000, most preferably from 13000 to 75000, and especially from 14000 to 70000.
  • the polydispersity of the polyisobutene is from 1.2 to 10, preferably from 1.3 to 9, more preferably from 1 .4 to 8, even more preferably from 1.5 to 6 and especially from 2 to 5.
  • a further object of the present invention is a process for preparation of compositions according to the present invention, comprising the steps of
  • polyisobutene composition with a content of polyisobutene species (A) bearing an alpha-double bond of at least 70 mol%
  • isobutene or an isobutenic starting material is polymerised in the presence of at least one Lewis Acid-donor complex and an initiator.
  • metal halides are used, preferably halides of boron, aluminium, iron, gallium, titanium, zinc or tin.
  • Typical examples are boron trifluoride, boron trichloride, aluminum trihalide, alkylaluminum dihalide, dialkylaluminum halide, iron trihalide, gallium trihalide, titanium tetrahalide, zinc dihalide, tin dihalide, tin tetrahalide, wherein the halide is preferably fluoride or chloride, more preferably chloride.
  • boron trifluoride aluminum trichloride, alkyl aluminum dichloride, dialkyl aluminum chloride, and iron trichloride
  • more preferred are boron trifluoride, aluminum trichloride, and alkyl aluminum dichloride, most preferred are boron trifluoride and aluminum trichloride with boron trifluoride being especially preferred.
  • Suitable donor compounds comprise at least one oxygen and/or nitrogen atom with at least one lone electron pair, preferably at least one oxygen atom with at least one lone electron pair and very preferably are selected from the group consisting of organic compounds with at least one ether function, organic compounds with at least one carboxylic ester function, organic compounds with at least one aldehyde function, organic compounds with at least one keto function, and organic compounds with at least one nitrogen containing heterocyclic ring.
  • Solely oxygen containing donor compounds are preferred over nitrogen-containing donor compounds.
  • the donor is selected from the group consisting of organic compounds with at least one ether function, organic compounds with at least one carboxylic ester function and organic compounds with at least one keto function, more preferably selected from the group consisting of organic compounds with at least one ether function and organic compounds with at least one carboxylic ester function, very preferably donors are organic compounds with at least one ether function, and especially organic compounds with exactly one ether function.
  • Compounds with at least one ether function are also understood to mean acetals and hemiacetals.
  • the ether compound may comprise one or more ether functions, e.g. one, two, three, four or even more ether functions, preferably one or two ether functions and very preferably one ether function.
  • the mixture of donors may comprise one, two, three, four or even more different compounds, preferably compounds with at least one ether function, preferably one or two different compounds and very preferably one compound.
  • a boron trihalide-donor complex in a preferred embodiment of the present invention, is used, which comprises, as the donor, at least one dihydrocarbyl ether the general formula R 8 -O- R 9 in which the variables R 8 and R 9 are each independently Ci- to C2
  • Haloalkyl and haloaryl mean preferably chloroalkyl or bromoalkyl and chloroaryl or bromoaryl, very preferably chloroalkyl and chloroaryl. Especially preferred are w-haloalkyl radicals.
  • Preferred examples are chloromethyl, 1-chloroeth-1-yl, 2-chloroeth-1-yl, 2-chloroprop-1-yl, 2- chloroprop-2-yl, 3-chloroprop-1-yl, and 4-chlorobut-1-yl.
  • chloroaryl Preferred examples for chloroaryl are 2-chlorophenyl, 3-chlorophenyl, and 4-chlorophenyl.
  • the dihydrocarbyl ethers mentioned may be open-chain or cyclic, where the two variables R 8 and R 9 in the case of the cyclic ethers may join to form a ring, where such rings may also comprise two or three ether oxygen atoms.
  • Examples of such open-chain and cyclic dihydrocarbyl ethers are dimethyl ether, chloromethyl methyl ether, bis (chloromethyl) ether, diethyl ether, chloromethyl ethyl ether, 2-chloroethyl ethyl ether (CEE), bis (2-chloroethyl) ether (CE), di-n- propyl ether, diisopropyl ether, di-n-butyl ether, di-sec-butyl ether, diisobutyl ether, di-n-pentyl ether, di-n-hexyl ether, di-n-heptyl ether, di-n-octyl ether, di-(2-ethylhexyl) ether, methyl n-butyl ether, methyl sec-butyl ether, methyl isobutyl ether, methyl tert-butyl ether, ethyl
  • difunctional ethers such as dialkoxybenzenes, preferably dimethoxybenzenes, very preferably veratrol, and ethylene glycol dialkylethers, preferably ethylene glycol dimethylether and ethylene glycol diethylether, are preferred.
  • dihydrocarbyl ethers mentioned diethyl ether, 2-chloroethyl ethyl ether, diisopropyl ether, di-n-butyl ether and diphenyl ether have been found to be particularly advantageous as donors for the boron trihalide-donor complexes, the aluminum trihalide-donor complexes or the alkylaluminum halide complexes or the iron trihalide-donor complexes or the gallium trihalide- donor complex or the titanium tetrahalide-donor complex or the zinc dihalide-donor complex or the tin dihalide-donor complex or the tin tetrahalide-donor complex or the boron trihalide-donor complex, very preferably boron trihalide-donor complexes, the aluminum trihalide-donor complexes or iron trihalide-donor complexes or boron trihalide-donor complex and especially the a boron trihalide-don
  • dihydrocarbyl ethers with at least one secondary or tertiary dihydrocarbyl group are preferred over dihydrocarbyl groups with primary groups only.
  • Ethers with primary dihydrocarbyl groups are those ethers in which both dihydrocarbyl groups are bound to the ether functional group with a primary carbon atom
  • ethers with at least one secondary or tertary dihydrocarbyl group are those ethers in which at least one dihydrocarbyl group is bound to the ether functional group with a secondary or tertiary carbon atom.
  • diisobutyl ether is deemed to be an ether with primary dihydrocarbyl groups, since the secondary carbon atom of the isobutyl group is not bound to the oxygen of the functional ether group but the hydrocarbyl group is bound via a primary carbon atom.
  • Preferred examples for ethers with primary dihydrocarbyl groups are diethyl ether, di-n-butyl ether, and di-n-propyl ether.
  • Preferred examples for ethers with at least one secondary or tertary dihydrocarbyl group are diisopropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, and anisole.
  • dihydrocarbyl ethers as donors for the boron trihalide- donor complexes, the aluminum trihalide-donor complexes or the alkylaluminum halide complexes, have been found to be those in which the donor compound has a total carbon number of 3 to 16, preferably of 4 to 16, especially of 4 to 12, in particular of 4 to 8.
  • halide-substituted ethers are preferred in combination with aluminum halide-donor complex or iron halide-donor complex or boron halide-donor complex.
  • Organic compounds with at least one carboxylic ester function are preferably hydrocarbyl carboxylates of the general formula R 10 -COOR 11 in which the variables R 10 and R 11 are each independently Ci- to C2o-alkyl radicals, especially Ci- to Cs alkyl radicals, Cs- to Cs-cycloalkyl radicals, Cs- to C2o-aryl radicals, especially Cs- to C12 aryl radicals, or C7- to C2o-arylalkyl radicals, especially C7- to Ci2-arylalkyl radicals.
  • the variables R 10 and R 11 are each independently Ci- to C2o-alkyl radicals, especially Ci- to Cs alkyl radicals, Cs- to Cs-cycloalkyl radicals, Cs- to C2o-aryl radicals, especially Cs- to C12 aryl radicals, or C7- to C2o-arylalkyl radicals, especially C7- to Ci2-arylalkyl radicals.
  • hydrocarbyl carboxylates mentioned are methyl formate, ethyl formate, n-pro- pyl formate, isopropyl formate, n-butyl formate, sec-butyl formate, isobutyl formate, tert-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, secbutyl acetate, isobutyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, sec-butyl propionate, isobutyl propionate, tert-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl format
  • hydrocarbyl carboxylates as donors have been found to be those in which the donor compound has a total carbon number of 3 to 16, preferably of 4 to 16, especially of 4 to 12, in particular of 4 to 8, preference is given in particular to those having a total of 3 to 10 and especially 4 to 6 carbon atoms.
  • Organic compounds with at least one aldehyde function, preferably exactly one aldehyde function and organic compounds with at least one keto function, preferably exactly one keto function typically have from 1 to 20, preferably from 2 to 10 carbon atoms. Functional groups other than the carbonyl group are preferably absent.
  • Preferred organic compounds with at least one aldehyde function are those of formula R 10 -CHO, in which R 10 has the above-mentioned meaning, very preferably are selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, and benzaldehyde.
  • Organic compounds with at least one nitrogen containing heterocyclic ring are preferably saturated, partly unsaturated or unsaturated nitrogen-containing five-membered or six-membered heterocyclic rings which comprises one, two or three ring nitrogen atoms and may have one or two further ring heteroatoms from the group of oxygen and sulphur and/or hydrocarbyl radicals, especially Ci- to C4-alkyl radicals and/or phenyl, and/or functional groups or heteroatoms as substituents, especially fluorine, chlorine, bromine, nitro and/or cyano, for example pyrrolidine, pyrrole, imidazole, 1 ,2,3- or 1 ,2,4-triazole, oxazole, thiazole, piperidine, pyrazane, pyrazole, pyridazine, pyrimidine, pyrazine, 1 ,2,3-, 1 ,2,4- or 1 ,2,5-triazine, 1 ,2,5-o
  • a very particularly suitable nitrogen-containing basic compound of this kind is pyridine or a derivative of pyridine (especially a mono-, di- or tri-Ci- to C4-alkyl-substituted pyridine) such as 2-, 3-, or 4-methylpyridine (picolines), 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or 3,6-dimethylpyridine (lutidines), 2,4,6-trimethylpyridine (collidine), 2-, 3,- or 4-tert-butylpyridine, 2-tert-butyl-6-methyl- pyridine, 2,4-, 2,5-, 2,6- or 3,5-di-tert-butylpyridine or else 2-, 3,- or 4-phenylpyridine.
  • pyridine or a derivative of pyridine especially a mono-, di- or tri-Ci- to C4-alkyl-substituted pyridine
  • 2-, 3-, or 4-methylpyridine picolines
  • the polymerization is preferably performed with additional use of a mono- or polyfunctional, especially mono-, di- or trifunctional, initiator which is selected from organic hydroxyl compounds, organic halogen compounds and water. It is also possible to use mixtures of the initiators mentioned, for example mixtures of two or more organic hydroxyl compounds, mixtures of two or more organic halogen compounds, mixtures of one or more organic hydroxyl compounds and one or more organic halogen compounds, mixtures of one or more organic hydroxyl compounds and water, or mixtures of one or more organic halogen compounds and water.
  • the initiator may be mono-, di- or polyfunctional, i.e.
  • one, two or more hydroxyl groups or halogen atoms, which start the polymerization reaction, may be present in the initiator molecule.
  • telechelic isobutene polymers with two or more, especially two or three, polyisobutene chain ends are typically obtained.
  • Organic hydroxyl compounds which have only one hydroxyl group in the molecule and are suitable as monofunctional initiators include especially alcohols and phenols, in particular those of the general formula R 12 -OH, in which R 12 denotes Ci- to C2o-alkyl radicals, especially Ci- to Cs- alkyl radicals, Cs- to Cs-cycloalkyl radicals, Cs- to C2o-aryl radicals, especially Cs- to Ci2-aryl radicals, or Cy to C2o-arylalkyl radicals, especially Cy to Ci2-arylalkyl radicals.
  • the R 12 radicals may also comprise mixtures of the abovementioned structures and/or have other functional groups than those already mentioned, for example a keto function, a nitroxide or a carboxyl group, and/or heterocyclic structural elements.
  • organic monohydroxyl compounds are methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol, cyclohexanol, phenol, p-methoxyphenol, o-, m- and p-cresol, benzyl alcohol, p-methoxybenzyl alcohol, 1- and 2-phenylethanol, 1- and 2-(p-methoxyphenyl)ethanol, 1-, 2- and 3-phenyl-1-propanol, 1-, 2- and 3-(p-methoxyphenyl)-1 -propanol, 1- and 2-phenyl-2- propanol, 1- and 2-(p-methoxyphenyl)-2-propanol, 1- and
  • Organic hydroxyl compounds which have two hydroxyl groups in the molecule and are suitable as bifunctional initiators are especially dihydric alcohols or diols having a total carbon number of 2 to 30, especially of 3 to 24, in particular of 4 to 20, and bisphenols having a total carbon number of 6 to 30, especially of 8 to 24, in particular of 10 to 20, for example ethylene glycol, 1 ,2- and 1 ,3-propylene glycol, 1 ,4-butylene glycol, 1 ,6-hexylene glycol, 1 ,2-, 1 ,3- or 1 ,4-bis(1- hydroxy-1-methylethyl)benzene (o-, m- or p-dicumyl alcohol), bisphenol A, 9,10-di-hydro-9,10- dimethyl-9,10-anthracenediol, 1 ,1-diphenylbutane-1 ,4-diol, 2-hydroxytriphenylcarbinol and 9-[2- (hydroxymethyl)phenyl]-9
  • Organic halogen compounds which have one halogen atom in the molecule and are suitable as monofunctional initiators are in particular compounds of the general formula R 13 -Hal in which Hal is a halogen atom selected from fluorine, iodine and especially chlorine and bromine, and R 13 denotes Ci- to C2o-alkyl radicals, especially Ci- to Cs-alkyl radicals, Cs- to Cs-cycloalkyl radicals or C7- to C2o-arylalkyl radicals, especially C7- to Ci2-arylalkyl radicals.
  • the R 13 radicals may also comprise mixtures of the abovementioned structures and/or have other functional groups than those already mentioned, for example a keto function, a nitroxide or a carboxyl group, and/or heterocyclic structural elements.
  • Typical examples of such monohalogen compounds are methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, 1 -chloropropane, 1 -bromopropane, 2-chloropropane, 2-bromopropane, 1 -chlorobutane, 1 -bromobutane, sec-butyl chloride, sec-butyl bromide, isobutyl chloride, isobutyl bromide, tert-butyl chloride, tert-butyl bromide, 1 -chloropentane, 1 -bromopentane, 1 -chloro- hexane, 1 -bromohexane, 1 -chloroheptane, 1 -bromoheptane, 1 -chlorooctane, 1 -bromooctane, 1- chloro-2-ethylhexane, 1-
  • Organic halogen compounds which have two halogen atoms in the molecule and are suitable as difunctional initiators are, for example, 1 ,3-bis(1-bromo-1-methylethyl)benzene, 1 ,3-bis(2-chloro- 2-propyl)benzene (1 ,3-dicumyl chloride) and 1 ,4-bis(2-chloro-2-propyl)benzene (1 ,4-dicumyl chloride).
  • the initiator is more preferably selected from organic hydroxyl compounds in which one or more hydroxyl groups are each bonded to an sp 3 -hybridized carbon atom, organic halogen compounds, in which one or more halogen atoms are each bonded to an sp 3 -hybridized carbon atom, and water.
  • organic hydroxyl compounds in which one or more hydroxyl groups are each bonded to an sp 3 - hybridized carbon atom.
  • organic halogen compounds as initiators, particular preference is further given to those in which the one or more halogen atoms are each bonded to a secondary or especially to a tertiary sp 3 -hybridized carbon atom.
  • the R 12 , R 13 and R 14 radicals which are each independently hydrogen, Ci- to C2o-alkyl, Cs- to Cs-cycloalkyl, Ce- to C2o-aryl, Cy to C2o-alkylaryl or phenyl, where any aromatic ring may also bear one or more, preferably one or two, Ci- to C4- alkyl, Ci- to C4-alkoxy, Ci- to C4-hydroxyalkyl or Ci- to C4-haloalkyl radicals as substituents, where not more than one of the variables R 12 , R 13 and R 14 is hydrogen and at least one of the variables R 12 , R 13 and R 14 is phenyl which may also bear one or more, preferably one or two, Ci- to C4-alkyl, Ci- to C4-alkoxy, Ci- to C4-
  • initiators selected from water, methanol, ethanol, 1-phenylethanol, 1-(p-methoxyphenyl)ethanol, n-propanol, isopropanol, 2- phenyl-2-propanol (cumene), n-butanol, isobutanol, sec.-butanol, tert-butanol, 1-phenyl-1- chloroethane, 2-phenyl-2-chloropropane (cumyl chloride), tert-butyl chloride and 1 ,3- or 1 ,4- bis(1 -hydroxy-1 -methylethyl)benzene.
  • initiators selected from water, methanol, ethanol, 1-phenylethanol, 1-(p-methoxyphenyl)ethanol, n-pro- panol, isopropanol, 2-phenyl-2-propanol (cumene), n-butanol, isobutanol, sec.-butanol, tertbutanol, 1-phenyl-1 -chloroethane and 1 ,3- or 1 ,4-bis(1 -hydroxy-1 -methylethyl)benzene.
  • suitable isobutene sources are both pure isobutene and isobutenic C4 hydrocarbon streams, for example C4 raffinates, especially "raffinate 1", C4 cuts from isobutane dehydrogenation, C4 cuts from steam crackers and from FCC crackers (fluid catalyzed cracking), provided that they have been substantially freed of 1 ,3-butadiene present therein.
  • C4 hydrocarbon stream from an FCC refinery unit is also known as "b/b" stream.
  • Suitable isobutenic C4 hydrocarbon streams are, for example, the product stream of a propylene-isobutane cooxidation or the product stream from a metathesis unit, which are generally used after customary pu- rification and/or concentration.
  • Suitable C4 hydrocarbon streams generally comprise less than 500 ppm, preferably less than 200 ppm, of butadiene.
  • the presence of 1 -butene and of cis- and trans-2-butene is substantially uncritical.
  • the isobutene concentration in the C4 hydrocarbon streams mentioned is in the range from 40 to 60% by weight.
  • raffinate 1 generally consists essentially of 30 to 50% by weight of isobutene, 10 to 50% by weight of 1- butene, 10 to 40% by weight of cis- and trans-2-butene, and 2 to 35% by weight of butanes; in the polymerization process according to the invention, the unbranched butenes in the raffinate 1 generally behave virtually inertly, and only the isobutene is polymerized.
  • the monomer source used for the polymerization is a technical C4 hydrocarbon stream with an isobutene content of 1 to 100% by weight, especially of 1 to 99% by weight, in particular of 1 to 90% by weight, more preferably of 30 to 60% by weight, especially a raffinate 1 stream, a b/b stream from an FCC refinery unit, a product stream from a propylene-isobutane cooxidation or a product stream from a metathesis unit.
  • a raffinate 1 stream is used as the isobutene source
  • the use of water as the sole initiator or as a further initiator has been found to be useful, in particular when polymerization is effected at temperatures of -20°C to +30°C, especially of 0°C to +20°C.
  • temperatures of -20°C to +30°C, especially of 0°C to +20°C when a raffinate 1 stream is used as the isobutene source, it is, however, also possible to dispense with the use of an initiator.
  • the isobutenic monomer mixture mentioned may comprise small amounts of contaminants such as water, carboxylic acids or mineral acids, without there being any critical yield or selectivity losses. It is appropriate to prevent enrichment of these impurities by removing such harmful substances from the isobutenic monomer mixture, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.
  • the monomer mixture preferably comprises at least 5% by weight, more preferably at least 10% by weight and especially at least 20% by weight of isobutene, and preferably at most 95% by weight, more preferably at most 90% by weight and especially at most 80% by weight of comonomers.
  • Useful copolymerizable monomers include: vinylaromatics such as styrene and a-methylstyrene, Ci- to C4-alkylstyrenes such as 2-, 3- and 4-methylstyrene, and 4-tert-butylsty- rene, halostyrenes such as 2-, 3- or 4-chlorostyrene, and isoolefins having 5 to 10 carbon atoms, such as 2-methylbutene-1 , 2-methylpentene-1 , 2-methylhexene-1 , 2-ethylpentene-1 , 2- ethylhexene-1 and 2-propylheptene-1.
  • Further useful comonomers include olefins which have a silyl group, such as 1 -trimethoxysilylethene, 1-(trimethoxysilyl)propene, 1-(trimethoxysilyl)-2- methylpropene-2, 1-[tri(methoxyethoxy)-silyl]ethene, 1-[tri(methoxyethoxy)silyl]propene, and 1-[tri(methoxyethoxy)silyl]-2-methylpro-pene-2.
  • useful comonomers also include isoprene, 1 -butene and cis- and trans-2-butene.
  • the process can be configured so as to preferentially form random polymers or to preferentially form block copolymers.
  • block copolymers for example, the different monomers can be supplied successively to the polymerization reaction, in which case the second comonomer is especially not added until the first comonomer is already at least partly polymerized.
  • diblock, triblock and higher block copolymers are obtainable, which, according to the sequence of monomer addition, have a block of one or the other comonomer as a terminal block.
  • block copolymers also form when all comonomers are supplied to the polymerization reaction simultaneously, but one of them polymerizes significantly more rapidly than the other(s). This is the case especially when isobutene and a vinylaromatic compound, especially styrene, are copolymerized in the process according to the invention. This preferably forms block copolymers with a terminal polystyrene block. This is attributable to the fact that the vi- nylaromatic compound, especially styrene, polymerizes significantly more slowly than isobutene.
  • the polymerization can be effected either continuously or batchwise. Continuous processes can be performed in analogy to known prior art processes for continuous polymerization of isobutene in the presence of boron trifluoride-based catalysts in the liquid phase.
  • the process according to the invention is suitable either for performance at low temperatures, e.g. at -90°C to 0°C, or at higher temperatures, i.e. at at least 0°C, e.g. at 0°C to +30°C or at 0°C to +50°C.
  • the polymerization in the process according to the invention is, however, preferably performed at relatively low temperatures, generally at -70°C to -10°C, especially at -60°C to -15°C.
  • the polymerization in the process according to the invention is effected at or above the boiling temperature of the monomer or monomer mixture to be polymerized, it is preferably performed in pressure vessels, for example in autoclaves or in pressure reactors.
  • the polymerization in the process may be performed in the presence of an inert diluent.
  • the inert diluent used should be suitable for reducing the increase in the viscosity of the reaction solution which generally occurs during the polymerization reaction to such an extent that the removal of the heat of reaction which evolves can be ensured.
  • Suitable diluents are those solvents or solvent mixtures which are inert toward the reagents used.
  • Suitable diluents are, for example, aliphatic hydrocarbons such as n-butane, n-pentane, n-hexane, n-heptane, n-octane and isooctane, cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and the xylenes, and halogenated hydrocarbons, especially halogenated aliphatic hydrocarbons, such as methyl chloride, dichloromethane and trichloromethane (chloroform), 1,1 -dichloroethane, 1,2-dichloroethane, trichloroethane and 1- chlorobutane, and also halogenated aromatic hydrocarbons and alkylaromatics halogenated in the alkyl side chains, such as chlorobenzene, monofluoromethylbenzene, diflu
  • the polymerization may be performed in a halogenated hydrocarbon, especially in a halogenated aliphatic hydrocarbon, or in a mixture of halogenated hydrocarbons, especially of halogenated aliphatic hydrocarbons, or in a mixture of at least one halogenated hydrocarbon, especially a halogenated aliphatic hydrocarbon, and at least one aliphatic, cycloaliphatic or aromatic hydrocarbon as an inert diluent, for example a mixture of dichloromethane and n-hexane, typically in a volume ratio of 10:90 to 90:10, especially of 50:50 to 85:15.
  • the diluents are preferably freed of impurities such as water, carboxylic acids or mineral acids, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.
  • the polymerization is performed in halogen-free aliphatic or especially halogen-free aromatic hydrocarbons, especially toluene.
  • halogen-free aliphatic or especially halogen-free aromatic hydrocarbons especially toluene.
  • water in combination with the organic hydroxyl compounds mentioned and/or the organic halogen compounds mentioned, or especially as the sole initiator, have been found to be particularly advantageous.
  • the polymerization is performed in halogen-free aliphatic or cycloaliphatic, preferably aliphatic hydrocarbons, especially hexane, pentane, heptane, cyclohexane, cyclopentane, and mixtures comprising them.
  • the polymerization is preferably performed under substantially aprotic and especially under substantially anhydrous reaction conditions.
  • substantially aprotic and substantially anhydrous reaction conditions are understood to mean that, respectively, the content of protic impurities and the water content in the reaction mixture are less than 50 ppm and especially less than 5 ppm.
  • the feedstocks will therefore be dried before use by physical and/or chemical measures.
  • an organometallic compound for example an organolithium, organomagnesium or organoalumi- num compound
  • the solvent thus treated is then preferably condensed directly into the reaction vessel. It is also possible to proceed in a similar manner with the monomers to be polymerized, especially with isobutene or with the isobutenic mixtures. Drying with other customary desiccants such as molecular sieves or predried oxides such as aluminum oxide, silicon dioxide, calcium oxide or barium oxide is also suitable.
  • halogenated solvents for which drying with metals such as sodium or potassium or with metal alkyls is not an option are freed of water or water traces with desiccants suitable for that purpose, for example with calcium chloride, phosphorus pentoxide or molecular sieves. It is also possible in an analogous manner to dry those feedstocks for which treatment with metal alkyls is likewise not an option, for example vinylaro- matic compounds. Even if some or all of the initiator used is water, residual moisture should preferably be very substantially or completely removed from solvents and monomers by drying prior to reaction, in order to be able to use the water initiator in a controlled, specified amount, as a result of which greater process control and reproducibility of the results are obtained.
  • the polymerization reaction is appropriately terminated by adding excess amounts of water or of basic material, for example gaseous or aqueous ammonia or aqueous alkali metal hydroxide solution such as sodium hydroxide solution.
  • water or of basic material for example gaseous or aqueous ammonia or aqueous alkali metal hydroxide solution such as sodium hydroxide solution.
  • the crude polymerization product is typically washed repeatedly with distilled or deionized water, in order to remove adhering inorganic constituents.
  • the polymerization reaction mixture can be fractionally distilled under reduced pressure.
  • polyisobutene composition with a content of polyisobutene species (A) bearing an alpha-double bond of at least 70 mol% is subjected to the double bond isomerisation process described below.
  • reaction mixture from the polymerisation after desactivation of the catalyst and optionally after removal of the hydrolysis products by washing in the double bond isomerisation process without further purification.
  • a reaction mixture may contain unreacted monomer and lower oligomers of isobutene.
  • the undistilled reaction mixture differs from the polyisobutene composition insofar that it additionally comprises isobutene and those lower oligomers of isobutene which are usually separated from the reaction mixture by distillation.
  • Such lower oligomers of isobutene can be diisobutene, triisobutene, tetraisobutene, pentaisobutene, hexaisobutene, heptaisobutene, and octaisobutene.
  • Higher oligomers of isobutene usually remain in the polyisobutene composition since they are not significantly volatile under distillation conditions, even under reduced pressure.
  • the content of unreacted isobutene may be up to 40 wt%, preferably up to 30 wt%, more preferably up to 20 wt%.
  • the content of unreacted lower oligomers mentioned above may be up to 5 wt%, preferably up to 3 wt%.
  • the distribution of double bond isomers (A), (B), and (C) among the oligomers is usually comparable to that of the polymer mixture, preferably it is the same. However, it has been observed that oligomer mixtures comprise less of isomer (C6) compared with polymer mixtures, sometimes up to 5 mol% of isomer (C6) less.
  • the content of oligomer species of formula (A) bearing an alpha-double bond is at least 70 mol%, preferably at least 75 mol%, more preferably at least 80 mol%, most preferably at least 85 mol% and especially at least 90 mol%.
  • a 10 to 90 wt% solution of the polyisobutene composition in a solvent, preferably in a halid-free solvent is used in the double bond isomerisation process, preferably a 15 to 60 wt% solution, more preferably a 20 to50, and especially 25 to 40 wt% solution.
  • the solvent may be the inert components of isobutenic C4 hydrocarbon streams.

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Abstract

La présente invention concerne des mélanges de polyisobutène moléculaire moyen ayant un poids moléculaire moyen en nombre Mn supérieur à 10000 et allant jusqu'à 100 000 g/mol avec une certaine distribution d'isomères présentant une certaine réactivité dans des photoréactions et/ou des réactions thermiques.
PCT/EP2023/052636 2022-02-11 2023-02-03 Polyisobutène moléculaire moyen avec une certaine distribution d'isomères à double liaison Ceased WO2023152033A1 (fr)

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CN202380021191.7A CN118679193A (zh) 2022-02-11 2023-02-03 具有特定双键异构体分布的中等分子量聚异丁烯
EP23702482.3A EP4476272A1 (fr) 2022-02-11 2023-02-03 Polyisobutène moléculaire moyen avec une certaine distribution d'isomères à double liaison
JP2024547514A JP2025506490A (ja) 2022-02-11 2023-02-03 特定の分布の二重結合異性体を有する中分子ポリイソブテン
US18/836,033 US20250179224A1 (en) 2022-02-11 2023-02-03 Medium molecular polyisobutene with a certain distribution of double bond isomers
KR1020247030254A KR20240144399A (ko) 2022-02-11 2023-02-03 이중 결합 이성질체의 특정 분포를 갖는 중간 분자 폴리이소부텐
CA3251435A CA3251435A1 (fr) 2022-02-11 2023-02-03 Polyisobutène moléculaire moyen avec une certaine distribution d'isomères à double liaison
EP23703473.1A EP4476273A1 (fr) 2022-02-11 2023-02-09 Polyisobutène de poids moléculaire moyen ayant une teneur élevée en certains isomères à double liaison
JP2024547540A JP2025505724A (ja) 2022-02-11 2023-02-09 特定の二重結合異性体を高含有量で含む中分子ポリイソブテン
CN202380021195.5A CN118679194A (zh) 2022-02-11 2023-02-09 带有高含量的某些双键异构体的中等分子量聚异丁烯
CA3251428A CA3251428A1 (fr) 2022-02-11 2023-02-09 Polyisobutène de poids moléculaire moyen ayant une teneur élevée en certains isomères à double liaison
US18/835,972 US20250145742A1 (en) 2022-02-11 2023-02-09 Medium molecular polyisobutene with a high content of certain double bond isomers
KR1020247026581A KR20240144197A (ko) 2022-02-11 2023-02-09 고함량의 특정 이중 결합 이성질체를 갖는 중분자 폴리이소부텐
PCT/EP2023/053253 WO2023152258A1 (fr) 2022-02-11 2023-02-09 Polyisobutène de poids moléculaire moyen ayant une teneur élevée en certains isomères à double liaison

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