Medium molecular weight polyisobutene containing a high content of specific double bond isomers

Abstract

The present invention relates to polyisobutenes, preferably low or medium molecular weight polyisobutenes, more preferably polyisobutenes having a number average molecular weight M of more than 10000 g / mol and up to 100000 g / mol, with a high content of tetrasubstituted double bond isomers which show high reactivity in thermal reactions and / or photoreactions and / or radical backbone functionalization and / or chlorine-based functionalization. n The present invention relates to a mixture of medium molecular weight polyisobutenes having the following formula:

Description

[Technical field]

[0001] The present invention relates to polyisobutenes, preferably low or medium molecular weight polyisobutenes, more preferably polyisobutenes having a number average molecular weight M of more than 10000 g / mol and up to 100000 g / mol, with a high content of tetrasubstituted double bond isomers which show high reactivity in photoreactions and / or radical backbone functionalization and / or chlorine-based functionalization. n The present invention relates to a mixture of medium molecular weight polyisobutenes having the following formula: [Background technology]

[0002] In the past, attempts were made to prepare highly reactive low molecular weight polyisobutenes by subsequent chemical reactions, such as subsequent hydroformylation, thermal ene reactions with maleic anhydride, or Friedel-Crafts alkylation of aromatic compounds. As a result, highly reactive polyisobutenes (also called HRPIBs) were developed with α-double bond contents of 80-90 mol % (isomer names are described below), and even 95, 97, and 98%.

[0003] An approach to preparing polyisobutenes of medium or high molecular weight and high in reactive double bonds is described, for example, in EP 807641, which describes the cationic polymerization of isobutene using boron trifluoride complex catalysts. A terminal double bond content of at least 50 mol % is claimed, although the actually achieved terminal double bond content and isomer distribution in the reaction mixture are not shown in the explicitly disclosed examples.

[0004] A further drawback of EP 807641 is the recycle process in which unreacted isobutene is recycled to the reaction with the aid of hexane. Under distillation conditions, not all of the unreacted monomer is removed, but additional hexane is introduced into the polymer. As both isobutene and hexane are toxic, polymers containing such contaminants are not suitable for certain applications.

[0005] To achieve high reactivity, for example in the thermal reaction with maleic anhydride, medium molecular weight polyisobutenes are required to have a high content of α- and / or β-double bonds (e.g., number average molecular weight M n (See WO 2017 / 216022, in which a polyisobutene having a molecular weight of 17000 g / mol, a content of α-double bonds of 40% and a content of β-double bonds of 47% is used in the examples.) However, it has been found that α-double bonds are more reactive in thermal reactions than β-double bonds.

[0006] Furthermore, the yield of the target product is influenced not only by the reactivity of the double bonds, but also by the distribution of isomers with double bonds of different reactivity and the content of isomers with no double bonds or with sterically hindered double bonds that are not available for reaction. WO 2017 / 216022 does not mention any further isomers in polyisobutene and its structural elements. In particular, the content of isomers that are reactive in reactions other than with maleic anhydride is not shown or revealed.

[0007] Thus, there is a need for compositions of medium molecular weight polyisobutenes that can achieve high yields in subsequent reactions.

[0008] Unpublished European Patent Application No. 20208053.7, filed on November 17, 2020 (published as WO 2022 / 106263), discloses a method for the photooxygenation of low molecular weight polyisobutenes, in which the reactivity of the double bonds in polyisobutenes to singlet oxygen is increased from α-double bonds to β-double bonds and finally to other tri- and even tetra-substituted double bonds. However, due to their high reactivity, such tetra-substituted double bonds tend to form two-step oxidized products rather than one-step oxidized products. That is, the selectivity of the oxidation reaction decreases with increasing reactivity of the double bonds. Thus, tetra-substituted double bond isomers are advantageous for applications in which polyisobutene derivatives with multiple oxidized functional groups in close proximity to each other are required. Furthermore, such tetra-substituted double bond isomers are advantageous for applications in which thermal stress is high, since they exhibit lower reactivity in thermal reactions and therefore less thermal decomposition than polyisobutenes with other double bonds. In addition, the stability of the radicals formed at their double bonds is increased, resulting in a more selective reaction. Furthermore, the polyisobutenes used in the described photooxygenation have a degree of polymerization of up to about 100, which corresponds to a molecular weight of up to 5600 g / mol, and are therefore low molecular weight. However, 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.

[0009] The examples in WO 2022 / 106263 use low molecular weight polyisobutenes in which the relative distribution of double bond isomers is shown, but the absolute amount of each isomer in the polyisobutene composition is unknown.

[0010] Therefore, there is also a need for polyisobutene compositions with increased content of tetra-substituted double bond isomers that render polyisobutene particularly reactive in photoreactions, radical backbone functionalization, and chlorine-based functionalization.

[0011] As described in unpublished European Patent Application No. 20208053.7, filed November 17, 2020, and published as WO 2022 / 106263, an exemplary photooxygenation reaction was considered, in which polyisobutene was reacted with oxygen.

[0012] Tetrasubstituted double bonds exhibit higher reactivity in photooxygenation than β-double bonds.

[0013] The reactivity of double bond isomers in polyisobutene in photooxygenation is preferably determined as follows: 10.0 g of polyisobutene (Mn approx. 17000 g / mol, commercially available, for example, as Oppanol B10 from BASF SE, Ludwigshafen), 2.5 mg of tetraphenylporphyrin, and 66.5 g of dichloromethane are placed in a batch photochemical reactor equipped with 88 405 nm LEDs. The reaction mixture is blown with oxygen (1.5 Nl / h) while being irradiated at 20° C. After 120 min, the reaction is stopped. After distilling off the solvent, the reaction mixture is analyzed by NMR spectroscopy.

[0014] Macromolecules, 2011, 44(7), pages 1831-1840, “Mechanism of Isomerization in the Cationic Polymerization”, R. Faust et al. disclose DFT calculations regarding the relative stability of different polyisobutene isomers.

[0015] The tetrasubstituted isomer (C4) has the lowest energy, while the other tetrasubstituted isomer (C3) has an energy content only 2.63 kJ / mol higher. In contrast, the isomer with an α-double bond (A) is 30.46 kJ / mol higher, and isomer (B) is even higher at 33.98 kJ / mol (see below for isomer nomenclature).

[0016] Thus, of these four isomers, isomer (B) is the highest in energy and is therefore expected to be the least likely to form at equilibrium under thermodynamic control of reaction conditions.

[0017] It is known that the reactivity of different double bond isomers in polyisobutene depends on the molecular weight. The reactivity of double bond isomers may be different for low, medium or high molecular weight polyisobutenes. For example, it is known from WO 2017 / 216022 that under conditions where low molecular weight polyisobutenes give a good yield of maleination product, only a small amount of product is obtained when high molecular weight polyisobutenes are used (see, for example, Example 3). When using higher molecular weight polyisobutenes, a much higher stoichiometric ratio of maleic anhydride, a higher reaction temperature and / or a longer reaction time are required to achieve a comparable yield. Summary of the Invention [Means for solving the problem]

[0018] The subject of the present invention is at least one isomer having a tetrasubstituted double bond, preferably [ka] (where PIB, PIB', and PIB'' refer to the appropriately abbreviated polymer backbone of polyisobutene). A polyisobutene composition comprising at least 5% (in total) of an isomer selected from the group consisting of:

[0019] Further isomers which may be present in the polyisobutene composition are [ka] (having an α-double bond), [ka] (having a β-double bond), [ka] It is.

[0020] The polyisobutene composition may be a low or medium molecular weight polyisobutene as defined herein, and is preferably a medium molecular weight polyisobutene.

[0021] In the above formulas (A) to (C8), the PIB, PIB', and each PIB'' group, together with any explicitly shown substructures, represent number average molecular weights M of up to 10,000 g / mol for low molecular weight polyisobutenes and from greater than 10,000 g / mol to 100,000 g / mol for medium molecular weight polyisobutenes. n In other words, the PIB, PIB', and respective PIB'' groups refer to polyisobutene polymers abbreviated by the moiety explicitly indicated.

[0022] Number average molecular weight M n For low molecular weight polyisobutene having a molecular weight of up to 10,000 g / mol, the average degree of polymerization is a maximum of 177, preferably 5-134, more preferably 6-107, even more preferably 9-89, particularly preferably 13-45, and even more preferably 16-20.

[0023] Number average molecular weight M n For medium molecular weight polyisobutenes having a molecular weight of more than 10,000 g / mol and up to 100,000 g / mol, the average degree of polymerization is 178 to 1786.

[0024] In an ideal homopolymer of isobutene, the residues PIB, PIB', and PIB'' are PIB: -[-(H3C)2C-CH2-] m -, PIB': -[-(H3C)2C-CH2-] n - and PIB'': -[-(H3C)2C-CH2-] o - where the polymer chains, in particular PIB and PIB', can be initiated with a suitable initiator (see below) and can preferably be bonded to hydrogen, m, n, and o are each independently a positive integer; It is provided that the sum of m, n, and o and the monomer units in the structure shown corresponds to the degree of polymerization of the low or medium molecular weight polyisobutene.

[0025] In the copolymers some of the isobutene units may be replaced by other monomer units, such as 1-butene, cis or trans 2-butene (see below).

[0026] In the case of formulas (A), (B), (C1) to (C5), and (C8), the integers m and n can be up to a value obtained by subtracting 1 or 2 from the degree of polymerization of the low- or medium-molecular weight polyisobutene.

[0027] In the case of formulas (C6) and (C7), the integers n and o are up to 1 minus the degree of polymerization of the low or medium molecular weight polyisobutene.

[0028] 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%.

[0029] 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%.

[0030] The content of isomers is 1 It is determined by H-NMR spectroscopy, the detection level being determined by the frequency used. Preferably, 700 MHz at 25 °C. 1 H-NMR spectroscopy is used. Highly preferably, the isomer content is determined as described in Guo et al., Journal of Polymer Science, Part A: Polymer Chemistry, 2013, 51, 4200-4212.

[0031] Because the isomers are part of a polymer mixture having a distribution of molecular weights, the weight and mole percent content of each isomer in the mixture is the same.

[0032] Another subject of the invention is a process for the preparation of such a composition having an increased content of tetrasubstituted double bonds, comprising the steps of: selecting as starting material a low- or medium-molecular polyisobutene composition having a content of polyisobutene species (A) having α-double bonds of at least 30 mol %, preferably at least 40 mol %, more preferably at least 50 mol %, most preferably at least 60 mol %, in particular at least 70 mol %, Optionally, selecting at least one solvent, the optionally dissolved polyisobutene composition, - in the presence of at least one acidic solid catalyst, optionally treated with at least one Brönsted base, - 10 minutes to 36 hours, - treating at a temperature of 40°C to 250°C; The method includes:

[0033] In a preferred embodiment, a low molecular weight polyisobutene composition having a content of polyisobutene species (A) having α-double bonds of at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, even more preferably at least 75 mol%, particularly at least 80 mol%, and even more preferably at least 85 mol% is selected as the starting material. Such low molecular weight polyisobutenes having a high content of α-double bonds are often called "highly reactive polyisobutenes".

[0034] In another preferred embodiment, a medium molecular weight polyisobutene composition having a content of 10 to 60 mol%, preferably 15 to 55 mol%, more preferably 20 to 50 mol%, even more preferably 25 to 50 mol%, particularly at least 25 to 45 mol% of polyisobutene species (A) having an α-double bond is selected as the starting material. The advantage of such an embodiment is that the relatively low content of thermally reactive double bonds, particularly α-double bonds, in such a medium molecular weight polyisobutene composition can be further reduced by the isomerization process according to the present invention.

[0035] In some cases, the content of polyisobutene species (A) having an α-double bond in the starting material may further preferably be at least 75 mol %, more preferably at least 80 mol %, most preferably at least 85 mol %, in particular at least 90 mol %.

[0036] Another subject of the invention is the use of such compositions with an increased content of tetrasubstituted double bonds in reactions to obtain further derivatives, preferably in oxidation reactions, more preferably in photooxygenation.

[0037] In the context of the present invention, the term isomers having a "β-double bond" refers to the following substructure: [ka] (B) refers to a polyisobutene isomer having the formula During the ceremony, "PIB" represents the polyisobutene polymer backbone excluding the final incorporated isobutene unit.

[0038] In contrast, the term isomer having an "α-double bond" refers to the following substructure: [ka] This refers to polyisobutene isomer (A) having the formula:

[0039] In the context of this specification, a "vinylidene double bond" refers to a double bond having two hydrogen substituents on the same carbon atom of the double bond, unless otherwise specified. Such a vinylidene double bond may be terminal, as in isomer (A), or internal, as in isomers (C6) or (C8).

[0040] Other polyisobutene isomers (C) are [ka] and PIB' and PIB'' in these formulas refer to appropriately abbreviated polymer backbones of polyisobutene. Such abbreviated polymer backbones, particularly PIB'', contain at least one isobutene unit in polymerized form.

[0041] In addition to components (A), (B), and (C), the mixture may contain other polyisobutene-derived species (D).

[0042] Furthermore, halogenated polyisobutenes (D1) may be present.

[0043] Furthermore, fully saturated polyisobutenes (D2) may be present which do not contain any multiple bonds and are not halogenated.

[0044] It has further been found that polyisobutene containing a certain content of halogen, preferably fluorine or chlorine, exhibits further improved reactivity in photoreaction. It is believed that the halogen, preferably chlorine, acts as a kind of photosensitizer in the photoreaction.

[0045] This constitutes a sub-aspect of the present invention, which is to provide low or medium molecular weight polyisobutenes having a content of halogen, preferably fluorine or chlorine, more preferably chlorine, of more than 5 ppm by weight, preferably at least 10 ppm by weight, more preferably at least 15 ppm by weight, even more preferably at least 20 ppm by weight, in particular at least 30 ppm by weight, or even at least 50 ppm by weight or 70 ppm by weight, the content being related to each halogen species.

[0046] The upper limit for halogen, preferably fluorine or chlorine, more preferably chlorine, is usually a maximum of 500 ppm by weight, preferably a maximum of 250 ppm by weight, more preferably a maximum of 150 ppm by weight.

[0047] The halogen content is determined by combustion ion chromatography (IC) analysis.

[0048] The halogen is preferably selected from the group consisting of fluorine, chlorine and bromine, more preferably fluorine or chlorine, especially chlorine.

[0049] The primary source of halogen is the Lewis acid or halogen-containing initiator used as the polymerization catalyst (see below), but may also be residual solvent in the polyisobutene composition.

[0050] The halogens can be incorporated into the polyisobutene, such as isomer (D1) above, or they can be part of the mixture without being chemically bound to the polyisobutene.

[0051] Isomers (C1) and (C2) also represent trisubstituted polyisobutene isomers with a β-double bond, but are distinguished from compound (B) because their reactivity in photooxygenation is different from that of compound (B). Compound (B) contains six (almost) equivalent hydrogen atoms in the two methyl groups at the allylic positions of the double bond and produces the same product in photooxygenation, whereas isomers (C1) and (C2) each contain two different methyl groups that result in different photooxygenation products. Thus, the use of compound (B) in photooxygenation results in a more homogeneous reaction mixture, and therefore compound (B) is preferred over compounds (C1) and (C2). Furthermore, under the reaction conditions of photooxygenation, compound (B) is considered to be less sterically hindered than isomers (C1) and (C2), which is an additional advantage of polyisobutene compositions with a higher content of compound (B).

[0052] In the context of the present invention, medium molecular weight polyisobutene refers to polyisobutene having a number average molecular weight M n is defined as a polyisobutene composition having a molecular weight of from greater than 10,000 to 100,000 g / mole.

[0053] The number average molecular weight M of the medium molecular weight polyisobutene according to the present invention n (determined by gel permeation chromatography) is 10,000 to 100,000, preferably 11,000 to 90,000, more preferably 12,000 to 80,000, most preferably 13,000 to 75,000, and particularly 14,000 to 70,000.

[0054] In contrast, low molecular weight polyisobutenes have a number average molecular weight M n is defined as a polyisobutene composition having a molecular weight of 10,000 g / mol or less, preferably 280 to 7,500, more preferably 330 to 6,000, even more preferably 500 to 5,000, particularly 750 to 2,500, and even more preferably 900 to 1,100 g / mol.

[0055] The polydispersity of the polyisobutene is 1.2-10, preferably 1.3-9, more preferably 1.4-8, further preferably 1.5-6, and particularly preferably 2-5.

[0056] The subject of the present invention is a polyisobutene composition comprising at least 5% (total) of isomers with tetrasubstituted double bonds, preferably at least one isomer selected from the group consisting of (C3), (C4) and (C5), together with their (E)- and (Z)-isomers (not shown), which represent tetrasubstituted isomers. Tetrasubstituted isomers are very reactive in photooxygenation and may result in complex reaction mixtures due to the number of different reactive sites in photooxygenation. The advantage of such tetrasubstituted isomers is that photooxygenation of such isomers results in reaction products with multiple oxidized functional groups in close proximity to each other. Such oxidized functional groups can then serve as starting functional groups for further functionalization of the original polyisobutene. Suitable oxidized functional groups may be hydroperoxyl groups (-OOH), hydroxy groups (-OH), aldehyde groups (-CHO), keto groups (-(C=O)-), or carboxy groups (-COOH).

[0057] A tetrasubstituted double bond is defined as a double bond >C=C< in which both carbon atoms of the double bond are attached to other carbon atoms that serve as links to substituents. Preferred illustrative examples are the isomers (C3), (C4), and (C6).

[0058] Another possible isomer of polyisobutene with a tetrasubstituted double bond can be PIB'-C(CH3)=C(CH3)-PIB" with an internal double bond.

[0059] The polyisobutene composition may contain one or more tetrasubstituted isomers, preferably one or more tetrasubstituted isomers selected from the group consisting of (C3), (C4), and (C5). Typically, the composition contains a mixture of such tetrasubstituted isomers. In the present invention, the term "tetrasubstituted isomer" is used synonymously with the term "isomer having a tetrasubstituted double bond."

[0060] The amount of tetrasubstituted isomers is calculated as the sum of these tetrasubstituted isomers, and is preferably calculated as described above. 1 Determined using H-NMR spectroscopy.

[0061] As explained above, the reactivity of different double bond isomers in polyisobutene depends on molecular weight.In addition, due to the difference in production process, low molecular weight polyisobutene and medium molecular weight polyisobutene usually show different double bond isomer distribution, so the content of tetrasubstituted isomer according to the present invention may be different in polyisobutene with different molecular weight.

[0062] Thus, the subject of the present invention is a medium molecular weight polyisobutene composition containing at least 5% (in total), preferably 10 to 90%, more preferably 15 to 80%, in particular 20 to 75%, and even more preferably 25 to 60%, of at least one isomer having a tetrasubstituted double bond.

[0063] Another subject of the present invention is a low molecular weight polyisobutene composition containing at least 5% or at least 10% (in total), preferably 15 to 95%, more preferably 20 to 80%, in particular 30 to 75% and even more preferably 45 to 60%, of at least one isomer having a tetrasubstituted double bond.

[0064] The percentages shown refer to the sum of all isomers having tetrasubstituted double bonds, preferably selected from the group consisting of isomers (C3), (C4), and (C5), based on the total amount of polyisobutene. The total amount of polyisobutene refers to the sum of all polyisobutene isomers (A) to (D) listed above.

[0065] Provided, of course, that the sum of all isomers always equals 100% by weight.

[0066] However, an advantage of tetrasubstituted double bonds is their low reactivity in thermal reactions, so when high temperature reactions are carried out with polyisobutenes containing such isomers, particularly polyisobutene (C3) containing tetrasubstituted end groups, it is preferred that the isomers (C3), (C4), and (C5) are present.

[0067] For applications where high temperature reactions are not required, polyisobutene compositions with a high amount of tetrasubstituted double bonds are preferred, which have a low content of polyisobutene isomers that have high reactivity in thermal reactions, preferably isomers (A), (C6), (C8), and (B), more preferably (A), (C6), and (C8), and even more preferably isomer (A).

[0068] The amount (in total) of such polyisobutene isomers which have a high reactivity in thermal reactions is usually not more than 50%, preferably not more than 40%, more preferably not more than 30% and in particular not more than 25%.

[0069] In particular, the content of isomer (A) in such compositions is less than or equal to 20%, preferably less than or equal to 15%, more preferably less than or equal to 10% and in particular less than or equal to 5%.

[0070] The polyisobutenes according to this embodiment have the advantage of being less reactive than the polyisobutenes according to other embodiments, and therefore less susceptible to weathering and more stable to oxidative or thermal degradation, making compositions including such polyisobutenes particularly useful in sealants, adhesives, coatings, or roofing materials.

[0071] Isomers (C6) and (C7) are isomers with internal double bonds since at least one isobutene unit in the polymerized form has a double bond away from the end of the polymer backbone, but isomer (C7) is less reactive than (C6) since it has a double bond within the polymer backbone, again highlighting the role of accessible double bonds in polyisobutene.

[0072] Isomer (C6) is advantageous because it is known to produce fuel and lubricant additive derivatives having superior performance properties, as disclosed in US Pat. No. 9,688,791 B2.

[0073] Isomer (C6) is highly reactive, especially in thermal reactions, whereas isomer (C7) shows an advantage in photoreactions, especially photooxygenation.

[0074] Isomer (C8) is the product of a methyl group rearrangement.

[0075] In another preferred embodiment, at least one of the isomers (C6) and (C8) is present in the composition according to the invention, preferably both (C6) and (C8) are present.

[0076] In another preferred embodiment, isomer (C7) is present in the composition according to the invention.

[0077] Such isomers, independently of one another, are present in the composition according to the invention in an amount of at least 0.5 mol %, preferably at least 1 mol %.

[0078] The amounts of isomers given throughout this specification refer to mole % unless expressly stated otherwise. Since the determination of individual isomers or groups of isomers is performed by NMR analysis (see below for details), the result of such NMR analysis is the percentage distribution of the specific NMR signals of these isomers relative to the integrals of the respective nuclei determined.

[0079] A further object of the invention is a process for the preparation of a composition according to the invention, comprising the steps of: selecting as starting material a polyisobutene composition having a content of polyisobutene species (A) having α-double bonds of at least 30 mol %, preferably at least 40 mol %, more preferably at least 50 mol %, most preferably at least 60 mol %, in particular at least 70 mol %, Optionally, selecting at least one solvent, the optionally dissolved polyisobutene composition, - in the presence of at least one acidic solid catalyst, optionally treated with at least one Brönsted base, - 10 minutes to 36 hours, - treating at a temperature of 40°C to 250°C; The method includes:

[0080] In one embodiment of the present invention, such a process uses a low molecular weight polyisobutene as a starting material.

[0081] In another embodiment of the present invention, such a process uses a medium molecular weight polyisobutene as a starting material.

[0082] Processes for the preparation of such polyisobutene compositions with a high content of α-double bonds are known in the prior art and are relevant to the present invention insofar as they are necessary for the preparation of the starting materials for the process according to the invention.

[0083] To prepare such polyisobutene compositions having a high α-double bond content, isobutene or an isobutene-based starting material is typically polymerized in the presence of at least one Lewis acid donor complex and an initiator.

[0084] As the Lewis acid, a metal halide is usually used, preferably a halide of boron, aluminum, iron, gallium, titanium, zinc or tin.

[0085] Typical examples are boron trifluoride, boron trichloride, aluminum trihalides, alkylaluminum dihalides, dialkylaluminum halides, iron trihalides, gallium trihalides, titanium tetrahalides, zinc dihalides, tin dihalides, tin tetrahalides, the halide being preferably a fluoride or a chloride, more preferably a chloride.

[0086] Preferred are boron trifluoride, aluminum trichloride, alkylaluminum dichlorides, dialkylaluminum chlorides, and iron trichloride, more preferred are boron trifluoride, aluminum trichloride, and alkylaluminum dichlorides, most preferred are boron trifluoride and aluminum trichloride, and boron trifluoride is particularly preferred.

[0087] Examples of suitable donor compounds contain at least one oxygen atom and / or nitrogen atom having at least one lone pair of electrons, preferably at least one oxygen atom having at least one lone pair of electrons, and very preferably are selected from the group consisting of organic compounds having at least one ether functional group, organic compounds having at least one carboxylic acid ester functional group, organic compounds having at least one aldehyde functional group, organic compounds having at least one keto functional group, and organic compounds having at least one nitrogen-containing heterocycle.

[0088] Donor compounds containing only oxygen are preferred over nitrogen-containing donor compounds.

[0089] Preferably, the donor is selected from the group consisting of organic compounds having at least one ether function, organic compounds having at least one carboxylic acid ester function and organic compounds having at least one keto function, more preferably from the group consisting of organic compounds having at least one ether function and organic compounds having at least one carboxylic acid ester function, and very preferably the donor is an organic compound having at least one ether function, in particular an organic compound having exactly one ether function.

[0090] Compounds having at least one ether function are also understood to mean acetals and hemiacetals. The ether compounds may contain one or more ether functions, for example 1, 2, 3, 4 or more ether functions, preferably 1 or 2 ether functions, very preferably 1 ether function.

[0091] The mixture of donors may comprise one, two, three, four or even more different compounds, preferably compounds having at least one ether functionality, preferably one or two different compounds, very preferably one compound.

[0092] It may be advantageous to use a mixture of two different donors, in particular two different ethers, see for example WO 2017 / 1140603 for aluminum halide donor complexes.

[0093] In a preferred embodiment of the present invention, boron trihalide donor complexes, aluminum trihalide donor complexes or alkylaluminum halide complexes, or iron trihalide donor complexes, or gallium trihalide donor complexes, or titanium tetrahalide donor complexes, or zinc dihalide donor complexes, or tin dihalide donor complexes, or tin tetrahalide donor complexes or boron trihalide donor complexes, very preferably boron trihalide donor complexes, aluminum trihalide donor complexes, or iron trihalide donor complexes or boron trihalide donor complexes, in particular boron trihalide donor complexes or aluminum trihalide donor complexes, are used which, as donors, have the general formula R 8 -OR 9 wherein the variable R 8 and R 9 are each independently C1 to C 20 Alkyl radicals, preferably C1-C8 alkyl radicals, in particular C1-C4 alkyl radicals, C1-C 20 Haloalkyl radicals, preferably C1-C8 haloalkyl radicals, in particular C1-C4 haloalkyl radicals, C5-C8 cycloalkyl radicals, preferably C5-C6 cycloalkyl radicals, C6-C 20 Aryl radicals, especially C6-C 12 Aryl radicals, C6-C 20 Haloaryl radicals, especially C6-C 12 Haloaryl radical, or C7-C 20 Arylalkyl radicals, especially C7-C 12 Arylalkyl radicals. C1-C4 alkyl radicals, C1-C4 haloalkyl radicals, C6-C 12 Aryl radicals and C7-C 12 Arylalkyl radicals are preferred.

[0094] Haloalkyl and haloaryl preferably mean chloroalkyl or bromoalkyl and chloroaryl or bromoaryl, very preferably chloroalkyl and chloroaryl. Particularly preferred are ω-haloalkyl radicals.

[0095] 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.

[0096] Preferred examples of chloroaryl are 2-chlorophenyl, 3-chlorophenyl, and 4-chlorophenyl.

[0097] The dihydrocarbyl ethers mentioned may be open-chain or cyclic, and in the case of cyclic ethers, the two variables R 8 and R 9may be linked to form a ring, and such a ring may also contain 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 n-butyl ether, ethyl sec-butyl ether, ethyl isobutyl ether, ethyl tert-butyl ether, n-propyl-n n-butyl ether, n-propyl sec-butyl ether, n-propyl isobutyl ether, n-propyl tert-butyl ether, isopropyl n-butyl ether, isopropyl sec-butyl ether, isopropyl isobutyl ether, isopropyl tert-butyl ether, methyl n-hexyl ether, methyl n-octyl ether, methyl 2-ethylhexyl ether, ethyl n-hexyl ether, ethyl n-octyl ether, ethyl 2-ethylhexyl ether, n-butyl n-octyl ether, n-butyl 2-ethylhexyl ether, tetrahydrofuran, tetrahydropyran, 1,2-, 1,3-, and 1,4-dioxane, dicyclohexyl ether, diphenyl ether, alkylaryl ethers such as anisole and phenetole, ditolyl ether, dixylyl ether, and dibenzyl ether.

[0098] Further preference is given to difunctional ethers such as dialkoxybenzenes, preferably dimethoxybenzene, very preferably veratrole, and ethylene glycol dialkyl ethers, preferably ethylene glycol dimethyl ether and ethylene glycol diethyl ether.

[0099] Among the 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 boron trihalide donor complexes, aluminium trihalide donor complexes or alkylaluminium halide complexes or iron trihalide donor complexes or gallium trihalide donor complexes or titanium tetrahalide donor complexes or zinc dihalide donor complexes or tin dihalide donor complexes or tin tetrahalide donor complexes or boron trihalide donor complexes, very preferably boron trihalide donor complexes, aluminium trihalide donor complexes or iron trihalide donor complexes or boron trihalide donor complexes, in particular boron trihalide donor complexes or aluminium trihalide donor complexes.

[0100] In a preferred embodiment, dihydrocarbyl ethers having at least one secondary or tertiary dihydrocarbyl group are preferred over dihydrocarbyl groups having only primary groups. An ether having a primary dihydrocarbyl group is an ether in which both dihydrocarbyl groups are bonded to an ether functional group having a primary carbon atom, while an ether having at least one secondary or tertiary dihydrocarbyl group is an ether in which at least one dihydrocarbyl group is bonded to an ether functional group having a secondary or tertiary carbon atom.

[0101] For clarity, for example, diisobutyl ether is considered to be an ether having a primary dihydrocarbyl group because the secondary carbon atom of the isobutyl group is not bonded to an oxygen of a functional ether group, but the hydrocarbyl group is bonded through a primary carbon atom.

[0102] Preferred examples of ethers having primary dihydrocarbyl groups are diethyl ether, di-n-butyl ether, and di-n-propyl ether.

[0103] Preferred examples of ethers having at least one secondary or tertiary dihydrocarbyl group are diisopropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, and anisole.

[0104] Furthermore, it has been found that dihydrocarbyl ethers which are particularly advantageous as donors for boron trihalide donor complexes, aluminum trihalide donor complexes, or alkylaluminum halide complexes are those in which the total carbon number in the donor compound is 3 to 16, preferably 4 to 16, even more preferably 4 to 12, and especially 4 to 8.

[0105] In another preferred embodiment, the halide substituted ethers are preferably in combination with aluminum halide donor complexes or iron halide donor complexes or boron halide donor complexes.

[0106] The organic compound having at least one carboxylic acid ester functional group is preferably represented by the general formula R 10 -COOR 11 and the variable R 10 and R 11 are each independently C1 to C 20 Alkyl radicals, especially C1-C8 alkyl radicals, C5-C8 cycloalkyl radicals, C6-C 20 Aryl radicals, especially C6-C 12 Aryl radical, or C7-C 20 Arylalkyl radicals, especially C7-C 12 It is an arylalkyl radical.

[0107] Examples of hydrocarbyl carboxylates which may be mentioned are methyl formate, ethyl formate, n-propyl 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, sec-butyl 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 butyrate, n-butyl butyrate, sec-butyl butyrate, isobutyl butyrate, tert-butyl butyrate, cyclohexyl ... The hydrocarbyl carboxylates are methyl benzoate, ethyl cyclohexanecarboxylate, n-propyl cyclohexanecarboxylate, isopropyl cyclohexanecarboxylate, n-butyl cyclohexanecarboxylate, sec-butyl cyclohexanecarboxylate, isobutyl cyclohexanecarboxylate, tert-butyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, n-propyl benzoate, isopropyl benzoate, n-butyl benzoate, sec-butyl benzoate, isobutyl benzoate, tert-butyl benzoate, methyl phenylacetate, ethyl phenylacetate, n-propyl phenylacetate, isopropyl phenylacetate, n-butyl phenylacetate, sec-butyl phenylacetate, isobutyl phenylacetate and tert-butyl phenylacetate. Among the abovementioned hydrocarbyl carboxylates, ethyl acetate has been found to be particularly advantageous as a complex donor.

[0108] In addition, it has been found that hydrocarbyl carboxylates which are particularly advantageous as donors are those in which the donor compound has a total carbon number of 3 to 16, preferably 4 to 16, even more preferably 4 to 12, and especially 4 to 8. In particular, those having a total of 3 to 10, especially 4 to 6 carbon atoms are preferred.

[0109] The organic compounds having at least one aldehyde functional group, preferably exactly one aldehyde functional group, and at least one keto functional group, preferably exactly one keto functional group, typically have from 1 to 20, preferably from 2 to 10 carbon atoms. Functional groups other than carbonyl groups are preferably not present.

[0110] Preferred organic compounds having at least one aldehyde functional group are represented by the formula R 10 -CHO(in the formula, R 10 has the meaning given above), and are very preferably selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde and benzaldehyde.

[0111] Preferred organic compounds having at least one keto functional group are represented by the formula R 10 -(C=O)-R 11 (In the formula, R 10 and R 11 has the meaning given above), very preferably selected from the group consisting of acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone and benzophenone. Acetone is the most preferred.

[0112] The organic compound having at least one nitrogen-containing heterocycle is preferably a saturated, partially unsaturated or unsaturated nitrogen-containing 5- or 6-membered heterocycle which contains 1, 2 or 3 ring nitrogen atoms and may also have one or two additional ring heteroatoms from the group of oxygen and sulfur and / or hydrocarbyl radicals (especially C1-C4 alkyl radicals and / or phenyl) and / or functional groups or heteroatoms as substituents (especially fluorine, chlorine, bromine, nitro and / or cyano), such as 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-oxathiazine, 2H-1,3,5-thiadiazine or morpholine.

[0113] However, particularly suitable nitrogen-containing basic compounds of this type are pyridine or derivatives of pyridine (especially mono-, di- or tri C1-C4 alkyl-substituted pyridines), such as 2-, 3- or 4-methylpyridine (picoline), 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or 3,6-dimethylpyridine (lutidine), 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 2-, 3- or 4-phenylpyridine.

[0114] Initiator: The polymerization is preferably carried out additionally using a mono- or polyfunctional, in particular mono-, di- or trifunctional initiator selected from organic hydroxyl compounds, organic halogen compounds and water. It is also possible to use mixtures of the mentioned initiators, 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. That is, one, two or more hydroxyl groups or halogen atoms that start the polymerization reaction may be present in the initiator molecule. In the case of di- or polyfunctional initiators, telechelic isobutene polymers with two or more, in particular two or three, polyisobutene chain ends are typically obtained.

[0115] Organic hydroxyl compounds having only one hydroxyl group in the molecule and suitable as monofunctional initiators include, in particular, alcohols and phenols, in particular compounds of the general formula R 12 -OH, and in the formula R 12 is C1~C 20 Alkyl radicals, especially C1-C8 alkyl radicals, C5-C8 cycloalkyl radicals, C6-C 20 Aryl radicals, especially C6-C 12 Aryl radical, or C7-C 20 Arylalkyl radicals, especially C7-C 12 Represents an arylalkyl radical. In addition, R 12 The radicals may contain mixtures of the above structures and / or may have functional groups other than those already mentioned, such as keto functions, nitroxide or carboxyl groups, and / or heterocyclic structural elements.

[0116] Typical examples of such 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-, 2-, 3-, and 4-phenyl-1-butanol, 1-, 2-, 3-, and 4-(p-methoxyphenyl)-1-butanol, 1-, 2-, 3-, and 4-phenyl-2-butanol, 1-, 2-, 3-, and 4-(p-methoxyphenyl)-2-butanol, 9-methyl-9H-fluorene 1,1-diphenylethanol, 1,1-diphenyl-2-propyn-1-ol, 1,1-diphenylpropanol, 4-(1-hydroxy-1-phenylethyl)benzonitrile, cyclopropyldiphenylmethanol, 1-hydroxy-1,1-diphenylpropan-2-one, benzilic acid, 9-phenyl-9-fluorenol, triphenylmethanol, diphenyl(4-pyridinyl)methanol, α,α-diphenyl-2-pyridinemethanol, 4-methoxytrityl alcohol (especially when polymer-bound as a solid phase) ), α-tert-butyl-4-chloro-4'-methylbenzhydrol, cyclohexyldiphenylmethanol, α-(p-tolyl)benzhydrol, 1,1,2-triphenylethanol, α,α-diphenyl-2-pyridineethanol, α,α-4-pyridylbenzhydrol N-oxide, 2-fluorotriphenylmethanol, triphenylpropargyl alcohol, 4-[(diphenyl)hydroxymethyl]benzonitrile, 1-(2,6-dimethoxyphenyl)-2-methyl-1-phenyl-1-propanol, 1,1,2-triphenylpropan-1-ol, and p-anisaldehyde carbinol.

[0117] In a preferred embodiment, a mixture of primary and secondary alcohols can be used as initiators, as described in WO 2013 / 120859.

[0118] Organic hydroxyl compounds having two hydroxyl groups in the molecule and suitable as bifunctional initiators are in particular dihydric alcohols or diols having a total carbon number of 2 to 30, furthermore 3 to 24, in particular 4 to 20, and bisphenols having a total carbon number of 6 to 30, furthermore 8 to 24, in particular 10 to 20, such as 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-dihydro-9,10-dimethyl-9,10-anthracenediol, 1,1-diphenylbutane-1,4-diol, 2-hydroxytriphenylcarbinol and 9-[2-(hydroxymethyl)-phenyl]-9-fluorenol.

[0119] Organic halogen compounds having one halogen atom in the molecule and suitable as monofunctional initiators are in particular those having the general formula R 13 -Hal, where Hal is a halogen atom selected from fluorine, iodine, in particular chlorine and bromine, and R 13 is C1~C 20 Alkyl radicals, in particular C1-C8 alkyl radicals, C5-C8 cycloalkyl radicals or C7-C 20 Arylalkyl radicals, especially C7-C 12 Represents an arylalkyl radical. In addition, R 13The radicals may contain mixtures of the above structures and / or may have functional groups other than those already mentioned, such as keto functions, nitroxide or carboxyl groups, and / or heterocyclic structural elements.

[0120] 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-chlorohexane, 1-bromohexane, 1-chloroheptane, 1-bromoheptane, 1-chlorooctane, 1-bromooctane, 1-chloro-2-ethylhexane, 1-bromo-2-ethylhexane, cyclohexyl chloride, cyclohexyl bromide, benzyl chloride, benzyl bromide, 1-phenyl-1-chloroethane, 1-phenyl-1-bromoethane, 1-phenyl-2-chloroethane, 1-phenyl-2-bromoethane, 1-phenyl-1-chloroethane, Propane, 1-phenyl-1-bromopropane, 1-phenyl-2-chloropropane, 1-phenyl-2-bromopropane, 2-phenyl-2-chloropropane, 2-phenyl-2-bromopropane, 1-phenyl-3-chloropropane, 1-phenyl-3-bromopropane, 1-phenyl-1-chlorobutane, 1-phenyl-1-bromobutane, 1-phenyl-2-chlorobutane, 1-phenyl-2-bromobutane, 1-phenyl These are 1-phenyl-3-chlorobutane, 1-phenyl-3-bromobutane, 1-phenyl-4-chlorobutane, 1-phenyl-4-bromobutane, 2-phenyl-1-chlorobutane, 2-phenyl-1-bromobutane, 2-phenyl-2-chlorobutane, 2-phenyl-2-bromobutane, 2-phenyl-3-chlorobutane, 2-phenyl-3-bromobutane, 2-phenyl-4-chlorobutane, and 2-phenyl-4-bromobutane.

[0121] Examples of organic halogen compounds suitable as bifunctional initiators having two halogen atoms in the molecule include 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).

[0122] More preferably, the initiator is one in which one or more hydroxyl groups are each sp 3 Organic hydroxyl compounds in which one or more halogen atoms are bonded to a hybridized carbon atom, each of which is sp 3 and water. Among these, at least one hydroxyl group is selected from the group consisting of an organic halogen compound in which one or more hydroxyl groups are bonded to a hybridized carbon atom, and water. 3 Particularly preferred are initiators selected from organic hydroxyl compounds bonded to hybridized carbon atoms.

[0123] In the case of organic halogen compounds as initiators, one or more halogen atoms are each secondary or, in particular, tertiary sp 3 Those attached to hybridized carbon atoms are particularly preferred.

[0124] In particular, in addition to the hydroxyl group, such sp 3 On the hybridized carbon atom, R 12 , R 13 , and R 14 Initiators which may have radicals are preferred, and these radicals are each independently hydrogen, C1 to C 20 Alkyl, C5-C8 cycloalkyl, C6-C 20 Aryl, C7-C 20 alkylaryl, or phenyl, any aromatic ring may also carry one or more, preferably one or two, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl, or C1-C4 haloalkyl radicals as substituents, and the variable R 12 , R 13 , and R 14 At most one of the variables R 12 , R 13 , and R14 At least one of is phenyl which may also bear one or more, preferably one or two, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl, or C1-C4 haloalkyl radicals as substituents.

[0125] For the present invention, 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 (cumene chloride), tert-butyl chloride, and 1,3- or 1,4-bis(1-hydroxy-1-methylethyl)benzene are particularly preferred. Among these, 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, and 1,3- or 1,4-bis(1-hydroxy-1-methylethyl)benzene are particularly preferred.

[0126] Particularly preferred is water.

[0127] Starting materials for polymerization When using isobutene or isobutene-containing monomer mixtures as the monomer to be polymerized, suitable isobutene sources are both pure isobutene and isobutene-based C4-hydrocarbon streams, such as C4 raffinates, especially "raffinate 1", C4 cuts from isobutane dehydrogenation, steam crackers and C4 cuts from FCC crackers (fluid catalytic cracking), provided that the 1,3-butadiene present therein has been substantially removed. C4-hydrocarbon streams from FCC refinery units are also known as "b / b" streams. Further suitable isobutene-containing C4-hydrocarbon streams are, for example, the product streams of propylene-isobutane cooxidation or the product streams from metathesis units, which are generally used after conventional purification and / or concentration. Suitable C4-hydrocarbon streams usually contain less than 500 ppm, preferably less than 200 ppm, of butadiene. The presence of 1-butene and cis- and trans-2-butene is substantially insignificant. Typically, the isobutene concentration in the above-mentioned C4 hydrocarbon stream is in the range of 40-60 wt.%. For example, raffinate 1 usually consists essentially of 30-50 wt.% isobutene, 10-50 wt.% 1-butene, 10-40 wt.% cis- and trans-2-butene, and 2-35 wt.% butane, and in the polymerization process according to the invention, the unbranched butenes in raffinate 1 are usually practically inert and only isobutene is polymerized.

[0128] In a preferred embodiment, the monomer source used for the polymerization is an industrial C4 hydrocarbon stream having an isobutene content of 1 to 100% by weight, even more preferably 1 to 99% by weight, in particular 1 to 90% by weight, more preferably 30 to 60% by weight, in particular 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.

[0129] It has been found to be useful to use water as the sole or additional initiator, especially when a raffinate 1 stream is used as the isobutene source, especially when the polymerization is carried out at temperatures between -20° C. and +30° C., in particular between 0° C. and +20° C. However, when a raffinate 1 stream is used as the isobutene source, it is also possible to omit the use of an initiator at temperatures between -20° C. and +30° C., in particular between 0° C. and +20° C.

[0130] The above isobutene monomer mixture may contain small amounts of impurities such as water, carboxylic acids, or mineral acids, but without serious deterioration of yield or selectivity. It is appropriate to avoid the concentration of these impurities by removing such harmful substances from the isobutene monomer mixture, for example, by adsorption onto a solid adsorbent such as activated carbon, molecular sieves, or ion exchangers.

[0131] It is also possible to convert the monomer mixture of isobutene or an isobutene-based hydrocarbon mixture with an olefinically unsaturated monomer copolymerizable with isobutene. When a monomer mixture of isobutene is copolymerized with a suitable comonomer, the monomer mixture preferably comprises at least 5% by weight, more preferably at least 10% by weight, in particular at least 20% by weight of isobutene and preferably up to 95% by weight, more preferably up to 90% by weight, in particular up to 80% by weight of the comonomer.

[0132] Useful copolymerizable monomers include vinyl aromatics such as styrene and alpha-methylstyrene, C1-C4 alkylstyrenes such as 2-, 3-, and 4-methylstyrene, 4-tert-butylstyrene, 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 having silyl groups 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-methylpropene-2. In addition, depending on the polymerization conditions, useful comonomers also include isoprene, 1-butene, and cis- and trans-2-butene.

[0133] When the method of the present invention is used to prepare copolymers, the method can be configured to preferentially form random polymers or to preferentially form block copolymers. To prepare block copolymers, for example, different monomers can be fed consecutively to the polymerization reaction, in which case the second comonomer is not added until the first comonomer has been at least partially polymerized. In this way, diblock, triblock and higher block copolymers are obtained, which have a block of one or the other comonomer as a terminal block, according to the order of monomer addition. However, in some cases, block copolymers are also formed when all comonomers are fed simultaneously to the polymerization reaction, but one of them polymerizes significantly faster than the other. This is especially the case when isobutene and vinyl aromatic compounds, especially styrene, are copolymerized in the method of the present invention. This preferably forms block copolymers with terminal polystyrene blocks. This is due to the fact that vinyl aromatic compounds, especially styrene, polymerize significantly slower than isobutene.

[0134] The polymerization can be carried out either continuously or batchwise. A continuous process can be carried out similarly to the known prior art processes for the continuous polymerization of isobutene in the presence of a boron trifluoride-based catalyst in the liquid phase.

[0135] The process according to the invention is suitable for carrying out at low temperatures, for example from -90°C to 0°C, or at high temperatures, i.e. at least 0°C, for example from 0°C to +30°C, or from 0°C to +50°C. However, the polymerization in the process according to the invention is preferably carried out at relatively low temperatures, usually from -70°C to -10°C, in particular from -60°C to -15°C.

[0136] When the polymerization in the process of the present invention is carried out at or above the boiling point of the monomer or monomer mixture to be polymerized, it is preferably carried out in a pressure vessel, such as an autoclave or pressure reactor.

[0137] The polymerization in this process can be carried out in the presence of an inert diluent. The inert diluent used must be suitable for reducing the increase in viscosity of the reaction solution that normally occurs during the polymerization reaction to a degree that ensures the removal of the heat of reaction that is generated. Suitable diluents are solvents or solvent mixtures that are inert to the reagents used. Suitable diluents include, for example, aliphatic hydrocarbons such as n-butane, n-pentane, n-hexane, n-heptane, n-octane, isooctane, cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, as well as halogenated hydrocarbons, in particular halogenated aliphatic hydrocarbons such as methyl chloride, dichloromethane, trichloromethane (chloroform), 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane, and 1-chlorobutane, as well as halogenated aromatic hydrocarbons and alkyl aromatics whose alkyl side chains are halogenated, such as chlorobenzene, monofluoromethylbenzene, difluoromethylbenzene, and trifluoromethylbenzene, as well as mixtures of the aforementioned diluents. The diluents used, or the components used in the aforementioned solvent mixtures, are also inert components of the isobutene-based C4 hydrocarbon stream. Non-halogenated solvents are preferred over the list of halogenated solvents.

[0138] The polymerization can be carried out in a halogenated hydrocarbon, in particular a halogenated aliphatic hydrocarbon, or in a mixture of halogenated hydrocarbons, in particular a halogenated aliphatic hydrocarbon, or in a mixture of at least one halogenated hydrocarbon, in particular a halogenated aliphatic hydrocarbon, with at least one aliphatic, cycloaliphatic or aromatic hydrocarbon as an inert diluent, for example a mixture of dichloromethane and n-hexane, the volume ratio of which is typically 10:90 to 90:10, in particular 50:50 to 85:15. Prior to use, impurities such as water, carboxylic acids or mineral acids are preferably removed from the diluent, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.

[0139] In a preferred embodiment, the polymerization is carried out in a halogen-free aliphatic hydrocarbon, in particular a halogen-free aromatic hydrocarbon, in particular toluene. In this embodiment, water in combination with said organic hydroxyl compounds and / or said organic halogen compounds, or especially water as the sole initiator, has been found to be particularly advantageous.

[0140] In another preferred embodiment, the polymerization is carried out in a halogen-free aliphatic or cycloaliphatic hydrocarbon, preferably an aliphatic hydrocarbon, in particular hexane, pentane, heptane, cyclohexane, cyclopentane, and mixtures containing thereof.

[0141] The polymerization is preferably carried out under substantially aprotic and in particular substantially anhydrous reaction conditions. Substantially aprotic and substantially anhydrous reaction conditions are understood to mean that the content of protic impurities and the water content in the reaction mixture are less than 50 ppm, in particular less than 5 ppm, respectively. Thus, the raw materials are usually dried by physical and / or chemical means before use. More specifically, it has been found useful to mix the aliphatic or cycloaliphatic hydrocarbons used as solvents, after customary pre-purification and pre-drying, with an amount of organometallic compounds, such as organolithium, organomagnesium or organoaluminum compounds, sufficient to substantially remove traces of water from the solvent. The solvent thus treated is then preferably condensed directly into the reaction vessel. The monomers to be polymerized, in particular isobutene or isobutene mixtures, can also be treated in a similar manner. Drying with other conventional drying agents, such as molecular sieves or pre-dried oxides, such as aluminum oxide, silicon dioxide, calcium oxide or barium oxide, is also suitable. For halogenated solvents where drying with metals such as sodium or potassium or metal alkyls is not an option, water or traces of water are removed using drying agents suitable for the purpose, such as calcium chloride, phosphorus pentoxide, or molecular sieves.Similarly, raw materials where treatment with metal alkyls is not an option, such as vinyl aromatic compounds, can be dried in a similar manner.Even if the initiator used is partially or entirely water, it is preferable to remove most or completely residual water from the solvent and monomers by drying before the reaction in order to be able to use the water initiator in a controlled and defined amount, which results in better process control and reproducibility of results.

[0142] The polymerization reaction is suitably terminated by adding an excess of water or a basic material, such as gaseous or aqueous ammonia, or an aqueous alkali metal hydroxide solution, such as sodium hydroxide solution.

[0143] After the unconverted C4 monomers have been removed, the crude polymerization product is typically washed repeatedly with distilled or deionized water to remove adhering inorganic components. To achieve high purity or to remove undesirable low and / or high molecular weight fractions, the polymerization reaction mixture can be fractionally distilled under reduced pressure.

[0144] The resulting polyisobutene composition having a content of at least 70 mol % of polyisobutene species (A) having α-double bonds is subjected to a double bond isomerization process as described below.

[0145] After deactivating the catalyst and, optionally, removing the hydrolysis products by washing, the reaction mixture from the polymerization can be used in the double bond isomerization process without further purification. In addition to the polyisobutene composition having a content of at least 70 mol % of polyisobutene species (A) having α-double bonds, such reaction mixtures can contain unreacted monomers and lower oligomers of isobutene.

[0146] The non-distilled reaction mixture differs from the polyisobutene composition in that it additionally contains isobutene and lower oligomers of isobutene, which are normally separated from the reaction mixture by distillation.

[0147] Such lower oligomers of isobutene may be diisobutene, triisobutene, tetraisobutene, pentaisobutene, hexaisobutene, heptaiisobutene, and octaisobutene. Higher oligomers of isobutene are generally not volatile under distillation conditions, even under reduced pressure, and therefore typically remain in the polyisobutene composition.

[0148] The content of unreacted isobutene is at most 40% by weight, preferably at most 30% by weight, more preferably at most 20% by weight.

[0149] The content of said unreacted lower oligomers may be up to 5% by weight, preferably up to 3% by weight.

[0150] The distribution of double bond isomers (A), (B) and (C) among the oligomers is usually comparable, and preferably the same, as that of the polymer mixture, however, it has been observed that the oligomer mixture contains less isomer (C6), in some cases up to 5 mol % less isomer (C6), compared to the polymer mixture.

[0151] Thus, the content of oligomeric species of formula (A) having an α-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 in particular at least 90 mol%.

[0152] In the isomerization process, a solution of the polyisobutene composition in at least one of the above-mentioned solvents can be used, or the polyisobutene composition can be used as is. In a preferred embodiment, a 10-90 wt% solution, preferably a 15-60 wt% solution, more preferably a 20-50 wt% solution, especially a 25-40 wt% solution of the polyisobutene composition dissolved in a solvent, preferably a halogen-free solvent, is used in the double bond isomerization process.

[0153] In one embodiment, the solvent may be an inert component of an isobutene C4 hydrocarbon stream.

[0154] After undergoing the double bond isomerization process, the solvent in the reaction mixture is preferably removed, more preferably by distillation.

[0155] Usually a single-stage evaporation without a rectification device is sufficient and can be carried out in a falling film evaporator, a rising film evaporator, a thin film evaporator, a long tube evaporator, a spiral tube evaporator, a forced circulation flash evaporator, a paddle dryer (e.g. Discotherm® dryers from List Technology AG, Switzerland), or a combination of these devices.

[0156] The distillation is carried out in principle at 80 to 320° C., preferably 100 to 300° C., and at 0.1 to 40 mbar, preferably 0.5 to 20 mbar.

[0157] Distillation can be aided by inert stripping, preferably with nitrogen, through the evaporator.

[0158] Such a distillation and optional stripping process results in polyisobutene with significantly reduced amounts of solvent and monomer, even when n-hexane is used as the solvent. Another object of the present invention is therefore a composition having an n-hexane content of not more than 1000 ppm by weight, preferably not more than 900 ppm by weight, more preferably not more than 800 ppm by weight, in particular not more than 750 ppm by weight, and at the same time an isobutene content of not more than 50 ppm by weight, preferably not more than 40 ppm by weight, more preferably not more than 30 ppm by weight, in particular not more than 25 ppm by weight, or even not more than 20 ppm by weight.

[0159] Such compositions are particularly suitable for use as chewing gums or plasters.

[0160] Isomerization Process According to another embodiment of the present invention, a polyisobutene composition having a content of polyisobutene species (A) having α-double bonds of at least 30 mol%, preferably at least 40 mol%, more preferably at least 50 mol%, most preferably at least 60 mol%, in particular at least 70 mol%, is contacted with at least one acidic solid catalyst and optionally treated with at least one Brønsted base to convert it into a polyisobutene composition having a content (in total) of tetrasubstituted double bond isomers, preferably isomers (C3) to (C5), for example of at least 5%, preferably 10 to 90%, even more preferably 15 to 80%, in particular 20 to 75%, or even 25 to 60%.

[0161] According to the process according to the invention, typically 5 to 60%, preferably 20 to 50% (relative to the starting value) of the polyisobutene species (A) having α-double bonds is converted into polyisobutene species having tetra-substituted double bond isomers (in total), preferably the isomers (C3) to (C5).

[0162] Optionally, such compositions may contain up to 20 mole % (combined) of polyisobutene isomers (C) and (D) other than the tetra-substituted double bond isomer; In this case, the sum of (A), (B), (C), and (D) always equals 100 mole %.

[0163] The advantage of the process according to the invention is that low or medium molecular weight polyisobutene (A) isomers having an α-double bond can be converted into isomers having tetrasubstituted double bonds.

[0164] The above-mentioned method is carried out at a temperature of 40°C to 250°C, preferably 50 to 230°C, more preferably 60 to 200°C, even more preferably 70 to 180°C, and particularly preferably 80 to 160°C, for 10 minutes to 36 hours, preferably 15 minutes to 24 hours, more preferably 30 minutes to 12 hours, and particularly preferably 1 hour to 6 hours.

[0165] The optimum contact time and reaction temperature between the polyisobutene composition and the catalyst can be determined by systematically varying the reaction parameters.

[0166] In the case of ion exchange resins (see below), the reaction temperature should not exceed 150°C, preferably is not more than 140°C, more preferably not more than 130°C, even more preferably not more than 120°C, especially not more than 110°C.

[0167] As a rule, polyisobutenes with a high content of isomers with α-double bonds are first converted to polyisobutene isomers with trisubstituted double bonds, preferably isomer (B), and then to isomers with tetrasubstituted double bonds. Therefore, if a high content of trisubstituted double bonds, preferably isomer (B), is desired, the reaction time should be selected shorter, preferably at most 4 hours, more preferably at most 3 hours, even more preferably at most 2 hours, or even at most 1 hour, depending on the reaction temperature. Similarly, the reaction temperature should be selected lower, for example at most 130°C, preferably at most 120°C, more preferably at most 110°C, even more preferably at most 100°C, in particular at most 90°C, or even at most 80°C.

[0168] If a higher content of isomers with tetrasubstituted double bonds is desired, a longer reaction time should be chosen, preferably more than 4 hours, more preferably at least 5 hours, even more preferably at least 6 hours. In order to obtain a favorable equilibrium, a higher reaction temperature is preferred.

[0169] An example of an acidic solid catalyst is one that exhibits temperature programmed desorption (TPD) of ammonia over physical adsorption. A method for determining the temperature programmed desorption (TPD) of ammonia can be found in Philip M. Kester, Jeffrey T. Miller, and Rajamani Gounder, Ammonia Titration Methods To Quantify Bronsted Acid Sites in Zeolites Substituted with Aluminum and Boron Heteroatoms, Industrial & Engineering Chemistry Research 2018 57(19), 6673-6683, Chapter 2.3.

[0170] Preferably, the acidic solid catalyst is selected from the group consisting of: - Natural clay minerals: kaolinite, bentonite, attapulgite, montmorillonite, clarit, fuller's earth, zeolites (X, Y, A, H-ZSM, etc.), cation-exchanged zeolites, and clays - Fixed acids: H2SO4, H3PO4, CH2(COOH)2 fixed in silica, quartz sand, alumina, or diatomaceous earth - Cation exchange resin - Metal oxides and sulfides: ZnO, CdO, Al2O3, CeO2, ThO2, TiO2, ZrO2, SnO2, PbO, As2O5, Bi2O3, Sb2O5, V2O5, Cr2O3, MoO3, WO3, CdS, ZnS - Metal salts: MgSO4, CaSO4, SrSO4, BaSO4, CuSO4, ZnSO4, CdSO4, Al2(SO4)3, FeSO4, Fe2(SO4)3, CoS O4, NiSO4, Cr2(SO4)3, KHSO4, K2SO4, (NH4)2SO4, Zn(NO3)2, Ca(NO3)2, Bi(NO3)3, Fe(NO3)3 , CaCO3, BPO4, AlPO4, CrPO4, FePO4, Cu3(PO4)2, Zn3(PO4)2, Mg3(PO4)2, Ti3(PO4)4, Zr3(P O4)4, Ni3(PO4)2, AgCl, CuCl, CaCl2, AlCl3, TiCl4, SnCl4, CaF2, BaF2, AgClO4, Mg(ClO4)2, - Mixed oxides: SiO2-Al2O3, SiO2-TiO2, SiO2-SnO2, SiO2-ZrO2, SiO2-BeO, SiO2-MgO, SiO2-Ca O, SiO2-SrO, SiO2-ZnO, SiO2-Ga2O3, SiO2-Y2O3, SiO2-La2O3, SiO2-MoO3, SiO2-WO3, Si O2-V2O5, SiO2-ThO2, Al2O,-MgO, Al2O3-ZnO, Al2O3-CdO, Al2O3-B2O3, Al2O3-ThO2, Al 2O3-TiO2, Al2O3-ZrO2, Al2O3-V2O5, Al2O3-MoO3, Al2O3-WO3, Al2O3-Cr2O3, Al2O3-Mn2 O3, Al2O3-Fe2O3, Al2O3-Co3O4, Al2O3-NiO, TiO2-CuO, TiO2-MgO, TiO2-ZnO, TiO2-CdO , TiO2-ZrO2, TiO2-SnO2, TiO2-Bi2O3, TiO2-Sb2O5, TiO2-V2O5, TiO2-Cr2O3, TiO2-MoO3 , TiO2-WO3, TiO2-Mn2O3, TiO2-Fe2O3, TiO2-Co3O4, TiO2-NiO, ZrO2-CdO, ZnO-MgO, ZnO -Fe2O3, MoO3-CoO-Al2O3, MoO3-NiO-Al2O3, TiO2-SiO2-MgO, MoO3-Al2O3-MgO, heteropolyacid.

[0171] More preferably, the acidic solid catalyst is selected from the group consisting of SiO2, Al2O3, TiO2, ZrO2, B2O3, ZnO2, Nb2O5, or mixtures thereof.

[0172] Highly preferably, the acidic solid catalyst is selected from the group consisting of silicates, aluminas, silicoaluminates and zeolites.

[0173] In particular, the acidic solid catalyst is a molecular sieve.

[0174] Such molecular sieves have an average pore diameter of 0.1 to 1 nm (1 to 10 Å), preferably 0.1 to 0.6 nm, and more preferably 0.2 to 0.5 nm.

[0175] Such molecular sieves are aluminosilicates having a silica-alumina ratio (SiO2 / Al2O3) of 1:0.1 to 1:5, preferably 1:0.2 to 1:3, more preferably 1:0.2 to 1:1, especially 1:0.5.

[0176] The approximate chemical composition of such aluminosilicates is: [(K2O) x (Na2O) y ]·Al2O3·2SiO2·9 / 2H2O and x is 0 to 1, preferably 0 to 0.7, more preferably 0 to 0.5, and particularly 0; y is 0 to 1, preferably 0.3 to 1, more preferably 0.5 to 1, and particularly 1; x+y=1.

[0177] In a preferred embodiment, the acidity of the acidic solid catalyst is adjusted by treatment with at least one Bronsted base, preferably at least one inorganic base, more preferably a hydroxide, an oxide, a C1-C4 carboxylate, preferably a formate or acetate, more preferably an alkali metal or alkaline earth metal acetate, carbonate or bicarbonate, even more preferably an acetate, carbonate or bicarbonate of sodium, potassium or calcium.

[0178] For this purpose, the acidic solid catalyst is treated with an aqueous solution of a Bronsted base in an amount sufficient to obtain the desired acidity, and then dried or calcined.

[0179] Preferably, the impregnated solid catalyst is calcined at a temperature of 400 to 1000°C.

[0180] By such treatment, it is possible to adjust the acidity, and therefore the reactivity, of the solid catalyst so that the reaction can be terminated when the concentration of the desired isomer having a tetrasubstituted double bond in the reaction mixture is maximized without significant side or subsequent reactions occurring.

[0181] In a preferred embodiment, the solid catalyst comprises an alumina component, a zeolite component, and an optional metal component added as a Bronsted base, preferably the added metal component is present in the solid catalyst. In a preferred embodiment, the solid catalyst is used as described in U.S. Pat. No. 8,147,588 B2, preferably as described in column 2, line 50 to column 5, line 32, which is incorporated herein by reference.

[0182] The acidic solid catalyst, optionally treated with at least one Bronsted base or ion exchanger, can be used in a variety of geometric shapes, such as powders, granules, beads, spheres, saddles, extrudates, strands, pellets, tablets, or meshes.

[0183] The catalyst loading, calculated as kg of polyisobutene composition per kg of solid catalyst and hour of reaction time, may vary from 0.1 to 10, preferably from 0.2 to 8, more preferably from 0.5 to 5 kg / (kg×h).

[0184] In a preferred embodiment, the process according to the invention is carried out in the presence of at least one initiator compound as defined above, more preferably in the presence of water or at least one organic hydroxyl compound, very preferably in the presence of water.

[0185] For this purpose, a polyisobutene composition containing a polyisobutene species (A) component as starting material is contacted with an acidic solid catalyst and treated with at least one Brønsted base, optionally in the presence of up to 5% by weight (based on polyisobutene species (A)), preferably up to 3% by weight, more preferably up to 2% by weight, in particular up to 1% by weight, of at least one initiator.

[0186] The process can optionally be carried out in the presence of at least one solvent, preferably in the presence of at least one solvent.

[0187] As the solvent, any of the solvents listed above in connection with the polymerization can be used, but preferably it is a non-halogenated solvent, and more preferably an aliphatic or aromatic hydrocarbon, in particular an aliphatic hydrocarbon.

[0188] In a preferred embodiment, the solvent, particularly the hydrocarbon, is treated with water, preferably saturated with water, prior to carrying out the isomerization reaction, so that the reaction is carried out in the presence of the solvent together with water.

[0189] The isomerization process can be carried out continuously or discontinuously, preferably continuously.

[0190] For discontinuous reactions, the polyisobutene composition, optional solvent, and solid catalyst are placed together in a reactor, heated to the target temperature, and the reaction is carried out with stirring or by pumping the reaction mixture in a circulation flow.

[0191] For a continuous reaction, the polyisobutene composition, optional solvent, and solid catalyst are delivered to a reactor in an upflow or downflow procedure, heated to a target temperature, and reacted in. The flow of liquids through the reactor is adjusted so that the residence time in the reactor corresponds to the target reaction time.

[0192] Typically, the reaction can be carried out at atmospheric pressure, although higher pressures may be useful to prevent the optional solvent from evaporating and to ensure that the reaction mixture remains in a single liquid phase.

[0193] The Langmuir specific surface area of ​​the acidic solid catalyst, optionally treated with at least one Bronsted base, employed in the process according to the invention is preferably between 50 and 1000 m 2 / g, more preferably 75 to 900m 2 / g, particularly preferably 100 to 800m 2 / g, more preferably 200 to 700, particularly preferably 300 to 500 m 2 / g. The Langmuir surface area is determined by nitrogen adsorption using the DIN 66132 method.

[0194] The pore volume determined by mercury porosimetry of the acidic solid catalyst, optionally treated with at least one Bronsted base, is preferably 0.01-0.3 ml / g, more preferably 0.03-0.2 ml / g. The average pore diameter determined by this method is preferably 0.1-10 nm, more preferably 0.2-9 nm, more preferably 0.3-5 nm.

[0195] The mercury pore volume and pore diameter for pores 0.3 nm and above are determined by the DIN 66133 method, for smaller pore diameters the nitrogen pore volume is used.

[0196] The acidity / basicity of the solid catalyst is determined using the pH value of an aqueous slurry of the solid catalyst (see Analytical Methods section below).

[0197] A preferred solid catalyst that has not been treated with a Bronsted base exhibits a pH value of 3 to 8, preferably 3.5 to 7, more preferably 4 to 6, especially 4 to 5.5, in the form of a 10% by weight aqueous slurry.

[0198] Preferred solid catalysts treated with at least one Bronsted base exhibit, in the form of a 10% by weight aqueous slurry, a pH value of 6 to 13, preferably 7 to 12.5, more preferably 8 to 12, especially 9 to 11.5.

[0199] In a particularly preferred embodiment, an acidic ion exchanger, preferably a strongly acidic ion exchanger, can be used as the acidic solid catalyst.

[0200] Ion exchange resins are usually based on styrene or (meth)acrylic acid. Weakly acidic ion exchangers are often based on polymers containing (meth)acrylic acid with carboxylic acid groups as acidic groups. Strongly acidic ion exchangers are usually based on styrene-divinylstyrene copolymers with sulfonic acid groups. Since the polymer backbone is organic, the reaction temperature should not be allowed to exceed certain limits (see above). Exceptions are perfluoropolymers such as Nafion® ion exchangers, which can also be used at higher temperatures. Further examples of commercially available ion exchangers are the acidic ion exchangers of the Amberlyst® or Amberlite® product ranges.

[0201] In the case of acidic ion exchangers, the concentration of acid sites based on the dry weight capacity should be at least 1.0 eq / kg, preferably at least 1.5 eq / kg, more preferably at least 2.0 eq / kg, even more preferably at least 2.5 eq / kg, in particular at least 3 eq / kg. The concentration of acid sites usually does not exceed 10.0 eq / kg.

[0202] Preferred ion exchangers have a molecular weight of 10 to 100, preferably 20 to 80, very preferably 30 to 70 m 2 The nitrogen BET specific surface area in g is shown.

[0203] The average pore size of the ion exchanger is preferably 50 to 1000 Å (angstroms), more preferably 100 to 800 Å, and more preferably 200 to 500 Å.

[0204] The total pore volume is preferably 0.1 to 0.9 ml / g, more preferably 0.2 to 0.8 ml / g, and further preferably 0.3 to 0.7 ml / g.

[0205] In a preferred embodiment, the ion exchanger is used in the form of beads, preferably having an average diameter of 0.1 to 5 mm, more preferably 0.2 to 3 mm, even more preferably 0.3 to 2.5 mm.

[0206] Generally, a high concentration of acid sites is preferred.

[0207] Surprisingly, the process of the present invention results in compositions having an increased content of polyisobutene species having tetrasubstituted double bonds, preferably selected from the group consisting of isomers (C3), (C4), and (C5).

[0208] Such compositions having an increased content of polyisobutene species having tetrasubstituted double bonds have very high reactivity in photoreactions, preferably photooxygenation, and therefore provide excellent utility as starting materials for chemical modification of such compositions when photoreaction is desired.

[0209] NMR spectroscopy of polyisobutene polymers was carried out on a Bruker 700 MHz spectrometer using 5 mm OD tubes containing appropriate concentrations of polyisobutene in deuterated chloroform (CDCl3) as solvent at 25 °C as described in Guo et al., Journal of Polymer Science, Part A: Polymer Chemistry, 2013, 51, 4200-4212. 1 H spectra were measured using tetramethylsilane (δ H =0.00) or the solvent signal (δ C = 77.0). For the structural characterization of polyisobutene, the distortion-free sensitivity enhancement by polarization transfer (DEPT) technique was further used.

[0210] The following examples are intended to illustrate the invention in detail without limiting it. EXAMPLES

[0211] Example 1 To obtain polyisobutene with the desired reactivity, isobutene was polymerized in hexane with the catalyst:cocatalyst ratios listed in the table below and contacted with the isomerization catalyst at elevated temperature in a fixed-bed isomerization tower (polyisobutene concentration in hexane: 35 wt %). The hexane solution of polyisobutene was then subjected to elevated temperature at 25 mbar (absolute pressure) for 90 minutes in the degassing section (see table below for details).

[0212] The isomerization catalyst used was a spherical alumina-zeolite composite with a surface area of ​​390 m. 2 / g, and the pH value of the slurry was 11.3.

[0213] [Table 1]

[0214] Example 2 - Isomerization of medium molecular weight polyisobutene A medium molecular weight polyisobutene having a number average molecular weight Mn of 18330 g / mol and a polydispersity index of 3.2 was dissolved in heptane to obtain a 35 wt % solution.

[0215] The solution was heated to 80° C. for 6 hours in a flask equipped with a reflux condenser together with 10% by weight (based on polyisobutene) of the isomerization catalyst listed in the table. After 6 hours, a sample was taken and analyzed according to the method described above. 1 The isomer distribution was determined by 1 H-NMR and the number average molecular weight was determined using GPC.

[0216] [Table 2]

[0217] Example 3 - Isomerization of low molecular weight polyisobutene A low molecular weight, highly reactive polyisobutene with a number average molecular weight Mn of 973 g / mol was isomerized using 10 wt. % Amberlyst® 15 as a strongly acidic ion exchanger as described in Example 2. Samples were taken every 2 hours and analyzed as outlined in Example 2.

[0218] [Table 3]

[0219] It is easy to see that the α-double bond isomerizes first to an isomer with a trisubstituted double bond and later to an isomer with a tetrasubstituted double bond.

[0220] Without wishing to be bound by theory, it is believed that isomerization to isomers with trisubstituted double bonds occurs under kinetic control, while conversion to isomers with tetrasubstituted double bonds proceeds under thermodynamic control.

Claims

1. at least one isomer having a number average molecular weight Mn of more than 10,000 g / mol to 100,000 g / mol, as determined by gel permeation chromatography, and having a tetrasubstituted double bond, preferably 【Chemistry 1】 where PIB, PIB', and PIB'' refer to the appropriately abbreviated polymer backbone of polyisobutene. A medium molecular weight polyisobutene composition comprising 20 to 75% (total), preferably 25 to 60% of an isomer selected from the group consisting of:

2. 2. The medium molecular weight polyisobutene composition according to claim 1, having a number average molecular weight Mn of 13,000 to 75,000, in particular 14,000 to 70,000, as determined by gel permeation chromatography.

3. 2. The medium molecular weight polyisobutene composition according to claim 1, comprising halogenated polyisobutene (D1) in an amount of up to 500 ppm by weight of halogen.

4. Use of the polyisobutene composition according to any one of claims 1 to 3 in photoreactions, preferably photooxidation.

5. Use of the polyisobutene composition according to any one of claims 1 to 3 as a sealant, adhesive, coating or roofing material.

6. A method for preparing the composition according to any one of claims 1 to 3, comprising the steps of: selecting as starting material a medium-molecular-weight polyisobutene composition having a content of polyisobutene species (A) having α-double bonds of at least 30 mol %, preferably at least 40 mol %, more preferably at least 50 mol %, most preferably at least 60 mol %, in particular at least 70 mol %, and having a number-average molecular weight Mn, determined by gel permeation chromatography, of more than 10 000 g / mol to 100 000 g / mol, preferably from 11 000 to 90 000, more preferably from 12 000 to 80 000, most preferably from 13 000 to 75 000, in particular from 14 000 to 70 000 g / mol; Optionally, also selecting at least one solvent; the optionally dissolved polyisobutene composition, in the presence of at least one acidic solid catalyst optionally treated with at least one Brönsted base, - 10 minutes to 36 hours, - At temperatures between 40℃ and 250℃ Processing steps and A method comprising:

7. the at least one acidic solid catalyst is Natural clay minerals: kaolinite, bentonite, attapulgite, montmorillonite, Clarit, fuller's earth, zeolites (X, Y, A, H-ZSM, etc.), cation-exchanged zeolites, and clays - Fixed acids: H fixed on silica, quartz sand, alumina, or diatomaceous earth ２ SO ４ , H ３ P.O. ４ , C.H. ２ (COOH) ２ - Cation exchange resin Metal oxides and sulfides: ZnO, CdO, Al ２ O ３ , CeO ２ , ThO ２ , TiO ２ , ZrO ２ , SnO ２ , PbO, As ２ O ５ , Bi ２ O ３ , Sb ２ O ５ , V ２ O ５ , Cr ２ O ３ , MoO ３ , W.O. ３ , CdS, ZnS - Metal salts: MgSO ４ , CaSO ４ , SrSO ４ , BaSO ４ , CuSO ４ , ZnSO ４ , CdSO ４ , Al ２ (SO ４ ) ３ , FeSO ４ , Fe ２ (SO ４ ) ３ , CoSO ４ , NiSO ４ , Cr ２ (SO ４ ) ３ , KHSO ４ , K ２ SO ４ , (NH ４ ) ２ SO ４ , Zn(NO ３ ) ２ , Ca(NO ３ ) ２ , Bi(NO ３ ) ３ , Fe(NO ３ ) ３ , CaCO ３ , BPO ４ , AlPO ４ , CrPO ４ , FePO ４ [[ID=7" , Cu ３ (PO ４ ) ２ , Zn ３ (PO ４ ) ２ , Mg ３ (PO ４ ) ２ , Ti ３ (PO ４ ) ４ , Zr ３ (PO ４ ) ４ , Ni ３ (PO [[ID=]" ４ ) ２ , AgCl, CuCl, CaCl ２ , AlCl ３ , TiCl ４ , SnCl ４ 、CaF ２ 、BaF ２ 、AgClO ４ 、Mg(ClO ４ ) ２ 、 - mixed oxides: SiO ２ -Al ２ Oh ３ 、SiO ２ -TiO ２ 、SiO ２ -Snt ２ 、SiO ２ -ZrO ２ 、SiO ２ -BeO、SiO ２ -MgO、SiO ２ -CaO、SiO ２ -SrO、SiO ２ -ZnO, SiO ２ -Ga ２ Oh ３ 、SiO ２ -- ２ Oh ３ 、SiO ２ -Yes ２ Oh ３ 、SiO ２ -MoO ３ 、SiO ２ -WO ３ 、SiO ２ -V ２ Oh ５ 、SiO ２ -ThO ２ 、Al ２ O, -MgO, Al ２ Oh ３ -ZnO, Al ２ Oh ３ -CdO, Al ２ Oh ３ -B ２ Oh ３ 、Al ２ Oh ３ -ThO ２ 、Al ２ Oh ３ -TiO ２ 、Al ２ Oh ３ -ZrO ２ 、Al ２ Oh ３ -V ２ Oh ５ 、Al ２ Oh ３ -MoO ３ 、Al ２ Oh ３ -WO ３ 、Al ２ O ３ -Cr ２ O ３ 、-- ２ O ３ -Mn ２ O ３ 、-- ２ O ３ -Fe ２ O ３ 、-- ２ O ３ -Co ３ O ４ 、-- ２ O ３ ---O、T-O ２ -COOTOO ２ -MOO、T-O ２ -Z.O、T-O ２ -CdO、T-O ２ -ZrO ２ 、T-O ２ -SnO ２ 、T-O ２ -Bi ２ O ３ 、T-O ２ -Sa ２ O ５ 、T-O ２ -V ２ O ５ 、T-O ２ -Cr ２ O ３ 、T-O ２ -MoO ３ 、T-O ２ -WO ３ 、T-O ２ -Mn ２ O ３ 、T-O ２ -Fe ２ O ３ 、T-O ２ -Co ３ O ４ 、T-O ２ ---O、ZrO ２ -CdO、ZO-MgO、ZO-Fe ２ O ３ 、MoO ３ -CoO-Al ２ O ３ 、MoO ３ -----AS ２ O ３ , TiO ２ -SiO ２ -MgO, MoO ３ -Al ２ O ３ -MgO, heteropolyacid 7. The method of claim 6, wherein the compound is selected from the group consisting of:

8. The method according to claim 7, wherein the temperature is from 40°C to 250°C, preferably from 50 to 230°C, more preferably from 60 to 200°C, even more preferably from 70 to 180°C, and in particular from 80 to 160°C, and the method is carried out for from 10 minutes to 36 hours, preferably from 15 minutes to 24 hours, more preferably from 30 minutes to 12 hours, and in particular from 1 hour to 6 hours.

9. 8. The process according to claim 7, wherein said at least one acidic solid catalyst is an acidic ion exchanger, preferably a strongly acidic ion exchanger.

10. 10. The process according to claim 9, wherein the reaction temperature does not exceed 150°C, preferably is 140°C or less, more preferably 130°C or less, even more preferably 120°C or less, especially 110°C or less.

11. 10. The method according to claim 9, wherein the concentration of acidic sites of the acidic ion exchanger based on dry weight capacity is at least 1.0 eq / kg, preferably at least 1.5 eq / kg, even more preferably at least 2.0 eq / kg, more preferably at least 2.5 eq / kg, in particular at least 3 eq / kg.

12. 4. The polyisobutene composition according to claim 1, wherein the content of halogen, preferably fluorine or chlorine, more preferably chlorine, is more than 5 ppm by weight, preferably at least 10 ppm by weight, more preferably at least 15 ppm by weight, even more preferably at least 20 ppm by weight, in particular at least 30 ppm by weight, or even at least 50 ppm or 70 ppm by weight.

13. 13. Polyisobutene composition according to claim 12, wherein the upper limit of the halogen, preferably fluorine or chlorine, more preferably chlorine, is at most 500 ppm by weight, preferably at most 250 ppm by weight, more preferably at most 150 ppm by weight.

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