Process for producing polyisobutene succinic anhydride

Abstract

The present invention relates to a process for producing polyisobutene succinic anhydride from certain polyisobutene mixtures.

Description

[Technical field]

[0001] The present invention relates to a process for producing polyisobutene succinic anhydride from certain polyisobutene mixtures. [Background technology]

[0002] Polyisobutene succinic anhydride can be obtained by reacting highly reactive polyisobutene with maleic anhydride by a thermal ene reaction. Such highly reactive polyisobutene exhibits a high content of α-double bonds, from 50 mol % up to 90 mol %, or even more, which are more reactive to react with maleic anhydride compared to other isomers also contained in such polyisobutene mixtures.

[0003] Thermal ene reactions are usually carried out with a stoichiometric excess of maleic anhydride at temperatures up to 280° C., see for example EP 156310 A2 or WO 2017 / 216022. Depending on the reaction conditions, excess pressure is often applied.

[0004] The problem is that the reaction mixture contains not only the desired product, polyisobutene succinic anhydride, which can be maleated once or twice, but also unreacted highly reactive polyisobutene and less reactive polyisobutene that was part of the starting material. Since these different compounds have similar molecular weights and the polarity is dominated by the polyisobutene long chain, it is usually not possible to separate the desired product, polyisobutene succinic anhydride, from the unwanted by-products that do not have succinic anhydride groups. Separation of these components is possible for analytical purposes, but not on a large scale, to determine the content of maleated polyisobutene.

[0005] Therefore, there is a need for a method for increasing the yield of polyisobutene succinic anhydride in the reaction of polyisobutene with maleic anhydride. Summary of the Invention [Means for solving the problem]

[0006] The problem is a process for preparing polyisobutene succinic anhydride by reacting highly reactive polyisobutene having a content of α-double bonds of at least 50 mol % with maleic anhydride for a period of 15 minutes up to 10 hours at a temperature of 150-260° C. in a stoichiometric molar ratio of 0.6 mol maleic anhydride:1 mol polyisobutene or more, wherein the highly reactive polyisobutene has a content of 0.8% by weight or more and is represented by the formula: PIB-OR 1 and having one or more ethers of During the ceremony, PIB represents a residue derived from polyisobutene; R 1 is C1~C 10 The problem is solved by a process characterized in that the compound is an alkyl group.

[0007] Another subject of the invention is an ether-containing mixture of highly reactive polyisobutenes and its use.

[0008] Preferably, the formula PIB-OR 1 The content of the one or more ethers is from 0.9 to 8.0% by weight, more preferably from 1.0 to 5.0% by weight, even more preferably from 1.1 to 4.0% by weight, and especially from 1.2 to 3.0% by weight.

[0009] An advantage of the present invention is that polyisobutene compositions containing certain amounts of ethers provide higher yields in the subsequent reaction with maleic anhydride.

[0010] The variable "PIB" represents the highly reactive polyisobutene and the alkanol R 1 OH or substructure-OR 1 Typically, this variable represents the residue derived from polyisobutene formed by reaction with an ether having the substituent -OR 1 corresponds to the saturated polyisobutene after removal of one hydrogen atom at position

[0011] residue R 1 is C1~C 10 Alkyl, preferably C1 to C8 alkyl, more preferably C1 to C6 alkyl, and even more preferably C1 to C4 alkyl.

[0012] R 1 Preferred examples of are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, more preferably methyl, ethyl, isopropyl, n-butyl, isobutyl and tert-butyl, even more preferably methyl, n-butyl and tert-butyl, with methyl being especially preferred.

[0013] Polyisobutene of the desired molecular weight can be obtained by polymerizing isobutene or an isobutene-containing raw material in the presence of at least one Lewis acid, usually in the presence of at least one donor and at least one initiator. Typical donors are ethers, alcohols, or ketones (see below). Substructure R 1 O-containing ether or alkanol R 1 When OH is used as a donor, the initiator moiety R 1 O- is incorporated into polyisobutene and has the formula PIB-OR 1 Ethers of the formula: [Brief description of the drawings]

[0014] [Figure 1] The multiplicity of signals is indicated. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] In one embodiment of the present application, the formula PIB-OR 1 The highly reactive polyisobutene containing one or more ethers of at least one alkanol R 1The at least one ether is obtained by polymerization of an isobutene-containing reaction mixture with at least one Lewis acid in the presence of OH. Optionally, the at least one ether may additionally be represented by the substructure R 1 It may be used with or without -O-, and preferably the substructure R 1 It may be used containing -O-.

[0016] In another embodiment of the present application, the formula PIB-OR 1 The highly reactive polyisobutenes containing one or more ethers of the substructure R 1 The ethers R are obtained by polymerization of an isobutene-containing reaction mixture with at least one Lewis acid in the presence of at least one ether containing -O-. 1 -OR 1 Or Ether R 1 -OR 1 ' is preferred, in which R 1 ' is R 1 has the same meaning as, but the residue R 1 Optionally, the polymerization is different from at least one alkanol R 1 It may be carried out in the presence of OH.

[0017] The subject of the present invention is therefore In a first step, a compound of the formula PIB-OR 1 at least one alkanol R under reaction conditions such that a polyisobutene having a content of at least 0.8% by weight of ethers of 1 polymerizing an isobutene-containing reaction mixture in the presence of at least one Lewis acid in the presence of OH; - in a second step, separating unreacted components of the reaction mixture from the polyisobutene-containing product, in a third step, the ether-containing polyisobutene thus obtained is reacted with maleic anhydride.

[0018] Processes for preparing highly reactive polyisobutene compositions (i.e., having a high content of α- and / or β-double bonds, especially α-double bonds) are known in the art.

[0019] Without being bound by any theory, it is believed that the reactivity of highly reactive polyisobutenes during the thermal ene reaction is mainly due to the content of α-double bonds in the polyisobutene. Although it is possible that β-double bonds or other isomers may also react under the reaction conditions, either directly or after isomerization of the double bonds to α-double bonds, this reaction usually occurs to a much lesser extent or even insignificantly.

[0020] In the context of the present invention, the term "β double bond" containing isomer refers to a polyisobutene isomer comprising the substructure [ka] During the ceremony, "Poly" refers to the polyisobutene polymer backbone excluding the final incorporated isobutene unit.

[0021] In contrast, the term isomers containing an "α double bond" refers to polyisobutene isomers that comprise the substructure. [ka]

[0022] To prepare such highly reactive polyisobutene compositions, isobutene or an isobutenic starting material is typically polymerized in the presence of at least one Lewis acid-donor complex and an initiator.

[0023] As the Lewis acid, a metal halide is usually used, and preferably a halide of boron, aluminum, iron, gallium, titanium, zinc, or tin is used.

[0024] 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, the halide being preferably a fluoride or chloride, more preferably a chloride.

[0025] Boron halides, aluminum halides, alkyl aluminum halides, and iron halides are preferred.

[0026] Boron trifluoride, aluminum trichloride, alkylaluminum dichlorides, dialkylaluminum chlorides, and iron trichloride are preferred, with boron trifluoride, aluminum trichloride, and alkylaluminum dichlorides being more preferred, boron trifluoride and aluminum trichloride being most preferred, and boron trifluoride being especially preferred.

[0027] Examples of suitable donor compounds contain at least one oxygen and / or nitrogen atom with at least one lone pair of electrons, preferably at least one oxygen atom with at least one lone pair of electrons, and are very preferably selected from the group consisting of organic compounds with at least one ether functional group, organic compounds with at least one carboxylic ester functional group, organic compounds with at least one aldehyde functional group, organic compounds with at least one keto functional group, and organic compounds with at least one nitrogen-containing heterocycle.

[0028] Only oxygen-containing donor compounds are preferred over nitrogen-containing donor compounds.

[0029] Preferably, the donor is selected from the group consisting of organic compounds comprising at least one ether functional group, organic compounds comprising at least one carboxylic acid ester functional group and organic compounds comprising at least one keto functional group, more preferably from the group consisting of organic compounds comprising at least one ether functional group and organic compounds comprising at least one carboxylic acid ester functional group, and very preferably the donor is an organic compound comprising at least one ether functional group, in particular an organic compound comprising exactly one ether functional group.

[0030] Compounds with 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 even more ether functions, preferably 1 or 2 ether functions, very preferably 1 ether function.

[0031] The mixture of donors may comprise one, two, three, four or even more different compounds, preferably compounds with at least one ether functionality, preferably one or two different compounds, very preferably one compound.

[0032] It may be advantageous to use a mixture of two different donors, in particular two different ethers, see for example WO 2017 / 1140603 for aluminium halide-donor complexes or two different alcohols, see for example WO 13 / 120859 for boron halide-donor complexes.

[0033] In one embodiment of the present invention, alkanol R 1When OH is used in the reaction, 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 contain as donor at least one dihydrocarbyl ether of the general formula R 8 -OR 9 wherein the variable R 8 and R 9 are 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.

[0034] General formula R 8 -OR 9 At least one dihydrocarbyl ether of the formula (I) is selected from the group consisting of ethers R1 -OR 1 or R 1 -OR 1 ' or may be different from such ethers.

[0035] Haloalkyl and haloaryl preferably mean chloroalkyl or bromoalkyl and chloroaryl or bromoaryl, very preferably chloroalkyl and chloroaryl. Particularly preferred are ω-haloalkyl radicals.

[0036] 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.

[0037] Preferred examples of chloroaryl are 2-chlorophenyl, 3-chlorophenyl, and 4-chlorophenyl.

[0038] The dihydrocarbyl ethers referred to 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, which 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- 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.

[0039] Furthermore, difunctional ethers such as dialkoxybenzenes, preferably dimethoxybenzene, very preferably veratrole, and also ethylene glycol dialkyl ethers, preferably ethylene glycol dimethyl ether and ethylene glycol diethyl ether, are preferred.

[0040] Among the dihydrocarbyl ethers mentioned, diethyl ether, 2-chloroethyl ether, diisopropyl ether, di-n-butyl ether and diphenyl ether have proven to be particularly advantageous as donors for 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.

[0041] In a preferred embodiment, dihydrocarbyl ethers with at least one secondary or tertiary dihydrocarbyl group are preferred over dihydrocarbyl groups with only primary groups. An ether with a primary dihydrocarbyl group is an ether in which both dihydrocarbyl groups are bonded to an ether functional group with a primary carbon atom, while an ether with 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.

[0042] For clarity, for example, diisobutyl ether is considered an ether having primary dihydrocarbyl groups because the hydrocarbyl groups are attached through a primary carbon atom rather than a secondary carbon atom of the isobutyl group being bonded to an oxygen of a functional ether group.

[0043] Preferred examples of ethers having primary dihydrocarbyl groups are diethyl ether, di-n-butyl ether, and di-n-propyl ether.

[0044] 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.

[0045] Furthermore, it has been found that particularly advantageous dihydrocarbyl ethers as donors for boron trihalide donor complexes, aluminum trihalide donor complexes or alkylaluminum halide complexes are those in which the donor compound has a total carbon number of 3 to 16, preferably 4 to 16, in particular 4 to 12, particularly 4 to 8.

[0046] In another preferred embodiment, the halide substituted ether is preferably in combination with an aluminum halide-donor complex, or an iron halide-donor complex, or a boron halide-donor complex.

[0047] The organic compound having at least one carboxylic acid ester functional group is preferably represented by the general formula R 10 -COOR 11 wherein 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.

[0048] Examples of the hydrocarbyl carboxylates 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 ... Among the hydrocarbyl carboxylates mentioned, ethyl cyclohexane carboxylate, n-propyl cyclohexane carboxylate, isopropyl cyclohexane carboxylate, n-butyl cyclohexane carboxylate, sec-butyl cyclohexane carboxylate, isobutyl cyclohexane carboxylate, tert-butyl cyclohexane carboxylate, 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 hydrocarbyl carboxylates mentioned, ethyl acetate has proven to be particularly advantageous as donor for the complex.

[0049] Furthermore, 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, especially 4 to 12, and specifically 4 to 8, and specifically those having a total of 3 to 10, especially 4 to 6 carbon atoms are preferred.

[0050] 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.

[0051] 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 mentioned above) and is very preferably selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde and benzaldehyde.

[0052] 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 mentioned above) and is 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.

[0053] 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 one, two or three ring nitrogen atoms and may have one or two further ring heteroatoms from the group of oxygen and sulfur, and / or hydrocarbyl radicals, in particular C1-C4 alkyl radicals, and / or phenyl, and / or functional groups or heteroatoms as substituents, in particular 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.

[0054] However, very particularly preferred nitrogen-containing basic compounds of this type are pyridine or derivatives of pyridine (in particular 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-methylpyridine, 2,4-, 2,5-, 2,6- or 3,5-di-tert-butylpyridine or 2-, 3- or 4-phenylpyridine.

[0055] The molar ratio of the mentioned donor compound to the Lewis acid, preferably a boron halide or an aluminum trihalide, or an alkylaluminum halide, in particular a boron fluoride or an aluminum trichloride, in the donor complex usually varies within the range of 0.3:1 to 1.5:1, in particular 0.5:1 to 1.2:1, in particular 0.7:1 to 1.1:1, and in most cases it is 1:1.

[0056] Initiator: The polymerization is preferably carried out by further 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, i.e. one, two or more hydroxyl groups or halogen atoms may be present in the molecule of the initiator, which initiate the polymerization reaction. 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.

[0057] Organic hydroxyl compounds which have only one hydroxyl group in the molecule and are suitable as monofunctional initiators include, in particular, alcohols and phenols, in particular those of the general formula R 12 -OH, wherein 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. 12 The radicals may also contain mixtures of the above mentioned structures and / or have other functional groups than those already mentioned, such as keto functions, nitroxide or carboxyl groups, and / or heterocyclic structural elements.

[0058] 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) ... 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-9- ol, 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 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.

[0059] In a preferred embodiment, a mixture of primary and secondary alcohols can be used as initiators, as described in WO 2013 / 120859.

[0060] In one preferred embodiment of the present invention, alkanol R is used as the initiator in the polymerization. 1 OH is used.

[0061] Alkanol R in the reaction mixture 1 The amount of OH is usually determined by the alkanol R 1 The molar ratio of OH:isobutene is 0.00025 to 0.0025:1, preferably 0.0004 to 0.002:1, more preferably 0.0005 to 0.001:1, and further more preferably 0.0006 to 0.0009:1.

[0062] Alkanol R 1 The molar ratio of OH:Lewis acid is from 1 to 2:1, preferably from 1.1 to 1.9:1, more preferably from 1.2 to 1.8:1, particularly preferably from 1.25 to 1.75:1.

[0063] 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, in particular 3 to 24, in particular 4 to 20, and bisphenols having a total carbon number of 6 to 30, in particular 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.

[0064] Organic halogen compounds having one halogen atom in the molecule and suitable as monofunctional initiators are in particular those of the general formula R 13 -Hal, where Hal is a halogen atom selected from fluorine, iodine and 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 Arylalkyl radicals. 13 The radicals may also contain mixtures of the above mentioned structures and / or have other functional groups than those already mentioned, such as keto functions, nitroxide or carboxyl groups, and / or heterocyclic structural elements.

[0065] 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.

[0066] Examples of organic halogen compounds having two halogen atoms in the molecule and suitable as bifunctional initiators 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).

[0067] 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, in which one or more hydroxyl groups are each bonded to a sp 3 Particularly preferred are initiators selected from organic hydroxyl compounds bonded to hybridized carbon atoms.

[0068] In the case of organic halogen compounds as initiators, it is further preferred that one or more halogen atoms are each secondary or, in particular, tertiary sp 3 Those attached to hybridized carbon atoms are particularly preferred.

[0069] In particular, these sp 3 On the hybridized carbon atom, in addition to the hydroxyl group, R 12 , R 13 , and R 14 radicals, each of which independently represents hydrogen, C1-C 20 Alkyl, C5-C8 cycloalkyl, C6-C 20 Aryl, C7-C 20 alkylaryl or phenyl, where either aromatic ring 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, where the variable R 12 , R 13 , and R 14 At most one of the variables is hydrogen, and the variable R 12 , R 13 , and R 14 is preferably an initiator in which at least one of the phenyl groups is phenyl, which may also have one or more, preferably one or two, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl, or C1-C4 haloalkyl radicals as substituents.

[0070] In 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 (cumyl chloride), tert-butyl chloride, and 1,3- or 1,4-bis(1-hydroxy-1-methylethyl)benzene are very particularly preferred. Among them, 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.

[0071] Water is particularly preferred.

[0072] 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, in particular "raffinate 1", C4 fractions obtained from the dehydrogenation of isobutane, C4 fractions obtained from steam crackers and FCC crackers (fluid catalyzed 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-based 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 generally 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 of the mentioned C4 hydrocarbon stream is in the range of 40-60% by weight. For example, raffinate 1 generally consists essentially of 30%-50% by weight isobutene, 10%-50% by weight 1-butene, 10%-40% by weight cis- and trans-2-butene, and 2%-35% by weight butane, and in the polymerization process of the present invention, the non-branched butenes in raffinate 1 generally behave substantially inertly, and only isobutene is polymerized.

[0073] 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, in particular 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 obtained from an FCC refinery unit, a product stream obtained from propylene-isobutane cooxidation, or a product stream obtained from a metathesis unit.

[0074] In particular, the use of water as the sole initiator or as an additional initiator has proven useful when the Raffinate 1 stream is used as an isobutene source, in particular when the polymerization is effected at temperatures of -20° C. to +30° C., in particular 0° C. to +20° C. However, at temperatures of -20° C. to +30° C., in particular 0° C. to +20° C., it is also possible to dispense with the use of an initiator when the Raffinate 1 stream is used as an isobutene source.

[0075] The mentioned isobutene-based monomer mixtures may contain small amounts of impurities, such as water, carboxylic acids, or mineral acids, without any significant loss of yield or selectivity. It is expedient to prevent the concentration of these impurities by removing such harmful substances from the isobutene-based monomer mixture, for example by adsorption on solid adsorbents, such as activated carbon, molecular sieves, or ion exchangers.

[0076] It is also possible to convert a monomer mixture of isobutene or an isobutene-based hydrocarbon mixture together 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.

[0077] Useful copolymerizable monomers include vinyl aromatic compounds such as styrene and α-methylstyrene, C1-C4-alkylstyrenes such as 2-, 3- and 4-methylstyrene, and 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.

[0078] When the process of the present invention is used to prepare copolymers, the process may be configured to preferentially form random polymers or to preferentially form block copolymers. To prepare block copolymers, for example, different monomers can be fed to the polymerization reaction in succession, in which case the second comonomer is not added until the first comonomer has already been at least partially polymerized. In this way, diblock, triblock and higher block copolymers can be obtained, which have blocks of one or the other comonomer as terminal blocks, depending on the order of addition of the monomers. However, in some cases, block copolymers can also be formed when all comonomers are fed to the polymerization reaction simultaneously, but one of them polymerizes significantly more quickly than the other. This is especially true when isobutene and vinyl aromatic compounds, especially styrene, are copolymerized during the process of the present invention. This results in the formation of block copolymers, preferably with terminal polystyrene blocks. This is due to the fact that vinyl aromatic compounds, especially styrene, polymerize significantly slower than isobutene.

[0079] The polymerization can be accomplished either continuously or batchwise. A continuous process can be carried out similarly to known prior art processes for the continuous polymerization of isobutene in the presence of a boron trifluoride-based catalyst in the liquid phase.

[0080] The process of the invention is suitable either 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 of the invention is preferably carried out at relatively low temperatures, typically from -70°C to -10°C, in particular from -60°C to -15°C.

[0081] When polymerization in the process of the present invention is effected at or above the boiling point of the monomer or mixture of monomers to be polymerized, it is preferably carried out in a pressure vessel, such as an autoclave or pressure reactor.

[0082] The polymerization of the present process can be carried out in the presence of an inert diluent. The inert diluent used should generally be suitable for reducing the increase in viscosity of the reaction solution occurring during the polymerization reaction to an extent that the removal of the heat of reaction released can be guaranteed. Suitable diluents are solvents or solvent mixtures that are inert to the reagents used. Suitable diluents are, for example, aliphatic hydrocarbons such as n-butane, n-pentane, n-hexane, n-heptane, n-octane and isooctane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons, in particular halogenated aliphatic hydrocarbons such as methyl chloride, dichloromethane and trichloromethane (chloroform), 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane and 1-chlorobutane, as well as halogenated aromatic hydrocarbons and alkyl aromatic compounds halogenated in the alkyl side chain, such as chlorobenzene, monofluoromethylbenzene, difluoromethylbenzene and trifluoromethylbenzene, and mixtures of the aforementioned diluents. The diluents used, or the components used in the solvent mixtures mentioned, are also inert components of the isobutene-based C4 hydrocarbon stream. Non-halogenated solvents are preferred over the halogenated solvents listed.

[0083] The polymerization can be carried out in a halogenated hydrocarbon, in particular a halogenated aliphatic hydrocarbon, as an inert diluent, or a mixture of halogenated hydrocarbons, in particular halogenated aliphatic hydrocarbons, or a mixture of at least one halogenated hydrocarbon, in particular a halogenated aliphatic hydrocarbon, with at least one aliphatic, cycloaliphatic or aromatic hydrocarbon, for example a mixture of dichloromethane and n-hexane, typically in a volume ratio of 10:90 to 90:10, in particular 50:50 to 85:15. It is preferable to remove impurities, such as water, carboxylic acids or mineral acids, from the diluent before use, for example by adsorption on a solid adsorbent, for example activated carbon, molecular sieves or ion exchangers. In a preferred embodiment, the polymerization is carried out in a halogen-free aliphatic or in particular halogen-free aromatic hydrocarbon, in particular toluene. In the case of this embodiment, water as initiator in combination with the mentioned organic hydroxyl compounds and / or the mentioned organic halogen compounds, or in particular alone, has proven to be particularly advantageous.

[0084] In another preferred embodiment, the polymerization is carried out in a halogen-free aliphatic or cycloaliphatic, preferably aliphatic, hydrocarbon, especially hexane, pentane, heptane, cyclohexane, cyclopentane, and mixtures containing thereof.

[0085] The polymerization is preferably carried out under substantially aprotic conditions, in particular under 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, as a rule, the raw materials are dried before use by physical and / or chemical means. More specifically, it has been found useful to mix the aliphatic or cycloaliphatic hydrocarbons used as solvents after conventional pre-purification and pre-drying with organometallic compounds, such as organolithium, organomagnesium or organoaluminum compounds, in an amount sufficient to substantially remove traces of water from the solvent. The solvent thus treated is then preferably concentrated directly into the reaction vessel. The monomers to be polymerized, in particular isobutene or isobutene-based mixtures, can also proceed 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. From halogenated solvents that cannot be dried by metals, such as sodium or potassium, or metal alkyls, water or traces of water are removed by drying agents suitable for the purpose, such as calcium chloride, phosphorus pentoxide, or molecular sieves. Similarly, raw materials that cannot be treated with metal alkyls, such as vinyl aromatic compounds, can also be dried in a similar manner. Even if the initiator used is partially or entirely water, it is desirable to very largely or completely remove residual moisture from the solvent and monomers, preferably by drying before reaction, in order to enable the water initiator to be used in a controlled and specific amount, which results in a higher process controllability and a higher reproducibility of results.

[0086] The polymerization reaction is suitably stopped 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.

[0087] After removal of unreacted C4 monomers, the crude polymerization product is typically washed repeatedly with distilled or deionized water to remove sticky inorganic components. To achieve high purity or to remove undesirable low and / or high molecular weight fractions, the polymerization reaction mixture may be fractionally distilled under reduced pressure.

[0088] The polyisobutene composition thus obtainable may have a content of polyisobutene species having an α-double bond of at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, even more preferably at least 80 mol%, in particular at least 90 mol%.

[0089] It is also possible to use the reaction mixture resulting from the polymerization after deactivation of the catalyst and, optionally, after removal of hydrolysis products by washing with maleic anhydride without further purification during the reaction. In addition to the polyisobutene composition with a content of at least 50 mol % of polyisobutene species having an α-double bond, such a reaction mixture may contain unreacted monomers and lower oligomers of isobutene.

[0090] The undistilled reaction mixture differs from the polyisobutene composition insofar as it additionally contains isobutene and those lower oligomers of isobutene which are normally separated from the reaction mixture by distillation.

[0091] These lower oligomers of isobutene can be diisobutene, triisobutene, tetraisobutene, pentaisobutene, hexaisobutene, heptaisobutene, and octaisobutene. The higher oligomers of isobutene are not very volatile under distillation conditions, even under reduced pressure, and therefore typically remain in the polyisobutene composition.

[0092] The content of unreacted isobutene may be at most 40% by weight, preferably at most 30% by weight, more preferably at most 20% by weight.

[0093] The content of said unreacted lower oligomers may be at most 5% by weight, preferably at most 3% by weight.

[0094] The distribution of α and β double bond isomers among the oligomers is usually comparable, and preferably the same, as that of the polymer mixture.

[0095] In one embodiment of the present application, the formula PIB-OR 1 The highly reactive polyisobutene containing one or more ethers of at least one alkanol R 1 The at least one ether is obtained by polymerization of an isobutene-containing reaction mixture with at least one Lewis acid in the presence of OH. Optionally, the at least one ether may additionally be represented by the substructure R 1 It may be used with or without -O-, and preferably the substructure R 1 It may be used containing -O-.

[0096] In another embodiment of the present application, the formula PIB-OR 1 The highly reactive polyisobutenes containing one or more ethers of the substructure R 1 The ethers R are obtained by polymerization of an isobutene-containing reaction mixture with at least one Lewis acid in the presence of at least one ether containing -O-. 1 -OR 1 Or Ether R 1 -OR 1 ' is preferred, in which R 1 ' is R 1 has the same meaning as, but the residue R 1 Optionally, the polymerization is different from at least one alkanol R 1 It may be carried out in the presence of OH.

[0097] Alkanol R 1 OH and / or Ether R 1 -OR 1 Or R 1 -OR 1' is used in part to form a donor complex with the Lewis acid used. See the molar ratios disclosed above. The excess alkanol R that is not used to form the donor complex 1 OH and / or Ether R 1 -OR 1 Or R 1 -OR 1 ' is incorporated into the polyisobutene chain and has the formula PIB-OR 1 forms an ether of

[0098] Therefore, alkanol R 1 OH and / or Ether R 1 -OR 1 Or R 1 -OR 1 The higher the content of ', the more commonly used the ether PIB-OR 1 The content increases.

[0099] In contrast, Alkanol R 1 OH and / or Ether R 1 -OR 1 Or R 1 -OR 1 The lower ' content is usually ether PIB-OR 1 The content of decreases.

[0100] Alkanol R 1 The OH may also be a mixture of alkanols, and the ether may also be an ether R 1 -OR 1 or R 1 -OR 1 It may be a mixture of.

[0101] Usually, methanol or methyl ether is used as the alkanol R 1 OH or Ether R 1 -OR 1 Or R 1 -OR 1 ' and exhibits the highest reactivity and incorporation into the polyisobutene chain.

[0102] Ether PIB-OR 1 The reaction conditions with respect to reaction temperature or reaction time to form are the same as those outlined above for the polymerization of isobutene.

[0103] The short reaction time is usually 1 is favorable for reducing the content, while a long reaction time results in an increase in the content.

[0104] In the case of the thermal ene reaction with maleic anhydride, it is also possible to use a solution of the polyisobutene composition in at least one of the above-mentioned solvents, or it is also possible to use the polyisobutene composition undiluted. In a preferred embodiment, a 10-90% by weight solution of the polyisobutene composition in a solvent, preferably a 15-60% by weight solution, more preferably a 20-50% by weight solution, in particular a 25-40% by weight solution in a solvent, preferably a halide-free solvent, is used for the thermal ene reaction with maleic anhydride.

[0105] In one embodiment, the solvent may be an inert component of an isobutene-based C4 hydrocarbon stream.

[0106] After being subjected to the thermal ene reaction with maleic anhydride, the solvent in the reaction mixture is preferably removed, more preferably by distillation.

[0107] Usually, a single-step evaporation without a rectification apparatus is sufficient, which can be achieved 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, or a paddle dryer, e.g. a Discotherm® dryer from List Technology AG (Switzerland), or a combination of these devices.

[0108] The distillation is as a rule effected at 80-320° C., preferably 100-300° C., and at 0.1-40 mbar, preferably 0.5-20 mbar.

[0109] The distillation may be assisted by introducing an inert stripping, preferably nitrogen, into the evaporator.

[0110] By this distillation and optional stripping process, polyisobutene can be obtained with a significantly reduced amount of solvent and monomer, even when n-hexane is used as a solvent. Therefore, it is possible to reduce the n-hexane content in the composition to 1000 ppm by weight or less, preferably 900 ppm by weight or less, more preferably 800 ppm by weight or less, particularly 750 ppm by weight or less, and at the same time reduce the isobutene content to 30 ppm by weight or less, preferably 25 ppm by weight or less, more preferably 20 ppm by weight or less, particularly 15 ppm by weight or less.

[0111] The amounts of isomers given throughout this document refer to mole % unless otherwise specified. The determination of single isomers or groups of isomers is performed by NMR analysis, and the result of such NMR analysis is the percentage distribution of the specific NMR signals of these isomers relative to the integrals of the corresponding nuclei determined.

[0112] Component contents in mole percent can be easily converted to weight percent by multiplying by the molecular weight of the corresponding species. Since all isomers have the same molecular weight, the mole percent and weight percent of an isomer are the same.

[0113] The number average molecular weight M of the polyisobutene composition n (as determined by gel permeation chromatography) is 500-10000, preferably 550-5000, more preferably 750-3000, most preferably 900-2500, especially 900-1100.

[0114] In the case of the thermal ene reaction with maleic anhydride, a stoichiometric molar ratio of 0.6 moles maleic anhydride:1 mole polyisobutene or more is used, preferably 0.8 moles maleic anhydride or more per mole polyisobutene, more preferably at least 1 mole maleic anhydride per mole polyisobutene, even more preferably at least 1.1:1, especially 1.2:1.

[0115] Since a large amount of excess maleic anhydride will increase the bis- or higher maleated products, a stoichiometric molar ratio of 10 moles maleic anhydride:1 mole polyisobutene is usually not exceeded, preferably at most 7.5:1, more preferably at most 5:1, even more preferably at most 4:1, and especially at most 3:1, unless more highly bis-maleated products are desired or tolerated.

[0116] The thermal ene reaction is carried out at a temperature of 150 to 260°C, preferably 175 to 250°C, and more preferably 190 to 240°C.

[0117] The reaction time is between 15 minutes and 10 hours, preferably between 30 minutes and 9 hours, more preferably between 1 and 8 hours, even more preferably between 2 and 7 hours, in particular between 3 and 6 hours. Of course, the reaction time depends on the temperature applied to the reaction mixture.

[0118] Efforts are made to achieve a conversion of at least 75%, preferably at least 80%, more preferably at least 85%, most preferably at least 90%, particularly at least 95%, or even at least 98% of the minor compound in the reaction mixture.

[0119] As noted above, the reaction is preferably carried out in solution, although it can less preferably be carried out neat.

[0120] In addition to the above solvents, high boiling point hydrocarbons can also be preferably used as the solvent.

[0121] Examples of such high-boiling hydrocarbons are, for example, non-polar organic solvents, such as aromatic and aliphatic hydrocarbons, for example toluene, xylene, white spirit, and products sold under the trade names SHELLSOL (Royal Dutch / Shell Group), Solvesso, and EXXSOL (ExxonMobil). If a solvent is used, the boiling point or boiling range should be selected higher than the reaction temperature mentioned above. Alternatively, but less preferred, the reaction may be carried out under pressure, for example at a pressure of up to 20 bar, preferably at a pressure of up to 10 bar, more preferably at a pressure of up to 5 bar, even more preferably at a pressure of up to 2 bar. The removal of volatile compounds or reaction products may be preferably assisted by applying a reduced pressure, for example up to 500 mbar, preferably 200, more preferably 100, even more preferably 50, in particular 20 mbar. The removal of volatile compounds may be further assisted by stripping with an inert gas stream.

[0122] Removal of volatile compounds from the reaction mixture also includes excess maleic anhydride, if present. Typically, the content of free unreacted maleic anhydride in the reaction mixture is 5% by weight or less, preferably 2.5% by weight or less, even more preferably 1% by weight or less, in particular 0.5% by weight or less.

[0123] In a preferred embodiment, the reaction is carried out under an inert atmosphere, preferably nitrogen, argon, carbon dioxide, or oxygen-depleted air, especially nitrogen.

[0124] The advantage of the present invention is that the ether PIB-OR 1 The maleation of the polyisobutenes of the present invention, which contain

[0125] Another object of the present invention is therefore to provide a method for the preparation of a polyisobutene having a major amount of highly reactive polyisobutene with a content of α-double bonds of at least 50 mol % and a minor amount of a polyisobutene having the formula PIB-OR 1 and one or more ethers of During the ceremony, PIB represents a polyisobutene residue; R 1 is C1~C 10 is alkyl, A mixture containing 0.8% by weight or more of ether.

[0126] Another subject of the invention is the use of such mixtures in reaction with maleic anhydride to prepare polyisobutene succinic anhydride. EXAMPLES

[0127] Process for producing highly reactive polyisobutene (HR PIB) Examples 1-4 following Table 1 were carried out in a continuous polymerization apparatus consisting of a loop reactor, a mixing pump, a raw material inlet, a circulation unit for hexane, and a quench / separation vessel. The polymerization mixture was quenched with hot water after leaving the reaction vessel. The amount of hot water was chosen so that the mixed temperature of the two phases was about 20°C. This had already evaporated part of the solvent (unreacted C4 hydrocarbons). After a residence time of about 20 minutes to allow the two phases to settle, the top (organic phase) was removed and the product sample was stripped of residual solvent in a rotary evaporator for analysis. Analysis of the obtained polymers was carried out via 1H NMR and GPC. The vinylidene content represents the content of =CH2- groups in polyisobutene determined by 1H NMR.

[0128] The ether content was determined by 1H NMR. 1 The multiplicity of signals was determined from the integrals of the corresponding hydrogens (usually in the range of δ = 3.0-3.5 (CDCl3)). 1 See FIG. 1.

[0129] Manufacturing process of polyisobutene succinic anhydride (PIBSA) from HR PIB1000 Polyisobutene succinic anhydride was synthesized in a steel pressure reactor under nitrogen atmosphere. The reactor was charged with highly reactive polyisobutene (1 equiv.) and then volatiles were removed under reduced pressure at 140°C. Maleic anhydride (MSA, 1.1 equiv.) was then added to the reactor and the temperature was increased to 215°C. After 5 hours, the reactor was cooled to 100°C and filtered through a pressure nutsche. Excess MSA was removed by distillation at 180°C and then the pressure was reduced. PIBSA yield was determined by column chromatography.

[0130] [Table 1]

[0131] The PIB ether content in weight percent is approximately the same as that in mole percent shown in the table, therefore Example 5 is in accordance with the invention and Example 6 is a comparative example.

[0132] Production process of polyisobutene succinic anhydride from HR PIB 2300 Polyisobutene succinic anhydride was synthesized in a steel pressure reactor under nitrogen atmosphere. The reactor was charged with polyisobutene (1 eq.) and then volatiles were removed under reduced pressure at 140°C. Maleic anhydride (MSA, 1.3 eq.) was then added to the reactor and the temperature was increased to 225°C. After 5 hours, the reactor was cooled to 100°C and filtered through a pressure nutsche. Excess MSA was removed by distillation at 200°C and then the pressure was reduced. PIBSA yield was determined by column chromatography.

[0133] [Table 2]

[0134] The PIB ether content in weight percent is approximately the same as that in mole percent shown in the table, therefore Example 7 is in accordance with the invention and Example 8 is a comparative example.

[0135] It can be readily seen that the maleation yield increases with increasing ether content, regardless of the molecular weight of the polyisobutene used.

[0136] [Table 3]

[0137] Abbreviation: MeOH Methanol iPrOH Isopropanol MTBE Methyl tert-butyl ether tBuOH tert-butanol IB Isobutene PIB Polyisobutene

Claims

1. A process for preparing polyisobutene succinic anhydride by reacting highly reactive polyisobutene having an α-double bond content of at least 50 mol% (measured by ¹H NMR spectroscopy) with maleic anhydride at a temperature of 150-260°C for 15 minutes to a maximum of 10 hours in a stoichiometric molar ratio of 0.6 mol maleic anhydride:1 mol polyisobutene or more, wherein the highly reactive polyisobutene is present in an amount of 0.8% by weight or more (measured by ¹H NMR spectroscopy) and is given by formula: PIB-O-R １ Having one or more ethers, During the ceremony, PIB represents a residue derived from polyisobutene, R １ is C １ ~C １０ A process characterized by being alkyl.

2. The process according to claim 1, characterized in that the highly reactive polyisobutene has an α-double bond content of at least 60 mol%.

3. The process according to claim 1, characterized in that the highly reactive polyisobutene has an α-double bond content of at least 70 mol%.

4. The process according to any one of claims 1 to 3, characterized in that the maleic anhydride is applied in a molar ratio of 1 or more per mole of polyisobutene.

5. The process according to any one of claims 1 to 3, characterized in that the maleic anhydride is applied in a molar ratio of 1.2 to 3 per mole of polyisobutene.

6. The process according to any one of claims 1 to 3, characterized in that the reaction temperature is 175°C to 250°C.

7. The process according to any one of claims 1 to 3, characterized in that the reaction is carried out under an inert atmosphere.

8. The process according to any one of claims 1 to 3, characterized in that the reaction is carried out in the absence of a solvent.

9. In the first step, the formula PIB-O-R １ Under reaction conditions such that a polyisobutene with an ether content of at least 0.8% by weight is obtained, at least one alkanol R １ Polymerization of an isobutene-containing reaction in the presence of at least one Lewis acid in the presence of OH, In the second step, the unreacted components of the reaction mixture are separated from the polyisobutene-containing product, In the third step, the ether-containing polyisobutene thus obtained is reacted with maleic anhydride, The process according to any one of claims 1 to 3, characterized by the following:

10. The process according to claim 9, wherein the Lewis acid is selected from the group consisting of boron halides, aluminum halides, alkylaluminum halides, and iron halides.

11. The aforementioned Alkanol R １ The process according to claim 9, wherein the OH group is selected from the group consisting of methanol, ethanol, isopropanol, sec-butanol, and tert-butanol, or mixtures thereof.

12. The polymerization in the first step is alkanol R １ The process according to claim 9, carried out with a molar ratio of OH to Lewis acid of 1 to 2:

1.

13. The polymerization in the first step is carried out with an alkanol R １ OH:isobutene molar ratio of 0.00025 to 0.0025:1, the process according to claim 9.

14. A large amount of highly reactive polyisobutene with an α-double bond content of at least 50 mol%, and a small amount of formula: PIB-O-R １ A mixture comprising one or more ethers, During the ceremony, PIB stands for polyisobutene residue, R １ is C １ ~C １０ It is alkyl, A mixture wherein the ether content is 0.8% by weight or more.

15. R １ However, C １ ~C ４ The mixture according to claim 14, wherein the alkyl group is preferably methyl, ethyl, n-butyl, tert-butyl, or tert-butyl.

16. The mixture according to claim 14 or 15, wherein the ether content is 0.9% by weight to 8.0% by weight.

17. Use of the mixture according to claim 14 or 15 in a reaction with maleic anhydride to prepare polyisobutene succinic anhydride.

Images