Method for preparing highly reactive isobutene homopolymers or copolymers

Abstract

The present invention relates to a novel method for preparing highly reactive isobutene homopolymers or copolymers.

Description

[Technical Field]

[0001] The present invention relates to a novel method for preparing a highly reactive isobutene homopolymer or copolymer having a content of at least 70 mol% terminal vinylidene double bonds per polyisobutene chain end. The present invention further relates to a novel isobutene polymer. [Background technology]

[0002] In contrast to so-called low-reactivity polymers, high-reactivity isobutene homopolymers or copolymers are understood to mean polyisobutenes containing terminal ethylenic double bonds (α-double bonds) and other reactive double bonds, such as β-double bonds, that are sensitive to subsequent reactions, such as the alder-ene reaction with maleic anhydride, in high concentrations, specifically, typically at least 60 mol%, preferably at least 70 mol%, and very preferably at least 75 mol% relative to the individual chain ends of the polyisobutene macromolecule. In the context of this application, the vinylidene group is defined as having a position in the polyisobutene macromolecule that corresponds to the general formula

[0003] [ka] This is understood to mean the terminal ethylenically bond described by, i.e., the double bond is located at the α-position of the polymer chain. "Polymer" refers to the polyisobutene group shortened by one isobutene unit. The vinylidene group exhibits the highest reactivity in many types of reactions, for example, in the thermal addition of sterically bulky reactants, such as maleic anhydride, while the double bond further inside the macromolecule exhibits low reactivity in most cases, even in functionalization reactions. Uses of highly reactive polyisobutene include, for example, its use as an intermediate for preparing additives for lubricants and fuels, as described in German Patent No. 2702604.

[0004] Furthermore, aluminum trichloride, a Lewis acid, has also been known for some time to be usable as a polymerization catalyst for isobutene, for example, from High Polymers, Vol. XXIV (Part 2), pp. 713-733 (edited by Edward C. Leonard), J. Wiley & Sons, New York, 1971.

[0005] The paper "Novel initiating system based on AlCl3 etherate for quasiliving cationic polymerization of styrene" by Sergei V. Kostjuk et al., published in Polymer Bulletin Vol. 52, pp. 227-234 (2004), describes a catalyst system for styrene polymerization consisting of 2-phenyl-2-propanol and an aluminum trichloride / di-n-butyl ether complex. Sergei V. Kostjuk et al., Macromolecules 2010, 43, 5503-5507, describes the polymerization of isobutene with a complex of AlCl3 and dibutylene ether to obtain highly reactive polyisobutene.

[0006] Dmitriy I. Shiman, Irina V. Vasilenko, and Sergei V. Kostjuk disclose the preparation of polyisobutene polymers by polymerization of isobutene in the presence of alkylaluminum halides and ether complexes as polymerization catalysts in the Journal of Polymer Science, Part A: Polymer Chemistry 2014, 52, 2386-2393.

[0007] International Publication No. 18 / 015306 discloses a method for preparing a highly reactive isobutene homopolymer or copolymer, in which a certain Lewis acid is used together with at least one donor and at least one ionic liquid.

[0008] Examples of such ionic liquids disclosed in International Publication No. 18 / 015306 are, in particular, phosphorescent compounds in which the cation is a permanent quaternary phosphonium salt.

[0009] However, the drawbacks of such ionic liquids are that they are expensive to prepare and dramatically reduce the reactivity of the Lewis acid used.

[0010] Kostjuk et al., Polym. Chem., 2016, 7, 5615-5619 and Polymer, 145(2018) 382-390, further point out that ionic liquids as catalysts for isobutene polymerization require considerably long reaction times to achieve moderate to high conversion rates of monomers. Figure 2 shows a figure excerpted from the latter document, which shows the conversion rate of isobutene and the exoselectivity of the reaction in the presence of [emim]Cl-AlCl3(1), [emim]Cl-FeCl3(2), and [emim]Cl-GaCl3(3) as a function of reaction time.

[0011] Chinese Patent Application Publication No. 102399308 (machine translation) discloses cationic polymerization of isobutene as a monomer in an emulsion using aluminum trichloride and triphenylphosphine oxide as catalysts. Sorbitol monooleate is used as an emulsifier in the polymerization mixture.

[0012] Information regarding the double bond content was not available, and only polyisobutene with a high molecular weight of 240,000 was obtained. [Overview of the project] [Problems that the invention aims to solve]

[0013] The object of the present invention was to provide a method for preparing highly reactive isobutene homopolymers or copolymers having an increased content of at least 60 mol% of terminal vinylidene double bonds (α-double bonds) and β-double bonds per polyisobutene chain end, in an acceptable yield and high reaction rate. The catalyst system must have sufficient activity and sufficient lifetime, and its preparation must be simple. A further object of the present invention is to develop a catalyst system that yields a high conversion rate and maintains the selectivity of reactive double bonds, particularly α-double bonds, even at high conversion rates. [Means for solving the problem]

[0014] The objective is to provide a method for preparing a highly reactive isobutene homopolymer or copolymer having a total content of α-double bonds and β-double bonds of at least 60 mol%, preferably at least 70 mol%, and very preferably at least 75 mol% per polyisobutene chain terminus, comprising polymerizing isobutene or an isobutene-containing monomer mixture in the presence of at least one Lewis acid effective as a polymerization catalyst, wherein the Lewis acid is selected from the group consisting of aluminum trihalide-donor complexes, alkylaluminum halide-donor complexes, iron trihalide-donor complexes, gallium trihalide-donor complexes, titanium tetrahalide-donor complexes, zinc dihalide-donor complexes, tin dihalide-donor complexes, tin tetrahalide-donor complexes, and boron trihalide-donor complexes, and the complex is used as a donor. - At least one organic compound (II) selected from the group consisting of an organic compound having at least one oxygen 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 at least one ether functional group, an organic compound having at least one carboxylic acid ester functional group, an organic compound having at least one aldehyde functional group, an organic compound having at least one keto functional group, and an organic compound having at least one nitrogen-containing heterocycle, and - Equation (I)

[0015] [Chemical formula] or formula (Ia) P(OR 1 )(OR 2 )(OR 3 ) or formula (Ib) P(OR 1 (OR 2 (OR 3 (OR 4 (OR 5 ) [[ID=...]] (wherein, X1, X2 and X3 are, independently of one another, oxygen, sulfur or a single bond, preferably oxygen or a single bond, very preferably a single bond, R 1 、R 2 、R 3 、R 4 and R 5 are, independently of one another, organic residues having up to 20 carbon atoms) at least one phosphorus-containing compound contains a mixture of provided that the complex formed from at least one Lewis acid and at least one phosphorus-containing compound of formula (I) or (Ia) or (Ib) has a melting point of 60 °C or lower, preferably 40 °C or lower, especially 20 °C or lower, is achieved by a method

[0016] R 1 、R 2 、R 3 、R 4 and R 5 are each, independently of one another, C1-C 20 alkyl, C2-C 20 alkyl interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, C6-C 12 aryl, C5-C 12 It should be noted that there are some unclear parts in the original text (such as the incomplete "C1-C ", "C2-C ", etc. in the later part), and the translation is done as accurately as possible based on the existing content.The group is a cycloalkyl group or a five- or six-membered heterocycle containing oxygen, nitrogen, and / or sulfur, or two of these groups together form an unsaturated, saturated, or aromatic ring which may be interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, and each of the groups referred to may be substituted with the functional groups aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatom, and / or heterocycle, respectively. The complex formed from at least one Lewis acid and at least one phosphorus-containing compound of formula (I) or (Ia) or (Ib) is a liquid under these conditions, and is therefore also called a “liquid coordination complex” or “LCC”. [Brief explanation of the drawing]

[0017] [Figure 1] This graph shows a typical 1H NMR spectrum. [Figure 2] This graph, extracted from the Polymer, 145(2018)382-390 document, shows the conversion rate of isobutene and the exoselectivity of the reaction in the presence of [emim]Cl-AlCl3(1), [emim]Cl-FeCl3(2), and [emim]Cl-GaCl3(3) as a function of reaction time. [Figure 3] This graph shows the reaction results in Example 5. [Modes for carrying out the invention]

[0018] JM Hogg, LC Brown, K. Matuszek, P. Latos, A. Chrobok, and M. Swadzba-Kwasny, Dalton Transaction, 2017, 46, 11561, reported the successful synthesis and liquid state at room temperature of complexes formed from tri-n-octylphosphine oxide with AlCl3 and TiCl4, respectively. However, only the Diels-Alder reaction of these complexes is disclosed, and the polymerization of isobutene remains unclear.

[0019] In these definitions, C1-C may be substituted with functional groups such as aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatom and / or heterocycle. 20Alkyls include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, eicosyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, benzhydryl, p-tolylmeth 1-(p-butylphenyl)ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxy(m-ethoxy)benzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di-(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxy San-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydro Hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, or 6-ethoxyhexyl, C2-C2 is interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups. 20 Alkyls include, for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5-oxanonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxaoctyl, 11-methoxy-3,6,9-trioxaundecyl, 7-methoxy-4-oxaheptyl These are 11-methoxy-4,8-dioxaundecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy-3-oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 11-ethoxy-4,8-dioxaundecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl, or 14-ethoxy-5,10-oxatetradecyl.

[0020] If the two groups form a ring, they may together be 1,3-propylene, 1,4-butylene, 1,5-pentylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propenylene, 1-aza-1,3-propenylene, 1-C1~C4 alkyl-1-aza-1,3-propenylene, 1,4-buta-1,3-dienylene, 1-aza-1,4-buta-1,3-dienylene, or 2-aza-1,4-buta-1,3-dienylene.

[0021] The number of oxygen and / or sulfur atoms and / or imino groups is not limited. Generally, there are five or fewer, preferably four or fewer, and very preferably three or fewer in the group.

[0022] Furthermore, generally, at least one carbon atom, preferably two carbon atoms, are present between any two heteroatoms.

[0023] The substituted and unsubstituted imino groups may be, for example, imino, methylimino, isopropylimino, n-butylimino, or tert-butylimino.

[0024] Furthermore, The functional group may be carboxy, carboxamide, hydroxy, di(C1-C4 alkyl)amino, C1-C4 alkyloxycarbonyl, cyano, or C1-C4 alkyloxy. C6-C may be substituted with functional groups such as aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatom and / or heterocycle. 12Aryls include, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl, or ethoxymethylphenyl. C5-C may be substituted with functional groups such as aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatom and / or heterocycle. 12 Cycloalkyls include, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, or saturated or unsaturated bicyclic systems, such as norbornyl or norbornenyl. Examples of five- or six-membered heterocycles containing oxygen, nitrogen, and / or sulfur include furyl, thienyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthienyl, isopropylthienyl, or tert-butylthienyl. C1-C4 alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl.

[0025] R 1 ~R 5 The residues are preferably C2-C 18 Alkyl or C6-C 12 Aryl, more preferably C4~C 16 Alkyl or C6-C 12 Ayl, and more preferably C4~C 16 It is alkyl or C6 aryl.

[0026] R 1 ~R 5 The residue may be saturated or unsaturated, preferably saturated.

[0027] R 1 ~R 5 The residues and X1, X2, and X3 may be the same or different, and in one embodiment of the present invention, they are the same.

[0028] Preferably, R 1 ~R 5 The residue does not contain any heteroatoms other than carbon or hydrogen.

[0029] Preferred compounds of formula (I), (Ia), or (Ib) are tri-n-hexylphosphine oxide, tri-n-octylphosphine oxide (P 888O), triisononylphosphine oxide, tri-n-decylphosphine oxide, tri-n-dodecylphosphine oxide, triisotridecylphosphine oxide, tri-n-tetradecylphosphine oxide, triisoheptadecylphosphine oxide, triphenylphosphine oxide (PPh3O), tritylphosphine oxide, trinaphthylphosphine oxide, tri(n-butyl) phosphate ester, tri(n-hexyl) phosphate ester, tri(2-ethylhexyl) phosphate ester, tri(n-octyl) phosphate ester, tri(2-propylheptyl) phosphate ester, tri(n-decyl) phosphate ester, tri(n-dodecyl) phosphate ester, tri(n-tetradecyl) phosphate ester These include ester, tri(n-hexadecyl) phosphate, tri-ethyl phosphite, tri-n-butyl phosphite, tri-n-hexyl phosphite, tri-n-octyl phosphite, triisononyl phosphite, tri-n-decyl phosphite, tri-n-dodecyl phosphite, triisotridecyl phosphite, tri-n-tetradecyl phosphite, triisoheptadecyl phosphite, triphenyl phosphite, penta(ethoxy)phosphoran, penta(n-butyloxy)phosphoran, penta(hexyloxy)phosphoran, penta(n-octyloxy)phosphoran, penta(2-ethylhexyloxy)phosphoran, and penta(phenoxy)phosphoran.

[0030] Corresponding phosphinite (P(OR 1 )R 2 2) Phosphonite (P(OR 1 )2R 2 ) and phosphonate (OP(OR 1 )2R 2 For example, diethylphenylphosphinite, di-n-butylphenylphosphinite, di(2-ethylhexyl)phenylphosphinite, ethyldiphenylphosphonite, n-butyldiphenylphosphonite, (2-ethylhexyl)diphenylphosphonite, diethylphenylphosphonate, di-n-butylphenylphosphonate, and di(2-ethylhexyl)phenylphosphonate are even more effective.

[0031] In the case of phosphite esters, the alcohol component may be a mixture of fatty acid alcohols derived from fatty acid mixtures that can be industrially obtained from the post-treatment of natural, vegetable, or animal fats and oils, particularly preferably from linseed oil, coconut oil, palm kernel oil, palm oil, soybean oil, peanut oil, cocoa butter, shea butter, cottonseed oil, corn oil, sunflower oil, rapeseed oil, or castor oil, and very preferably from linseed oil, palm oil, soybean oil, peanut oil, cocoa butter, shea butter, cottonseed oil, corn oil, sunflower oil, rapeseed oil, or castor oil.

[0032] Another object of the present invention is at least one iron trihalide, - Optionally (optionally), at least one organic compound (II) selected from the group consisting of an organic compound having at least one oxygen 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 at least one ether functional group, an organic compound having at least one carboxylic acid ester functional group, an organic compound having at least one aldehyde functional group, an organic compound having at least one keto functional group, and an organic compound having at least one nitrogen-containing heterocycle, and - Equation (I)

[0033] [ka] Or formula (Ia) P(OR 1 )(OR 2 )(OR 3 ) Alternatively, formula (Ib) P(OR 1 )(OR 2 )(OR 3 )(OR 4 )(OR 5 ) (In the formula, X1, X2, and X3 are, independently of each other, oxygen, sulfur, or a single bond, preferably oxygen or a single bond, very preferably a single bond. R 1 , R 2 , R 3 , R 4 and R 5 (These are organic residues that have up to 20 carbon atoms, independently of each other.) at least one phosphorus-containing compound It is a trihalide iron-donor complex consisting of [the specified components].

[0034] In one preferred embodiment of this objective of the present invention, compound (II) exists.

[0035] A further embodiment of this object of the present invention is an iron trihalide-donor complex in which the complex formed from at least one iron trihalide and at least one phosphorus-containing compound of formula (I), (Ia), or (Ib) has a melting point of 60°C or lower, preferably 40°C or lower, and particularly 20°C or lower.

[0036] In a further embodiment of this object of the present invention, the molar ratio of iron trihalide, the compound of formula (II), and the compound of formula (I), (Ia), or (Ib) in such an iron trihalide-donor complex is generally 1:0 to 10:0.1 to 10, preferably 1:0.1 to 10:0.2 to 5, and more preferably 1:0.2 to 5:0.3 to 3.

[0037] Another object of the present invention is the use of such iron trihalide donor complexes as catalysts for the polymerization of unsaturated monomers, preferably unsaturated monomers, more preferably ethylenically unsaturated monomers, even more preferably alkenes, and in particular isobutene-containing monomer mixtures.

[0038] Another particularly preferred object of the present invention is at least one boron trihalide, - Depending on the circumstances, at least one organic compound (II) selected from the group consisting of an organic compound having at least one oxygen 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 at least one ether functional group, an organic compound having at least one carboxylic acid ester functional group, an organic compound having at least one aldehyde functional group, an organic compound having at least one keto functional group, and an organic compound having at least one nitrogen-containing heterocycle, and - Equation (I)

[0039] [ka] Or formula (Ia) P(OR 1 )(OR 2 )(OR 3 ) Alternatively, formula (Ib) P(OR 1 )(OR 2 )(OR 3 )(OR 4 )(OR 5 ) (In the formula, X1, X2, and X3 are, independently of each other, oxygen, sulfur, or a single bond, preferably oxygen or a single bond, very preferably a single bond. R 1 , R 2 , R 3 , R 4 and R 5 (These are organic residues that have up to 20 carbon atoms, independently of each other.) at least one phosphorus-containing compound It is a boron trihalide-donor complex consisting of the following.

[0040] In one embodiment of this objective of the present invention, compound (II) exists.

[0041] A further embodiment of this object of the present invention is a boron trihalide-donor complex formed from at least one boron trihalide and at least one phosphorus-containing compound of formula (I), (Ia), or (Ib), having a melting point of 60°C or lower, preferably 40°C or lower, and particularly 20°C or lower.

[0042] In a further embodiment of this object of the present invention, the molar ratio of boron trihalide, the compound of formula (II), and the compound of formula (I), (Ia), or (Ib) in such a boron trihalide-donor complex is generally 1:0 to 10:0.1 to 10, preferably 1:0.1 to 10:0.2 to 5, and more preferably 1:0.2 to 5:0.3 to 3.

[0043] Another object of the present invention is the use of such boron trihalide donor complexes as catalysts for the polymerization of unsaturated monomers, preferably unsaturated monomers, more preferably ethylenically unsaturated monomers, even more preferably alkenes, and in particular isobutene-containing monomer mixtures.

[0044] Another objective of the present invention is, - At least one metal halide selected from the group consisting of aluminum trihalides, alkylaluminum halides, gallium trihalides, titanium tetrahalides, zinc dihalides, tin dihalides, tin tetrahalides, and boron trihalides. - At least one organic compound (II) selected from the group consisting of an organic compound having at least one oxygen 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 at least one ether functional group, an organic compound having at least one carboxylic acid ester functional group, an organic compound having at least one aldehyde functional group, an organic compound having at least one keto functional group, and an organic compound having at least one nitrogen-containing heterocycle, and - Equation (I)

[0045] [ka] Or formula (Ia) P(OR 1 )(OR 2 )(OR 3 ) Alternatively, formula (Ib) P(OR 1 )(OR 2 )(OR 3 )(OR 4 )(OR 5 ) (In the formula, X1, X2, and X3 are, independently of each other, oxygen, sulfur, or a single bond, preferably oxygen or a single bond, very preferably a single bond. R 1 , R 2 , R 3 , R 4 and R 5 (These are organic residues that have up to 20 carbon atoms, independently of each other.) at least one phosphorus-containing compound It is a metal halide-donor complex consisting of [the specified components].

[0046] The metal halide is preferably selected from the group consisting of aluminum trihalides, alkylaluminum halides, titanium tetrahalides, tin tetrahalides, and boron trihalides; more preferably selected from the group consisting of aluminum trihalides, alkylaluminum halides, titanium tetrahalides, and boron trihalides; even more preferably selected from the group consisting of aluminum trihalides, alkylaluminum halides, and boron trihalides; in particular, the metal halide is aluminum trihalides or even more preferably aluminum trichloride.

[0047] A further embodiment of this object of the present invention is a metal halide-donor complex in which the complex formed from at least one metal halide and at least one phosphorus-containing compound of formula (I), (Ia), or (Ib) has a melting point of 60°C or lower, preferably 40°C or lower, and particularly 20°C or lower.

[0048] In a further embodiment of this object of the present invention, the molar ratio of such metal halide, the compound of formula (II), and the compound of formula (I), (Ia), or (Ib) in such metal halide-donor complexes is generally 1:0 to 10:0.1 to 10, preferably 1:0.1 to 10:0.2 to 5, and more preferably 1:0.2 to 5:0.3 to 3.

[0049] Another object of the present invention is the use of such metal halide-donor complexes as catalysts for the polymerization of unsaturated monomers, preferably unsaturated monomers, more preferably ethylenically unsaturated monomers, even more preferably alkenes, and especially for the cationic polymerization of isobutene-containing monomer mixtures.

[0050] In the context of the present invention, isobutene homopolymer is understood to mean a polymer based on a polymer in which at least 98 mol%, preferably at least 99 mol%, isobutene is formed. Therefore, isobutene copolymer is understood to mean a polymer containing less than 2 mol%, preferably less than 1 mol%, very preferably less than 0.7 mol%, and especially less than 0.5 mol%, copolymer monomers other than isobutene, such as isoprene or linear butene, preferably 1-butene, cis-2-butene, and trans-2-butene.

[0051] In the context of this invention, the following definitions apply to the groups collectively defined: C1-C8 alkyl groups are linear or branched alkyl groups having 1 to 8 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, and their structural isomers, such as 2-ethylhexyl. Such C1-C8 alkyl groups may also contain, to a small extent, heteroatoms, such as oxygen, nitrogen, or halogen atoms, such as chlorine, and / or aprotic functional groups, such as carboxyl ester groups, cyano groups, or nitro groups.

[0052] C1~C 20 Alkyl groups are linear or branched alkyl groups having 1 to 20 carbon atoms. Examples include the C1-C8 alkyl groups mentioned above, as well as n-nonyl, isononyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and n-eicosyl. 20 Alkyl groups may also contain, to a small extent, heteroatoms, such as oxygen, nitrogen, or halogen atoms, such as chlorine, and / or aprotic functional groups, such as carboxyl ester groups, cyano groups, or nitro groups.

[0053] The C5-C8 cycloalkyl group is a saturated cyclic group which may contain an alkyl side chain. Examples thereof are cyclopentyl, 2- or 3-methylcyclopentyl, 2,3-, 2,4- or 2,5-dimethylcyclopentyl, cyclohexyl, 2-, 3- or 4-methylcyclohexyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or 3,6-dimethylcyclohexyl, cycloheptyl, 2-, 3- or 4-methylcycloheptyl, cyclooctyl, 2-, 3-, 4- or 5-methylcyclooctyl. Such a C5-C8 cycloalkyl group may also contain, to a small extent, heteroatoms such as oxygen, nitrogen or halogen atoms such as chlorine, and / or aprotic functional groups such as carboxyl ester groups, cyano groups or nitro groups.

[0054] C6-C 20 aryl group or C6-C 12 The aryl group is preferably optionally substituted phenyl, optionally substituted naphthyl, optionally substituted anthracenyl or optionally substituted phenanthrenyl. Such an aryl group has 1 to 5 aprotic substituents or aprotic functional groups such as C1-C8 alkyl, C1-C8 haloalkyl such as C1-C8 chloroalkyl or C1-C8 fluoroalkyl, halogen such as chlorine or fluorine, nitro, cyano or phenyl. Examples of such aryl groups are phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, tolyl, nitrophenyl, chlorophenyl, dichlorophenyl, pentafluorophenyl, pentachlorophenyl, (trifluoromethyl)phenyl, bis(trifluoromethyl)phenyl, (trichloro)methylphenyl and bis(trichloromethyl)phenyl.

[0055] C7-C 20 arylalkyl group or C7-C 12The arylalkyl group is preferably optionally substituted C1-C4 alkylphenyl, such as benzyl, o-, m- or p-methylbenzyl, 1- or 2-phenylethyl, 1-, 2- or 3-phenylpropyl, or 1-, 2-, 3- or 4-phenylbutyl, optionally substituted C1-C4 alkylnaphthyl, such as naphthylmethyl, optionally substituted C1-C4 alkylanthracenyl, such as anthracenylmethyl, or optionally substituted C1-C4 alkylphenantrenyl, such as phenantrenylmethyl. Such arylalkyl groups may have, in particular, 1 to 5 aprotic substituents or aprotic functional groups in the aryl portion, such as C1-C8 alkyl, C1-C8 haloalkyl, such as C1-C8 chloroalkyl, or C1-C8 fluoroalkyl, halogens, such as chlorine or fluorine, nitro, or phenyl.

[0056] Suitable aluminum trihalides are, in particular, aluminum trifluoride, aluminum trichloride, or aluminum tribromide, preferably aluminum trichloride.

[0057] Useful alkylaluminum halides include, in particular, mono(C1-C4 alkyl)aluminum dihalides or di(C1-C4 alkyl)aluminum monohalides, such as methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, dimethylaluminum chloride, or diethylaluminum chloride, diisobutylaluminum chloride, preferably ethylaluminum dichloride, isobutylaluminum dichloride, diethylaluminum chloride, or diisobutylaluminum chloride, and very preferably ethylaluminum dichloride and isobutylaluminum dichloride.

[0058] Particularly preferred iron trihalides are iron trifluoride, iron trichloride, or iron tribromide, preferably iron trichloride.

[0059] Particularly preferred gallium trihalides are gallium trifluoride, gallium trichloride, or gallium tribromide, preferably gallium trichloride.

[0060] Particularly preferred titanium tetrahalides are titanium tetrafluoride, titanium tetrachloride, or titanium tetrabromide, preferably titanium tetrachloride.

[0061] Particularly suitable zinc dihalides are zinc difluoride, zinc dichloride, or zinc dibromide, preferably zinc dichloride.

[0062] Particularly suitable tin dihalides are tin difluoride, tin dichloride, or tin dibromide, preferably tin dichloride.

[0063] Particularly preferred tin tetrahalides are tin tetrafluoride, tin tetrachloride, or tin tetrabromide, preferably tin tetrachloride.

[0064] Particularly preferred boron trihalides are boron trifluoride, boron trichloride, and boron tribromide, preferably boron trifluoride and boron trichloride, and more preferably boron trifluoride.

[0065] Among these Lewis acids, aluminum trihalides, alkylaluminum halides, iron trihalides, titanium tetrahalides, and boron trihalides are preferred.

[0066] Aluminum trihalides, alkylaluminum halides, iron trihalides, and boron trihalides are very preferred, with aluminum trihalides, and especially aluminum trichloride, being particularly preferred.

[0067] In preferred embodiments, isobutene or an isobutene-containing monomer mixture is polymerized in the presence of an alkylaluminum dichloride donor complex or a dialkylaluminum chloride donor complex, which is effective as a polymerization catalyst, and very preferably in the presence of an aluminum trichloride donor complex or an iron trichloride donor complex.

[0068] The molar ratio of the Lewis acid to the compound of formula (I), (Ia), or (Ib) is generally 1:0.1 to 10, preferably 1:0.2 to 5, more preferably 1:0.3 to 3, even more preferably 1:0.4 to 2, and particularly 1:0.5 to 1. However, as described above, the complex formed from at least one Lewis acid and at least one phosphorus-containing compound of formula (I), (Ia), or (Ib) has a melting point of 60°C or lower, preferably 40°C or lower, and particularly 20°C or lower.

[0069] An essential aspect of the present invention is that a complex formed from at least one Lewis acid and at least one phosphorus-containing compound of formula (I), (Ia), or (Ib) has a melting point of 60°C or lower, preferably 40°C or lower, particularly 20°C or lower, preferably 10°C or lower, and more preferably 0°C or lower (determined in the range of -20°C to 150°C at a heating rate of 5°C / min by differential scanning calorimetry).

[0070] According to the present invention, aluminum trihalide-donor complexes, alkylaluminum halide-donor complexes, iron trihalide-donor complexes, gallium trihalide-donor complexes, titanium tetrahalide-donor complexes, zinc dihalide-donor complexes, tin dihalide-donor complexes, tin tetrahalide-donor complexes, or boron trihalide-donor complexes, which are effective as polymerization catalysts, are used as donors. - At least one organic compound (II) selected from the group consisting of an organic compound having at least one oxygen 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 at least one ether functional group, an organic compound having at least one carboxylic acid ester functional group, an organic compound having at least one aldehyde functional group, an organic compound having at least one keto functional group, and an organic compound having at least one nitrogen-containing heterocycle, and - At least one compound of formula (I), formula (Ia), or formula (Ib) as defined above. It contains a mixture of, However, the complex formed from at least one Lewis acid and at least one phosphorus-containing compound of formula (I), (Ia), or (Ib) has a melting point of 60°C or lower, preferably 40°C or lower, and particularly 20°C or lower.

[0071] Compound (I) is preferred over compound (Ia) or (Ib).

[0072] Compound (II) is selected from the group consisting of an organic compound having at least one oxygen 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 having at least one ether functional group, an organic compound having at least one carboxylic acid ester functional group, an organic compound having at least one aldehyde functional group, an organic compound having at least one keto functional group, and an organic compound having at least one nitrogen-containing heterocycle.

[0073] Compound (II) containing only oxygen is preferred over compound (II) containing nitrogen.

[0074] Preferably, compound (II) is 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, and organic compounds having at least one keto functional group; more preferably, compound (II) is selected from the group consisting of organic compounds having at least one ether functional group and organic compounds having at least one carboxylic acid ester functional group; and very preferably, compound (II) is an organic compound having at least one ether functional group, particularly an organic compound having just one ether functional group.

[0075] It is understood that a compound having at least one ether functional group also means an acetal and a hemiacetal. The ether compound may contain one or more ether functional groups, for example, one, two, three, four or even more ether functional groups, preferably one or two ether functional groups and very preferably one ether functional group.

[0076] The mixture of donors may contain one, two, three, four or even more different compounds (II), preferably a compound having at least one ether functional group, preferably one or two different compounds, very preferably one compound.

[0077] In a preferred embodiment of the present invention, an aluminum trihalide-donor complex or an alkylaluminum halide complex or an iron trihalide-donor complex or a gallium trihalide-donor complex or a titanium tetrachloride-donor complex or a zinc dichloride-donor complex or a tin dichloride-donor complex or a tin tetrachloride-donor complex or a boron trihalide-donor complex, very preferably an aluminum trihalide-donor complex or an iron trihalide-donor complex or a boron trihalide-donor complex, especially an aluminum trihalide-donor complex is used, and these are used as donors - General formula R 8 -O-R 9 (where the variable elements R 8 and R 9 are each independently a C1-C 20 alkyl group, preferably a C1-C8 alkyl group, especially a C1-C4 alkyl group, a C1-C 20 haloalkyl group, preferably a C1-C8 haloalkyl group, especially a C1-C4 haloalkyl group, a C5-C8 cycloalkyl group, preferably a C5-C6 cycloalkyl group, a C6-C 20 aryl group, especially a C6-C 12 aryl group, a C6-C 20 haloaryl group, especially a C6-C 12 haloaryl group or a C7-C 20 arylalkyl group, especially a C7-C12 These are arylalkyl groups. C1-C4 alkyl groups, C1-C4 haloalkyl groups, C6-C 12 Aryl group and C7~C 12 At least one dihydrocarbyl ether (arylalkyl preferred), and - At least one compound of formula (I), formula (Ia), or formula (Ib), It contains a mixture of, However, the complex formed from at least one Lewis acid and at least one phosphorus-containing compound of formula (I), (Ia), or (Ib) has a melting point of 60°C or lower, preferably 40°C or lower, and particularly 20°C or lower.

[0078] Haloalkyl and haloaryl preferably mean chloroalkyl or bromoalkyl and chloroaryl or bromoaryl, and very preferably chloroalkyl and chloroaryl. ω-haloalkyl groups are particularly preferred.

[0079] Preferred examples include chloromethyl, 1-chloroethanol-1-yl, 2-chloroethanol-1-yl, 2-chloropropane-1-yl, 2-chloropropane-2-yl, 3-chloropropane-1-yl, and 4-chlorobuta-1-yl.

[0080] Preferred examples of chloroaryls are 2-chlorophenyl, 3-chlorophenyl, and 4-chlorophenyl.

[0081] The dihydrocarbyl ethers mentioned may be open-chain or cyclic, where there are two variable elements R 8 and R 9In the case of cyclic ethers, they may bond 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-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 ether, such as anisole and phenethole, ditril ether, dixylyl ether and dibenzyl ether.

[0082] Furthermore, bifunctional ethers, such as dialkoxybenzene, preferably dimethoxybenzene, very preferably veratrol, and ethylene glycol dialkyl ethers, preferably ethylene glycol dimethyl ether and ethylene glycol diethyl ether, are preferred.

[0083] 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 aluminum trihalide donor complexes or alkylaluminum halide donor 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, and especially as donors for aluminum trihalide donor complexes.

[0084] In preferred embodiments, dihydrocarbyl ethers having at least one secondary or tertiary dihydrocarbyl group are preferred over dihydrocarbyl groups having only a primary group. An ether having a primary dihydrocarbyl group is an ether in which both dihydrocarbyl groups are bonded to an ether functional group by primary carbon atoms, 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 by a secondary or tertiary carbon atom.

[0085] To clarify, for example, diisobutyl ether is considered an ether having a primary dihydrocarbyl group because, although the secondary carbon atom of the isobutyl group is not bonded to the oxygen of the ether functional group, the hydrocarbyl group is bonded via a primary carbon atom.

[0086] Preferred examples of ethers having a primary dihydrocarbyl group are diethyl ether, di-n-butyl ether, and di-n-propyl ether.

[0087] 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.

[0088] In addition, it was found that dihydrocarbyl ethers that are particularly advantageous as donors for aluminum trihalide-donor complexes or alkylaluminum halide complexes have a total carbon number of 3 to 16, preferably 4 to 16, particularly 4 to 12, and especially 4 to 8 carbon atoms in the donor compound.

[0089] In another preferred embodiment, the halogenated substituted ether is preferably paired with an aluminum halide-donor complex, an iron halide-donor complex, or a boron halide-donor complex.

[0090] Organic compounds having at least one carboxylic acid ester functional group are preferably of the general formula R 10 -COOR 11 (In the formula, the variable element R 10 and R 11 These are, independently, C1~C 20 Alkyl alkyl groups, particularly C1-C8 alkyl groups, C5-C8 cycloalkyl groups, and C6-C 20 Aryl groups, particularly C6-C 12 Aryl group, or C7~C 20 Aryl alkyl groups, especially C7-C 12 It is a hydrocarbyl carboxylate of an arylalkyl group.

[0091] Examples of hydrocarbyl carboxylates mentioned include 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 These include methylcyclohexanecarboxylate, ethylcyclohexanecarboxylate, n-propylcyclohexanecarboxylate, isopropylcyclohexanecarboxylate, n-butylcyclohexanecarboxylate, sec-butylcyclohexanecarboxylate, isobutylcyclohexanecarboxylate, tert-butylcyclohexanecarboxylate, methyl benzoate, ethyl benzoate, n-propyl benzoate, isopropyl benzoate, n-butyl benzoate, sec-butyl benzoate, isobutyl benzoate, tert-butyl benzoate, methylphenyl acetate, ethyl phenyl acetate, n-propyl phenyl acetate, isopropyl phenyl acetate, n-butyl phenyl acetate, sec-butyl phenyl acetate, isobutyl phenyl acetate, and tert-butyl phenyl acetate. Among the hydrocarbyl carboxylates mentioned, ethyl acetate has been found to be particularly favorable as a donor for complexes.

[0092] In addition, it has been found that hydrocarbyl carboxylates that are particularly advantageous as donors have a total number of carbon atoms of 3 to 16, preferably 4 to 16, particularly 4 to 12, and especially 4 to 8, with particular preference given to those having a total of 3 to 10 carbon atoms, particularly 4 to 6.

[0093] Organic compounds having at least one aldehyde functional group, preferably exactly one aldehyde functional group, and organic compounds having at least one keto functional group, preferably exactly one keto functional group, typically have 1 to 20, preferably 2 to 10 carbon atoms. Functional groups other than carbonyl groups are preferably absent.

[0094] A preferred organic compound having at least one aldehyde functional group is, formula R 10 -CHO(in the formula, R 10 (The above-mentioned meaning applies to the following substances), and is very preferably selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, and benzaldehyde.

[0095] A preferred organic compound having at least one keto functional group is given by formula R 10 -(C=O)-R 11 (In the formula, R 10 and R 11 (The above-mentioned meaning applies) 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.

[0096] Organic compounds having at least one nitrogen-containing heterocycle are preferably 5- or 6-membered heterocycles containing saturated, partially unsaturated, or unsaturated nitrogen, which include 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 groups, particularly C1-C4 alkyl groups and / or phenyl, and / or functional groups or heteroatoms as substituents, particularly fluorine, chlorine, bromine, nitro and / or cyano, for example, pyrrolidine, pyrrole, imidazole, 1,2,3- or 1,2,4-triazole, oxazole, thiazole, piperidine, pyrazane, pyrazole, pyridazine, pyrimidine, pyrazine, 1,2,3-, 1,2,4- or 1,2,5-triazine, 1,2,5-oxathiaidine, 2H-1,3,5-thiadiazine, or morpholine.

[0097] 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-methylpyridine, 2,4-, 2,5-, 2,6- or 3,5-di-tert-butylpyridine, or other 2-,3- or 4-phenylpyridine.

[0098] The molar ratio of the donor compounds mentioned (calculated by adding the sum of compounds (II) in the mixture, preferably the sum of ethers, to the sum of compounds of formula (I), (Ia), or (Ib)) to aluminum trihalide, or alkylaluminum halide, or iron trihalide, or gallium trihalide, or titanium tetrahalide, or zinc dihalide, or tin dihalide, or tin tetrahalide, or boron trihalide in the donor complex generally varies in the range of 0.4:1 to 2.0:1, particularly 0.5:1 to 1.8:1, and especially 0.7:1 to 1.6:1, and in most cases is 0.9:1 to 1.5:1. However, it is also possible to treat with a greater excess of donor compounds, often up to 10 times, and particularly 3 times molar excess. In this case, the excess donor compound further acts as a solvent or diluent.

[0099] The molar ratio of compound (II), preferably the ether compound (calculated as the total of compound (II) and the total of the ether, respectively) in the mixture to the compound of formula (I), (Ia), or (Ib) (calculated as the total of the compounds of formula (I), (Ia), or (Ib)) generally varies from 0.1:1 to 1:0.1, preferably 0.2:1 to 1:0.2, very preferably 0.25:1 to 1:0.5, more preferably 0.3:1 to 1:0.66, particularly 0.3:1 to 1:1, and even more preferably 0.35:1 to 1:1. In a preferred embodiment, compound (II) and the ether are present in equimolar molar ratios.

[0100] The molar ratio of the Lewis acid mentioned, preferably the aluminum trihalide or alkylaluminum halide, to the isobutene monomer used in the homopolymerization of isobutene, or to the total amount of polymerizable monomer used in the copolymerization of isobutene, is generally 0.001:1 to 0.2:1, preferably 0.002:1 to 0.1:1, very preferably 0.003:1 to 0.08:1, particularly 0.005:1 to 0.05:1, and especially 0.007:1 to 0.03:1, with respect to each individual functional site of the Lewis acid mentioned, preferably the aluminum trihalide or alkylaluminum halide.

[0101] Typically, Lewis acid-donor complexes, preferably aluminum trihalide-donor complexes or alkylaluminum halides, particularly alkylaluminum dichloride-donor complexes or dialkylaluminum chloride-donor complexes, are prepared separately before polymerization from each metal halide, preferably aluminum trihalide or alkylaluminum halides, particularly anhydrous alkylaluminum dichloride or dialkylaluminum chloride, and the donor compound, and then—usually dissolved in an inert solvent, such as a halogenated hydrocarbon, such as dichloromethane, or more preferably a non-halogenated hydrocarbon—and added to the polymerization medium. However, in less preferred embodiments, the complexes may also be prepared in situ before polymerization.

[0102] An advantage of the present invention is that the complex of the Lewis acid and the compound of formula (I), (Ia), or (Ib) is a liquid and can therefore be easily applied as a reaction medium.

[0103] A further advantage of complexes of Lewis acids and compounds of formula (I), (Ia), or (Ib) is that, compared to complexes of Lewis acids and ionic liquids, they can be prepared much more easily by simply mixing the Lewis acid and the compound of formula (I), (Ia), or (Ib), and the reactivity of the complex can be broadly modified by adjusting the ratio of the Lewis acid to the compound of formula (I), (Ia), or (Ib).

[0104] If the polymerization catalyst is not completely soluble in the solvent used, it may be advantageous to disperse the polymerization catalyst in the inert solvent, for example, by vigorously stirring the dispersion. Dispersion can be carried out with any apparatus suitable for dispersion. For example, a shaking device such as those made by Skandex may be mentioned as an example, or it can be carried out by grinding in an ultrasonic device, a high-pressure homogenizer, a two-, three-, four- or five-roll mill, a mini-mill, a Henschel mixer, a shaking mill, an ang mill, a gear mill, a bead mill, a wet mill, a sand mill, an attritor, a colloid mill, an ultrasonic homogenizer equipped with an Ultra Turrax stirrer, and in particular by grinding in a two-, three-, four- or five-roll mill, a mini-mill, a shaking mill, an ang mill, a gear mill, a bead mill, a wet mill, a sand mill, a colloid mill, a ball mill, specifically a stirring ball mill.

[0105] In preferred embodiments, sonication of the Lewis acid-donor complex, preferably an aluminum trihalide-donor complex, an alkylaluminum halide complex, an iron trihalide-donor complex, or a boron halide-donor complex in an inert solvent before polymerization helps to improve the polymerization conversion rate.

[0106] In preferred embodiments of the present invention, polymerization is carried out by further use of monofunctional or polyfunctional, particularly monofunctional, difunctional, or trifunctional, initiators selected from organic hydroxyl compounds, organic halogen compounds, and water. Mixtures of the initiators mentioned, such as 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, can also be used. The initiators may be monofunctional, difunctional, or polyfunctional, i.e., one, two or more hydroxyl groups or halogen atoms that initiate the polymerization reaction may be present in the initiator molecule. In the case of difunctional or polyfunctional initiators, telechelic isobutene polymers having two or more, particularly two or three, polyisobutene chain ends are typically obtained.

[0107] Organic hydroxyl compounds having only one hydroxyl group in the molecule and suitable as monofunctional initiators include, in particular, alcohols and phenols, especially those with the general formula R 12 -OH(in the formula, R 12 is C1~C 20 Alkyl alkyl groups, particularly C1-C8 alkyl groups, C5-C8 cycloalkyl groups, and C6-C 20 Aryl groups, particularly C6-C 12 Aryl group or C7~C 20 Aryl alkyl groups, especially C7-C 12 Examples include those exhibiting arylalkyl groups. In addition, R 12 The group may also contain a mixture of the structures described above, and / or may have other functional groups other than those already mentioned, such as keto functional groups, nitroxide or carboxyl groups, and / or heterocyclic structural elements.

[0108] Typical examples of such organic monohydroxy compounds include 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, and 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-9-o 1,1-Diphenylethanol, 1,1-Diphenyl-2-propyne-1-ol, 1,1-Diphenylpropanol, 4-(1-Hydroxy-1-phenylethyl)benzonitrile, Cyclopropyldiphenylmethanol, 1-Hydroxy-1,1-Diphenylpropan-2-one, Benzyl acid, 9-Phenyl-9-Fluorenol, Triphenylmethanol, Diphenyl(4-Pyridinyl)methanol, α,α-Diphenyl-2-Pyridinemethanol, 4-Methoxytrityl alcohol (especially polymer-bonded 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,These are 2-triphenylpropan-1-ol and p-anisaldehyde carbinol.

[0109] Organic hydroxyl compounds having two hydroxyl groups in the molecule and suitable as bifunctional initiators include particularly dihydric alcohols or diols having a total number of carbon atoms of 2 to 30, particularly 3 to 24, and especially 4 to 20, and bisphenols having a total number of carbon atoms of 6 to 30, particularly 8 to 24, and especially 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.

[0110] Organic halogen compounds having one halogen atom in the molecule and suitable as monofunctional initiators are particularly those with the general formula R 13 -Hal(wherein Hal is a halogen atom selected from fluorine, iodine, and especially chlorine and bromine, R 13 C1~C 20 Alkyl alkyl groups, particularly C1-C8 alkyl groups, C5-C8 cycloalkyl groups, or C7-C 20 Aryl alkyl groups, especially C7-C 12 It is a compound (showing an arylalkyl group). In addition, R 13 The group may also contain a mixture of the structures described above, and / or may have other functional groups other than those already mentioned, such as keto functional groups, nitroxide or carboxyl groups and / or heterocyclic structural elements.

[0111] Typical examples of such monohalogen compounds include 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-chloro 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 yl-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.

[0112] Organic halogen compounds having two halogen atoms in their molecule and suitable as difunctional initiators include, for example, 1,3-bis(1-bromo-1-methylethyl)benzene, 1,3-bis(2-chloro-2-propyl)benzene (1,3-dicumyl chloride), and 1,4-bis(2-chloro-2-propyl)benzene (1,4-dicumyl chloride).

[0113] The initiator more preferably has one or more hydroxyl groups each sp 3 Organic hydroxyl compounds bonded to hybrid carbon atoms, with one or more halogen atoms each being sp 3 Selected from organic halogen compounds bonded to hybrid carbon atoms and water. In particular, if one or more hydroxyl groups are each sp 3 Initiators selected from organic hydroxyl compounds bonded to hybrid carbon atoms are preferred.

[0114] In the case of organic halogen compounds as initiators, furthermore, one or more halogen atoms are secondary or especially tertiary sp. 3 Those bonded to hybrid carbon atoms are given particular priority.

[0115] Such sp 3 On the hybrid carbon atoms, in addition to the hydroxyl group, R 12 , R 13 and R 14 Initiators that may have a group are particularly preferred, R 12 , R 13 and R 14 Each group is independently of hydrogen, C1-C 20 Alkyl, C5-C8 cycloalkyl, C6-C 20 Aryl, C7~C 20 The alkylaryl or phenyl, where each aromatic ring may have one or more substituents, preferably one or two C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or C1-C4 haloalkyl groups, and the variable element R 12 , R 13 and R 14 One or fewer of these are hydrogen, and the variable element R 12 , R 13 and R 14 At least one of the compounds is a phenyl which may have one or more, preferably one or two, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl, or C1-C4 haloalkyl groups as substituents.

[0116] 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 of very particular preference. 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 of very particular preference.

[0117] The molar ratio of the initiator mentioned to the isobutene monomer used in the homopolymerization of isobutene, or to the total amount of polymerizable monomer used in the copolymerization of isobutene, is generally 0.0005:1 to 0.1:1, particularly 0.001:1 to 0.075:1, and especially 0.0025:1 to 0.05:1, for each individual functional site of the initiator. When water is used as the sole initiator or in combination with an organic hydroxyl compound and / or organic halogen compound as a further initiator, the molar ratio of water to the isobutene monomer used in the homopolymerization of isobutene, or to the total amount of polymerizable monomer used in the copolymerization of isobutene, is particularly 0.0001:1 to 0.1:1, especially 0.0002:1 to 0.05:1, preferably 0.0008:1 to 0.04:1, and very preferably especially 0.001:1 to 0.03:1.

[0118] In a preferred embodiment, the amount of initiator in the monomer mixture is 10% by weight or less, preferably 7.5% by weight or less, more preferably 5% by weight or less, even more preferably 3% by weight or less, and particularly 2% by weight or less.

[0119] When water is used as the sole initiator or in combination with an organic hydroxyl compound, the amount of initiator in the monomer mixture is 3.2% by weight or less, preferably 2.5% by weight or less, more preferably 2% by weight or less, even more preferably 1.5% by weight or less, and particularly 1% by weight or less.

[0120] A certain proportion of initiator molecules, added as organic hydroxyl or halogen compounds, are incorporated into the polymer chain. The proportion of polymer chains initiated by these incorporated organic initiator molecules (I eff The polymer chains can be up to 100%, and are generally between 5% and 90%. The remaining polymer chains are generated either from trace amounts of water acting as initiator molecules or from chain transfer reactions.

[0121] In a more preferred embodiment of the present invention, polymerization is carried out in the presence of 0.01 to 10 mmol, particularly 0.05 to 5.0 mmol, and especially 0.1 to 1.0 mmol, of a nitrogen-containing basic compound based on 1 mol of isobutene monomer used in the case of isobutene homopolymerization, or 1 mol of the total amount of polymerizable monomer used in the case of isobutene copolymerization.

[0122] The nitrogen-containing basic compounds used are those with the general formula R 14 -NR 15 R 16 (In the formula, the variable element R 14 , R 15 and R 16 These are hydrogen, C1~C, each independently. 20 Alkyl alkyl groups, particularly C1-C8 alkyl groups, C5-C8 cycloalkyl groups, and C6-C 20 Aryl groups, particularly C6-C 12 Aryl group or C7~C 20 Aryl alkyl groups, especially C7-C 12The amine may be an aliphatic, alicyclic, or aromatic amine (which is an arylalkyl group), or ammonia. If none of these variable elements are hydrogen, the amine is a tertiary amine. If one of these variable elements is hydrogen, the amine is a secondary amine. If two of these variable elements are hydrogen, the amine is a primary amine. If all of these variable elements are hydrogen, the amine is ammonia.

[0123] General formula R 14 -NR 15 R 16 Typical examples of such amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, sec-butylamine, isobutylamine, tert-amylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, cyclopentylamine, cyclohexylamine, aniline, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine, di-sec-butylamine, diisobutylamine, di-tert-amylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-(2-ethylhexyl)amine, dicyclopentylamine. These are methylamine, dicyclohexylamine, diphenylamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, tri-sec-butylamine, triisobutylamine, tri-tert-amylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-(2-ethylhexyl)amine, tricyclopentylamine, tricyclohexylamine, triphenylamine, dimethylethylamine, methyl-n-butylamine, N-methyl-N-phenylamine, N,N-dimethyl-N-phenylamine, N-methyl-N,N-diphenylamine, or N-methyl-N-ethyl-Nn-butylamine.

[0124] In addition, the nitrogen-containing basic compounds used may also be compounds having multiple nitrogen atoms, particularly two or three nitrogen atoms and 2 to 20 carbon atoms, each of which nitrogen atoms may independently have a hydrogen atom or an aliphatic, alicyclic, or aromatic substituent. Examples of such polyamines are 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, diethylenetriamine, N-methyl-1,2-ethylenediamine, N,N-dimethyl-1,2-ethylenediamine, N,N'-dimethyl-1,2-ethylenediamine, or N,N-dimethyl-1,3-propylenediamine.

[0125] However, preferred nitrogen-containing basic compounds of this type are, in particular, five- or six-membered heterocycles containing saturated, partially unsaturated or unsaturated nitrogen, which include 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 groups, in particular C1-C4 alkyl groups and / or phenyl, and / or functional groups or heteroatoms as substituents, in particular fluorine, chlorine, bromine, nitro and / or cyano, for example pyrrolidine, pyrrole, imidazole, 1,2,3- or 1,2,4-triazole, oxazole, thiazole, piperidine, pyrazane, pyrazole, pyridazine, pyrimidine, pyrazine, 1,2,3-, 1,2,4- or 1,2,5-triazine, 1,2,5-oxathiaidine, 2H-1,3,5-thiadiazine, or morpholine.

[0126] 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-methylpyridine, 2,4-, 2,5-, 2,6- or 3,5-di-tert-butylpyridine, or other 2-,3- or 4-phenylpyridine.

[0127] It is possible to use a single nitrogen-containing basic compound or a mixture of such nitrogen-containing basic compounds.

[0128] For the use of isobutene or isobutene-containing monomer mixtures as monomers to be polymerized, suitable isobutene sources are pure isobutene and isobutene-based C4 hydrocarbon streams, such as C4 raffinate, particularly "raffinate 1", C4 fractions from isobutane dehydrogenation, and C4 fractions from steam crackers and FCC crackers (fluid catalytic cracking), provided that substantially present 1,3-butadiene is removed from these. C4 hydrocarbon streams from FCC purification units are also known as "b / b" streams. More suitable isobutene-based C4 hydrocarbon streams are, for example, product streams from propylene-isobutane co-oxidation or 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 in the C4 hydrocarbon streams mentioned is in the range of 40% to 60% by weight. For example, Raffinate 1 generally consists of essentially 30% to 50% by weight of isobutene, 10% to 50% by weight of 1-butene, 10% to 40% by weight of cis- and trans-2-butene, and 2% to 35% by weight of butane. In the polymerization method according to the present invention, the unbranched-chain butene in Raffinate 1 generally behaves virtually inactively, and only isobutene is polymerized.

[0129] In a preferred embodiment, the monomer source used for polymerization is an industrial C4 hydrocarbon stream having an isobutene content of 1% to 100% by weight, particularly 1% to 99% by weight, especially 1% to 90% by weight, and more preferably 30% to 60% by weight, particularly a raffinate stream, a b / b stream from an FCC purification unit, a product stream from propylene-isobutane co-oxidation, or a product stream from a metathesis unit.

[0130] In particular, when raffinate stream 1 is used as the isobutene source, the use of water as the sole initiator or as a further initiator has been found to be useful, especially when polymerization takes place at temperatures of -20°C to +30°C, particularly 0°C to +20°C. However, when raffinate stream 1 is used as the isobutene source at temperatures of -20°C to +30°C, particularly 0°C to +20°C, the use of an initiator can be omitted.

[0131] The isobutene monomer mixtures mentioned may contain small amounts of impurities, such as water, carboxylic acids, or mineral acids, without significant loss of yield or selectivity. It is appropriate to prevent 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.

[0132] A monomer mixture of isobutene or an isobutene-based hydrocarbon mixture can also be converted together with an olefinic unsaturated monomer copolymerizable with isobutene. When the isobutene monomer mixture is copolymerized with a suitable comonomer, the monomer mixture preferably contains at least 5% by weight, more preferably at least 10% by weight, and particularly at least 20% by weight of isobutene, preferably up to 95% by weight, more preferably up to 90% by weight, and particularly up to 80% by weight of comonomer.

[0133] Useful copolymerizable monomers include vinyl aromatics, 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 5-10 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 a silyl group, such as 1-trimethoxysilylethene, 1-(trimethoxysilyl)propene, 1-(trimethoxysilyl)-2-methylpropene-2, 1-[tri(methoxyethoxy)-silyl]ethene, 1-[tri(methoxyethoxy)silyl]propene, and 1-[tri(methoxyethoxy)silyl]-2-methylpropene-2. In addition, depending on the polymerization conditions, useful comonomers include isoprene, 1-butene, and cis- and trans-2-butene.

[0134] When the method according to the present invention is used to prepare copolymers, the method may be configured to preferentially form random polymers or block copolymers. To prepare block copolymers, for example, different monomers may be supplied to the polymerization reaction sequentially, in which case the second comonomer is not added, in particular, until the first comonomer has already been at least partially polymerized. In this configuration, diblocks, triblocks and higher-order block copolymers can be obtained, having a block of one or the other comonomer as a terminal block, depending on the order of monomer addition. However, in some cases, block copolymers are also formed when all comonomers are supplied to the polymerization reaction simultaneously, but one of them polymerizes significantly faster than the others (many may be). This is particularly true when isobutene and vinyl aromatic compounds, especially styrene, are copolymerized in the method according to the present invention. This results in the formation of block copolymers preferably having terminal polystyrene blocks. This is due to the fact that vinyl aromatic compounds, especially styrene, polymerize significantly slower than isobutene.

[0135] Polymerization can be carried out either in a continuous or batch manner. The continuous method can be carried out in the same manner as known prior art methods for the continuous polymerization of isobutene in the presence of a boron trifluoride-based catalyst in the liquid phase.

[0136] The method according to the present invention is suitable for implementation at low temperatures, for example, -90°C to 0°C, or at high temperatures, i.e., at least 0°C, for example, 0°C to +30°C or 0°C to +50°C. However, polymerization in the method according to the present invention is preferably carried out at relatively low temperatures, generally -70°C to -10°C, and particularly at -60°C to -15°C.

[0137] If polymerization in the method according to the present invention is carried out at or above the boiling point of the monomer or monomer mixture to be polymerized, this is preferably carried out in a pressure vessel, such as an autoclave or pressure reactor.

[0138] According to the present invention, polymerization is carried out as polymerization in bulk or in solution.

[0139] Polymerization in the method according to the present invention is preferably 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 occurs during the polymerization reaction to such an extent that the heat of the proceeding reaction can be ensured. 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 and isooctane; alicyclic hydrocarbons, such as cyclopentane and cyclohexane; aromatic hydrocarbons, such as benzene, toluene and xylene; and halogenated hydrocarbons, particularly 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 aromatics halogenated in the alkyl side chain, such as chlorobenzene, monofluoromethylbenzene, difluoromethylbenzene and trifluoromethylbenzene; and mixtures of the above-mentioned diluents. The components used in the diluents or solvent mixtures mentioned are also inert components of isobutene-based C4 hydrocarbons. Non-halogenated solvents are preferred over the list of halogenated solvents.

[0140] The polymerization of the present invention may be carried out in halogenated hydrocarbons, particularly in aliphatic halogenated hydrocarbons, or in a mixture of halogenated hydrocarbons, particularly aliphatic halogenated hydrocarbons, or in a mixture of at least one halogenated hydrocarbon, particularly aliphatic halogenated hydrocarbon, and at least one aliphatic, alicyclic, or aromatic hydrocarbon, for example, in a mixture of dichloromethane and n-hexane, typically in a volume ratio of 10:90 to 90:10, particularly 50:50 to 85:15. Before use, impurities, such as water, carboxylic acids, or mineral acids, are removed from the diluent, more preferably by adsorption to a solid adsorbent, such as activated carbon, molecular sieve, or ion exchanger.

[0141] In preferred embodiments, polymerization of the present invention is carried out in halogen-free aliphatic or, in particular, halogen-free aromatic hydrocarbons, especially toluene. For these embodiments, water, in combination with or, in particular, the organic hydroxyl compounds and / or organic halogen compounds mentioned, has proven to be particularly advantageous as an initiator.

[0142] In another preferred embodiment, the polymerization of the present invention is carried out in halogen-free aliphatic or alicyclic hydrocarbons, preferably aliphatic hydrocarbons, in particular hexane, pentane, heptane, cyclohexane, cyclopentane, and mixtures thereof.

[0143] Polymerization in the method according to the present invention is preferably carried out under substantially aprotic reaction conditions, and in particular under substantially anhydrous reaction conditions. Substantially aprotic reaction conditions and substantially anhydrous reaction conditions are understood to mean that the content of protic impurities and water in the reaction mixture is less than 50 ppm, and in particular less than 5 ppm, respectively. Therefore, generally, the feedstock is dried before use by physical and / or chemical means. More specifically, it has been found useful to mix the aliphatic or alicyclic hydrocarbon to be used as the solvent after conventional pre-purification and pre-drying with an organometallic compound, such as an organolithium, organomagnesium, or organoaluminum compound, in an amount sufficient to substantially remove trace amounts of water from the solvent. The solvent thus treated is then preferably concentrated directly in the reaction vessel. It is also possible to proceed in a similar manner with the monomer to be polymerized, in particular isobutene or isobutene mixtures. Drying with other conventional drying materials, such as molecular sieves or pre-dried oxides, such as aluminum oxide, silicon dioxide, calcium oxide, or barium oxide, is also preferable. For halogenated solvents where drying with metals, such as sodium or potassium, or metal alkyls is not an option, water or trace amounts of water are removed by a suitable drying agent, such as calcium chloride, phosphorus pentoxide, or a molecular sieve. Similarly, feedstocks where treatment with metal alkyls is not an option, such as vinyl aromatic compounds, can be dried in a similar manner. Even when some or all of the initiators used are water, it is preferable to remove a very large or complete amount of residual water from the solvent and monomers by pre-reaction drying to allow the use of controlled, specific amounts of water as the initiator, resulting in greater process control and higher reproducibility of the results.

[0144] Polymerization of isobutene or isobutene-based starting materials generally proceeds simultaneously when a Lewis acid-donor complex, preferably an aluminum trihalide-donor complex or an alkylaluminum halide complex, particularly an alkylaluminum dichloride-donor complex or a dialkylaluminum chloride-donor complex, comes into contact with isobutene or an isobutene-based monomer mixture at a desired reaction temperature. Here, the procedure may involve first filling the monomers, optionally with a diluent, bringing the reaction temperature to a certain level, and then adding the Lewis acid-donor complex, preferably an aluminum trihalide-donor complex or an alkylaluminum halide complex, particularly an alkylaluminum dichloride-donor complex or a dialkylaluminum chloride-donor complex. Alternatively, the procedure may involve first filling the Lewis acid-donor complex, preferably an aluminum trihalide-donor complex or an alkylaluminum halide complex, particularly an alkylaluminum dichloride-donor complex or a dialkylaluminum chloride-donor complex, optionally with a diluent, and then adding the monomers. In this case, the start of polymerization is considered to be when all reactants are present in the reaction vessel.

[0145] To prepare isobutene copolymers, the procedure may involve first loading the monomers, optionally into a diluent, and then adding a Lewis acid-donor complex, preferably an aluminum trihalide-donor complex or an alkylaluminum halide complex, particularly an alkylaluminum dichloride-donor complex or a dialkylaluminum chloride-donor complex. The reaction temperature can be established before and after the addition of the Lewis acid-donor complex, preferably an aluminum trihalide-donor complex or an alkylaluminum halide complex, particularly an alkylaluminum dichloride-donor complex or a dialkylaluminum chloride-donor complex. Alternatively, the procedure may involve first loading only one of the monomers, optionally into a diluent, and then adding a Lewis acid-donor complex, preferably an aluminum trihalide-donor complex or an alkylaluminum halide complex, particularly an alkylaluminum dichloride-donor complex or a dialkylaluminum chloride-donor complex, and then adding further monomers only after a certain period of time, for example, when at least 60%, at least 80%, or at least 90% of the monomers have been converted. Alternatively, a Lewis acid donor complex, preferably an aluminum trihalide donor complex or an alkylaluminum halide complex, particularly an alkylaluminum dichloride donor complex or a dialkylaluminum chloride donor complex, may be initially packed into the diluent, then monomers may be added simultaneously or sequentially, and then a desired reaction temperature may be established. In this case, the start of polymerization is considered to be when the Lewis acid donor complex, preferably an aluminum trihalide donor complex or an alkylaluminum halide complex, particularly an alkylaluminum dichloride donor complex or a dialkylaluminum chloride donor complex, and at least one monomer are present in the reaction vessel.

[0146] In addition to the batch procedure described herein, polymerization in the method according to the present invention may also be configured as a continuous method. In this case, feedstocks, i.e., monomers(s) to be polymerized, optionally diluents, and optionally Lewis acid-donor complexes, preferably aluminum trihalide-donor complexes or alkylaluminum halide complexes, in particular alkylaluminum dichloride-donor complexes or dialkylaluminum chloride-donor complexes, are continuously supplied to the polymerization reaction, and the reaction products are continuously withdrawn so that near-steady-state polymerization conditions are established in the reactor. The monomers(s) to be polymerized may be supplied as is, diluted with a diluent or solvent, or supplied as a monomer-containing hydrocarbon stream.

[0147] Lewis acid donor complexes, preferably aluminum trihalide donor complexes or alkylaluminum halide complexes, particularly alkylaluminum dichloride donor complexes or dialkylaluminum chloride donor complexes, which are effective as polymerization catalysts, generally exist in a dissolved, dispersed, or suspended form in the polymerization medium. It is also possible to support Lewis acid donor complexes, preferably aluminum trihalide donor complexes or alkylaluminum halide complexes, particularly alkylaluminum dichloride donor complexes or dialkylaluminum chloride donor complexes, on conventional carrier materials. Suitable reactor types for the polymerization method of the present invention are typically stirred-tank reactors, loop reactors and tubular reactors, as well as fluidized-bed reactors, stirred-tank reactors with or without solvents, fluidized-bed reactors, continuous fixed-bed reactors and batch-type fixed-bed reactors (batch type).

[0148] In the method according to the present invention, aluminum trihalide donor complexes, alkylaluminum halide complexes, iron trihalide donor complexes, gallium trihalide donor complexes, titanium tetrahalide donor complexes, zinc dihalide donor complexes, tin dihalide donor complexes, tin tetrahalide donor complexes, or boron trihalide donor complexes, particularly alkylaluminum dichloride donor complexes or dialkylaluminum chloride donor complexes, are effective as polymerization catalysts. Generally, gold in Lewis acid donor complexes... The amount used is such that the molar ratio of aluminum in the aluminum trihalide-donor complex or alkylaluminum halide complex, particularly in the alkylaluminum dichloride-donor complex or dialkylaluminum chloride-donor complex, to isobutene in the case of isobutene homopolymerization, or to the total amount of polymerizable monomer used in the case of isobutene copolymerization, is in the range of 1:5 to 1:5000, preferably 1:10 to 1:5000, particularly 1:15 to 1:1000, and especially 1:20 to 1:250.

[0149] In a preferred embodiment of the present invention, the reaction conditions are selected such that the monomer conversion rate is at least 80%, preferably at least 85%, and more preferably at least 90%.

[0150] An advantage of the present invention is that the complex according to the present invention exhibits high selectivity for polymers having terminal ethylenic double bonds (α-double bonds) and other reactive double bonds, such as β-double bonds, preferably terminal ethylenic double bonds (α-double bonds), even at such high conversion rates. In particular, the selectivity for α-double bonds is often observed to decrease when the monomer conversion rate exceeds the above-mentioned value. Furthermore, it can be observed that the amount of reactive double bonds, particularly α-double bonds, formed during the reaction process decreases at high conversion rates. The advantages of the complex according to the present invention are that high selectivity is maintained at high conversion rates, and that the formed reactive double bonds are less degraded than in the case of other catalysts.

[0151] To stop the reaction, the reaction mixture is preferably deactivated by adding, for example, a protic compound, particularly water, alcohol, such as methanol, ethanol, n-propanol, and isopropanol, or a mixture thereof with water; or by adding an aqueous solution of an aqueous base, such as an alkali metal or alkaline earth metal hydroxide, such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, or calcium hydroxide; an alkali metal or alkaline earth metal carbonate, such as sodium carbonate, potassium carbonate, magnesium carbonate, or calcium carbonate; or an aqueous solution of an alkali metal or alkaline earth metal bicarbonate, such as sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, or calcium bicarbonate.

[0152] The method according to the present invention is useful for preparing highly reactive isobutene homopolymers or copolymers having a content of at least 60 mol%, preferably at least 70 mol%, and very preferably at least 75 mol%, of terminal vinylidene double bonds (α-double bonds) and other reactive double bonds, such as β-double bonds, per polyisobutene chain end. More specifically, it is useful for preparing highly reactive isobutene copolymers formed from isobutene and at least one vinyl aromatic monomer, particularly styrene, having a content of at least 60 mol%, preferably at least 70 mol%, and preferably at least 75 mol%, of terminal vinylidene double bonds (α-double bonds) and other reactive double bonds, such as β-double bonds, per polyisobutene chain end. To prepare such copolymers of isobutene and at least one vinyl aromatic monomer, particularly styrene, isobutene or an isobutene hydrocarbon fraction is copolymerized with at least one vinyl aromatic monomer in a weight ratio of isobutene to vinyl aromatic compound of 5:95 to 95:5, particularly 30:70 to 70:30.

[0153] The highly reactive isobutene homopolymer or copolymer prepared by the method according to the present invention, and specifically the isobutene homopolymer, preferably has a polydispersity (PDI=M) of 1.05 to less than 3.5, preferably 1.05 to less than 3.0, preferably 1.05 to less than 2.5, preferably 1.05 to 2.3, more preferably 1.05 to 2.0, and particularly 1.1 to 1.85. w / M n ) has. For an optimal process plan, a typical PDI value is 1.2 to 1.7.

[0154] The highly reactive isobutene homopolymer or copolymer prepared by the method according to the present invention preferably has a number average molecular weight M of 500 to 100,000, more preferably 500 to 25,000, and particularly 500 to 5,000. n The isobutene homopolymer has (determined by gel filtration chromatography). More preferably, the isobutene homopolymer has a number average molecular weight M of 500 to 10000, particularly 500 to 5000, for example, about 1000 or about 2300. n It has.

[0155] Having terminal vinylidene double bonds and incorporating initiator molecules, a portion of the isobutene polymers that arise in a dominant proportion in the isobutene homopolymers prepared according to the present invention are novel compounds. Therefore, the present invention also relates to General Formula III

[0156] [ka] (In the formula, R 17 , R 18 and R 19 These are, independently, hydrogen, C1~C 20 Alkyl, C5-C8 cycloalkyl, C6-C 20 Aryl, C7~C 20 It is an alkylaryl or phenyl compound, and each aromatic ring has one or more C1-C4 alkyl- or C1-C4 alkoxy groups as substituents or general formula IV

[0157] [ka] It may have a part there, where the variable element R 17 , R 18 or R 19 One or fewer of these are hydrogen, and the variable element R 17 , R 18 or R 19 At least one of them is a phenyl which may have one or more C1-C4 alkyl- or C1-C4 alkoxy groups or a part of general formula II as substituents. n is a number between 9 and 4500, preferably between 9 and 180, particularly between 9 and 100, and especially between 12 and 50. We also offer isobutene polymers.

[0158] In a preferred embodiment, R 17 , R 18 or R 19 Each is independently hydrogen, a C1-C4 alkyl group, particularly methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, or a phenyl which may have one or two C1-C4 alkyl- or C1-C4 alkoxy groups or a part of general formula II as substituents, where the variable element R 17 , R 18 and R 19 One or fewer of these are hydrogen, and the variable element R 17 , R 18 and R 19 At least one of the compounds is a phenyl which may have one or two C1-C4 alkyl or C1-C4 alkoxy groups or a portion of general formula II as substituents, where n is a number from 9 to 4500, preferably 9 to 180, particularly 9 to 90, and especially 15 to 45.

[0159] The method according to the present invention successfully polymerizes isobutene or an isobutene-containing monomer mixture under cationic conditions at a satisfactory conversion rate, generally 20-100%, particularly 35-90%, for a short reaction time, generally 5-120 minutes, particularly 30-120 minutes, to obtain a highly reactive isobutene homopolymer or copolymer having an α- and β-double bond content of at least 60 mol%, preferably at least 70 mol%, and very preferably at least 75 mol% per polyisobutene chain end.

[0160] The advantage of the method according to the present invention is that, by using a mixture of at least one organic compound (II), preferably at least one organic compound having at least one ether functional group and at least one compound of general formula (I), (Ia), or (Ib), as a donor, a product with a higher α- and β-double bond content per polyisobutene chain end can be obtained compared to the same reaction carried out under equivalent reaction conditions in the presence of a compound of general formula (I), (Ia), or (Ib) alone as a donor.

[0161] A further advantage of the present invention is that the complexes formed from the Lewis acid and the compound of formula (I), (Ia), or (Ib) are liquids and therefore easy to handle.

[0162] Furthermore, since ionic liquids require chemical reactions and purification, while Lewis acids and compounds of formula (I), (Ia), or (Ib) only need to be mixed in desired ratios, the complexes according to the present invention can be produced more easily than ionic liquids disclosed in the prior art. The reactivity of the complex formed from the Lewis acid and the compound of formula (I), (Ia), or (Ib) and at least one organic compound (II) can be further adjusted by simply changing the molar ratios of these compounds in the complex. [Examples]

[0163] The following examples are intended to illustrate the present invention in detail, and the invention is not limited thereto.

[0164] Material Isobutylene (“IB”, Aldrich, 99.99%) was dried in the gaseous state by passing it through a laboratory gas drying unit. n-Hexane (Sigma-Aldrich, >95%) and CH2Cl2 (Sigma-Aldrich, >99.5%) were treated with sulfuric acid, washed with an aqueous sodium hydrogen carbonate solution, dried over CaCl2, and distilled twice from CaH2 under an inert atmosphere. BF3 (BASF, >99%) was used in the gaseous state without further purification. Diisopropyl ether ( i Pr2O, Fluka, ≧98.5%) was distilled from CaH2 under an inert atmosphere. 2-Chloroethyl ethyl ether (CEE, Aldrich, 99%) and bis(2-chloroethyl) ether (CE, Alrdich, >99%) were distilled from CaH2 under reduced pressure. Ethyl acetate (EtOAc, Aldrich, 99.8%) was refluxed and distilled over P2O5 under an inert atmosphere. Triphenylphosphine oxide (P 888 O, Acros Organics, 99%), triphenylphosphine oxide (PPh3O, Acros Organics, 99%) were vacuum dried for 5 hours before use. AlCl3 (Aldrich, 99.999%), FeCl3 (Sigma-Aldrich, >97%), CDCl3 (Euriso-top (registered trademark)), ethanol (Sigma-Aldrich, >96%), tetrahydrofuran (anhydrous, Sigma-Aldrich, ≧99.9%) were used as received. TiCl4 (Sigma-Aldrich, ≧99.9%) was distilled on a copper chip at 51 - 52 °C and 40 mmHg.

[0165] Measuring means Size exclusion chromatography (SEC) was performed on an Ultimate 3000 Thermo Scientific instrument equipped with an Agilent PLgel 5μm MIXED-C (300×7.5 mm) maintained at a constant temperature of 30 °C and one precolumn (PL Gel 5μm guard 50×7.5 mm). Detection was achieved using a differential refractometer (RI) and a diode array detector (UV). Tetrahydrofuran (THF) was eluted at a flow rate of 1.0 ml / min. Molecular weight and polydispersity D were calculated using polystyrene standards (Polymer Labs, Germany). 1 1H NMR (500 MHz) spectra were recorded on a Bruker AC-500 spectrometer at 25 °C in CDCl3 and corrected with respect to the internal (residual) solvent resonance. UV-Vis absorption spectra were recorded using an SM2203 (Solar) spectrophotometer.

[0166] Catalyst Preparation The liquid coordination complex was synthesized by simple mixing of the required amounts of dried phosphorus-containing electron donors and the corresponding anhydrous Lewis acids under an argon atmosphere according to the procedure reported by F. Coleman, G. Srinivasan and M. Swadzba-Kwasny, Angew. Chem., 2013, 52, 12582. The mixture was then stirred in the temperature range of 30 °C to 80 °C for 0.5 to 5 hours.

[0167] P 888 The synthesis of O-AlCl3 LCC (χ(AlCl3) = 0.6) was carried out as follows: 0.52 g of AlCl3 was added to 1 g of P 888 O under an argon atmosphere. The reaction mixture was then stirred at 40 °C until homogeneous (1 hour).

[0168] P 888 The synthesis of O-FeCl3 LCC (χ(FeCl3) = 0.6) involves: 0.63 g of FeCl3 was added to 1 g of P 888 O under an argon atmosphere. The reaction mixture was then stirred at 50 °C until the phosphine was completely dissolved (0.5 hour).

[0169] P 888 The synthesis of the 0×0.67AlCl3 donor-acceptor complex was carried out as follows: 3 mL of dry CH2Cl2 was mixed with 0.52 g of AlCl3 and 1 g of P under an argon atmosphere. 888 It was added to the mixture of O. The reaction mixture was then stirred at room temperature until homogeneous (0.5 hours).

[0170] P 888 The synthesis of the 0×0.67FeCl3 donor-acceptor complex was carried out as follows: 3 mL of dry CH2Cl2 was mixed with 0.63 g of FeCl3 and 1 g of P under an argon atmosphere. 888 It was added to the mixture of O. Then, the reaction mixture was heated at room temperature and P 888 The mixture was stirred until it was completely dissolved (0.5 hours).

[0171] P 888 The synthesis of the 0×0.58BF3 donor-acceptor complex was carried out as follows: 11.3 mL of dry CH2Cl2 was mixed with 4 g of P under an argon atmosphere. 888 It was added to O. The reaction mixture was then converted to P at -20°C under inert conditions using gaseous BF3. 888 The mixture was purged until the desired ratio of O to BF3 was reached.

[0172] Polymerization procedure The polymerization reaction was carried out in a glass tube equipped with a cold finger condenser under an argon atmosphere at a temperature of 0°C to 20°C. As an example of a typical procedure, polymerization was carried out using a 1M solution of diisopropyl ether in 0.11 mL of n-hexane and 0.11 mL of P 888 Isobutylene (2.86 g, 5.1 × 10) is added to a mixture of 5 mL total volume consisting of O-FeCl3 (χ(FeCl3) = 0.6) and n-hexane (4.8 mL). -2Polymerization was initiated by adding (mol) monomers. The reaction mixture was stirred for 3-5 minutes before the addition of monomers. After a predetermined time, approximately 2 mL of aqueous ammonia (25%) was added to the glass reactor to stop polymerization. The quenched reaction mixture was diluted with n-hexane and centrifuged to separate trace amounts of LCC from the polymer solution, which were finally precipitated in cold ethanol. The solvent was evaporated under reduced pressure to obtain the product polymer, which was then vacuum-dried (≤60°C). The monomer conversion rate was determined by gravimetric analysis.

[0173] PIB end group content, 1 The protons were determined by ¹H NMR spectroscopy (see Figure 1 for a typical ¹H NMR spectrum). Proton signals from the exoolefin terminal groups (b, b') appeared at 4.64 and 4.85 ppm, respectively, while those from the endoolefin terminal group (d) appeared at 5.15 ppm. Proton signals from the trisubstituted (e) and tetrasubstituted (g) olefinic terminal groups appeared at 5.15 and 2.84 ppm, respectively, while the proton signals from the CH2(l) and CH3(k) groups belonging to chlorine-terminated terminal groups were located at 1.96 and 1.68 ppm, respectively. The small signal at 4.80 ppm corresponds to the proton of the conjugated PIB chain (m). The exoolefin terminal group content was calculated according to the following equation: Exo(%) = I[(b+b') / 2] / I[k / 6+(b+b'+n) / 2+d+e+g](Figure 1).

[0174] In the context of this invention, the term "exo" refers to the terminal ethylenic double bond, vinylidene group, or α-double bond shown in the formula on page 1. These terms are used synonymously throughout this document.

[0175] The term "total vinylidene" refers to the terminal ethylenic double bond, referred to as exo above, and the following formula

[0176] [ka] This refers to further double bonds located within the polymer backbone shown.

[0177] The terms "end" and "trisubstituted" refer to the β-double bond shown in the second line of Figure 1. These terms are used synonymously throughout this document.

[0178] Furthermore, as shown in the upper right formula of Figure 1, a "tetrasubstituted" structural element can be found. Furthermore, chlorinated polyisobutene (PIBCl) was found.

[0179] [Examples] [Example 1] Formation of Liquid Complex The following combinations of phosphorus-containing electron donors and Lewis acids according to formula (II) were briefly tested for the possibility of preparing LCC.

[0180] [Table 1]

[0181] The liquid complexes listed in Table 1 were further investigated in the polymerization of isobutene.

[0182] [Example 2] According to the general procedure outlined above, isobutylene was polymerized in the presence of PPh3O-AlCl3 as a catalyst in n-hexane. Furthermore, for the conditions mentioned in Table 2, the polymerization was carried out as follows: Mole fraction χ(AlCl3) = 0.6; [IB] = 5.2 M; T = 0 °C; reaction time = 30 minutes.

[0183] [Table 2]

[0184] [Example 3] According to the general procedure outlined above, isobutylene was polymerized in the presence of P 888 O-AlCl3 as a catalyst in n-hexane. Furthermore, for the conditions mentioned in Table 3, the polymerization was carried out as follows: Mole fraction χ(AlCl3) = 0.6; [IB] = 5.2M; [P 888 [O-AlCl3] = 44 mM; [ether] = 11 mM; time = 30 minutes.

[0185] [Table 3]

[0186] [Example 4] Following the general procedure outlined above, isobutylene is used as a catalyst in n-hexane. 888 Polymerization was carried out at 0°C in the presence of O-FeCl3. Furthermore, polymerization was performed as follows under the conditions mentioned in Table 4: Mole fraction χ(FeCl3) = 0.6; [P 888 O-FeCl3] = 22mM; [IB] = 5.2M.

[0187] [Table 4]

[0188] [Example 5] To gain further insight into the polymerization mechanism, [ i Pr2O] / [P 888 P at O-FeCl3]=0.5 888 O-FeCl3 / i The dynamics of isobutylene polymerization using a Pr2O initiation system were briefly investigated.

[0189] The results are shown in Figure 3.

[0190] It is readily apparent that the reaction according to the present invention yields a much higher conversion rate than the reaction with [emim]Cl-FeCl3(2) according to Polymer, 145(2018)382-390 shown in Figure 2.

[0191] P 888 O-FeCl3 / i The Pr2O complex not only provides a higher conversion rate of isobutene in a shorter time than the [emim]Cl-FeCl3 system, but also...

[0192] At the same time, the exoselectivity at a certain conversion rate is higher for the complex according to the present invention than for the one used in the reaction shown in Figure 2.

[0193] [Example 6] The polymerization reaction was carried out at -20°C under an inert atmosphere in a steel container equipped with a cold finger type condenser. Polymerization was performed using 0.02 mL of MeOH and 10.00 mL of P. 888 Isobutylene (25.20 g, 45.0 × 10) was added to a mixture of 150.02 mL total volume consisting of O-BF3 (χ(BF3) = 0.58) and n-hexane (140.00 mL). -2 Polymerization was initiated by adding (mol) of [amount]. After 1 hour, polymerization was stopped by injecting 5 mL of MeOH into a steel container. The quenched reaction mixture was diluted with n-hexane and washed three times with MeOH. The solvent was evaporated under reduced pressure at 190°C to obtain the product polymer. The monomer conversion rate was determined by gravimetric analysis.

[0194] [Table 5] Several embodiments are shown below. Item 1 Preferably, the number average molecular weight M is 500 to 100,000. n A bulk or solution polymerization method for preparing a highly reactive isobutene homopolymer or copolymer having a total α-double bond and β-double bond content of at least 60 mol% per polyisobutene chain end (determined by gel filtration chromatography), comprising polymerizing isobutene or an isobutene-containing monomer mixture in the presence of at least one Lewis acid effective as a polymerization catalyst, wherein the Lewis acid is selected from the group consisting of aluminum trihalide-donor complexes, alkylaluminum halide-donor complexes, iron trihalide-donor complexes, gallium trihalide-donor complexes, titanium tetrahalide-donor complexes, zinc dihalide-donor complexes, tin dihalide-donor complexes, tin tetrahalide-donor complexes, and boron trihalide-donor complexes, and the complex is used as a donor. - At least one organic compound (II) selected from the group consisting of an organic compound having at least one oxygen 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 at least one ether functional group, an organic compound having at least one carboxylic acid ester functional group, an organic compound having at least one aldehyde functional group, an organic compound having at least one keto functional group, and an organic compound having at least one nitrogen-containing heterocycle, and - Equation (I) [ka] Or formula (Ia) P(OR 1 )(OR 2 )(OR 3 ) Alternatively, formula (Ib) P(OR 1 )(OR 2 )(OR 3 )(OR 4 )(OR 5 ) (In the formula, X 1 、X 2 and X 3 These are, independently of each other, oxygen, sulfur, or a single bond, preferably oxygen or a single bond, very preferably a single bond. R 1 、R 2 、R 3 、R 4 and R 5 (These are organic residues that have up to 20 carbon atoms, independently of each other.) at least one phosphorus-containing compound It contains a mixture of, However, the complex formed from at least one Lewis acid and at least one phosphorus-containing compound of formula (I), (Ia), or (Ib) has a melting point of 60°C or lower, preferably 40°C or lower, and particularly 20°C or lower. method. Section 2 X 1 、X 2 and X 3 The method described in item 1, wherein each of them is a single bond. Section 3 R 1 ~R 5 Each of these is C 2 ~C 18 Alkyl or C 6 ~C 12 The method according to item 1 or 2, wherein the material is an aryl compound. Section 4 The compounds of formula (II) are tri-n-hexylphosphine oxide, tri-n-octylphosphine oxide, triisononylphosphine oxide, tri-n-decylphosphine oxide, tri-n-dodecylphosphine oxide, triisotridecylphosphine oxide, tri-n-tetradecylphosphine oxide, triisoheptadecylphosphine oxide, triphenylphosphine oxide, tritylphosphine oxide, trinaphthylphosphine oxide, tri(n-butyl) phosphate ester, tri(n-hexyl) phosphate ester, tri(2-ethylhexyl) phosphate ester, tri(n-octyl) phosphate ester, tri(2-propylheptyl) phosphate ester, tri(n-decyl) phosphate ester, tri(n-dodecyl) phosphate ester, tri(n- The method according to claim 1, selected from the group consisting of tetradecyl) ester, tri(n-hexadecyl) phosphite, tri-ethyl phosphite, tri-n-butyl phosphite, tri-n-hexyl phosphite, tri-n-octyl phosphite, triisononyl phosphite, tri-n-decyl phosphite, tri-n-dodecyl phosphite, triisotridecyl phosphite, tri-n-tetradecyl phosphite, triisoheptadecyl phosphite, triphenyl phosphite, penta(ethoxy)phosphoran, penta(n-butyloxy)phosphoran, penta(hexyloxy)phosphoran, penta(n-octyloxy)phosphoran, penta(2-ethylhexyloxy)phosphoran, and penta(phenoxy)phosphoran. Section 5 The method according to any one of claims 1 to 4, wherein isobutene or an isobutene-containing monomer mixture is polymerized in the presence of an aluminum trihalide donor complex, an alkylaluminum halide donor complex, or an iron trihalide donor complex. Section 6 The method according to any one of claims 1 to 4, wherein isobutene or an isobutene-containing monomer mixture is polymerized in the presence of an iron trihalide donor complex that is effective as a polymerization catalyst. Section 7 The method according to any one of items 1 to 6, wherein the molar ratio of the Lewis acid to the compound of formula (I) is 1:0.1 to 10. Section 8 The method according to any one of claims 1 to 7, wherein at least one organic compound (II) is selected from the group consisting of an organic compound having at least one ether functional group, an organic compound having at least one carboxylic acid ester functional group, an organic compound having at least one aldehyde functional group, and an organic compound having at least one keto functional group. Section 9 A Lewis acid-donor complex, preferably an aluminum trihalide-donor complex, an alkylaluminum halide-donor complex, or an iron trihalide-donor complex, is compound (II) of the general formula R 8 -OR 9 (In the formula, the variable element R 8 and R 9 Each of them is independent of C 1 ~C 20 Alkyl alkyl group, C 1 ~C 20 Haloalkyl group, C 5 ~C 8 Cycloalkyl groups, C 6 ~C 20 Aryl group, C 6 ~C 20 Haloaryl group or C 7 ~C 20 The method according to any one of claims 1 to 7, comprising at least one organic compound having at least one ether functional group which is a dihydrocarbyl ether of an arylalkyl group, wherein the complex is used. Item 10 The method according to any one of claims 1 to 7, wherein at least one organic compound having at least one ether functional group is selected from the group consisting of diethyl ether, di-n-butyl ether, di-isopropyl ether and di-n-propyl ether, bis(2-chloroethyl) ether and 2-chloroethyl ethyl ether. Section 11 The method according to any one of claims 1 to 10, wherein the molar ratio of aluminum trihalide or alkylaluminum halide to isobutene monomer used in the homopolymerization of isobutene, or to the total amount of polymerizable monomer used in the copolymerization of isobutene, is 0.001:1 to 0.2:1 for each individual functional site of aluminum trihalide or alkylaluminum halide. Item 12 Polymerization occurs when one or more hydroxyl groups are each sp 3 Organic hydroxyl compounds bonded to hybrid carbon atoms, with one or more halogen atoms each being sp 3 The method according to any one of claims 1 to 11, further comprising the use of an organohalogen compound bonded to a hybrid carbon atom and a monofunctional or polyfunctional initiator selected from water. Section 13 The method according to claim 12, wherein the initiator is selected from water, methanol, ethanol, 1-phenylethanol, 1-(p-methoxyphenyl)ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane, tert-butyl chloride, and 1,3 or 1,4-bis(1-hydroxy-1-methylethyl)benzene. Section 14 The method according to item 12 or 13, wherein the molar ratio of the initiator mentioned to the isobutene monomer used in the homopolymerization of isobutene, or to the total amount of polymerizable monomer used in the copolymerization of isobutene, is 0.0005:1 to 0.1:1 for each individual functional site of the initiator, or, when water is used as the sole initiator or in combination with an organic hydroxyl compound and / or organic halogen compound as a further initiator, the molar ratio of water to the isobutene monomer used in the homopolymerization of isobutene, or to the total amount of polymerizable monomer used in the copolymerization of isobutene, is 0.0001:1 to 0.1:1. Section 15 The method according to any one of claims 1 to 14, wherein polymerization is carried out at a temperature of -90°C to +30°C. Section 16 At least one type of iron trihalide, - Depending on the circumstances, at least one organic compound (II) selected from the group consisting of an organic compound having at least one oxygen 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 at least one ether functional group, an organic compound having at least one carboxylic acid ester functional group, an organic compound having at least one aldehyde functional group, an organic compound having at least one keto functional group, and an organic compound having at least one nitrogen-containing heterocycle, and - Equation (I)

change

change

change

Claims

1. Number average molecular weight M between 500 and 100,000 n A bulk or solution polymerization method for preparing a highly reactive isobutene homopolymer or copolymer having a total α-double bond and β-double bond content of at least 60 mol% per polyisobutene chain end (determined by gel filtration chromatography), comprising polymerizing isobutene or an isobutene-containing monomer mixture in the presence of at least one Lewis acid-donor complex effective as a polymerization catalyst, selected from the group consisting of aluminum trihalide-donor complexes, alkylaluminum halide-donor complexes, iron trihalide-donor complexes, gallium trihalide-donor complexes, titanium tetrahalide-donor complexes, zinc dihalide-donor complexes, tin dihalide-donor complexes, tin tetrahalide-donor complexes, and boron trihalide-donor complexes, wherein the Lewis acid-donor complex effective as a polymerization catalyst is a donor - At least one organic compound (II) having at least one ether functional group, and - Equation (I) 【Chemistry 1】 Or formula (Ia) P(OR 1 )(OR 2 )(OR 3 ) Alternatively, formula (Ib) P(OR 1 )(OR 2 )(OR 3 )(OR 4 )(OR 5 ) (In the formula, X 1 , X 2 and X 3 These are, independently of each other, oxygen, sulfur, or single bonds. R 1 , R 2 , R 3 , R 4 and R 5 (These are organic residues that have up to 20 carbon atoms, independently of each other.) at least one phosphorus-containing compound It contains a mixture of, However, the complex formed from at least one Lewis acid and at least one phosphorus-containing compound of formula (I), (Ia), or (Ib) has a melting point of 60°C or lower. At least one organic compound (II) having at least one ether functional group in the mixture is of the general formula R 8 -OR 9 (In the formula, the variable element R 8 and R 9 Each of them is independent of C 1 ~C 20 Alkyl alkyl group, C 1 ~C 20 Haloalkyl group, C 5 ~C 8 Cycloalkyl groups, C 6 ~C 20 Aryl group, C 6 ~C 20 Haloaryl group or C 7 ~C 20 It is a dihydrocarbyl ether of an arylalkyl group. method.

2. X 1 , X 2 and X 3 The method according to claim 1, wherein each of them is a single bond.

3. R 1 ~R 5 Each of these is C 2 ~C 18 Alkyl or C 6 ~C 12 The method according to claim 1 or 2, wherein the material is an aryl.

4. At least one phosphorus-containing compound of formula (I), (Ia), or (Ib) is tri-n-hexylphosphine oxide, tri-n-octylphosphine oxide, triisononylphosphine oxide, tri-n-decylphosphine oxide, tri-n-dodecylphosphine oxide, triisotridecylphosphine oxide, tri-n-tetradecylphosphine oxide, triisoheptadecylphosphine oxide, triphenylphosphine oxide, tritylphosphine oxide, trinaphthylphosphine oxide, tri(n-butyl) phosphate ester, tri(n-hexyl) phosphate ester, tri(2-ethylhexyl) phosphate ester, tri(n-octyl) phosphate ester, tri(2-propylheptyl) phosphate ester, tri(n-decyl) phosphate ester, tri(n-dodecyl) phosphate ester The method according to claim 1, wherein a phosphate selected from the group consisting of phosphate, tri(n-tetradecyl) phosphate, tri(n-hexadecyl) phosphate, tri-ethyl phosphite, tri-n-butyl phosphite, tri-n-hexyl phosphite, tri-n-octyl phosphite, triisononyl phosphite, tri-n-decyl phosphite, tri-n-dodecyl phosphite, triisotridecyl phosphite, tri-n-tetradecyl phosphite, triisoheptadecyl phosphite, triphenyl phosphite, penta(ethoxy)phosphoran, penta(n-butyloxy)phosphoran, penta(hexyloxy)phosphoran, penta(n-octyloxy)phosphoran, penta(2-ethylhexyloxy)phosphoran, and penta(phenoxy)phosphoran is used.

5. The method according to any one of claims 1 to 4, wherein isobutene or an isobutene-containing monomer mixture is polymerized in the presence of an aluminum trihalide donor complex, an alkylaluminum halide donor complex, or an iron trihalide donor complex.

6. The method according to any one of claims 1 to 4, wherein isobutene or an isobutene-containing monomer mixture is polymerized in the presence of an iron trihalide donor complex that is effective as a polymerization catalyst.

7. The method according to any one of claims 1 to 6, wherein the molar ratio of the Lewis acid to the compound of formula (I) is 1:0.1 to 10.

8. The method according to any one of claims 1 to 7, wherein at least one organic compound (II) having at least one ether functional group is selected from the group consisting of diethyl ether, di-n-butyl ether, di-isopropyl ether, di-n-propyl ether, bis(2-chloroethyl) ether and 2-chloroethyl ethyl ether.

9. The method according to any one of claims 1 to 8, wherein the molar ratio of aluminum trihalide or alkylaluminum halide to isobutene monomer used in the homopolymerization of isobutene, or to the total amount of polymerizable monomer used in the copolymerization of isobutene, is 0.001:1 to 0.2:1 for each individual functional site of aluminum trihalide or alkylaluminum halide.

10. Polymerization occurs when one or more hydroxyl groups are each sp 3 Organic hydroxyl compounds bonded to hybrid carbon atoms, with one or more halogen atoms each being sp 3 The method according to any one of claims 1 to 9, further comprising the use of an organohalogen compound bonded to a hybrid carbon atom and a monofunctional or polyfunctional initiator selected from water.

11. The method according to claim 10, wherein the initiator is selected from water, methanol, ethanol, 1-phenylethanol, 1-(p-methoxyphenyl)ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane, tert-butyl chloride, and 1,3 or 1,4-bis(1-hydroxy-1-methylethyl)benzene.

12. The method according to claim 10 or 11, wherein the molar ratio of the initiator to the isobutene monomer used in the homopolymerization of isobutene, or to the total amount of polymerizable monomer used in the copolymerization of isobutene, is 0.0005:1 to 0.1:1 for each individual functional site of the initiator.

13. The method according to claim 10 or 11, wherein the initiator is water, and the molar ratio of water to the isobutene monomer used in the homopolymerization of isobutene, or the total amount of polymerizable monomer used in the copolymerization of isobutene, is 0.0001:1 to 0.1:

1.

14. The method according to any one of claims 1 to 13, wherein polymerization is carried out at a temperature of -90°C to +30°C.

15. At least one type of iron trihalide, - At least one organic compound (II) containing at least one oxygen or nitrogen atom having at least one lone pair of electrons, and - Equation (I) 【Chemistry 2】 Or formula (Ia) P(OR 1 )(OR 2 )(OR 3 ) Alternatively, formula (Ib) P(OR 1 )(OR 2 )(OR 3 )(OR 4 )(OR 5 ) (In the formula, X 1 , X 2 and X 3 These are, independently of each other, oxygen, sulfur, or single bonds. R 1 , R 2 , R 3 , R 4 and R 5 (These are organic residues that have up to 20 carbon atoms, independently of each other.) at least one phosphorus-containing compound A trihalide iron-donor complex comprising, A complex formed from at least one iron trihalide and at least one phosphorus-containing compound of formula (I), formula (Ia), or formula (Ib) has a melting point of 60°C or lower. Iron trihalide donor complex.

16. At least one type of boron trihalide, - At least one organic compound (II) containing at least one oxygen or nitrogen atom having at least one lone pair of electrons, and - Equation (I) 【Transformation 3】 Or formula (Ia) P(OR 1 )(OR 2 )(OR 3 ) Alternatively, formula (Ib) P(OR 1 )(OR 2 )(OR 3 )(OR 4 )(OR 5 ) (In the formula, X 1 , X 2 and X 3 These are, independently of each other, oxygen, sulfur, or single bonds. R 1 , R 2 , R 3 , R 4 and R 5 (These are organic residues that have up to 20 carbon atoms, independently of each other.) at least one phosphorus-containing compound A boron trihalide donor complex comprising, A complex formed from at least one boron trihalide and at least one phosphorus-containing compound of formula (I), formula (Ia), or formula (Ib) has a melting point of 60°C or lower. Boron trihalide donor complex.

17. - At least one metal halide selected from the group consisting of aluminum trihalides, alkylaluminum halides, gallium trihalides, titanium tetrahalides, zinc dihalides, tin dihalides, tin tetrahalides, and boron trihalides. - At least one organic compound (II) containing at least one oxygen or nitrogen atom having at least one lone pair of electrons, and - Equation (I) 【Chemistry 4】 Or formula (Ia) P(OR 1 )(OR 2 )(OR 3 ) Alternatively, formula (Ib) P(OR 1 )(OR 2 )(OR 3 )(OR 4 )(OR 5 ) (In the formula, X 1 , X 2 and X 3 These are, independently of each other, oxygen, sulfur, or single bonds. R 1 、R 2 、R 3 、R 4 and R 5 are, independently of one another, organic residues having up to 20 carbon atoms) at least one phosphorus-containing compound A metal halide-donor complex consisting of the above.

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