Process for the preparation of highly reactive isobutene homopolymers or copolymers

Abstract

The invention relates to a new process for the preparation of highly reactive isobutene homopolymers or copolymers.

Description

[0001] This invention relates to a novel method for preparing highly reactive isobutylene homopolymers or copolymers, wherein the content of terminal vinyl double bonds at the end of each polyisobutylene chain in the isobutylene homopolymer or copolymer is at least 70 mol%. This invention also relates to novel isobutylene polymers.

[0002] Compared to so-called low-reactive polymers, highly reactive isobutylene homopolymers or copolymers should be understood to mean polyisobutylenes containing, based on the chain ends of the polyisobutylene macromolecule, a high content, particularly typically at least 60 mol%, preferably at least 70 mol%, and very preferably at least 75 mol%, of terminal olefinic double bonds (α-double bonds) and other reactive double bonds readily capable of subsequent reactions (e.g., Alder-Ene-reaction with maleic anhydride). In the context of this application, vinylene should be understood to mean such terminal olefinic double bonds whose position in the polyisobutylene macromolecule is described by the following general formula:

[0003] polymer ,

[0004] This means the double bond is located at the α-position of the polymer chain. "Polymer" is an abbreviation for polyisobutylene unit. Vinylene exhibits the highest reactivity in many types of reactions, such as in thermal addition to sterically hindered reactants (e.g., maleic anhydride), while double bonds closer to the interior of the macromolecule generally exhibit lower reactivity in functionalization reactions (if any). Uses of highly reactive polyisobutylene include its use as an intermediate in the preparation of lubricants and fuel additives, for example, as described in DE-A2702604.

[0005] In addition, it has been known for some time that Lewis acid aluminum trichloride can also be used as a polymerization catalyst for isobutylene, for example, as known from High Polymers, Volume XXIV (Part 2), pp. 713-733 (edited by Edward C. Leonard), J. Wiley & Sons publishers, New York, 1971.

[0006] In the article "Novelinitiating system based on AlCl3 etherate for quasiliving cationic polymerization of styrene" in Polymer Bulletin, Vol. 52, pp. 227-234 (2004), Sergei V. Kostjuk et al. described a catalyst system for the polymerization of styrene consisting of a 2-phenyl-2-propanol and aluminum trichloride / n-butyl ether complex. Sergei V. Kostjuk et al., Macromolecules 2010, 43, 5503-5507, documented the polymerization of isobutylene with AlCl3 and butyl ether to form highly reactive polyisobutylene.

[0007] Dmitriy I. Shiman, Irina V. Vasilenko, Sergei V. Kostjuk, Journal of Polymer Science, Part A: Polymer Chemistry 2014, 52, 2386–2393 discloses a method for preparing polyisobutylene polymers by polymerizing isobutylene in the presence of an alkyl aluminum halide complex as a polymerization catalyst.

[0008] WO 18 / 015306 discloses a method for preparing highly reactive isobutylene homopolymers or copolymers, wherein certain Lewis acids are used in conjunction with at least one donor and at least one ionic liquid.

[0009] Examples of such ionic liquids disclosed in WO 18 / 015306 are, in particular, phosphorus-containing compounds in which the cation is a perdentate quaternary phosphonium salt.

[0010] However, the disadvantages of this type of ionic liquid are that they are expensive to prepare and significantly reduce the reactivity of the Lewis acids used.

[0011] Kostjuk et al., Polym. Chem., 2016, 7, 5615–5619 and Polymer, 145 (2018) 382–390, further pointed out that ionic liquids as catalysts for isobutylene polymerization require a fairly long reaction time to achieve medium to high monomer conversion rates. Figure 2 The graphs taken from the latter document show the relationship between the conversion of isobutylene and the exo-selectivity of the reaction with respect to reaction time in the presence of [emim]Cl–AlCl3(1), [emim]Cl-FeCl3(2), and [emim]Cl-GaCl3(3).

[0012] CN 102399308 A (machine translation) discloses a cationic emulsion polymerization of isobutylene monomers using aluminum trichloride and triphenylphosphine oxide as catalysts. Sorbitol monooleate is used as an emulsifier in the polymerization mixture.

[0013] No information was given regarding the double bond content; only a high molecular weight polyisobutylene of 240,000 was obtained.

[0014] One object of the present invention is to provide a method for preparing highly reactive isobutylene homopolymers or copolymers in acceptable yields and with high reaction rates, wherein the content of terminal vinylidene double bonds (α-double bonds) and β-double bonds at each polyisobutylene chain end of the isobutylene homopolymer or copolymer is at least 60 mol%. The catalytic system should possess both sufficient activity and lifetime, and should be easily prepared. Another object of the present invention is to develop a catalyst system that produces high conversion rates and maintains selectivity for reactive double bonds, particularly α-double bonds, even at high conversion rates.

[0015] This objective is achieved by a method for preparing highly reactive isobutylene homopolymers or copolymers, wherein the content (total) of α-double bonds and β-double bonds at the end of each polyisobutylene chain in the isobutylene homopolymer or copolymer is at least 60 mol%, preferably at least 70 mol%, and very preferably at least 75 mol%, the method comprising polymerizing isobutylene or a mixture of monomers containing isobutylene in the presence of at least one Lewis acid effective as a polymerization catalyst, the Lewis acid being selected from aluminum trihalide donor complexes, alkyl aluminum 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, the complexes comprising a mixture of the following as donors:

[0016] - At least one organic compound (II) comprising at least one oxygen or nitrogen atom having at least one lone pair of electrons, preferably comprising at least one oxygen atom having at least one lone pair of electrons, said organic compound being very preferably selected from organic compounds having at least one ether functional group, organic compounds having at least one carboxylic acid ester functional group, organic compounds having at least one aldehyde functional group, organic compounds having at least one ketone functional group, and organic compounds having at least one nitrogen-containing heterocycle, and

[0017] -At least one of the following phosphorus-containing compounds:

[0018] Formula (I)

[0019]

[0020] Or formula (Ia)

[0021] P(OR 1 (OR) 2 (OR) 3 )

[0022] Or (Ib)

[0023] P(OR 1 (OR) 2 (OR) 3 (OR) 4 (OR) 5 )

[0024] in

[0025] X1, X2, and X3 are independently oxygen, sulfur, or single bonds, preferably oxygen or single bonds, very preferably single bonds, and...

[0026] R 1 R 2 R 3 R 4 and R 5 Each is an organic group that has up to 20 carbon atoms and exists independently of the others.

[0027] The condition is that the melting point of the complex formed by at least one Lewis acid and at least one phosphorus-containing compound of formula (I), (Ia), or (Ib) is not greater than 60°C, preferably not greater than 40°C, and especially not greater than 20°C.

[0028] R 1 R 2 R 3 R 4 and R 5 Each of the C1–C atoms is independently separated by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imine atoms. 20 -alkyl, C2-C 20 -alkyl; C6–C 12 -Aryl; C5–C 12 - A cycloalkyl or five- or six-membered oxygen-, nitrogen-, and / or sulfur-containing heterocycle, or two of them together, forming an unsaturated, saturated, or aromatic ring, said ring being spaced by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, said groups being each substituted with the following functional groups: aryl, alkyl, aryloxy, alkoxy, halogen, heteroatom, and / or heterocycle. Because the complex formed from at least one Lewis acid and at least one phosphorus-containing compound of formula (I), (Ia), or (Ib) is liquid under these conditions, it is also called a "liquid coordination complex" or "LCC".

[0029] JM Hogg, LC Brown, K. Matuszek, P. Latos, A. Chrobok and M. Dalton Transaction, 2017, 46, 11561, reported the successful synthesis of complexes that are liquid at room temperature, formed by the reaction of tri-n-octylphosphine oxide with AlCl3 and TiCl4, respectively. However, only the Diels-Alder reaction of these complexes was disclosed, which did not make the polymerization of isobutylene readily apparent.

[0030] In these definitions

[0031] C1–C can be substituted with functional groups aryl, alkyl, aryloxy, alkoxy, halogen, heteroatom and / or heterocycle. 20-alkyl groups 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, heptadecanyl, octadecyl, eicosyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, diphenylmethyl, p-tolylmethyl, 1-(p-butylphenyl)ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl. m-ethoxybenzyl, 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-dioxane-2-yl, 1,3-dioxane-2-yl, 2-methyl-1,3-dioxane-2-yl, 4-methyl-1,3-dioxane-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-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 2-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, and

[0032] C2–C can be spaced by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imine atoms. 20The alkyl group is, 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-trioxapentadecanyl, 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, 11-methoxy 4,8-dioxaundecyl, 15-methoxy-4,8,12-trioxapentadecanyl, 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-trioxapentadecanyl, 9-ethoxy-5-oxanonyl, or 14-ethoxy-5,10-tetradecyl.

[0033] If two groups form a ring, they together can be 1,3-propylidene, 1,4-butylidene, 1,5-pentylidene, 2-oxa-1,3-propylidene, 1-oxa-1,3-propylidene, 2-oxa-1,3-propylidene, 1-oxa-1,3-propenyne, 1-aza-1,3-propenyne, 1-C1-C4-alkyl-1-aza-1,3-propenyne, 1,4-but-1,3-dieneidene, 1-aza-1,4-but-1,3-dieneidene, or 2-aza-1,4-but-1,3-dieneidene.

[0034] There is no limitation on the number of oxygen and / or sulfur atoms and / or imino groups. Typically, the number in the group will not exceed 5, preferably not more than 4, and very particularly preferably not more than 3.

[0035] In addition, at least one carbon atom is usually present between any two heteroatoms, preferably at least two carbon atoms.

[0036] The substituted and unsubstituted imino groups can be, for example, imino, methylimino, isopropylimino, n-butylimino, or tert-butylimino.

[0037] also,

[0038] The functional group can be carboxyl, carboxylic acid amide, hydroxyl, di(C1-C4-alkyl)amino, C1-C4-alkyloxycarbonyl, cyano, or C1-C4-alkyloxy.

[0039] C6–C atoms that can be substituted with functional groups aryl, alkyl, aryloxy, alkoxy, halogen, heteroatom and / or heterocycle 12 -The aryl group can be, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexoxyphenyl, 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.

[0040] C5–C atoms that can be substituted with functional groups aryl, alkyl, aryloxy, alkoxy, halogen, heteroatom and / or heterocycle 12 -The cycloalkyl group is, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, or a saturated or unsaturated bicyclic system, such as norbornyl or norbornenyl.

[0041] Five- or six-membered oxygen, nitrogen, and / or sulfur-containing heterocycles are, for example, furanyl, thiophene, pyrrole, pyridyl, indolyl, benzoxazolyl, dioxacyclopentenyl, dioxacyclohexenyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolinyl, dimethylpyrrole, methoxyfuranyl, dimethoxypyridyl, difluoropyridyl, methylthiophene, isopropylthiophene, or tert-butylthiophene.

[0042] C1 to C4 alkyl groups are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl.

[0043] Group R 1 To R 5 C2-C is preferred. 18 -alkyl or C6-C 12 -Aryl, more preferably C4-C 16 -alkyl or C6-C 12 -Aryl, or even better C4-C 16 -alkyl or C6-aryl.

[0044] Group R 1 To R 5 It can be saturated or unsaturated, but saturated is preferred.

[0045] Group R 1 To R 5 And X1, X2 and X3 may each be the same or different; in one embodiment of the invention, they are each the same.

[0046] Preferred group R 1 To R 5 It does not contain any heteroatoms other than carbon and hydrogen.

[0047] Preferred compounds of formula (I) or (Ia) or (Ib) are tri-n-hexylphosphine oxide, tri-n-octylphosphine oxide (P 888 O), triisononylphosphine oxide, tri-n-decylphosphine oxide, tri-n-dodecylphosphine oxide, triisotridecylphosphine oxide, tri-n-tetradecylphosphine oxide, triisoheptadecylphosphine oxide, triphenylphosphine oxide (PPh3O), trimethylphosphine oxide, trinaphthylphosphine oxide, tri(n-butyl) phosphite, tri(n-hexyl) phosphite, tri(2-ethylhexyl) phosphite, tri(n-octyl) phosphite, tri(2-propylheptyl) phosphite, tri(n-decyl) phosphite, tri(n-dodecyl) phosphite, phosphoric acid Tri(tetradecyl) ester, tri(hexadecyl) ester of phosphite, triethyl 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)phosphine, penta(n-butoxy)phosphine, penta(hexoxy)phosphine, penta(n-octoxy)phosphine, penta(2-ethylhexyloxy)phosphine, and penta(phenoxy)phosphine.

[0048] Other active substances are the corresponding hypophosphite (P(OR) 1 )R 2 2) Phosphite (P(OR) 1 )2R 2 ) and phosphonates (OP(OR) 1 )2R 2 Examples include diethylphenylphosphonate, di-n-butylphenylphosphonate, di(2-ethylhexyl)phenylphosphonate, ethyl diphenylphosphonite, n-butyl diphenylphosphonite, (2-ethylhexyl) diphenylphosphonite, diethylphenylphosphonate, di-n-butylphenylphosphonate, and di(2-ethylhexyl)phenylphosphonate.

[0049] In the case of phosphites, the alcohol component may be a mixture of fatty alcohols derived from a mixture of fatty acids, which may be industrially obtained from the processing 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 particularly 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.

[0050] Another object of the present invention is a ferric trihalide donor complex comprising: at least one ferric trihalide,

[0051] - Optionally at least one organic compound (II) comprising at least one oxygen or nitrogen atom having at least one lone pair of electrons, preferably comprising at least one oxygen atom having at least one lone pair of electrons, and very preferably selected from organic compounds having at least one ether functional group, organic compounds having at least one carboxylic acid ester functional group, organic compounds having at least one aldehyde functional group, organic compounds having at least one ketone functional group, and organic compounds having at least one nitrogen-containing heterocycle, and

[0052] -At least one of the following phosphorus-containing compounds:

[0053] Formula (I)

[0054]

[0055] Or formula (Ia)

[0056] P(OR 1 (OR) 2 (OR) 3 )

[0057] Or (Ib)

[0058] P(OR 1 (OR) 2 (OR) 3 (OR) 4 (OR) 5 )

[0059] in

[0060] X1, X2, and X3 are independently oxygen, sulfur, or single bonds, preferably oxygen or single bonds, very preferably single bonds, and...

[0061] R 1 R 2 R 3 R 4 and R 5Each is an organic group that has up to 20 carbon atoms and is independent of the others.

[0062] In a preferred embodiment of the invention, compound (II) is present.

[0063] Another embodiment of this objective is a ferric trihalide donor complex, wherein the complex formed by at least one ferric trihalide and at least one phosphorus-containing compound of formula (I) or (Ia) or (Ib) has a melting point of not more than 60°C, preferably not more than 40°C and especially not more than 20°C.

[0064] In another embodiment of the present invention, the molar ratio of ferric trihalide, compound of formula (II), and compound of formula (I), (Ia), or (Ib) in the ferric trihalide donor complex is typically 1:0 to 10:0.1 to 10, preferably 1:0.1 to 10:0.2 to 5, more preferably 1:0.2 to 5:0.3 to 3.

[0065] Another object of the present invention is the use of the iron trihalide donor complex as a catalyst in the polymerization of unsaturated monomers, preferably in the cationic polymerization of unsaturated monomers, more preferably in olefinic unsaturated monomers, and even more preferably in the cationic polymerization of olefins, especially mixtures of isobutylene-containing monomers.

[0066] Another particularly preferred object of the present invention is a boron trihalide donor complex consisting of at least one boron trihalide.

[0067] - Optionally at least one organic compound (II) comprising at least one oxygen or nitrogen atom having at least one lone pair of electrons, preferably comprising at least one oxygen atom having at least one lone pair of electrons, and very preferably selected from organic compounds having at least one ether functional group, organic compounds having at least one carboxylic acid ester functional group, organic compounds having at least one aldehyde functional group, organic compounds having at least one ketone functional group, and organic compounds having at least one nitrogen-containing heterocycle, and

[0068] -At least one of the following phosphorus-containing compounds:

[0069] Formula (I)

[0070]

[0071] Or formula (Ia)

[0072] P(OR 1 (OR) 2 (OR) 3 )

[0073] Or (Ib)

[0074] P(OR 1(OR) 2 (OR) 3 (OR) 4 (OR) 5 )

[0075] in

[0076] X1, X2, and X3 are independently oxygen, sulfur, or single bonds, preferably oxygen or single bonds, very preferably single bonds, and...

[0077] R 1 R 2 R 3 R 4 and R 5 Each is an organic group that has up to 20 carbon atoms and is independent of the others.

[0078] In one embodiment of this invention, compound (II) is present.

[0079] Another embodiment of this objective is a boron trihalide donor complex, wherein the complex formed by at least one boron trihalide and at least one phosphorus-containing compound of formula (I) or (Ia) or (Ib) has a melting point of not more than 60°C, preferably not more than 40°C and especially not more than 20°C.

[0080] In another embodiment of the present invention, the molar ratio of boron trihalide, compound of formula (II), and compound of formula (I), (Ia), or (Ib) in the boron trihalide donor complex is typically 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.

[0081] Another object of the present invention is the use of the boron trihalide donor complex as a catalyst in the polymerization of unsaturated monomers, preferably in the cationic polymerization of unsaturated monomers, more preferably in olefinic unsaturated monomers, and even more preferably in the cationic polymerization of olefins, especially mixtures of isobutylene-containing monomers.

[0082] Another object of the present invention is a metal halide donor complex composed of the following:

[0083] - At least one metal halide selected from aluminum trihalide, aluminum alkyl halide, gallium trihalide, titanium tetrahalide, zinc dihalide, tin dihalide, tin tetrahalide, and boron trihalide.

[0084] - At least one organic compound (II) comprising at least one oxygen or nitrogen atom having at least one lone pair of electrons, preferably comprising at least one oxygen atom having at least one lone pair of electrons, and very preferably selected from organic compounds having at least one ether functional group, organic compounds having at least one carboxylic acid ester functional group, organic compounds having at least one aldehyde functional group, organic compounds having at least one ketone functional group, and organic compounds having at least one nitrogen-containing heterocycle, and

[0085] -At least one of the following phosphorus-containing compounds:

[0086] Formula (I)

[0087]

[0088] Or formula (Ia)

[0089] P(OR 1 (OR) 2 (OR) 3 )

[0090] Or (Ib)

[0091] P(OR 1 (OR) 2 (OR) 3 (OR) 4 (OR) 5 )

[0092] in

[0093] X1, X2, and X3 are independently oxygen, sulfur, or single bonds, preferably oxygen or single bonds, very preferably single bonds, and...

[0094] R 1 R 2 R 3 R 4 and R 5 Each is an organic group that has up to 20 carbon atoms and is independent of the others.

[0095] The metal halide is preferably selected from aluminum trihalide, alkyl aluminum halide, titanium tetrahalide, tin tetrahalide and boron trihalide, more preferably from aluminum trihalide, alkyl aluminum halide, titanium tetrahalide and boron trihalide, even more preferably from aluminum trihalide, alkyl aluminum halide and boron trihalide, and particularly the metal halide is aluminum trihalide or even aluminum trichloride.

[0096] Another embodiment of this objective of the invention is a metal halide donor complex, wherein the complex formed of at least one metal halide and at least one phosphorus-containing compound of formula (I) or (Ia) or (Ib) has a melting point of not more than 60°C, preferably not more than 40°C and especially not more than 20°C.

[0097] In another embodiment of the present invention, the molar ratio of the metal halide, the compound of formula (II), and the compound of formula (I), (Ia), or (Ib) in the metal halide donor complex is typically 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.

[0098] Another object of the present invention is the use of the metal halide donor complex as a catalyst in the polymerization of unsaturated monomers, preferably in the cationic polymerization of unsaturated monomers, more preferably in olefinic unsaturated monomers, and even more preferably in the cationic polymerization of olefins, especially mixtures of isobutylene-containing monomers.

[0099] In the context of this invention, isobutylene homopolymers should be understood to refer to those polymers formed from isobutylene at a level of at least 98 mol%, preferably at least 99 mol%, based on the polymer. Therefore, isobutylene copolymers should be understood to refer to those polymers containing less than 2 mol%, preferably less than 1 mol%, very preferably less than 0.7 mol%, and especially less than 0.5 mol% of comonomers other than isobutylene (such as isoprene or linear butene, preferably 1-butene, cis-2-butene, and trans-2-butene).

[0100] In the context of this invention, the following definitions apply to groups as generally defined:

[0101] C1- to C8-alkyl are straight-chain or branched alkyl groups having 1 to 8 carbon atoms. Examples of such compounds 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. These C1- to C8-alkyl groups may also contain, to a very small extent, heteroatoms such as oxygen, nitrogen, or halogen atoms, such as chlorine, and / or aprotic functional groups such as carboxylic acid esters, cyano groups, or nitro groups.

[0102] C1 to C 20-alkyl groups are straight-chain or branched alkyl groups having 1 to 20 carbon atoms. Examples include the C1- to C8-alkyl groups mentioned above, as well as n-nonyl, isononyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, isotriadecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and n-eicosyl. These C1- to C8-alkyl groups... 20 -Alkyl groups may also contain, to a very small extent, heteroatoms such as oxygen, nitrogen, or halogen atoms, such as chlorine, and / or aprotic functional groups such as carboxylic acid esters, cyano groups, or nitro groups.

[0103] C5- to C8-cycloalkyl groups are saturated cyclic groups that may contain alkyl side chains. Examples include cyclopentyl, 2-methylcyclopentyl or 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, 2,4-dimethylcyclopentyl or 2,5-dimethylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl or 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl or 3,6-dimethylcyclohexyl, cycloheptyl, 2-methylcycloheptyl, 3-methylcycloheptyl or 4-methylcycloheptyl, cyclooctyl, 2-methylcyclooctyl, 3-methylcyclooctyl, 4-methylcyclooctyl or 5-methylcyclooctyl. These C5- to C8-cycloalkyl groups may also contain heteroatoms such as oxygen, nitrogen, or halogen atoms, such as chlorine, and / or aprotic functional groups such as carboxylic acid esters, cyano groups, or nitro groups to a very small extent.

[0104] C6-to-C 20 -Aryl or C6-to-C 12 - The aryl group is preferably a substituted phenyl, a substituted naphthyl, a substituted anthracene, or a substituted phenanthryl. Such aryl groups may have 1 to 5 aprotic substituents or aprotic functional groups, such as C1- to C8-alkyl, C1- to C8-haloalkyl such as C1- to C8-chloroalkyl or C1- to C8-fluoroalkyl, halogens such as chlorine or fluorine, nitro, cyano, or phenyl. Examples of such aryl groups are phenyl, naphthyl, biphenyl, anthracene, phenanthryl, tolyl, nitrophenyl, chlorophenyl, dichlorophenyl, pentafluorophenyl, pentachlorophenyl, (trifluoromethyl)phenyl, bis(trifluoromethyl)phenyl, (trichloro)methylphenyl, and bis(trichloromethyl)phenyl.

[0105] C7 to C 20 -Arylalkyl or C7-to-C7 12-The arylalkyl group is preferably an optionally substituted C1- to C4-alkylphenyl group, such as benzyl, o-methylbenzyl, m-methylbenzyl, or p-methylbenzyl, 1-phenylethyl or 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, or 3-phenylpropyl, or 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl, or 4-phenylbutyl, optionally substituted C1- to C4-alkylnaphthyl such as naphthylmethyl, optionally substituted C1- to C4-alkylanthrayl such as anthracenemethyl, or optionally substituted C1- to C4-alkylphenanthryl such as phenanthrylmethyl. Such arylalkyl groups may—especially at the aryl moiety—have 1 to 5 aprotic substituents or aprotic functional groups, such as C1- to C8-alkyl, C1- to C8-haloalkyl such as C1- to C8-chloroalkyl or C1- to C8-fluoroalkyl, halogen such as chlorine or fluorine, nitro or phenyl.

[0106] Suitable aluminum trihalides are, in particular, aluminum trifluoride, aluminum trichloride or aluminum tribromide, with aluminum trichloride being preferred.

[0107] Useful alkyl aluminum halides are particularly mono(C1- to C4-alkyl) aluminum halides or di(C1- to C4-alkyl) monoalloys, such as methyl aluminum chloride, ethyl aluminum chloride, isobutyl aluminum chloride, dimethyl aluminum chloride or diethyl aluminum chloride, diisobutyl aluminum chloride, preferably ethyl aluminum chloride, isobutyl aluminum chloride, diethyl aluminum chloride or diisobutyl aluminum chloride, and very preferably ethyl aluminum chloride and isobutyl aluminum chloride.

[0108] Particularly suitable ferric halides are ferric fluoride, ferric chloride, or ferric bromide, with ferric chloride being preferred.

[0109] Gallium trihalides that are particularly suitable are gallium trifluoride, gallium trichloride or gallium tribromide, with gallium trichloride being preferred.

[0110] Particularly suitable titanium tetrahalides are titanium tetrafluoride, titanium tetrachloride or titanium tetrabromide, with titanium tetrachloride being preferred.

[0111] Particularly suitable zinc dihalides are zinc difluoride, zinc dichloride, or zinc dibromide, with zinc dichloride being preferred.

[0112] Particularly suitable tin dihalides are tin difluoride, tin dichloride, or tin dibromide, with tin dichloride being preferred.

[0113] Particularly suitable tin tetrachloride are tin tetrafluoride, tin tetrachloride or tin tetrabromide, with tin tetrachloride being preferred.

[0114] Particularly suitable boron trihalides are boron trifluoride, boron trichloride and boron tribromide, with boron trifluoride and boron trichloride being preferred, and boron trifluoride being more preferred.

[0115] Among these Lewis acids, aluminum trihalides, alkyl aluminum halides, iron trihalides, titanium tetrahalides, and boron trihalides are preferred.

[0116] Very preferred are aluminum trihalides, aluminum alkyl halides, iron trihalides, and boron trihalides, with aluminum trihalides being particularly preferred, especially aluminum trichloride.

[0117] In a preferred embodiment, isobutylene or a mixture of monomers containing isobutylene is polymerized in the presence of an alkyl aluminum chloride donor complex or a dialkyl aluminum chloride donor complex as a polymer catalyst, most preferably in the presence of an aluminum chloride donor complex or a ferric chloride donor complex.

[0118] The molar ratio of the Lewis acid to the compound of formula (I) or (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. Under these conditions, the melting point of the complex formed by at least one Lewis acid and at least one phosphorus-containing compound of formula (I) or (Ia) or (Ib) is not greater than 60°C, preferably not greater than 40°C, and especially not greater than 20°C.

[0119] An unavoidable aspect of the invention is that the melting point of the complex formed by at least one Lewis acid and at least one phosphorus-containing compound of formula (I), (Ia), or (Ib) is not greater than 60°C, preferably not greater than 40°C, and especially not greater than 20°C, more preferably not greater than 10°C, and more preferably not greater than 0°C (determined by differential scanning calorimetry at a heating rate of 5°C / min in the range of -20°C to 150°C).

[0120] According to the present invention, the aluminum trihalide donor complex, alkyl aluminum halide donor complex, iron trihalide donor complex, gallium trihalide donor complex, titanium tetrahalide donor complex, zinc dihalide donor complex, tin dihalide donor complex, tin tetrahalide donor complex, or boron trihalide donor complex, which are effective as polymerization catalysts, contain a mixture of the following as donors:

[0121] - At least one organic compound (II) comprising at least one oxygen or nitrogen atom having at least one lone pair of electrons, preferably comprising at least one oxygen atom having at least one lone pair of electrons, and very preferably selected from organic compounds having at least one ether functional group, organic compounds having at least one carboxylic acid ester functional group, organic compounds having at least one aldehyde functional group, organic compounds having at least one ketone functional group, and organic compounds having at least one nitrogen-containing heterocycle.

[0122] - and at least one compound of formula (I) or (Ia) or (Ib) as defined above, provided that the melting point of the complex formed by at least one Lewis acid and at least one phosphorus-containing compound of formula (I) or (Ia) or (Ib) is not greater than 60°C, preferably not greater than 40°C and especially not greater than 20°C.

[0123] The compound of formula (I) is preferred over the compounds of formula (Ia) or (Ib).

[0124] Compound (II) contains at least one oxygen atom and / or nitrogen atom having at least one lone pair of electrons, preferably at least one oxygen atom having at least one lone pair of electrons, and is very preferably selected from organic compounds having at least one ether functional group, organic compounds having at least one carboxylic acid ester functional group, organic compounds having at least one aldehyde functional group, organic compounds having at least one ketone functional group, and organic compounds having at least one nitrogen-containing heterocycle.

[0125] Compared to nitrogen-containing compound (II), compound (II) containing only oxygen is preferred.

[0126] Preferably, compound (II) is selected from 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 ketone functional group; more preferably, it is selected from organic compounds having at least one ether functional group and organic compounds having at least one carboxylic acid ester functional group; and most preferably, compound (II) is an organic compound having at least one ether functional group, especially an organic compound having exactly one ether functional group.

[0127] Compounds having at least one ether functional group are also understood to refer to acetals and hemiacetals. The ether compound may contain one or more ether functional groups, such as one, two, three, four or even more ether functional groups, preferably one or two ether functional groups, and very preferably one ether functional group.

[0128] The donor mixture may contain one, two, three, four or even more different compounds (II), preferably compounds having at least one ether functional group, preferably one or two different compounds and very preferably one compound.

[0129] In a preferred embodiment of the invention, an aluminum trihalide donor complex or an alkyl aluminum halide complex, or an iron trihalide donor complex, or a gallium trihalide donor complex, or a titanium tetrahalide donor complex, or a zinc dihalide donor complex, or a tin dihalide donor complex, or a tin tetrahalide donor complex, or a boron trihalide donor complex are used. Aluminum trihalide donor complexes, iron trihalide donor complexes, or boron trihalide donor complexes are particularly preferred. Aluminum trihalide donor complexes, in particular, contain a mixture of the following substances as donors:

[0130] - at least one general formula R 8 -OR 9 dialkyl ethers, where the variable R 8 and R 9 Each independently is C1- to C 20-alkyl, preferably C1- to C8 alkyl, especially C1- to C4 alkyl, C1- to C8 ... 20 - Haloalkyl, preferably C1- to C8 haloalkyl, especially C1- to C4 haloalkyl, C5- to C8 cycloalkyl, preferably C5- to C6 cycloalkyl, C6- to C8 cycloalkyl, 20 -Aryl groups, especially C6-to-C6 12 Aryl, C6-to-C 20 -Halogenated aryl groups, especially C6-to-C6 12 Halogenated aryl, or C7-to-C 20 -Arylalkyl, especially C7- to C6 12 -Arylalkyl. Preferably C1- to C4 alkyl, C1- to C4 haloalkyl, C6- to C4 ...-alkyl, C6- to C4-alkyl, C6- to C4-alkyl, C6- to C4-alkyl, C6- 12 Aryl and C7-to-C 12 -arylalkyl, and

[0131] - at least one compound of formula (I), (Ia), or (Ib),

[0132] The condition is that the melting point of the complex formed by at least one Lewis acid and at least one phosphorus-containing compound of formula (I), (Ia), or (Ib) is not greater than 60°C, preferably not greater than 40°C, and especially not greater than 20°C.

[0133] Halogenated alkyl and halogenated aryl groups preferably refer to chloroalkyl or bromoalkyl and chloroaryl or bromoaryl groups, with chloroalkyl and chloroaryl groups being very preferred. ω-halogenated alkyl groups are particularly preferred.

[0134] Preferred examples are chloromethyl, 1-chloroethyl-1-yl, 2-chloroethyl-1-yl, 2-chloropropyl-1-yl, 2-chloropropyl-2-yl, 3-chloropropyl-1-yl, and 4-chlorobutyl-1-yl.

[0135] Preferred examples of chloroaryl groups are 2-chlorophenyl, 3-chlorophenyl and 4-chlorophenyl.

[0136] The dialkyl ether can be open-chain or cyclic, wherein in the case of a cyclic ether, the two variables R... 8 and R 9They can combine to form rings, wherein the rings may also contain two or three ether oxygen atoms. Examples of open-chain and cyclic dialkyl ethers are methyl ether, chloromethyl methyl ether, bis(chloromethyl) ether, diethyl ether, chloromethyl ethyl ether, 2-chloroethyl ethyl ether (CEE), bis(2-chloroethyl) ether (CE), n-propyl ether, isopropyl ether, n-butyl ether, sec-butyl ether, isobutyl ether, n-pentyl ether, n-hexyl ether, n-heptyl ether, 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-dioxane, 1,3-dioxane, 1,4-dioxane, dicyclohexyl ether, diphenyl ether, alkyl aryl ethers (such as anisole and phenethyl ether, xylyl ether, bis-xylyl ether and dibenzyl ether).

[0137] In addition, difunctional ethers such as dialkoxybenzene are preferred, dimethoxybenzene is preferred, and o-dimethoxybenzene is very preferred; as well as ethylene glycol dialkyl ethers, preferably ethylene glycol dimethyl ether and ethylene glycol diethyl ether.

[0138] Among the dialkyl ethers mentioned, diethyl ether, 2-chloroethyl ethyl ether, isopropyl ether, n-butyl ether, and diphenyl ether have been found to be particularly advantageous as donors of: aluminum trihalide donor complexes or alkyl aluminum halide complexes or iron trihalide donor complexes or gallium trihalide donor complexes or titanium tetrahalide donor complexes or zinc dihalide donor complexes or tin dihalide donor complexes or tin tetrahalide donor complexes or boron trihalide donor complexes, with aluminum trihalide donor complexes or iron trihalide donor complexes or boron trihalide donor complexes being particularly preferred, especially aluminum trihalide donor complexes.

[0139] In another preferred embodiment, a dialkyl ether having at least one secondary or tertiary dialkyl group is preferred over a dialkyl group having only a primary group. An ether having a primary dialkyl group is one in which both dialkyl groups are bonded to an ether functional group having a primary carbon atom, while an ether having at least one secondary or tertiary dialkyl group is one in which at least one dialkyl group is bonded to an ether functional group having a secondary or tertiary carbon atom.

[0140] For clarity, isobutyl ether, for example, is considered an ether with a primary dialkyl group because the secondary carbon atom of the isobutyl group does not bind to the oxygen in the functional ether group, but rather binds to the hydrocarbon group through the primary carbon atom.

[0141] Preferred examples of ethers having a primary dialkyl group are diethyl ether, n-butyl ether, and n-propyl ether.

[0142] Preferred examples of ethers having at least one secondary or tertiary dialkyl group are isopropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, and anisole.

[0143] In addition, dialkyl ethers have been found to be particularly advantageous as donors of aluminum trihalide or alkyl aluminum halide complexes, wherein the total number of carbon atoms in the donor compound is 3 to 16, preferably 4 to 16, especially 4 to 12, and particularly those with 4 to 8.

[0144] In another preferred embodiment, the halide-substituted ether is preferably combined with an aluminum halide donor complex, an iron halide donor complex, or a boron halide donor complex.

[0145] Organic compounds having at least one carboxylic acid ester functional group are preferably of the general formula R. 10 -COOR 11 Hydrocarbon carboxylic acid esters, where the variable R 10 and R 11 Each independently is C1- to C 20 -alkyl, especially C1- to C8 alkyl, C5- to C8 cycloalkyl, C6- to C8 cycloalkyl 20 -Aryl groups, especially C6-to-C6 12 Aryl, or C7-to-C 20 -Arylalkyl, especially C7- to C6 12 -Arylalkyl.

[0146] Examples of the alkyl carboxylic acid esters are methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, sec-butyl formate, isobutyl formate, tert-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, sec-butyl acetate, isobutyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, sec-butyl propionate, isobutyl propionate, tert-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, sec-butyl butyrate, and isobutyl butyrate. Butyl ester, tert-butyl butyrate, methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, n-propyl cyclohexanecarboxylate, isopropyl cyclohexanecarboxylate, n-butyl cyclohexanecarboxylate, sec-butyl cyclohexanecarboxylate, isobutyl cyclohexanecarboxylate, tert-butyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, n-propyl phenylacetate, isopropyl phenylacetate, n-butyl phenylacetate, sec-butyl phenylacetate, isobutyl phenylacetate, tert-butyl phenylacetate, and tert-butyl phenylacetate. Among these hydrocarbon carboxylic acid esters, ethyl acetate has been found to be particularly advantageous as a donor for the complex.

[0147] In addition, hydrocarbon carboxylic esters have been found to be particularly advantageous as donors, wherein the total number of carbon atoms in the donor compound is 3 to 16, preferably 4 to 16, especially 4 to 12, particularly those with 4 to 8, and especially those with a total of 3 to 10, and especially 4 to 6 carbon atoms.

[0148] Organic compounds having at least one aldehyde functional group, preferably exactly one aldehyde functional group, and organic compounds having at least one ketone functional group, preferably exactly one ketone functional group, typically have 1 to 20, preferably 2 to 10 carbon atoms. Preferably, no functional groups other than a carbonyl group are present.

[0149] Preferred organic compounds having at least one aldehyde functional group are those of formula R. 10 Those of -CHO, among which R 10 With the above-mentioned characteristics, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, and benzaldehyde are highly preferred.

[0150] Preferred organic compounds having at least one ketone functional group are of formula R 10 -(C=O)-R 11 Of those, R 10 and R 11 Having the above-mentioned characteristics, the most preferred selection is from acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, and benzophenone. Acetone is the most preferred.

[0151] Organic compounds having at least one nitrogen-containing heterocycle are preferably saturated, partially unsaturated, or unsaturated nitrogen-containing five- or six-membered heterocycles, said heterocycle comprising one, two, or three cyclic nitrogen atoms and may have one or two other cyclic heteroatoms selected from oxygen and sulfur, as well as a hydrocarbon group, especially C1- to C4-alkyl and / or phenyl as a substituent, and / or a functional group or heteroatom, especially fluorine, chlorine, bromine, nitro, and / or cyano, such as pyrrolidine, pyrrole, imidazole, 1,2,3-triazole or 1,2,4-triazole, oxazole, thiazole, piperidine, pyrazane, pyrazole, pyridazine, pyrimidine, pyrazine, 1,2,3-triazine, 1,2,4-triazine or 1,2,5-triazine, 1,2,5-oxathiazine, 2H-1,3,5-thiadiazine, or morpholine.

[0152] However, very particularly suitable nitrogen-containing basic compounds of this class are pyridine or pyridine derivatives (especially mono-, di-, or tri-C1- to C4-alkyl-substituted pyridines), such as 2-, 3-, or 4-methylpyridine (methylpyridines), 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-, or 3,6-dimethylpyridine (dimethylpyridines), 2,4,6-trimethylpyridine (trimethylpyridine), 2-, 3-, or 4-tert-butylpyridine, 2-tert-butyl-6-methylpyridine, 2,4-, 2,5-, 2,6-, or 3,5-di-tert-butylpyridine, or 2-, 3-, or 4-phenylpyridine.

[0153] The molar ratio of the donor compound (based on the sum of compound (II) in the mixture, preferably the sum of ethers plus the sum of compounds of formula (I) or (Ia) or (Ib)) to aluminum trihalide or alkyl aluminum halide or iron trihalide or gallium trihalide or titanium tetrahalide or zinc dihalide or tin dihalide or tin tetrahalide or boron trihalide typically varies from 0.4:1 to 2.0:1, especially from 0.5:1 to 1.8:1, particularly from 0.7:1 to 1.6:1; in most cases it is from 0.9:1 to 1.5:1. However, a larger excess of the donor compound can also be used, typically up to 10 times, especially 3 times; the excess donor compound is then used additionally as a solvent or diluent.

[0154] The molar ratio of compound (II), preferably an ether compound (based on all of compound (II) and all of the ether, respectively), to compounds of formula (I), (Ia), or (Ib) (based on all of formula (I), (Ia), or (Ib)) in the mixture is typically from 0.1:1 to 1:0.1, preferably from 0.2:1 to 1:0.2, very preferably from 0.25:1 to 1:0.5, more preferably from 0.3:1 to 1:0.66, especially from 0.3:1 to 1:1, and even varying within the range of 0.35:1 to 1:1. In a preferred embodiment, compound (II) and the ether are present in equimolar ratios.

[0155] The Lewis acid, preferably the aluminum trihalide or alkyl aluminum halide, is typically 0.001:1 to 0.2:1, preferably 0.002:1 to 0.1:1, very preferably 0.003:1 to 0.08:1, especially 0.005:1 to 0.05:1, particularly 0.007:1 to 0.03:1, based on the individual functional sites of the aluminum trihalide or alkyl aluminum halide.

[0156] Typically, Lewis acid donor complexes, preferably aluminum trihalide donor complexes or alkyl aluminum halide complexes, especially alkyl aluminum dichloride complexes, are prepared separately from the corresponding metal halide (preferably aluminum trihalide or alkyl aluminum halide, especially anhydrous alkyl aluminum dichloride or dialkyl aluminum chloride) and the donor compound prior to polymerization, and then—usually dissolved in an inert solvent such as a haloalkane, for example dichloromethane, or more preferably dissolved in an unhalogenated hydrocarbon—are added to the polymerization medium. However, in less preferred embodiments, the complexes may also be prepared in situ prior to polymerization.

[0157] The advantage of this invention is that the complexes of Lewis acids with compounds of formula (I), (Ia), or (Ib) are liquids, and therefore can be easily applied to reaction media.

[0158] Compared to complexes of Lewis acids with ionic liquids, another advantage of complexes of Lewis acids with compounds of formula (I), (Ia), or (Ib) is that they are very easy to prepare by simply mixing the Lewis acid with the compound of formula (I), (Ia), or (Ib), and the reactivity of the complex can be varied over a wide range by adjusting the ratio of the Lewis acid to the compound of formula (I), (Ia), or (Ib).

[0159] When the polymerization catalyst cannot be completely dissolved in the solvent used, it is advantageous to disperse the polymerization catalyst in an inert solvent, for example, by vigorous stirring of the dispersion. Dispersion can be carried out in any equipment suitable for dispersion. Vibrating devices, such as those from Skandex, can be mentioned by way of example or used in ultrasonic devices, high-pressure homogenizers, 2-roll mills, 3-roll mills, 4-roll mills or 5-roll mills, small mills, Henschel mixers, vibratory mills, Ang mills, gear mills, bead mills, wet mills, sand mills, ultrafine mills, colloid mills, ultrasonic homogenizers, using Ultra Turrax stirrers, especially by grinding, for example in 2-roll mills, 3-roll mills, 4-roll mills or 5-roll mills, small mills, vibratory mills, Ang mills, gear mills, bead mills, wet mills, sand mills, colloid mills, ball mills, especially stirred ball mills.

[0160] In a preferred embodiment, ultrasonic treatment of the Lewis acid donor complex, preferably an aluminum trihalide donor complex, an alkyl aluminum halide complex, an iron trihalide donor complex, or a boron halide donor complex, in an inert solvent prior to polymerization helps to improve the polymerization conversion rate.

[0161] In a preferred embodiment of the invention, polymerization is further carried out using a monofunctional or polyfunctional, particularly monofunctional, difunctional, or trifunctional, initiator selected from organic hydroxyl compounds, organic halogen compounds, and water. Mixtures of the aforementioned initiators can also be used, 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. The initiator can be monofunctional, difunctional, or polyfunctional, meaning that the initiator molecule may contain one, two, or more hydroxyl or halogen atoms that initiate the polymerization reaction. In the case of difunctional or polyfunctional initiators, telechelic isobutylene polymers having two or more, particularly two or three, polyisobutylene chain ends are typically obtained.

[0162] Organic hydroxyl compounds with only one hydroxyl group in the molecule and suitable as monofunctional initiators include alcohols and phenols, especially those with the general formula R. 12 Those with -OH, of which R 12 Indicates C1 to C 20 -alkyl, especially C1- to C8-alkyl; C5- to C8-cycloalkyl; C6- to C8-cycloalkyl 20 -Aryl, especially C6- to C 12 -Aryl; or C7-to-C 20 -Arylalkyl, especially C7- to C6 12 -Arylalkyl. Furthermore, R 12 The group may also contain a mixture of the above structures and / or have other functional groups besides those already mentioned, such as ketone functional groups, nitroxide or carboxyl groups, and / or heterocyclic structural units.

[0163] 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-cresol, m-cresol and p-cresol, benzyl alcohol, p-methoxybenzyl alcohol, 1-phenylethanol and 2-phenylethanol, 1-(p-methoxyphenyl)ethanol and 2-(p-methoxyphenyl)ethanol, 1-phenyl-1-propanol, 2-phenyl-1-propanol and 3-phenyl-1-propanol, 1-(p-methoxyphenyl)-1-propanol, 2-(p-methoxyphenyl)-1-propanol and 3-(p-methoxyphenyl)-1-propanol, 1-phenyl-2-propanol and 2-phenyl-2-propanol, 1-(p-methoxyphenyl)-2-propanol and 2-(p-methoxyphenyl)-2-propanol, 1-phenyl-1-butanol, 2-phenyl-1-butanol, 3-phenyl-1-butanol and 4-phenyl-1-butanol, 1-(p-methoxyphenyl)-1-butanol, 2-(p-methoxyphenyl)-1-butanol, 3-(p-methoxyphenyl)-1-butanol and 4-(p-methoxyphenyl)-1-butanol, 1-phenyl-2-butanol, 2-phenyl-2-butanol, 3-phenyl-2-butanol and 4-phenyl-2-butanol 1-Butanol, 1-(p-methoxyphenyl)-2-butanol, 2-(p-methoxyphenyl)-2-butanol, 3-(p-methoxyphenyl)-2-butanol and 4-(p-methoxyphenyl)-2-butanol, 9-methyl-9H-fluorene-9-ol, 1,1-diphenylethanol, 1,1-diphenyl-2-propyn-1-ol, 1,1-diphenylpropanol, 4-(1-hydroxy-1-phenylethyl)benzonitrile, cyclopropyl diphenylmethanol, 1-hydroxy-1,1-diphenylprop-2-one, diphenylethanolic acid, 9-phenyl-9-fluoreneol, triphenylmethanol, diphenyl(4-pyridyl)methanol, α,α-diphenyl- 2-Pyridinemethanol, 4-methoxytriphenylmethanol (especially when combined with polymers as a solid phase), α-tert-butyl-4-chloro-4'-methyldiphenylmethanol, cyclohexyldiphenylmethanol, α-(p-tolyl)-diphenylmethanol, 1,1,2-triphenylethanol, α,α-diphenyl-2-pyridineethanol, α,α-4-pyridyldiphenylmethanol N-oxide, 2-fluorotriphenylmethanol, triphenylpropynyl alcohol, 4-[(diphenyl)hydroxymethyl]benzonitrile, 1-(2,6-dimethoxyphenyl)-2-methyl-1-phenyl-1-propanol, 1,1,2-triphenylprop-1-ol, and p-anisaldehydemethanol.

[0164] Organic hydroxyl compounds having two hydroxyl groups in their molecules and suitable as bifunctional initiators are, in particular, diols or glycols having a total carbon number of 2 to 30, especially 3 to 24, particularly 4 to 20, and bisphenols having a total carbon number of 6 to 30, especially 8 to 24, particularly 10 to 20, such as ethylene glycol, 1,2-propanediol and 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-bis(1-hydroxy- 1-Methylethyl)benzene, 1,3-bis(1-hydroxy-1-methylethyl)benzene or 1,4-bis(1-hydroxy-1-methylethyl)benzene (o-dicumyl alcohol, m-dicumyl alcohol or p-dicumyl alcohol), bisphenol A, 9,10-dihydro-9,10-dimethyl-9,10-anthracitediol, 1,1-diphenylbutane-1,4-diol, 2-hydroxytriphenylmethanol and 9-[2-(hydroxymethyl)phenyl]-9-fluorenol.

[0165] Organohalogen compounds with one halogen atom in the molecule and suitable as monofunctional initiators, especially those of the general formula R 13 Compounds of -Hal, wherein Hal is a halogen atom selected from fluorine, iodine, and especially chlorine and bromine, and R 13 Indicates C1 to C 20 -alkyl, especially C1- to C8-alkyl, C5- to C8-cycloalkyl or C7- to C8-cycloalkyl 20 -Arylalkyl, especially C7- to C8- 12 -Arylalkyl. Additionally, the R group... 13 It may also contain a mixture of the above structures and / or have other functional groups besides those already mentioned, such as ketone functional groups, nitro oxygen or carboxyl groups, and / or heterocyclic structural units.

[0166] Typical examples of these 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-chloropropane, 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-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.

[0167] Organohalogen compounds with two halogen atoms in their molecules and suitable as bifunctional 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).

[0168] The initiator is more preferably selected from one or more hydroxyl groups, each bonded to sp. 3 Organic hydroxyl compounds with hybridized carbon atoms, wherein one or more halogen atoms are each bonded to sp 3 An organic halogen compound with hybridized carbon atoms, and water. Particularly preferred are those selected from one or more hydroxyl groups each bonded to sp... 3 Initiators for organic hydroxyl compounds with hybridized carbon atoms.

[0169] When an organohalogen compound is used as an initiator, it is particularly preferred that one or more halogen atoms are each bonded to a secondary sp. 3 Hybridized carbon atoms, or especially tertiary sp atoms 3 Those that are hybridized carbon atoms.

[0170] Especially preferred in such sp 3 Hybridized carbon atoms can carry R 12 R13 and R 14 Initiators with groups other than hydroxyl groups, wherein R 12 R 13 and R 14 Each group is independently hydrogen, C1- to C1-. 20 -alkyl, C5- to C8-cycloalkyl, C6- to C 20 -Aryl or C7-to-C 20 -alkylaryl or phenyl, wherein any aromatic ring may also have one or more, preferably one or two C1- to C4-alkyl, C1- to C4-alkoxy, C1- to C4-hydroxyalkyl or C1- to C4-haloalkyl as substituents, wherein variable R 12 R 13 and R 14 No more than one of them is hydrogen, and the variable R 12 R 13 and R 14 At least one of them is a phenyl group, and the phenyl group may also have one or more, preferably one or two, C1- to C4-alkyl, C1- to C4-alkoxy, C1- to C4-hydroxyalkyl or C1- to C4-haloalkyl groups as substituents.

[0171] For the purposes of this invention, initiators selected from the following are particularly preferred: water, methanol, ethanol, 1-phenylethanol, 1-(p-methoxyphenyl)ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol (cumene), n-butanol, isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane (cumene chloride), tert-butyl chloride, and 1,3-bis(1-hydroxy-1-methylethyl)benzene or 1,4-bis(1-hydroxy-1-methylethyl)benzene. Of particular preference are 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-bis(1-hydroxy-1-methylethyl)benzene or 1,4-bis(1-hydroxy-1-methylethyl)benzene.

[0172] The molar ratio of the initiator to the isobutylene monomer used in the case of isobutylene homopolymerization, or to the total amount of polymerizable monomers used in the case of isobutylene copolymerization, is typically 0.0005:1 to 0.1:1, particularly 0.001:1 to 0.075:1, especially 0.0025:1 to 0.05:1, based on the individual functional sites of the initiator. When water is used as the sole initiator or in combination with an organic hydroxyl compound and / or an organic halogen compound as another initiator, the molar ratio of water to the isobutylene monomer used in the case of isobutylene homopolymerization, or to the total amount of polymerizable monomers used in the case of isobutylene copolymerization, 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.

[0173] In a preferred embodiment, the amount of initiator in the monomer mixture is no more than 10 wt%, preferably no more than 7.5 wt%, more preferably no more than 5 wt%, even more preferably no more than 3 wt%, and especially no more than 2 wt%.

[0174] If water is used as the sole initiator or combined with an organic hydroxyl compound, the amount of initiator in the monomer mixture shall not exceed 3.2% by weight, preferably not more than 2.5% by weight, more preferably not more than 2% by weight, even more preferably not more than 1.5% by weight, and especially not more than 1% by weight.

[0175] A portion of the initiator molecules, added as organic hydroxyl or halogen compounds, are incorporated into the polymer chain. The proportion of polymer chains initiated by the incorporated organic initiator molecules (I) eff The percentage can be as high as 100%, and is typically between 5% and 90%. The remaining polymer chains originate from water, which acts as an initiator molecule, derived from trace amounts of moisture, or from chain transfer reactions.

[0176] In another preferred embodiment of the invention, polymerization is carried out in the presence of 0.01 to 10 mmol, especially 0.05 to 5.0 mmol, particularly 0.1 to 1.0 mmol of a nitrogen-containing basic compound, in each case based on 1 mole of isobutylene monomer used in the case of isobutylene homopolymerization, or based on 1 mole of total polymerizable monomer used in the case of isobutylene copolymerization.

[0177] The nitrogen-containing basic compounds used can be of the general formula R. 14 -NR 15 R 16 Aliphatic, alicyclic, or aromatic amines, or ammonia, wherein the variable R 14 R 15 and R 16Each independently consists of hydrogen, C1- to C1-. 20 -alkyl, especially C1- to C8-alkyl, C5- to C8-cycloalkyl, C6- to C8-cycloalkyl 20 -Aryl groups, especially C6-to-C6 12 -Aryl or C7-to-C 20 -Arylalkyl, especially C7- to C6 12 -Arylalkyl. When none of these variables are hydrogen, the amine is a tertiary amine. When one of these variables is hydrogen, the amine is a secondary amine. When two of these variables are hydrogen, the amine is a primary amine. When all of these variables are hydrogen, the amine is ammonia.

[0178] General formula R 14 -NR 15 R 16 Typical examples of this type of amine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, sec-butylamine, isobutylamine, tert-pentylamine, 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-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-(2-ethylhexyl)amine, dicyclopentylamine, dicyclohexylamine, and di-(2-ethylhexyl)amine. Aniline, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, tri-sec-butylamine, triisobutylamine, tri-tert-pentylamine, 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-N-n-butylamine.

[0179] Furthermore, the nitrogen-containing basic compounds used can also be compounds having multiple, especially two or three nitrogen atoms and 2 to 20 carbon atoms, wherein each nitrogen atom may independently have a hydrogen atom or an aliphatic, alicyclic, or aromatic substituent. Examples of such polyamines are 1,2-ethylenediamine, 1,3-propylidenediamine, 1,4-butylidenediamine, diethylenetriamine, N-methyl-1,2-ethylenediamine, N,N-dimethyl-1,2-ethylenediamine, N,N'-dimethyl-1,2-ethylenediamine, or N,N-dimethyl-1,3-propanediamine.

[0180] However, suitable nitrogen-containing basic compounds of this kind are especially saturated, partially unsaturated, or unsaturated 5- or 6-membered nitrogen-containing heterocycles containing 1, 2, or 3 cyclic nitrogen atoms and may have 1 or 2 other cyclic heteroatoms selected from oxygen and sulfur and / or hydrocarbon groups, especially C1- to C4-alkyl and / or phenyl and / or functional groups or heteroatoms as substituents, especially fluorine, chlorine, bromine, nitro, and / or cyano, such as pyrrolidine, pyrrole, imidazole, 1,2,3-triazole or 1,2,4-triazole, oxazole, thiazole, piperidine, pyrazane, pyrazole, pyridazine, pyrimidine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,2,5-triazine, 1,2,5-oxathiazine, 2H-1,3,5-thiadiazine, or morpholine.

[0181] However, particularly suitable nitrogen-containing basic compounds of this class are pyridines or pyridine derivatives (especially mono-C1- to C4-alkyl-substituted, di-C1- to C4-alkyl-substituted, or tri-C1- to C4-alkyl-substituted pyridines), such as 2-methylpyridine, 3-methylpyridine, or 4-methylpyridine (methylpyridines); 2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,4-dimethylpyridine, etc. Methylpyridine, 3,5-dimethylpyridine, or 3,6-dimethylpyridine (dimethylpyridine class); 2,4,6-trimethylpyridine (trimethylpyridine class); 2-tert-butylpyridine, 3-tert-butylpyridine, or 4-tert-butylpyridine; 2-tert-butyl-6-methylpyridine; 2,4-di-tert-butylpyridine, 2,5-di-tert-butylpyridine, 2,6-di-tert-butylpyridine, or 3,5-di-tert-butylpyridine, or 2-phenylpyridine, 3-phenylpyridine, or 4-phenylpyridine.

[0182] A single nitrogen-containing basic compound or a mixture of such nitrogen-containing basic compounds may be used.

[0183] For the use of isobutene or isobutene-containing monomer mixtures as monomers to be polymerized, suitable sources of isobutene are pure isobutene and isobutene-based C4 hydrocarbon feed streams, such as C4 raffinate, especially "raffinate 1," from the C4 fraction (cut) of isobutane dehydrogenation, and from the C4 fraction of steam crackers and FCC crackers (fluid catalytic cracking), provided that the 1,3-butadiene present therein has been substantially removed. C4 hydrocarbon feed streams from FCC refining units are also referred to as "b / b" feed streams. Other suitable isobutene-based C4 hydrocarbon feed streams are, for example, product streams from propylene-isobutane co-oxidation or product streams from metathesis units, which are typically used after routine purification and / or concentration. Suitable C4 hydrocarbon feed streams typically contain less than 500 ppm, preferably less than 200 ppm, of butadiene. The presence of 1-butene, as well as cis-2-butene and trans-2-butene, is essentially negligible. Typically, the concentration of isobutylene in the mentioned C4 hydrocarbon feed stream is 40-60% by weight. For example, raffinate 1 typically consists essentially of 30-50% by weight isobutylene, 10-50% by weight 1-butene, 10-40% by weight cis-2-butene and trans-2-butene, and 2-35% by weight butane; in the polymerization method of the present invention, the unbranched butene in raffinate 1 generally exhibits almost inertness, and only isobutylene polymerizes.

[0184] In a preferred embodiment, the monomer source for polymerization is an industrial C4 hydrocarbon stream containing 1 to 100% by weight, especially 1 to 99% by weight, particularly 1 to 90% by weight, more preferably 30 to 60% by weight of isobutylene, especially a raffinate stream, a b / b stream from an FCC refining unit, a product stream from propylene-isobutane co-oxidation, or a product stream from a metathesis unit.

[0185] Especially when the raffinate stream 1 is used as a source of isobutylene, it has been found useful to use water as the sole initiator or as another initiator, particularly when polymerization is carried out at temperatures ranging from -20°C to +30°C, especially from 0°C to +20°C. However, at temperatures ranging from -20°C to +30°C, especially from 0°C to +20°C, when the raffinate stream 1 is used as a source of isobutylene, the use of an initiator can also be omitted.

[0186] The aforementioned mixture of isobutylene monomers may contain small amounts of contaminants such as water, carboxylic acids, or inorganic acids without any significant loss of yield or selectivity. It is suitable to prevent the enrichment of these impurities by removing them from the isobutylene monomer mixture, for example, by adsorption on solid adsorbents such as activated carbon, molecular sieves, or ion exchangers.

[0187] The monomer mixture of isobutylene or a mixture of isobutylene hydrocarbons can also be converted using olefinic unsaturated monomers that can copolymerize with isobutylene. When copolymerizing the monomer mixture of isobutylene with a suitable comonomer, the monomer mixture preferably contains at least 5% by weight, more preferably at least 10% by weight, and especially at least 20% by weight of isobutylene, and preferably at most 95% by weight, more preferably at most 90% by weight, and especially at most 80% by weight of comonomer.

[0188] Useful copolymerizable monomers include: vinyl aromatics, such as styrene and α-methylstyrene; C1- to C4-alkylstyrene, such as 2-methylstyrene, 3-methylstyrene, and 4-methylstyrene; and 4-tert-butylstyrene; halostyrene, such as 2-chlorostyrene, 3-chlorostyrene, or 4-chlorostyrene; and isoolefins having 5 to 10 carbon atoms, such as 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhexene-1, and 2-propylhepten-1. Other useful copolymerizable monomers include olefins having a silyl group, such as 1-trimethoxysilylethylene, 1-(trimethoxysilyl)propylene, 1-(trimethoxysilyl)-2-methylpropene-2, 1-[tri(methoxyethoxy)silyl]ethylene, 1-[tri(methoxyethoxy)silyl]propylene, and 1-[tri(methoxyethoxy)silyl]-2-methylpropene-2. In addition, depending on the polymerization conditions, useful comonomers also include isoprene, 1-butene, as well as cis-2-butene and trans-2-butene.

[0189] When preparing copolymers using the method of the present invention, the method can be configured to preferentially form random polymers or preferentially form block copolymers. To prepare block copolymers, different monomers can be supplied sequentially to the polymerization reaction, in particular the second comonomer is added only after the first comonomer has at least partially polymerized. In this way, diblock, triblock, and higher block copolymers can be obtained, which have blocks of one comonomer or another comonomer as terminal blocks, 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. This is particularly true in the method of the present invention when isobutylene and vinyl aromatic compounds, especially styrene, are copolymerized. This preferably forms block copolymers with polystyrene terminal blocks. This can be attributed to the fact that vinyl aromatic compounds, especially styrene, polymerize significantly slower than isobutylene.

[0190] The polymerization can be carried out continuously or intermittently. Continuous methods can be similar to those known in the art for the continuous polymerization of isobutylene in the liquid phase in the presence of a boron trifluoride-based catalyst.

[0191] The method of the present invention is suitable for carrying out at low temperatures (e.g., between -90°C and 0°C) or at higher temperatures (i.e., at least 0°C, for example, between 0°C and +30°C or between 0°C and +50°C). However, in the method of the present invention, polymerization is preferably carried out at lower temperatures, typically between -70°C and -10°C, and especially between -60°C and -15°C.

[0192] When polymerization in the method of the present invention is carried out at or above the boiling point temperature of the monomer or monomer mixture to be polymerized, it is preferably carried out in a pressure vessel, such as an autoclave or pressure reactor.

[0193] According to the present invention, polymerization is carried out in the form of bulk polymerization or solution polymerization.

[0194] The polymerization in the method of the present invention is preferably carried out in the presence of an inert diluent. The inert diluent used should be suitable for reducing the increase in viscosity of the reaction solution that usually occurs during the polymerization reaction to a degree that ensures the removal of the heat of reaction. Suitable diluents are solvents or solvent mixtures that are inert to the reagents used. Suitable diluents are, for example, aliphatic hydrocarbons such as n-butane, n-pentane, n-hexane, n-heptane, n-octane and isooctane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylenes; and halogenated hydrocarbons, especially halogenated aliphatic hydrocarbons such as methyl chloride, dichloromethane and trichloromethane (chloroform), 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane and 1-chlorobutane, as well as halogenated aromatic hydrocarbons and alkyl aromatic hydrocarbons halogenated in the alkyl side chain, such as chlorobenzene, monofluoromethylbenzene, difluoromethylbenzene and trifluorotoluene, and mixtures of the above diluents. The components used in the diluent or solvent mixture are also inert components of the isobutylene-based C4 hydrocarbon stream. Non-halogenated solvents are preferred over the listed halogenated solvents.

[0195] The polymerization of the present invention can be carried out in a halogenated hydrocarbon, especially a halogenated aliphatic hydrocarbon, as an inert diluent; or in a mixture of halogenated hydrocarbons, especially halogenated aliphatic hydrocarbons; or in a mixture of at least one halogenated hydrocarbon, especially a halogenated aliphatic hydrocarbon, and at least one aliphatic, alicyclic, or aromatic hydrocarbon, for example, in a mixture of dichloromethane and n-hexane, with a volume ratio typically from 10:90 to 90:10, especially from 50:50 to 85:15. Prior to use, it is preferable to remove impurities such as water, carboxylic acids, or inorganic acids from the diluent, for example by adsorption onto a solid adsorbent such as activated carbon, molecular sieves, or ion exchangers.

[0196] In a preferred embodiment, the polymerization of the present invention is carried out in a halogen-free aliphatic hydrocarbon or, in particular, a halogen-free aromatic hydrocarbon, especially toluene. For this embodiment, it has been found particularly advantageous to use water in combination with the mentioned organic hydroxyl compounds and / or the mentioned organic halogen compounds, or especially water as the sole initiator.

[0197] In another preferred embodiment, the polymerization of the present invention is carried out in halogen-free aliphatic or alicyclic hydrocarbons, preferably aliphatic hydrocarbons, especially hexane, pentane, heptane, cyclohexane, cyclopentane and mixtures thereof.

[0198] The polymerization in the method of the present invention is preferably carried out under substantially aprotic reaction conditions, especially substantially anhydrous reaction conditions. Substantially aprotic and substantially anhydrous reaction conditions should be understood to mean that the content of protic impurities and water in the reaction mixture is less than 50 ppm, particularly less than 5 ppm, respectively. Therefore, the raw materials are typically dried before use by physical and / or chemical measures. More specifically, it has been found useful to incorporate an organometallic compound, such as an organolithium, organomagnesium, or organoaluminum compound, into the aliphatic or alicyclic hydrocarbon used as a solvent in an amount sufficient to substantially remove trace amounts of water from said solvent, after conventional pre-purification and pre-drying. The solvent thus treated is then preferably condensed directly into the reaction vessel. Monomers to be polymerized, especially isobutylene or mixtures of isobutylenes, can also be treated in a similar manner. Drying with other conventional drying agents such as molecular sieves or pre-dried oxides such as alumina, silica, calcium oxide, or barium oxide is also suitable. For halogenated solvents that cannot be dried with metals such as sodium or potassium or with metal alkyl compounds, a suitable drying agent, such as calcium chloride, phosphorus pentoxide, or molecular sieves, is used to remove water or trace amounts of water. Raw materials that also cannot be treated with metal alkyl compounds, such as vinyl aromatic compounds, can be dried in a similar manner. Even if some or all of the initiator used is water, residual water should preferably be substantially or completely removed from the solvent and monomer by drying before the reaction to allow for the use of water-based initiators in controlled, prescribed amounts, thereby achieving better method control and reproducibility of results.

[0199] When a Lewis acid donor complex, preferably an aluminum trihalide donor complex or an alkyl aluminum halide complex, especially an alkyl aluminum dichloride donor complex or a dialkyl aluminum chloride donor complex, is contacted with isobutylene or a mixture of isobutylene monomers at the desired reaction temperature, the polymerization of isobutylene or isobutylene-based feedstocks typically proceeds spontaneously. The procedure may involve first optionally adding the monomer to a diluent to reach the reaction temperature, and then adding the Lewis acid donor complex, preferably an aluminum trihalide donor complex or an alkyl aluminum halide complex, especially an alkyl aluminum dichloride donor complex or a dialkyl aluminum chloride donor complex. Alternatively, the procedure may involve first optionally adding the Lewis acid donor complex, preferably an aluminum trihalide donor complex or an alkyl aluminum halide complex, especially an alkyl aluminum dichloride donor complex or a dialkyl aluminum chloride donor complex, to a diluent, and then adding the monomer. In this case, the start of polymerization is considered to be the moment when all reactants are present in the reaction vessel.

[0200] To prepare isobutylene copolymers, the procedure can be to first optionally add a monomer to a diluent, followed by the addition of a Lewis acid donor complex, preferably an aluminum trihalide donor complex or an alkyl aluminum halide complex, especially an alkyl aluminum dichloride donor complex or a dialkyl aluminum chloride donor complex. The reaction temperature can be established before or after the Lewis acid donor complex, preferably an aluminum trihalide donor complex or an alkyl aluminum halide complex, especially an alkyl aluminum dichloride donor complex or a dialkyl aluminum chloride donor complex. Alternatively, the procedure can be to first optionally add only one monomer to a diluent, followed by the addition of a Lewis acid donor complex, preferably an aluminum trihalide donor complex or an alkyl aluminum halide complex, especially an alkyl aluminum dichloride donor complex or a dialkyl aluminum chloride donor complex, and only after a certain time, for example, when at least 60%, at least 80%, or at least 90% of the monomer has been converted, add other monomers. Alternatively, a Lewis acid donor complex, preferably an aluminum trihalide donor complex or an alkyl aluminum halide donor complex, especially an alkyl aluminum dichloride donor complex or a dialkyl aluminum chloride donor complex, can be added to the diluent first. Then, the monomer can be added simultaneously or sequentially, and the desired reaction temperature can be established. In this case, polymerization is considered to begin when the Lewis acid donor complex, preferably an aluminum trihalide donor complex or an alkyl aluminum halide donor complex, especially an alkyl aluminum dichloride donor complex or a dialkyl aluminum chloride donor complex, and at least one monomer are present in the reaction vessel.

[0201] In addition to the batch process described herein, polymerization in the method of the present invention can also be configured as a continuous process. In this case, the raw materials (i.e., the monomers to be polymerized), optionally a diluent, and optionally a Lewis acid donor complex, preferably an aluminum trihalide donor complex or an alkyl aluminum halide complex, especially an alkyl aluminum dichloride donor complex or a dialkyl aluminum chloride donor complex, are continuously supplied to the polymerization reaction, and the reaction products are continuously removed, thereby establishing near-steady-state polymerization conditions in the reactor. The monomers to be polymerized can be supplied in their natural form, diluted with a diluent or solvent, or as a monomer-containing hydrocarbon feed stream.

[0202] Lewis acid donor complexes, preferably aluminum trihalide donor complexes or alkyl aluminum halide complexes, especially alkyl aluminum dichloride donor complexes or dialkyl aluminum chloride donor complexes, are effective as polymerization catalysts and are typically present in the polymerization medium in dissolved, dispersed, or suspended form. Loading of Lewis acid donor complexes, preferably aluminum trihalide donor complexes or alkyl aluminum halide complexes, especially alkyl aluminum dichloride donor complexes or dialkyl aluminum chloride donor complexes, on conventional support materials is also possible. Suitable reactor types for the polymerization method of this invention are typically stirred tank reactors, circulating reactors, and tubular reactors, as well as fluidized bed reactors, stirred tank reactors with or without solvent, fluidized bed reactors, continuous fixed bed reactors, and batch fixed bed reactors (batch mode).

[0203] In the method of the present invention, aluminum trihalide donor complexes, or alkyl aluminum halide complexes, or iron trihalide donor complexes, or gallium trihalide donor complexes, or titanium tetrahalide donor complexes, or zinc dihalide donor complexes, or tin dihalide donor complexes, or tin tetrahalide donor complexes, or boron trihalide donor complexes, especially alkyl aluminum dichloride donor complexes or dialkyl aluminum chloride donor complexes, are typically used in amounts such that Lewis acids The metal in the donor complex, preferably aluminum trihalide donor complex or alkyl aluminum halide complex, especially aluminum in alkyl aluminum dichloride donor complex or dialkyl aluminum chloride donor complex, has a molar ratio of 1:5 to 1:5000, preferably 1:10 to 1:5000, especially 1:15 to 1:1000, and particularly 1:20 to 1:250, to the total amount of polymerizable monomers used in the case of isobutylene homopolymerization or copolymerization of isobutylene.

[0204] In a preferred embodiment of the invention, reaction conditions are selected such that the conversion rate of the monomer is at least 80%, preferably at least 85%, and more preferably at least 90%.

[0205] The advantage of this invention is that the complexes according to the invention exhibit high selectivity for polymers having terminal olefinic double bonds (α-double bonds) and other reactive double bonds (e.g., β-double bonds, preferably terminal olefinic double bonds (α-double bonds)), even at such high conversion rates. It is frequently observed that once the monomer conversion exceeds the aforementioned values, the selectivity, especially for α-double bonds, decreases. It can also be observed that the amount of reactive double bonds formed during the reaction, particularly α-double bonds, decreases at high conversion rates. The advantage of the complexes according to the invention is that high selectivity is maintained at high conversion rates, and the degree of degradation of the formed reactive double bonds is less than with other catalysts.

[0206] To stop the reaction, it is preferable to deactivate the reaction mixture, for example by adding a protic compound, especially by adding water, an alcohol (such as methanol, ethanol, n-propanol, and isopropanol) or a mixture thereof with water, or by adding an aqueous base, such as an aqueous solution of: alkali metal hydroxides or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, or calcium hydroxide; alkali metal carbonates or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate, magnesium carbonate, or calcium carbonate; or alkali metal bicarbonates or alkaline earth metal bicarbonates such as sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, or calcium bicarbonate.

[0207] The method of the present invention is used to prepare highly reactive isobutylene homopolymers or copolymers, wherein the content of terminal vinylidene double bonds (α-double bonds) and other reactive double bonds (e.g., β-double bonds) at the end of each polyisobutylene chain is at least 60 mol%, preferably at least 70 mol%, very preferably at least 75 mol%. More specifically, it is also used to prepare highly reactive isobutylene copolymers formed from isobutylene and at least one vinyl aromatic monomer, especially styrene, wherein the content of terminal vinylidene double bonds (α-double bonds) and other reactive double bonds (e.g., β-double bonds) at the end of each polyisobutylene chain is at least 60 mol%, preferably at least 70 mol%, preferably at least 75 mol%. To prepare such copolymers of isobutylene and at least one vinyl aromatic monomer, especially styrene, isobutylene or isobutylene hydrocarbon fractions are copolymerized with at least one vinyl aromatic monomer at a weight ratio of isobutylene to vinyl aromatic compound of 5:95 to 95:5, especially 30:70 to 70:30.

[0208] The highly reactive isobutylene homopolymers or copolymers prepared by the method of the present invention, especially isobutylene homopolymers, preferably have polydispersity (PDI = M). w / M n The PDI value is 1.05 to less than 3.5, preferably 1.05 to less than 3.0, more preferably 1.05 to less than 2.5, more preferably 1.05 to 2.3, even more preferably 1.05 to 2.0, and especially 1.1 to 1.85. A typical PDI value is 1.2 to 1.7 under optimal process conditions.

[0209] The highly reactive isobutylene homopolymer or copolymer prepared by the method of the present invention preferably has a number-average molecular weight M. n (Determined by gel permeation chromatography) Preferably 500 to 100,000, even more preferably 500 to 25,000, especially 500 to 5,000. Isobutylene homopolymers, even more preferably, have a number-average molecular weight M. n The range is 500 to 10,000, especially 500 to 5,000, such as about 1,000 or about 2,300.

[0210] Some isobutylene polymers having terminal vinylidene double bonds and also containing introduced initiator molecules, and present in a major proportion in the isobutylene homopolymers prepared according to the present invention, are novel compounds. Therefore, the present invention also provides isobutylene polymers of general formula III.

[0211]

[0212] Where R 17 R 18 and R 19 Each independently consists of hydrogen, C1- to C1-. 20-alkyl, C5- to C8-cycloalkyl, C6- to C 20 -Aryl, C7-to-C 20 -alkylaryl or phenyl, wherein any aromatic ring may also have one or more C1- to C4-alkyl- or C1- to C4-alkoxy or a moiety of general formula IV as a substituent.

[0213]

[0214] Where variable R 17 R 18 or R 19 No more than one of them is hydrogen and the variable R 17 R 18 or R 19 At least one of them is a phenyl group, and the phenyl group may also have one or more C1- to C4-alkyl- or C1- to C4-alkoxy groups or a moiety of general formula II as substituents, and

[0215] n is a value from 9 to 4500, preferably from 9 to 180, especially from 9 to 100, and particularly from 12 to 50.

[0216] In a preferred embodiment, R 17 R 18 and R 19 Each is independently hydrogen, C1- to C4-alkyl, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, or phenyl, said phenyl may also have one or two C1- to C4-alkyl- or C1- to C4-alkoxy or a moiety of general formula II as substituents, wherein variable R 17 R 18 and R 19 No more than one of them is hydrogen and the variable R 17 R 18 and R 19 At least one of them is a phenyl group, which may also have one or more C1- to C4-alkyl or C1- to C4-alkoxy or a portion of general formula II as a substituent, and n is a value of 9 to 4500, preferably 9 to 180, especially 9 to 90, particularly 15 to 45.

[0217] The method of the present invention successfully polymerizes isobutylene or a mixture of isobutylene monomers under cationic conditions with a satisfactory high conversion rate, typically 20% to 100%, especially 35% to 90%, and within a short reaction time, typically 5 to 120 minutes, especially 30 to 120 minutes, to obtain a highly reactive isobutylene homopolymer or copolymer, wherein the content of α- and β-double bonds at the end of each polyisobutylene chain in the isobutylene homopolymer or copolymer is at least 60 mol%, preferably at least 70 mol%, and very preferably at least 75 mol%.

[0218] The advantage of the method of the present invention is that 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) or (Ia) or (Ib) as a donor, yields a product with a high content of α- and β-double bonds at each polyisobutylene chain end, compared with the same reaction carried out under comparable reaction conditions in the presence of a compound of general formula (I) or (Ia) or (Ib) as a donor alone.

[0219] Another advantage of the present invention is that the complexes formed by Lewis acids and compounds of formula (I) or (Ia) or (Ib) are liquids and therefore can be easily handled.

[0220] Furthermore, the complexes of the present invention can be prepared more easily than ionic liquids disclosed in the prior art because Lewis acids and compounds of formula (I) or (Ia) or (Ib) only need to be mixed in the desired proportions, while ionic liquids require chemical reaction and purification. The reactivity of the complexes formed therefrom can be further tuned by simply changing the molar ratio of the Lewis acid and the compound of formula (I) or (Ia) or (Ib) and at least one organic compound (II) in the complex.

[0221] The following examples are intended to illustrate the invention in detail rather than to limit it.

[0222] Material

[0223] Isobutylene ("IB", Aldrich, 99.99%) was dried in the gaseous state using a laboratory gas drying apparatus. Hexane (Sigma-Aldrich, >95%) and CH₂Cl₂ (Sigma-Aldrich, >99.5%) were treated with sulfuric acid, washed with aqueous sodium bicarbonate solution, dried with CaCl₂, and distilled twice from CaH₂ under an inert atmosphere. Gaseous BF₃ (BASF, >99%) was used without further purification. Isopropyl ether ( i Pr₂O (Fluka, ≥98.5%) was distilled from CaH₂. 2-Chloroethyl ethyl ether (CEE, Aldrich, 99%) and bis(2-chloroethyl) ether (CE, Aldrich, >99%) were distilled from CaH₂ under reduced pressure. Ethyl acetate (EtOAc, Aldrich, 99.8%) was refluxed and distilled over P₂O₅ under an inert atmosphere. Tri-n-octylphosphine oxide (P… 888O (Acros Organics, 99%) and triphenylphosphine oxide (PPh3O, Acros Organics, 99%) were dried under vacuum for 5 hours before use. AlCl3 (Aldrich, 99.999%), FeCl3 (Sigma-Aldrich, >97%), and CDCl3 were also dried under vacuum for 5 hours before use. Ethanol (Sigma-Aldrich, >96%) and tetrahydrofuran (anhydrous, Sigma-Aldrich, ≥99.9%) were used as is. TiCl4 (Sigma-Aldrich, 99.9%) was distilled on a copper plate at 51–52 °C and 40 mmHg.

[0224] instrument

[0225] Size exclusion chromatography (SEC) was performed on an Ultimate 3000 Thermo Scientific apparatus equipped with an Agilent PLgel 5 μm MIXED-C column (300 × 7.5 mm) and a pre-column (PLgel 5 μm guard 50 × 7.5 mm) kept at a constant temperature of 30 °C. Detection was achieved by differential refractometer (RI) and diode array detector (UV). Tetrahydrofuran (THF) was eluted at a flow rate of 1.0 mL / min. Molecular weight and polydispersity were determined using polystyrene standards (Polymer Labs, Germany). The calculation. 1 ¹H NMR (500 MHz) spectra were recorded in CDCl₃ at 25 °C on a Bruker AC-500 spectrometer and calibrated relative to residual solvent resonance. UV-Vis absorption spectra were recorded using an SM2203 (Solar) spectrophotometer.

[0226] Catalyst preparation

[0227] According to F. Coleman, G. Srinivasan and M. The method described in Angew. Chem., 2013, 52, 12582, involves synthesizing liquid coordination complexes by simply mixing the desired amounts of a dry phosphorus-containing electron donor and the corresponding anhydrous Lewis acid under an argon atmosphere. The mixture is then stirred at 30°C to 80°C for 0.5–5 hours.

[0228] P 888 The synthesis of O–AlCl3 LCC (χ(AlCl3)=0.6) is as follows: Under an argon atmosphere, 0.52 g of AlCl3 was added to 1 g of P 888 O. Then, stir the reaction mixture at 40°C until it becomes homogeneous (1 hour).

[0229] P 888 The synthesis of O–FeCl3 LCC (χ(FeCl3)=0.6) includes the following steps: Under an argon atmosphere, 0.63 g of FeCl3 is added to 1 g of P 888 O. Then, stir the reaction mixture at 50°C until the phosphine is completely dissolved (0.5 hours).

[0230] P 888 The synthesis of the O×0.67AlCl3 donor-acceptor complex is as follows: Under an argon atmosphere, 3 mL of anhydrous CH2Cl2 was added to 0.52 g of AlCl3 and 1 g of P. 888 The mixture of O was then stirred at room temperature until homogeneous (0.5 hours).

[0231] P 888 The synthesis of the O×0.67FeCl3 donor-acceptor complex is as follows: Under an argon atmosphere, 3 mL of anhydrous CH2Cl2 was added to 0.63 g of FeCl3 and 1 g of P. 888 In a mixture of O. Then, stir the reaction mixture at room temperature until P is completely dissolved. 888 (0.5 hours).

[0232] P 888 The synthesis of the O×0.58BF3 donor-acceptor complex is as follows: Under an argon atmosphere, 11.3 mL of anhydrous CH2Cl2 was added to 4 g of P 888 In O. The reaction mixture was purged with gaseous BF3 under inert conditions at -20°C until P was reached. 888 The required ratio of O to BF3.

[0233] Aggregation method steps

[0234] The polymerization reaction was carried out in a glass tube equipped with a finger condenser under an argon atmosphere at a temperature ranging from 0°C to 20°C. As an example of a typical process step, isobutylene (2.86 g, 5.1 × 10⁻⁶ g) was used. –2 The polymerization reaction was initiated by adding 0.11 mL of a 1 M diisopropyl ether solution in hexane to a total volume of 5 mL. 888The reaction mixture consisted of O–FeCl3 (χ(FeCl3)=0.6) and n-hexane (4.8 mL). The reaction mixture was stirred for 3–5 minutes before adding the monomer. After a predetermined time, approximately 2 mL of ammonia (25%) was poured into the glass reactor to terminate the polymerization reaction. The quenched reaction mixture was diluted with n-hexane, centrifuged to separate trace amounts of LCC from the polymer solution, and finally precipitated in cold ethanol. The solvent was evaporated under reduced pressure to obtain the product polymer, which was then dried under vacuum (≤60 °C). The monomer conversion was determined by gravimetric analysis.

[0235] pass 1 ¹H NMR spectroscopy for determining PIB end-group content (for typical ¹H NMR spectra, see [reference]). Figure 1 The proton signals for exo-olefin end groups (b, b') appeared at 4.64 and 4.85 ppm, while those for endo-olefin end groups (d) appeared at 5.15 ppm. The proton signals for tri-(e) and tetra-substituted (g) olefin end groups appeared at 5.15 and 2.84 ppm, respectively, while the proton signals for CH2(l) and CH3(k) groups belonging to chlorinated end groups were at 1.96 and 1.68 ppm, respectively. The small signal at 4.80 ppm corresponds to the protons of the coupled PIB chain (m). The content of exo-olefin end groups was calculated according to the following equation:

[0236] exo(%)=I[(b+b') / 2] / I[k / 6+(b+b'+n) / 2+d+e+g]( Figure 1 )

[0237] In the context of this invention, the term "exo" refers to a terminal olefinic double bond, vinylidene double bond, or α-double bond, as illustrated in the formula on page 1 of this document. These terms are used synonymously throughout.

[0238] The term "all vinylenes" refers to the terminal olefinic double bond referred to as exo above, as well as the additional double bonds located within the polymer backbone as shown in the following formula:

[0239]

[0240] The terms "endo" and "trisubstituted" refer to β-double bonds, such as... Figure 1 The formula in the second line is shown. These terms are used synonymously throughout the text.

[0241] Furthermore, the "quadri-substitution" structural unit can be used in... Figure 1 The formula in the upper right corner can be found there. Additionally, chlorinated polyisobutylene (PIBCI) was found. Example

[0242] Example 1: Formation of liquid complexes

[0243] The possibility of preparing LCCs by combining phosphorus-containing electron donors according to formula (II) with Lewis acids was briefly tested:

[0244] Table 1

[0245]

[0246] The liquid complexes listed in Table 1 were further investigated in the polymerization of isobutylene.

[0247] Example 2

[0248] Based on the general method steps outlined above, isobutylene is polymerized in n-hexane in the presence of PPh3O-AlCl3 as a catalyst. Furthermore, under the conditions mentioned in Table 2, the polymerization is carried out as follows:

[0249] Mole fraction χ(AlCl3) = 0.6; [IB] = 5.2 M; T = 0 °C; reaction time = 30 min.

[0250]

[0251] b. Time = 10 min.

[0252] Example 3

[0253] Based on the general method steps outlined above, isobutylene is used as a catalyst in P... 888 Polymerization in n-hexane was carried out in the presence of O-AlCl3. Furthermore, under the conditions mentioned in Table 3, the polymerization proceeded as follows:

[0254] Mole fraction χ(AlCl3) = 0.6; [IB] = 5.2 M; [P] 888 [O–AlCl3] = 44 mM; [ether] = 11 mM; time = 30 min

[0255]

[0256] b [P 888 [O–AlCl3] = 22 mM.

[0257] Example 4

[0258] Based on the general method steps outlined above, isobutylene is reacted at 0°C with P as a catalyst. 888 Polymerization in n-hexane was carried out in the presence of O-FeCl3. Furthermore, under the conditions mentioned in Table 4, the polymerization proceeded as follows:

[0259] Mole fraction χ(FeCl3) = 0.6; [P 888 O–FeCl3]=22mM; [IB]=5.2M

[0260]

[0261] Example 5

[0262] To gain a deeper understanding of the polymerization mechanism, a brief study was conducted on […]. i Pr2O] / [P 888 Using P at O–FeCl3] = 0.5 888 O–FeCl3 / i Kinetics of isobutylene polymerization initiated by Pr2O.

[0263] The results are shown in Figure 3 .

[0264] It can be readily seen that the reaction according to the invention produces a much higher conversion rate compared to the reaction using [emim]Cl-FeCl3(2) according to Polymer, 145 (2018) 382-390, such as Figure 2 As shown.

[0265] Compared to the system [emim]Cl-FeCl3, the complex P 888 O–FeCl3 / i Pr2O not only produced a higher isobutylene conversion rate in a shorter time.

[0266] Furthermore, the complexes according to the present invention exhibit higher exo-selectivity at a certain conversion rate than those used according to... Figure 2 Those reactions.

[0267] Example 6

[0268] The polymerization reaction was carried out at -20°C in an inert atmosphere in a steel container equipped with a finger condenser.

[0269] By using isobutylene (25.20g, 45.0×10) –2 The polymerization reaction was initiated by adding 0.02 mL of MeOH and 10.00 mL of P to a mixture of 150.02 mL total volume. 888 The reaction mixture consisted of O–BF3 (χ(BF3)=0.58) and n-hexane (140.00 mL). After 1 hour, 5 mL of MeOH was poured into a steel container to terminate the polymerization reaction. 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 was determined by gravimetric analysis.

[0270]

Claims

1. A bulk or solution polymerization method for preparing highly reactive isobutylene homopolymers or copolymers, wherein the number-average molecular weight M of the isobutylene homopolymer or copolymer is... n The content of α-double bonds and β-double bonds at the end of each polyisobutylene chain, determined by gel permeation chromatography, is between 500 and 100,000, and the total content is at least 60 mol%. The method comprises polymerizing isobutylene or a mixture of monomers containing isobutylene in the presence of at least one Lewis acid, selected from aluminum trihalide donor complexes, alkyl aluminum halide donor complexes, and iron trihalide donor complexes, wherein the complexes comprise a mixture of the following as donors: - At least one organic compound (II), said compound (II) having the general formula R 8 -OR 9 ethers, where variable R 8 and R 9 Each is independently a C1-C4 alkyl or a C1-C4 haloalkyl, and -At least one of the following phosphorus-containing compounds: Formula (I) X1, X2, and X3 are each single bonds, and R 1 R 2 and R 3 Each is C2-C 18 -alkyl or C6-C 12 -Aryl The condition is that the melting point of the complex formed by at least one Lewis acid and at least one phosphorus-containing compound of formula (I) is not greater than 60°C.

2. The method according to claim 1, wherein the melting point of the complex formed by at least one Lewis acid and at least one phosphorus-containing compound of formula (I) is not greater than 40°C.

3. The method according to claim 2, wherein the melting point of the complex formed by at least one Lewis acid and at least one phosphorus-containing compound of formula (I) is not greater than 20°C.

4. The method according to claim 1, wherein the phosphorus-containing compound of formula (I) is selected from 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, trimethylylphosphine oxide, and trinaphthylphosphine oxide.

5. The method of claim 1, wherein isobutylene or a mixture of monomers containing isobutylene is polymerized in the presence of an aluminum trihalide donor complex, an alkyl aluminum halide donor complex, or an iron trihalide donor complex.

6. The method of claim 1, wherein isobutylene or a mixture of monomers containing isobutylene is polymerized in the presence of a ferric trihalide donor complex that effectively acts as a polymerization catalyst.

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

8. The method according to claim 1, wherein the organic compound (II) is selected from diethyl ether, n-butyl ether, isopropyl ether and n-propyl ether, bis(2-chloroethyl) ether and 2-chloroethylethyl ether.

9. The method of claim 1, wherein the molar ratio of the aluminum trihalide or alkyl aluminum halide to the isobutylene monomer used in the case of isobutylene homopolymerization, or to the total amount of polymerizable monomers used in the case of isobutylene copolymerization, is from 0.001:1 to 0.2:1, based on the respective individual functional sites of the aluminum trihalide or alkyl aluminum halide.

10. The method of claim 1, wherein the polymerization is carried out in the presence of a monofunctional or polyfunctional initiator selected from one or more hydroxyl groups each bonded to sp... 3 Organic hydroxyl compounds with hybridized carbon atoms, wherein one or more halogen atoms are each bonded to sp 3 Organic halogen compounds with hybridized carbon atoms, and 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-bis(1-hydroxy-1-methylethyl)benzene or 1,4-bis(1-hydroxy-1-methylethyl)benzene.

12. The method of claim 10, wherein the molar ratio of the initiator to the isobutylene monomer used in the case of isobutylene homopolymerization, or to the total amount of polymerizable monomers used in the case of isobutylene copolymerization, is from 0.0005:1 to 0.1:1, based on the individual functional sites of the initiator.

13. The method of claim 10, wherein when water is used as the sole initiator or in combination with an organic hydroxyl compound and / or an organic halogen compound as another initiator, the molar ratio of water to the isobutylene monomer used in the case of isobutylene homopolymerization, or to the total amount of polymerizable monomers used in the case of isobutylene copolymerization, is from 0.0001:1 to 0.1:

1.

14. The method of claim 1, wherein polymerization is carried out at a temperature of -90°C to +30°C.

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