Process for preparing high-reactivity isobutene homo- or copolymers

Patent metadata

Field	Value
Publication number	US-10975175-B2
Application number	US-201716318749-A
Country	US
Kind code	B2
Filing date	Jul 14, 2017
Priority date	Jul 22, 2016
Publication date	Apr 13, 2021
Grant date	Apr 13, 2021

Abstract

The present invention relates to a novel process for preparing high-reactivity isobutene homo- or copolymers with a content of terminal vinylidene double bonds per polyisobutene chain end of at least 70 mol %. The present invention further relates to novel isobutene polymers.

First claim

The invention claimed is:

1. A process for preparing high-reactivity isobutene homopolymers or copolymers with a content of terminal vinylidene double bonds per polyisobutene chain end of at least 70 mol %, the process comprising:
polymerizing a monomer comprising isobutene in the presence of a Lewis acid polymerization catalyst comprising (a) an aluminum trihalide-donor complex, an alkylaluminum halide-donor complex, an iron trihalide-donor complex, a gallium trihalide-donor complex, a titanium tetrahalide-donor complex, a zinc dihalide-donor complex, a tin dihalide-donor complex, and/or a tin tetrahalide-donor complex (b) a mixture comprising an organic compound (II) comprising an oxygen or nitrogen atom with at least one lone electron pair, and (c) an ionic liquid,
thereby obtaining the high-reactivity isobutene homopolymers or copolymers having a number-average molecular weight in a range of from 500 to 10,000, determined by gel permeation chromatography, and having the content of the terminal vinylidene double bonds per polyisobutene chain end of at least 70 mol %.

2. The process of claim 1 , wherein the ionic liquid comprises a cation of a formula (Ia) to (Iw):

and oligomers and polymers in which these structures are present,
wherein

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are independently C 1 -C 18 -alkyl, C 2 -C 18 -alkyl interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, C 6 -C 12 -aryl, C 5 -C 12 -cycloalkyl or a five- or six-membered, oxygen-, nitrogen- and/or sulfur-containing heterocycle or two of them together form an unsaturated, saturated or aromatic ring which may be interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, where the radicals mentioned are optionally substituted by functional groups comprising an aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatom, and/or heterocycle.

3. The process of claim 1 , wherein the ionic liquid comprises a fluoride, chloride, bromide, iodide, thiocyanate, hexafluorophosphate, trifluoromethanesulfonate, methanesulfonate, carboxylate, mandelate, nitrate, nitrite, trifluoroacetate, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, 1-propyl sulfate, 1-butyl sulfate, 1-hexyl sulfate, 1-octylsulfate, sulfite, hydrogensulfite, phosphate, dihydrogenphosphate, hydrogenphosphate, C 1 -C 4 -dialkylphosphate, carbonate, hydrogencarbonate, propionate, tetrachloroaluminate, Al 2 Cl 7 —, Al 3 Cl 10 —, chlorozincate, chloroferrate, chlorocuprate, bis(trifluoromethylsulfonyl)imide, bis(pentafluoroethylsulfonyl)imide, bis(methylsulfonyl)imide, bis(p-tolylsulfonyl)imide, tris(trifluoromethylsulfonyl)methide, bis(pentafluoroethylsulfonyl)methide, p-tolylsulfonate, tetracarbonylcobaltate, dimethyleneglycolmonomethylethersulfate, oleate, stearate, acrylate, methacrylate, maleate, hydrogencitrate, vinylphosphonate, bis(pentafluoroethyl)phosphinate, borate, dicyanamide, tris(pentafluoroethyl)trifluorophosphate, tris(heptafluoropropyl)trifluorophosphate, cyclic arylphosphate, and/or chlorocobaltate anion.

4. The process of claim 1 , wherein the ionic liquid is an imidazolium salt of formula (I):

wherein:
R a and R c are independently an organic radical comprising 1 to 3000 carbon atoms,
R b , R d , and R e are independently hydrogen or an organic radical comprising 1 to 3000 carbon atoms,
X is an anion, and
n is 1, 2, or 3.

5. The process of claim 1 , wherein the polymerization catalyst comprising the aluminum trihalide-donor complex, an alkylaluminum halide-donor complex, an iron trihalide-donor complex, a gallium trihalide-donor complex, or a titanium tetrahalide-donor complex.

6. The process of claim 1 , wherein the Lewis acid polymerization catalyst comprises an aluminum trichloride-donor complex or an alkylaluminum halide-donor complex or an iron-trihalide donor complex.

7. The process of claim 1 , wherein the organic compound (II) comprises an ether, carboxylic ester, aldehyde function, or keto function.

8. The process of claim 5 , wherein the organic compound (II) is an ether of formula
R 8 —O—R 9

wherein
R 8 and R 9 are each independently a C 1 - to C 20 -alkyl radical, C 1 - to C 20 -haloalkyl radical, C 5 - to C 8 -cycloalkyl radical, C 6 - to C 20 -aryl radical, C 6 - to C 20 -haloaryl radicals, or C 7 - to C 20 -arylalkyl radical.

9. The process of claim 1 , wherein the organic compound (II) comprises an ether comprising a secondary hydrocarbon group, tertiary hydrocarbon group, or halide-substituted hydrocarbon.

10. The process of claim 1 , wherein the organic compound (II) is diethyl ether, di-n-butyl ether, di-isopropyl ether, di-n-propyl ether, and/or chloroethyl ethyl ether.

11. The process of claim 4 , wherein R a to R e are independently a C 1 - to C 20 -alkyl group, R b , R d , and R e optionally being hydrogen.

12. The process of claim 4 , wherein R a and R c are independently a C 1 - to C 20 -alkyl group, R b , R d , and R e are each hydrogen.

13. The process of claim 4 , wherein R a and R c are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, 2-methylpentyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, tallow fatty alkyl radicals, or n-eicosyl.

14. The process of claim 4 , wherein X is sulfate, alkylsulfate, alkylsulfonate, alkylcarbonate, halide, pseudohalide, carboxylate, phosphate, phosphonate, nitrate, nitrite, N(SO 2 CF 3 ) 2 − , or tricyanomethanide.

15. The process of claim 1 , wherein a homopolymerization of isobutene is carried out and a molar ratio of the aluminum trihalide or alkylaluminum halide to the isobutene, based on each individual functional site of the aluminum trihalide or alkylaluminum halide, is in a range of from 0.001:1 to 0.2:1, or
wherein a copolymerization of isobutene is carried out and a molar ratio of the aluminum trihalide or alkylaluminum halide to a total amount of polymerizable monomers, based on each individual functional site of the aluminum trihalide or alkylaluminum halide, is in a range of from 0.001:1 to 0.2:1.

16. The process of claim 1 , wherein the polymerization is performed with additional use of a monofunctional or polyfunctional initiator which is an organic hydroxyl compound comprising a hydroxyl group bonded to an sp 3 -hybridized carbon atom, or an organic halogen compound comprising a halogen atom bonded to an sp 3 -hybridized carbon atom and water.

17. The process of claim 16 , wherein the initiator is 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, 1,3-bis(1-hydroxy-1-methylethyl)benzene, or 1,4-bis(1-hydroxy-1-methylethyl)benzene.

18. The process of claim 16 , wherein a molar ratio of the initiator to the isobutene monomer used in the case of homopolymerization of the isobutene, or to a total amount of polymerizable monomers used in copolymerization of the isobutene, based on each individual functional site of the initiator, is in a range of from 0.0005:1

Assignees

• Basf Se

Inventors

• Corberan Roc Rosa
• Muehlbach Klaus
• Wettling Thomas
• Kostjuk Sergei V
• Vasilenko Irina
• Shiman Dmitryi
• Berazianka Ivan

Classifications

• B01J31/0277

  comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature · CPC title

• B01J31/0298

  the ionic liquids being characterised by the counter-anions · CPC title

• C08F10/10 Primary

  Isobutene · CPC title

• C08K5/50

  Phosphorus bound to carbon only · CPC title

• C08K5/353

  Five-membered rings · CPC title