Preparation of isobutene homo- or copolymer derivatives

Patent metadata

Field	Value
Publication number	US-9296841-B2
Application number	US-201113305283-A
Country	US
Kind code	B2
Filing date	Nov 28, 2011
Priority date	Nov 30, 2010
Publication date	Mar 29, 2016
Grant date	Mar 29, 2016

Abstract

A process for preparing isobutene homo- or copolymer derivatives by (i) polymerizing isobutene or an isobutene-comprising monomer mixture in the presence of an iron halide-donor complex, an aluminum trihalide-donor complex, or an alkylaluminum halide-donor complex, (ii) reacting a resulting high-reactivity isobutene polymer with a compound which introduces a low molecular weight polar group or a substructure thereof, and (iii) in the case of reaction with a substructure, further reacting to complete the formation of the low molecular weight polar group. The homo- or copolymer derivatives include a radical of a hydrophobic polyisobutene polymer having a number-average molecular weight of 110 to 250,000 and low molecular weight polar groups including amino functions, nitro groups, hydroxyl groups, mercaptan groups, carboxylic acid or carboxylic acid derivative functions, sulfonic acid or sulfonic acid derivative functions, aldehyde functions and/or silyl groups.

First claim

The invention claimed is:

1. A process for preparing an isobutene homo- or copolymer derivative of formula (I):
POL(-A) n   (1),

wherein:
POL represents an n-functional radical of a hydrophobic polyisobutene homo- or copolymer having a number-average molecular weight (M n ) of 110 to 250 000;
A independently represents a low molecular weight polar group comprising at least one selected from the group consisting of an amino group, a nitro group, a hydroxyl group, a mercaptan group, a carboxylic acid group, a carboxylic acid derivative group, a sulfonic acid group, a sulfonic acid derivative group, an aldehyde group and a silyl group; and
n represents 1, 2 or 3, such that A may be the same or different when n=2 and n=3,

the process comprising:
polymerizing isobutene or a monomer mixture comprising isobutene in the presence of
(A) an iron halide-donor complex, an aluminum trihalide-donor complex, or an alkylaluminum halide-donor complex, effective as a polymerization catalyst, comprising, as the donor, an organic compound comprising at least one ether function or a carboxylic ester function, wherein water is used as a sole initiator in a molar ratio of watenisobutene monomer of from 0.001:1 to 0.075:1, or
(B) at least one Lewis acid suitable as a polymerization catalyst or a complex which is effective as a polymerization catalyst and is formed from at least one Lewis acid and at least one donor, and in the presence of at least one organic sulfonic acid of the general formula Z—SO 3 H, as an initiator, in which the variable Z represents a C 1 - to C 20 -alkyl radical, a C 1 - to C 20 -haloalkyl radical, a C 5 - to C 8 -cycloalkyl radical, a C 6 - to C 20 -aryl radical or a C 7 - to C 20 -arylalkyl radical, wherein the polymerization is performed at a temperature of from 0° C. to 30° C.,

to obtain a resulting high-reactivity isobutene homo- or copolymer having a content of terminal vinylidene double bonds of at least 50 mol% per polyisobutene chain end;
reacting the resulting high-reactivity isobutene homo- or copolymer with at least n equivalents of a compound to obtain (i) an isobutene homo- or copolymer comprising the low molecular weight polar group, or (ii) an isobutene homo- or copolymer comprising a precursor of the low molecular weight polar group; and
optionally further reacting the isobutene homo- or copolymer (ii) comprising the precursor of the low molecular weight polar group to obtain the isobutene homo- or copolymer (i) comprising the low molecular weight polar group.

2. The process according to claim 1 , comprising polymerizing the monomer mixture comprising isobutene in the presence of (A) the iron chloride-donor complex or the aluminum trichloride-donor complex.

3. The process according to claim 1 , comprising polymerizing in the presence of (A) the iron halide-donor complex, the aluminum trihalide-donor complex or the alkylaluminum halide-donor complex, comprising, as the donor, a dihydrocarbyl ether of formula R 1 —O—R 2 in which the variables R 1 and R 2 arc each independently a C 1 - to C 20 -alkyl radical, a C 5 - to C 8 -cycloalkyl radical, a C 6 - to C 20 -aryl radical or a C 7 - to C 20 -arylalkyl radical.

4. The process according to claim 1 , comprising polymerizing in the presence of (A) the iron halide-donor complex, the aluminum trihalide-donor complex or the alkylaluminum halide-donor complex, comprising, as the donor, a hydrocarbyl carboxylate of formula R 3 —COOR 4 in which the variables R 3 and R 4 are each independently a C 1 - to C 20 -alkyl radical, a C 5 - to C 8 -cycloalkyl radical, a C 6 - to C 20 -aryl radical or a C 7 - to C 20 -arylalkyl radical.

5. The process according to claim 1 , comprising polymerizing in the presence of (A) the iron halide-donor complex, the aluminum trihalide-donor complex or the alkylaluminum halide-donor complex, comprising, as the donor, an organic compound having a total carbon number of 3 to 16.

6. The process according to claim 1 , comprising polymerizing in the presence of (A) the iron halide-donor complex, the aluminum trihalide-donor complex, or the alkylaluminum halide-donor complex, in the presence of 0.01 to 10 mmol, based on 1 mol of the isobutane in the case of homopolymerization or on 1 mol of a total amount of polymerizable monomers in the case of copolymerization, of a basic nitrogen compound.

7. The process according to claim 6 , wherein the basic nitrogen compound is pyridine or a derivative of pyridine.

8. The process according to claim 1 , comprising polymerizing in the presence of (A) the iron halide-donor complex, the aluminum trihalide-donor complex, or the alkylaluminum halide-donor complex, in a halogenated aliphatic hydrocarbon or in a mixture of halogenated aliphatic hydrocarbons or in a mixture of at least one halogenated aliphatic hydrocarbon and at least one aliphatic, cycloaliphatic or aromatic hydrocarbon or in a halogen-free aliphatic or halogen-free aromatic hydrocarbon as an inert diluent.

9. The process according to claim 1 , comprising polymerizing in the presence of (B) the at least one Lewis acid or the complex, wherein the at least one initiator is an organic sulfonic acid selected from the group consisting of methanesulfonic acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic acid, toluenesulfonic acid, and mixtures thereof.

10. The process according to claim 1 or 9 , comprising polymerizing in the presence of (B) a complex formed from at least one Lewis acid selected from the group consisting of
a binary chlorine compound of an element of transition groups 1 to 8 of the Periodic Table,
a binary chlorine compound of an element of main groups 3 to 5 of the Periodic Table,
a fluorine compound of an element of transition groups 1 to 8 of the Period Table,
a fluorine compound of an element of main groups 3 to 5 of the Periodic Table, and mixtures thereof.

11. The process according to claim 10 , wherein the Lewis acid is a binary chlorine or fluorine compound selected from the group consisting of BCl 3 , AlCl 3 , TiCl 4 , FeCl 2 , FeCl 3 , ZnCl 2 , BF 3 , AlF 3 , TiF 4 , FeF 2 , FeF 3 and ZnF 2 .

12. The process according to claim 1 , comprising polymerizing in the presence of (B) the complex formed from at least one Lewis acid and at least one donor, which is an organic compound comprising at least one ether function or a carboxylic ester function.

13. The process according to claim 12 , wherein the organic compound is
a dihydrocarbyl ether of formula R 1 —O—R 2 , in which the variables R 1 and R 2 each independently denote a C 1 - to C 20 -alkyl radical, a C 5 - to C 8 -cycloalkyl radical, a C 6 - to C 20 -aryl radical or a C 7 - to C 20 -arylalkyl radical, or
a hydrocarbyl carboxylate of the general formula R 3 —COOR 4 , in which the variables R 3 and R 4 each independently denote a C 1 - to C 20 -alkyl radical, a C 5 - to C 8 -cycloalkyl radical, a C 6 - to C 20 -aryl radical or a C 7 - to C 20 -arylalkyl radical.

14. The process according to claim 13 , wherein the organic compound has a total carbon number of 3 to 16.

15. The process according to claim 1 , comprising polymerizing in the presence of (B) the at least one Lewis acid or the complex, in the presence of 0.01 to 10 mmol, based on 1 mol of the isobutene in the case of homopolymerization or on 1 mol of a total amount of polymerizable monomers in the case of copolymerization, of a basic nitrogen compound.

16. The process according to claim 15 , wherein the basic nitrogen compound is pyridine or a derivative of pyridine.

17. The process according to claim 1 , compr

Assignees

• König Hannah Maria
• Mühlbach Klaus
• Mach Helmut
• Eichenauer Ulrich
• Basf Se

Inventors

• König Hannah Maria
• Mühlbach Klaus
• Mach Helmut
• Eichenauer Ulrich

Classifications

• C08F210/10

  Isobutene · CPC title

• C08F10/10 Primary

  Isobutene · CPC title

• C08F8/46

  Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation · CPC title

• C08F4/26

  of manganese, iron group metals or platinum group metals · CPC title

• C08F8/34

  Introducing sulfur atoms or sulfur-containing groups · CPC title