High-reactivity polyisobutylene having a high content of vinylidene double bonds in the side chains

Patent metadata

Field	Value
Publication number	US-2016145362-A1
Application number	US-201414905658-A
Country	US
Kind code	A1
Filing date	Jul 7, 2014
Priority date	Jul 17, 2013
Publication date	May 26, 2016
Grant date	—

Abstract

A polyisobutylene having a total content of vinylidene double bonds of more than 50 mol % and a number-average molecular weight of 500 to 10 000 daltons, where at least 10% of all the vinylidene double bonds in the polyisobutylene are part of one or more side chains composed of at least 2 carbon atoms from the main polyisobutylene chain. Such a polyisobutylene is suitable for production of fuel and lubricant additives.

First claim

1 : A polyisobutylene, having a total content of vinylidene double bonds of more than 50 mol % and a number-average molecular weight (M n ) of 500 to 10,000 daltons, wherein at least 10% of all the vinylidene double bonds in the polyisobutylene are part of a side chain comprising at least 2 carbon atoms from the main polyisobutylene chain.

2 : The polyisobutylene according to claim 1 , having a total content of vinylidene double bonds of more than 70 mol % and a number-average molecular weight (M n ) of 900 to 2500 daltons, wherein at least 12% of all the vinylidene double bonds in the polyisobutylene are part of the side chain comprising at least 2 carbon atoms from the main polyisobutylene chain.

3 : The polyisobutylene according to claim 1 , wherein the vinylidene double bonds which are part of the side chain comprising at least 2 carbon atoms from the main polyisobutylene chain are each arranged in the α position at a distal end of the side chain.

4 : The polyisobutylene according to claim 1 , having a polydispersity of 1.05 to 2.0.

5 : A process for preparing a polyisobutylene according to claim 1 , comprising polymerizing, in a polymerization medium in a polymerization apparatus, isobutene or an isobutene-containing C 4 hydrocarbon mixture in the presence of a mixture consisting essentially of isobutene oligomers consisting of 2 to 5 isobutene units at temperatures of −100° C. to +100° C. with a Brønsted acid-based or Lewis acid-based polymerization catalyst, wherein a molar ratio of the vinylidene double bonds present in the isobutene oligomer mixture present in the polymerization medium to the double bonds in the isobutene monomer used is at least 1:100.

6 : The process according to claim 5 , wherein the mixture consisting essentially of isobutene oligomers consisting of 2 to 5 isobutene units is prepared separately and introduced into the polymerization medium before or during the polymerization of the isobutene or of the isobutene-containing C 4 hydrocarbon mixture.

7 : The polyisobutylene according to claim 1 , wherein the polyisobutylene is suitable for preparation of derivatives suitable as fuel and lubricant additives.

8 : A process for preparing polyisobutylene derivatives of formula I
POL(-A) n   (I)
wherein POL denotes the n-functional radical of a polyisobutylene according to claim 1 , A is a low molecular weight polar group comprising in each case one or more amino functions and/or nitro groups and/or hydroxyl groups and/or mercaptan groups and/or carboxylic acid or carboxylic acid derivative functions, and the variable n is a number from 1 to 10, where the variables A may be the same or different when n>1, the process comprising reacting the polyisobutylene with at least n equivalents of a compound which introduces the low molecular weight polar group A or a substructure of the low molecular weight polar group A and, in the case of reaction with a substructure, completing the formation of the low molecular weight polar group A by further reactions.

9 : The process according to claim 8 , wherein the low molecular weight polar group A is selected from
(a) mono- or polyamino groups having up to 6 nitrogen atoms, where a nitrogen atom has basic properties; (b) nitro groups, optionally in combination with hydroxyl groups; (c) hydroxyl groups, optionally in combination with mono- or polyamino groups, where a nitrogen atom has basic properties; (d) carboxyl groups or the alkali metal or alkaline earth metal salts thereof; (e) sulfo groups or the alkali metal or alkaline earth metal salts thereof; (f) polyoxy-C 2 -C 4 -alkylene moieties terminated by hydroxyl groups, by mono- or polyamino groups, where a nitrogen atom has basic properties, or by carbamate groups; (g) carboxylic ester groups; (h) succinic anhydride or moieties which derive from succinic anhydride and have hydroxyl and/or amino and/or quaternized amino and/or amido and/or imido groups, which have been prepared by thermal or halogen-catalyzed maleation of the internal double bonds and of the vinylidene double bonds of the parent polyisobutylene of the POL with maleic anhydride and, in the case of moieties which derive from succinic anhydride and have hydroxyl and/or amino and/or quaternized amino and/or amido and/or imido groups, by appropriate further reactions, and any resulting carboxamide or carboximide derivative can be modified by further conversion with a C 2 - to C 12 -dicarboxylic anhydride, with a C 2 - to C 4 -alkylene carbonate and/or with boric acid; (j) moieties obtained by Mannich reaction of POL-substituted phenols with aldehydes and mono- or polyamines; (k) phenol, alkylphenol or (hydroxyalkyl)phenol moieties; (l) hydroxymethyl groups; (m) moieties which have been obtained by epoxidation of the vinylidene double bonds of the parent polyisobutylene of the POL and subsequent
(i) hydrolysis to the 1,2-diol,
(ii) reaction with a thiol or a polythiol,
(iii) reaction with ammonia, a monoamine or a polyamine,
(iv) reaction with a borane to give a borate ester and oxidative cleavage of the borate ester to the 1,3-diol,
(v) conversion to an aldehyde,
(vi) conversion to an aldehyde and conversion of the aldehyde to an oxime and reduction of the oxime to the amine,
(vii) conversion to an aldehyde and conversion of the aldehyde to an azomethine cation and hydrolysis to the amine,
(viii) conversion to an aldehyde and conversion of the aldehyde to an alcohol or
(ix) conversion to an aldehyde and conversion of the aldehyde to a Schiff base or an enamine and reduction of the Schiff base or of the enamine to the amine;
(n) moieties which have been obtained by hydroboration of vinylidene double bonds of the parent polyisobutylene of the POL and subsequent oxidation of the primary hydroboration product; and (o) moieties which have been obtained by hydrosilylation of vinylidene double bonds of the parent polyisobutylene of the POL.

10 : The process according to claim 8 , wherein A is a low molecular weight polar group comprising an amino function, wherein the polyisobutylene is hydroformylated with a suitable catalyst in the presence of carbon monoxide and hydrogen and then reductively aminated in the presence of at least n equivalents of ammonia or of a mono- or polyamine.

11 : The process according to claim 8 , wherein A is a low molecular weight polar group comprising an amino function, wherein the polyisobutylene is treated with a suitable activator, especially with chlorine, and then reacted with n equivalents of ammonia or of a mono- or polyamine.

12 : The process according to claim 8 , wherein A is a low molecular weight polar group comprising an amino function, wherein the polyisobutylene is reacted with an ethylenically unsaturated C 4 - to C 12 -dicarboxylic acid or a reactive derivative thereof, especially with maleic anhydride, thermally or with halogen catalysis and then optionally converting it with a mono- or polyamine to the corresponding carboxamide or carboximide derivative, and the resulting carboxamide or carboximide derivative can be modified by further reaction with at least one C 2 - to C 12 -dicarboxylic anhydride, with at least one C 2 - to C 4 -alkylene carbonate and/or with boric acid.

13 : The process according to claim 8 , wherein A is a low molecular weight polar group comprising an amino function, wherein the polyisobutylene is converted with a phenol to the corresponding alkylphenol and the latter is subsequently converted by reaction with an aldehyde and a primary or secondary amine to the corresponding Mannich adduct.

Assignees

• Basf Se

Inventors

• Wettling Thomas
• Hirsch Stefan
• Brym Markus
• Weis Markus

Classifications

• C08F210/10 Primary

  Isobutene · CPC title

• C08F8/46

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

• C08F110/10 Primary

  Isobutene · CPC title

• C08F8/32

  by reaction with amines · CPC title

• C08F8/00

  Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C) · CPC title