Process for the preparation of lightly-branched hydrophobes and the corresponding surfactants and applications thereof

Patent metadata

Field	Value
Publication number	US-10196336-B2
Application number	US-201414901057-A
Country	US
Kind code	B2
Filing date	Jun 18, 2014
Priority date	Jun 28, 2013
Publication date	Feb 5, 2019
Grant date	Feb 5, 2019

Abstract

Processes to prepare lightly branched surfactant products comprise combining at least one olefin and a coordination-insertion catalyst under conditions such that at least one oligomer product is formed. The surfactant products comprise a main carbon chain containing an average of between 0.5 and 2.5 branches, wherein more than 50% of the branches are ethyl branches, wherein the branches are located more than one carbon away from each end of the main carbon chain in more than 20% of surfactant product molecules.

First claim

What is claimed is:

1. A process for preparing an aldehyde product or a sulfonated surfactant product, comprising:
(1) combining at least one olefin and at least one coordination-insertion catalyst and, optionally, an alpha-olefin,
wherein the coordination-insertion catalyst is a metal-ligand complex wherein the metal is selected from zirconium, hafnium and titanium,
and has an ethylene/octene reactivity ratio up to 20 at an operating reactor temperature, and a kinetic chain length up to 20 monomer units;
under conditions such that at least one oligomer product is formed,
wherein the oligomer product includes a main carbon chain containing an average of between 0.5 and 2.5 branches, wherein more than 50% of the branches are ethyl branches, wherein the branches are located on average more than one carbon away from each end of the main carbon chain in more than 20% of oligomer product molecules, wherein the branches are situated at a second carbon relative to an unsaturated end of the main carbon chain in less than 40% of the oligomer product molecules, and wherein the oligomer product contains greater than 50% vinyl olefin;
(2) fractionating the oligomer product to produce a fractionated oligomer product, such that the average carbon number of the fractionated oligomer product is between 8 and 28;
(3) hydroformylating the fractionated oligomer product to produce an aldehyde product or sulfonating the fractionated oligomer product to produce a sulfonated surfactant product; and
wherein the coordination-insertion catalyst is selected from the group consisting of:

and combinations thereof.

2. A process according to claim 1 , wherein the at least one olefin is ethylene and an alpha-olefin is not used.

3. A process according to claim 1 , wherein the at least one olefin is an olefin mixture.

4. A process according to claim 3 , wherein the olefin mixture includes olefins with vinyl groups, olefins with vinylidene groups, and olefins with vinylene groups.

5. A process according to claim 1 , further comprising use of a rhodium catalyst with an organophosphorus ligand in the hydroformylating step (3).

6. A process for preparing an aldehyde product or a sulfonated surfactant product, comprising:
(1) combining at least one olefin and at least one coordination-insertion catalyst and, optionally, an alpha-olefin,
wherein the coordination-insertion catalyst is a metal-ligand complex wherein the metal is selected from zirconium, hafnium and titanium,
and has an ethylene/octene reactivity ratio up to 20 at an operating reactor temperature, and a kinetic chain length up to 20 monomer units;
under conditions such that at least one oligomer product is formed,
wherein the oligomer product includes a main carbon chain containing an average of between 0.5 and 2.5 branches, wherein more than 50% of the branches are ethyl branches, wherein the branches are located on average more than one carbon away from each end of the main carbon chain in more than 20% of oligomer product molecules, wherein the branches are situated at a second carbon relative to an unsaturated end of the main carbon chain in less than 40% of the oligomer product molecules, and wherein the oligomer product contains greater than 50% vinyl olefin;
(2) fractionating the oligomer product to produce a fractionated oligomer product, such that the average carbon number of the fractionated oligomer product is between 8 and 28;
(3) hydroformylating the fractionated oligomer product to produce an aldehyde product or sulfonating the fractionated oligomer product to produce a sulfonated surfactant product; and
wherein the metal-ligand complex is a compound of the formula

 wherein M is the metal center, and is a Group 4 metal selected from titanium, zirconium or hafnium;
 T is an optional bridging group which, if present, is selected from dialkylsilyl, dialkylmethyl, ethylenyl (—CH 2 —CH 2 —) or hydrocarbylethylenyl wherein one, two, three or four of the hydrogen atoms in ethylenyl are substituted by hydrocarbyl, where hydrocarbyl can be independently C 1 to C 16 alkyl or phenyl, tolyl, or xylyl, and when T is present, the catalyst represented can be in a racemic or a meso form;
L 1 and L 2 are the same or different cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl rings, optionally substituted, that are each bonded to M, or L 1 and L 2 are the same or different cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl, which are optionally substituted, in which any two adjacent R groups on these rings are optionally joined to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
Z is nitrogen, oxygen or phosphorus;
R′ is a cyclic linear or branched C 1 , C 40 alkyl or substituted alkyl group; and X 1 and X 2 are, independently, hydrogen, halogen, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbyl radicals, or substituted germylcarbyl radicals; or both X are joined and bound to the metal atom to form a metallacycle ring containing from 3 to 20 carbon atoms; or both together can be an olefin, diolefin or aryne ligand.

7. A process according to claim 6 , wherein the at least one olefin is ethylene and an alpha-olefin is not used.

8. A process according to claim 6 , wherein the at least one olefin is an olefin mixture.

9. A process according to claim 8 , wherein the olefin mixture includes olefins with vinyl groups, olefins with vinylidene groups, and olefins with vinylene groups.

10. A process according to claim 6 , further comprising use of a rhodium catalyst with an organophosphorus ligand in the hydroformylating step (3).

Assignees

• Dow Global Technologies Llc

Inventors

• Elowe Paul R
• Yu Wanglin
• Bailey Brad C
• Tulchinsky Michael L
• Argenton Andre B
• Arriola Daniel J
• Klosin Jerzy J

Classifications

• B01J31/2213

  At least two complexing oxygen atoms present in an at least bidentate or bridging ligand · CPC title

• C11D3/168

  Organometallic compounds or orgometallic complexes · CPC title

• C07C45/505 Primary

  Asymmetric hydroformylation · CPC title

• B01J31/223

  At least two oxygen atoms present in one at least bidentate or bridging ligand · CPC title

• C07C11/02

  Alkenes · CPC title