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

Patent metadata

Field	Value
Publication number	US-2016130206-A1
Application number	US-201414901057-A
Country	US
Kind code	A1
Filing date	Jun 18, 2014
Priority date	Jun 28, 2013
Publication date	May 12, 2016
Grant date	—

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 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; and (3) hydroformylating the fractionated oligomer product to produce an aldehyde product or sulfonating the fractionated oligomer product to produce a sulfonated surfactant product.

2 . A process 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; and (4) hydrogenating the aldehyde product to produce an alcohol product.

3 . A process according to claim 2 , further comprising alkoxylating the alcohol product to produce an alkoxylate surfactant product.

4 . A process according to claim 3 , further comprising sulfating the alkoxylate surfactant product to produce an anionic ether sulfate surfactant product.

5 . A process according to claim 2 , further comprising sulfating the alcohol product to produce an anionic sulfate surfactant product.

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

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

8 . A process according to claim 7 , wherein the olefin mixture includes olefins with vinyl groups, olefins with vinylidene groups, and olefins with vinylene groups.

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

10 . A process according to claim 1 , wherein the metal-ligand complex is a compound of the formula

wherein M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4;
n is an integer of from 0 to 3, wherein when n is 0, X is absent;
each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic, or two X are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic;
X and n are selected such that the metal-ligand complex of formula (I) is, overall, neutral;
each Z is independently O, S, N(C 1 -C 40 )hydrocarbyl, or P(C 1 -C 40 )hydrocarbyl;
L is (C 1 -C 40 )hydrocarbylene or (C 1 -C 40 )heterohydrocarbylene, wherein the (C 1 -C 40 )-hydrocarbylene has a portion that comprises a 2-carbon atom linker backbone linking the Z atoms in formula (I) and the (C 1 -C 40 )heterohydrocarbylene has a portion that comprises a 2-atom atom linker backbone linking the Z atoms in formula (I), wherein each atom of the 2-atom linker of the (C 1 -C 40 )-heterohydrocarbylene independently is a carbon atom or a heteroatom, wherein each heteroatom independently is O, S, S(O), S(O) 2 , Si(R C ) 2 , Ge(R C ) 2 , P(R P ), or N(R N ), wherein independently each R C is unsubstituted (C 1 -C 18 )hydrocarbyl or the two R C are taken together to form a (C 2 -C 19 )alkylene, each R P is unsubstituted (C 1 -C 18 )hydrocarbyl; and each R N is unsubstituted (C 1 -C 18 )hydrocarbyl, a hydrogen atom or absent; R 1a , R 2a , R 1b , and R 2b independently is a hydrogen, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )-heterohydrocarbyl, N(R N ) 2 , NO 2 , OR C , SR C , Si(R C ) 3 , Ge(R C ) 3 , CN, CF 3 , F 3 CO, halogen atom; and each of the others of R 1a , R 2a , R 1b , and R 2b independently is a hydrogen, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )-heterohydrocarbyl, N(R N ) 2 , NO 2 , OR C , SR C , Si(R C ) 3 , CN, CF 3 , F 3 CO or halogen atom; each of R 3a , R 4a , R 3b , R 4b , R 6c , R 7c , R 8c , R 6d , R 7d , and R 8d independently is a hydrogen atom; (C 1 -C 40 )hydrocarbyl; (C 1 -C 40 )-heterohydrocarbyl; Si(R C ) 3 , Ge(R C ) 3 , P(R P ) 2 , N(R N ) 2 , OR C , SR C , NO 2 , CN, CF 3 , RCS(O)—, RCS(O) 2 —, (RC) 2 C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)— or halogen atom;
each of R 5c and R 5d is independently a (C 6 -C 40 )aryl or (C 1 -C 40 )heteroaryl;
each of the aforementioned aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl, hydrocarbylene, and heterohydrocarbylene groups is independently unsubstituted or substituted with 1 to 5 more substituents R S ; and
each R S is independently a halogen atom, polyfluoro substitution, perfluoro substitution, unsubstituted (C 1 -C 8 )alkyl, F 3 C—, FCH 2 O—, F 2 HCO—, F 3 CO—, R 3 Si—, R 3 Ge—, RO—, RS—, RS(O)—, RS(O) 2 —, R 2 P—, R 2 N—, R 2 C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R 2 NC(O)—, or two of the R S are taken together to form an unsubstituted (C 1 -C 18 )alkylene, wherein each R independently is an unsubstituted (C 1 -C 18 )alkyl.

11 . The process according to claim 1 , wherein the coordination-insertion catalyst is selected from the group consisting of

and combinations thereof.

12 . A process according to claim 1 , 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, i

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

• B01J2531/48

  Zirconium · CPC title

• C07C7/04

  by distillation · CPC title

• B01J2231/20

  Olefin oligomerisation or telomerisation · CPC title

• C07C29/141

  with hydrogen or hydrogen-containing gases · CPC title

• C07C41/01

  Preparation of ethers · CPC title