Hyperbranched ethylene-based oils and greases

Patent metadata

Field	Value
Publication number	US-9643900-B2
Application number	US-201414893732-A
Country	US
Kind code	B2
Filing date	Jun 24, 2014
Priority date	Mar 25, 2011
Publication date	May 9, 2017
Grant date	May 9, 2017

Abstract

A process to prepare a relatively inexpensive utility fluid comprises contacting together ethylene and a coordination-insertion catalyst and, optionally, an alpha-olefin, in a continuously-fed backmixed reactor zone under conditions such that a mixture of a hyperbranched oligomer and a branched oligomer is formed. The hyperbranched oligomer has an average of at least 1.5 methine carbons per oligomer molecule, and at least 40 methine carbons per one-thousand total carbons, and at least 40 percent of the methine carbons is derived from the ethylene, and the average number of carbons per molecule is from 25 to 100, and at least 25 percent of the hyperbranched oligomer molecules has a vinyl group and can be separated from the branched oligomer, which has an average number of carbons per molecule of up to 20. The coordination-insertion catalyst is characterized as having an ethylene/octene reactivity ratio up to 20 and a kinetic chain length up to 20 monomer units.

First claim

The invention claimed is:

1. A process to prepare a utility fluid composition comprising:
(1) contacting together ethylene 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, and a kinetic chain length up to 20 monomer units;
in a continuously-fed backmixed reactor zone
under conditions such that a mixture of at least two oligomer products is formed,
the mixture including
a hyperbranched oligomer having an average of at least 1.5 methine carbons per oligomer molecule,
and having at least 40 methine carbons per one-thousand total carbons, and
wherein at least 40 percent of the methine carbons is derived from the ethylene, and
wherein the average number of carbons per molecule is from 25 to 100, and
wherein at least 25 percent of the hyperbranched oligomer molecules has a vinyl group;

and at least one branched oligomer having an average number of carbons per molecule that is less than 20;
(2) separating the hyperbranched oligomer from the branched oligomer; and
(3) recovering the hyperbranched oligomer, the branched oligomer, or both.

2. The process of 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 the formula 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 the formula and the (C 1 -C 40 )heterohydrocarbylene has a portion that comprises a 2-atom atom linker backbone linking the Z atoms in the formula, 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, or 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 18 )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.

3. The process of claim 1 wherein the coordination-insertion catalyst is selected from the group consisting of

and combinations thereof.

4. The process of 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, is selected from dialkylsilyl, diarylsilyl, 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 some or different cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl, the rings of which are optionally substituted with one or more R groups, with any two adjacent R groups being 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 to 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 form an olefin, diolefin or aryne ligand.

5. The process of claim 1 , further comprising (4) performing a hydrogenation, halogenation, etherification, hydroxylation, esterification, oxidation, or hydroformylation of the hyperbranched oligomer, the branched oligomer, or both.

6. The process of claim 1 , wherein at least 55 percent of the methine carbons is derived from the ethylene.

7. The process of claim 6 , wherein at least 70 percent of the methine carbons is derived from the ethylene.

8. The process of claim 1 wherein at least 50 percent of the hyperbranched oligomer molecules has a vinyl group.

9. The process of claim 8 where at least 75 percent of the hyperbranched oligomer molecules has a vinyl group.

10. A utility fluid composition prepared by the process of claim 1 .

Assignees

• Dow Global Technologies Llc

Inventors

• Arriola Daniel J
• Bailey Brad C
• Klosin Jerzy
• Lysenko Zenon
• Roof Gordon R
• Smith Austin J

Classifications

• C10G2300/1088

  Olefins · CPC title

• B01J2531/46

  Titanium · CPC title

• C10M105/00

  Lubricating compositions characterised by the base-material being a non-macromolecular organic compound · CPC title

• B01J31/223

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

• B01J2531/0238

  Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P · CPC title