Process for producing low molecular weight ethylene- and alpha-olefin-based materials

Patent metadata

Field	Value
Publication number	US-9522855-B2
Application number	US-201214361552-A
Country	US
Kind code	B2
Filing date	Nov 28, 2012
Priority date	Dec 29, 2011
Publication date	Dec 20, 2016
Grant date	Dec 20, 2016

Abstract

The present invention generally relates to a process that prepares polyethylenes, poly-α-olefins or poly(co-ethylene-α-olefin) having backbone weight average molecular weights less than 2500 daltons. The process uses a metal-ligand complex as a precatalyst and can be carried out at temperatures ranging from 30° C. to 300° C. The relatively low molecular weight of the products enables improved viscosity control for a wide variety of applications.

First claim

What is claimed is:

1. A process for preparing a low molecular weight ethylene-based material comprising a step of contacting together (1) a monomer selected from (a) ethylene; (b) a non-ethylene α-olefin; or (c) a combination thereof; and (2) a catalytic amount of a catalyst; wherein the catalyst comprises a mixture or reaction product of ingredients (2a) and (2b) that is prepared before the contacting step, wherein ingredient (2a) is at least one metal-ligand complex, and wherein ingredient (2b) is at least one activating co-catalyst; the metal-ligand complex of ingredient (2a) being at least one metal-ligand complex of formula (I):

wherein M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; n is an integer 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 chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral; each Z independently is 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; at least one of R 1a , R 2a , R 1b , and R 2b independently is a (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 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)— or halogen atom; each of R 5c and R 5d independently is a (C 6 -C 40 )aryl or (C 1 -C 40 )heteroaryl; each of the aforementioned aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl, hydrocarbylene, and heterohydrocarbylene groups independently is unsubstituted or substituted with one or more substituents R S ; and each R S independently is 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; such that the ratio of total number of moles of the at least one metal-ligand complex (2a) to total number of moles of the at least one activating co-catalyst (2b) is from 1:10,000 to 100:1; under conditions such that a polyethylene, poly-α-olefin, or poly(co-ethylene-α-olefin), having a backbone weight average molecular weight (Mw) that is less than 1500 daltons (Da), is formed.

2. The process of claim 1 wherein M is zirconium or hafnium.

3. The process of claim 1 wherein each Z is O.

4. The process of claim 1 wherein R 1a and R 1b are methyl, ethyl or isopropyl.

5. The process of claim 1 wherein R 1a and R 1b are fluorine atoms, chlorine atoms, bromine atoms or iodine atoms.

6. The process of claim 1 wherein L is —CH 2 CH 2 —, —CH(CH 3 )CH(CH 3 )—, 1,2-cyclopentanediyl or 1,2-cyclohexane-diyl.

7. The process of claim 1 wherein R 5d independently is a 2,7-disubstituted 9H-carbazol-9-yl or a 3,6-disubstituted 9H-carbazol-9-yl, 9H-carbazol-9-yl, wherein each substituent is R S .

8. The process of claim 1 wherein R 5d independently is a (C 6 -C 40 )aryl that is a 2,4-disubstituted phenyl, wherein each substituent is R S ; 2,5-disubstituted phenyl wherein each substituent is R S ; 2,6-disubstituted phenyl wherein each substituent is R S ; 3,5-disubstituted phenyl wherein each substituent is R S ; 2,4,6-trisubstituted phenyl wherein each substituent is R S ; naphthyl or substituted naphthyl wherein each substituent is R S ; 1,2,3,4-tetrahydronaphthyl; anthracenyl; 1,2,3,4-tetrahydroanthracenyl; 1,2,3,4,5,6,7,8-octahydroanthracenyl; phenanthrenyl; or 1,2,3,4,5,6,7,8-octahydrophenanthrenyl.

9. The process of claim 1 wherein the conditions include a temperature from 30° C. to 300° C.

Assignees

• Dow Global Technologies Llc

Inventors

• Klosin Jerzy
• Thomas Pulikkottil J

Classifications

• C08F10/00 Primary

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C07C2531/22

  Organic complexes · CPC title

• C07C2/32 Primary

  as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)} · CPC title

• C08F4/64186

  Dianionic ligand · CPC title

• C08F4/64196

  OSSO · CPC title