Catalysts for preparing ultra high molecular weight polyethylene (UHMWPE)

Patent metadata

Field	Value
Publication number	US-9617362-B2
Application number	US-201514828577-A
Country	US
Kind code	B2
Filing date	Aug 18, 2015
Priority date	Aug 5, 2011
Publication date	Apr 11, 2017
Grant date	Apr 11, 2017

Abstract

Group 4 transition metal complexes of bidentate iminonaphthol pro-ligands can be used as catalysts to polymerize olefins, such as ethylene. Group 4 transition metal complexes of bidentate iminonaphthol pro-ligands can have a single-site nature, allowing the catalysts to be used to prepare ultra high molecular weight polyethylene having a narrow molecular weight distribution.

First claim

The invention claimed is:

1. A process for preparing a bi-dentate pro-ligand comprising:
providing a 2-methoxynaphthalene of formula II:

reacting the 2-methoxynaphthalene of formula II with R 2 X′ in the presence of a first base, wherein X′ is a leaving group,
wherein R 2 is independently selected from an unsubstituted or substituted aryl or cycloalkyl group having from 1 to 12 carbon atoms, or from Z(R 9 ) 3 wherein Z is an atom selected from Group 14 of the Periodic Table and each R 9 is independently selected from a hydrogen, substituted or unsubstituted aryl, alkyl or cycloalkyl group having from 1 to 12 carbon atoms, with the restriction that R 2 is a bulky group, at least as sterically bulky as tert-butyl, and
wherein R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from hydrogen, alkyl, cycloalkyl or aryl group comprising from 1 to 12 carbon atoms, a halogen, or a silyl group, wherein two or more of said groups can be linked together to form one or more rings, to obtain a compound of formula III:

reacting the compound of formula III with an electrophilic bromine source to obtain a compound of formula IV:

reacting the compound of formula IV with acylchloride R 1 COCl in the presence of a second base to obtain a compound of formula V′:

wherein R 1 is an unsubstituted or substituted aryl, alkyl, or cycloalkyl group comprising from 1 to 12 carbon atoms, a halogen, or a silyl group;
deprotecting the compound of formula V′ in order to obtain a compound of formula VI:

condensation of the compound of formula VI with an amine R 8 —NH 2 in the presence of catalytic amounts of an acid, optionally in the presence of tetraethyl orthosilicate or titanium tetrachloride, to obtain compounds of formula I and its tautomeric form I′, being a bidentate pro-ligand:

wherein A is nitrogen.

2. The process of claim 1 , wherein the first base is sec-BuLi.

3. The process of claim 1 , wherein the electrophilic bromine source is N-bromosuccinimide or bromine Br 2 .

4. The process of claim 1 , wherein the second base is tert-BuLi.

5. The process of claim 1 , wherein the deprotecting of the compound of formula V′ comprises treatment with BBr 3 .

6. The process of claim 1 , wherein the acid is formic acid (HCOOH), acetic acid (CH 3 COOH), sulphuric acid (H 2 SO 4 ), or p-toluenesulfonic acid (PTSA).

7. The process of claim 1 , wherein the condensation of the compound of formula VI with the amine R 8 —NH 2 is performed in the presence of tetraethyl orthosilicate or titanium tetrachloride.

Assignees

• Total Res & Technology Feluy

Inventors

• Wassenaar Jeroen

Classifications

• C08F10/00 Primary

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

• B01J31/18

  containing nitrogen, phosphorus, arsenic or antimony {as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms (double metal cyanides B01J27/26; N-heterocyclic carbenes B01J31/2265)} · CPC title

• C08F4/64048

  NO · CPC title

• C07F7/006

  Chemistry & Metallurgy · mapped topic

• C08F110/02 Primary

  Ethene · CPC title