Additives for fuels and oils comprising functionalised diblock copolymers

Patent metadata

Field	Value
Publication number	US-9845375-B2
Application number	US-201615368868-A
Country	US
Kind code	B2
Filing date	Dec 5, 2016
Priority date	Jul 9, 2012
Publication date	Dec 19, 2017
Grant date	Dec 19, 2017

Abstract

Concentrates containing specific functionalized diblock copolymers serve as effective additives for improving the cold flow behavior of fuels and oils, the copolymers being derived from a terminally-unsaturated intermediate polymer obtained via a metallocene process involving hydrogen.

First claim

What is claimed is:

1. A process for manufacture of a functionalised diblock copolymer comprising 2 polymeric blocks wherein:
(i) the first block consists of a chain of ethylenic structural traits, optionally interrupted by one or more structural units derived from 1-alkene co-monomers higher than ethylene, and
(ii) the second Hock comprises a chain of structural units derived from one or more α,β-unsaturated monomers selected from styrene, substituted styrene, acrylate, methacrylate and diene compounds,

and wherein said first and second Hocks of the copolymer are terminally joined by means of the following structural linkage:

wherein each R group independently represents an alkyl or aryl group and R′ represents hydrogen or an alkyl group, and wherein the aromatic ring substituent joined to the second block is positioned meta or para to the aromatic ring substituent joined to the first block;
the process comprising the following steps:
a) in a first step, polymerising ethylene, and optionally one or more 1-alkene co-monomers higher than ethylene, in the presence of a metallocene catalyst system to form a first polymer block, being a chain consisting of ethylenic structural units optionally bearing pendent alkyl groups originating from 1-alkene comonomer(s), the reaction being carried out in solution at a temperature of at least 50° C. in the presence of a compound of the formula (I):

in a reaction vessel pressurised with hydrogen gas, wherein, in the course of the reaction, the compound (I) is terminally incorporated onto the first polymer block resulting in the formation of a terminally unsaturated intermediate of the formula (II):

b) in a second step, recovering the intermediate (II) from the reaction mixture of the first step; and
c) in a third step, reacting the intermediate (II) at its terminal double bond in a subsequent polymerisation reaction to form a second polymer block, so yielding a diblock polymer of the structure defined above.

2. The process of claim 1 , wherein the compound (I) has the structure:

wherein each R group independently represents an alkyl group having from 1 to 4 carbon atoms.

3. The process of claim 2 , wherein the compound (I) has the structure:

4. The process of claim 1 , wherein R′ represents n-butyl.

5. The process of claim 1 , wherein, in the compound of formula (I), the aromatic ring substituent joined to the second block is positioned meta to the substituent joined to the first block.

6. The process of claim 1 wherein the third step c) is an anionic polymerisation reaction, wherein the terminal double bond of the intermediate of formula (II) is reacted with a metallating reagent to form an anion which initiates polymerisation therefrom upon the addition of one or more α,β-unsaturated monomers selected from styrene, substituted styrene, acrylate, methacrylate and diene compounds.

7. The process of claim 6 , wherein the metallating agent is an alkyl metal compound R′M and the intermediate of the formula (II) has the structure:

wherein each R group independently represents an alkyl group having from 1 to 4 carbon atoms; and wherein, in the course of the third reaction step c), the alkyl group R′ of the alkyl metal compound inserts onto the less-substituted carbon of the double bond, giving rise to a reactive anionic intermediate having the structure of the formula (III):

wherein alkyl represents the inserted alkyl group originating from the alkyl metal compound, (−) represents the metallated carbanionic site from which the anionic polymerisation of the third reaction step thereafter proceeds, and M (+) represents the metal cation originating from the metal M of the alkyl metal compound.

8. The process of claim 6 wherein the metallating reagent comprises n-butyl lithium or sec-butyl lithium.

9. The process of claim 6 wherein the intermediate of the formula (II) has the structure

and the metallating reagent comprises n-butyl lithium.

10. The isolated intermediate compound of the formula (II):

wherein each R group independently represents an alkyl or aryl group, and wherein the aromatic ring substituent —C(R)═CH 2 is positioned meta or para to the substituent joined to the first block.

11. The anionic intermediate of the formula (III):

wherein each R group independently represents an alkyl or aryl group and wherein the aromatic ring substituent —C (−) (R)—CH 2 (R′) is positioned meta or para to the aromatic ring substituent joined to the first block; wherein R′ represents an alkyl group and M + represents a metal cation, and C (−) represents a metallated carboanionic site.

12. The intermediate of claim 10 wherein each R group independently represents an alkyl group having from 1 to 4 carbon atoms.

13. The intermediate of claim 12 wherein each R group independently represents a methyl group.

14. The intermediate of claim 13 wherein R′ represents n-butyl.

15. The intermediate of claim 14 wherein the other aromatic ring substituent is positioned meta to the substituent joined to the first block.

16. The intermediate of claim 15 wherein the first block consists of a polyethylene chain.

17. The intermediate of claim 16 wherein the first block has a number average molecular weight (Mn), as measured by GPC against polystyrene standards, in the range of 500 to 20000 g mol −1 .

18. The intermediate of claim 11 wherein each R group independently represents an alkyl group having from 1 to 4 carbon atoms.

19. The intermediate of claim 18 wherein each R group independently represents a methyl group.

20. The intermediate of claim 19 wherein R′ represents n-butyl.

21. The intermediate of claim 20 wherein the other aromatic ring substituent is positioned meta to the substituent joined to the first block.

22. The intermediate of claim 21 wherein the first block consists of a polyethylene chain.

23. The intermediate of claim 22 wherein the first block has a number average molecular weight (Mn), as measured by GPC against polystyrene standards, in the range of 500 to 20,000 g mol −1 .

24. The anionic intermediate (III) of claim 11 , wherein M + represents a lithium cation.

Assignees

• Infineum Int Ltd
• Infineon International Ltd

Inventors

• Waterson Carl
• Lewtas Kenneth
• Scott Peter
• Kay Christopher J
• Theaker Giles W
• Wright Peter M

Classifications

• C10L1/236

  obtained by reactions involving only carbon-to-carbon unsaturated bonds {derivatives thereof (C10L1/221 takes precedence)} · CPC title

• C10N2030/08

  Resistance to extreme temperature · CPC title

• C10L1/143

  mixtures of organic macromolecular compounds with organic non-macromolecular compounds · CPC title

• C10N2020/02

  Viscosity; Viscosity index · CPC title

• C08F297/02 Primary

  using a catalyst of the anionic type · CPC title