Ring opening cross metathesis of vinyl terminated polymers and their functionalized derivatives for fouling mitigation in hydrocarbon refining processes

Patent metadata

Field	Value
Publication number	US-2016264891-A1
Application number	US-201615131461-A
Country	US
Kind code	A1
Filing date	Apr 18, 2016
Priority date	Mar 14, 2013
Publication date	Sep 15, 2016
Grant date	—

Abstract

A compound useful for reducing fouling in a hydrocarbon refining process is provided. A method for preparing the compound includes functionalizing a polymer having a vinyl chain end to obtain a terminal group having one or more anhydride units, and reacting the anhydride units with a polyamine. Methods of using the compound and compositions thereof are also provided.

First claim

1 . A compound represented by:

wherein R 1 is a branched or straight-chained C 10 -C 800 alkyl or alkenyl group;
y is an integer between 1 to 20 inclusive;
m is an integer between 0 and 10 inclusive;
a and b are C—C bonds in cis-configuration with respect to each other and in either cis- or trans- configuration with respect to bond c;
R 2 and R 3 are each independently a C 1 -C 4 branched or straight chained alkylene group;
R 31 is hydrogen or —R 8 —R 9 , wherein either (a) R 8 is C 1 -C 4 branched or straight chained alkylene group, and R 9 is

wherein R 91 is a branched or straight-chained C 10 -C 800 alkyl or alkenyl group, the asterisk (*) indicates a connecting point with R 8 , d and e are C—C bonds in cis-configuration with respect to each other and in either cis- or trans- configuration with respect to bond f, and z is an integer between 1 to 20 inclusive; or (b) R 8 and R 9 together are a C i -C 4 branched or straight chained alkyl group optionally substituted with one or more amine groups; and wherein the —N(R 31 )—R 3 — repeat unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group; and
wherein R 4 and R 5 are each independently selected from (a) hydrogen, (b) —R 6 —R 7 , wherein R 6 is C 1 -C 4 branched or straight chained alkylene group, and R 7 is

wherein R 71 is a branched or straight-chained C 10 -C 800 alkyl or alkenyl group, the asterisk (*) indicates a connecting point with R 6 , g and h are C—C bonds in cis-configuration with respect to each other and in either cis- or trans-configuration with respect to bond j, and q is an integer between 1 to 20 inclusive; or (c) a bond connected to R 31 in the m-th —N(R 31 )—R 3 — 0 repeat unit.

2 . The compound of claim 1 , wherein at least one of R 1 , R 71 , and R 91 comprises polypropylene.

3 . The compound of claim 2 , wherein the polypropylene is atactic polypropylene, isotactic polypropylene, or syndiotactic polypropylene.

4 . The compound of claim 2 , wherein the polypropylene is amorphous.

5 . The compound of claim 2 , wherein the polypropylene includes isotactic or syndiotactic crystallizable units.

6 . The compound of claim 2 , wherein the polypropylene includes meso diads constituting from about 30% to about 99.5% of the total diads of the polypropylene.

7 . The compound of claim 2 , wherein at least one of R 1 , R 71 , and R 91 has a number-averaged molecular weight of from about 300 to about 30000 g/mol.

8 . The compound of claim 2 , wherein at least one of R 1 , R 71 , and R 91 has a number-averaged molecular weight of from about 500 to about 5000 g/mol.

9 . The compound of claim 1 , wherein at least one of R 1 , R 71 , and R 91 comprises polyethylene.

10 . The compound of claim 1 , wherein at least one of R 1 , R 71 , and R 91 comprises poly(ethylene-co-propylene).

11 . The compound of claim 10 , wherein at least one of R 1 , R 71 , and R 91 comprises from about 1 mole % to about 90 mole % of ethylene units and from about 99 mole % to about 10 mole % propylene units.

12 . The compound of claim 11 , wherein at least one of R 1 , R 71 , and R 91 comprises from about 10 mole % to about 50 mole % of ethylene units.

13 . The compound of claim 1 , wherein at least one of R 1 , R 71 , and R 91 comprises poly(higher alpha-olefin), the higher alpha-olefin including two or more carbon atoms on each side chain.

14 . The compound of claim 1 , wherein at least one of R 1 , R 71 , and R 91 comprises poly(propylene-co-higher alpha-olefin), the higher alpha-olefin including two or more carbon atoms on each side chain.

15 . The compound of claim 1 , wherein the nitrogen content in the compound is about 1 wt % to about 10 wt % based on the total weight of the compound.

16 . The compound of claim 1 , wherein R 3 is —CH 2 —CH 2 —, and R 31 is hydrogen.

17 . The compound of claim 16 , wherein the —N(R 31 )—R 3 — repeat unit is interrupted in one or more places by a 1,4-diethylenediamine.

18 .- 40 . (canceled)

41 . A compound produced by the method comprising:
(a) converting a polymer base unit R 11 which is a branched or straight-chained C 10 -C 800 alkyl or alkenyl group having a vinyl terminal group, to a polymer having polyanhydride terminal group represented by:

wherein y is an integer between 1 and 20 inclusive, a and b are C—C bonds in cis-configuration with respect to each other and in either cis- or trans-configuration with respect to bond c; and
(b) reacting the polymer obtained in (a) with a polyamine represented by

wherein R 12 is hydrogen or a C 1 -C 4 branched or straight chained alkyl optionally substituted with one or more amine groups, R 13 is a C 1 -C 4 branched or straight chained alkylene group, and x is an integer between 1 and 10, and further wherein the —N(R 12 )—R 13 — unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group, and wherein when the x-th —N(R 12 )—R 13 — unit along with the terminal nitrogen atom forms a heterocyclic cycloalkyl group, the terminal —NH 2 is replaced by a —NH— group for valency.

42 . The compound of claim 41 , wherein R 11 comprises polypropylene.

43 . The compound of claim 42 , wherein the polypropylene is atactic polypropylene, isotactic polypropylene, or syndiotactic polypropylene.

44 . The compound of claim 42 , wherein the polypropylene is amorphous.

45 . The compound of claim 42 , wherein the polypropylene includes isotactic or syndiotactic crystallizable units.

46 . The compound of claim 42 , wherein the polypropylene includes meso diads constituting from about 30% to about 99.5% of the total diads of the polypropylene.

47 . The compound of claim 41 , wherein the molar ratio of R 11 polyamine is between about 5:1 and about 1:5.

48 . The compound of claim 41 , wherein R 11 has a number-averaged molecular weight of from about 300 to about 30000 g/mol.

49 . The compound of claim 48 , wherein R 11 has a number-averaged molecular weight of from about 500 to about 5000 g/mol.

50 . The compound of claim 41 , wherein R 11 comprises polyethylene.

51 . The compound of claim 41 , wherein R 11 comprises poly(ethylene-co-propylene).

52 . The compound of claim 41 , wherein R 11 comprises from about 10 mole % to about 90 mole % of ethylene units and from about 90 mole % to about 10 mole % propylene units.

53 . The compound of claim 52 , wherein R 11 comprises from about 20 mole % to about 50 mole % of ethylene units.

54 . The compound of claim 41 , wherein R 11 comprises poly(higher alpha-olefin), the higher alpha-olefin including two or more carbon atoms on each side chain.

Assignees

• Exxonmobil Res & Eng Co

Inventors

• Ng Man Kit
• Brons Glen B
• Holtcamp Matthew W
• Crowther Donna J
• Brant Patrick
• Cheng Hong
• Chase Clarence

Classifications

• C08F210/08

  Butenes · CPC title

• C08F8/32

  by reaction with amines · CPC title

• C08F210/06

  Propene · CPC title

• C10L10/04

  for minimising corrosion or incrustation · CPC title

• C10G75/04 Primary

  by addition of antifouling agents · CPC title