Associative polymers and related compositions, methods and systems
Described herein are associative polymers capable of controlling a physical and/or chemical property of non-polar compositions and related compositions, methods and systems. Associative polymers herein described have a non-polar backbone and functional groups presented at ends of the non-polar backbone, with a number of the functional groups presented at the ends of the non-polar backbone formed by associative functional groups capable of undergoing an associative interaction with another associative functional group with an association constant (k) such that the strength of each associative interaction is less than the strength of a covalent bond between atoms and in particular less than the strength of a covalent bond between backbone atoms.
1. A method to control resistance to flow and/or flow rate enhancement of a non-polar composition alone or in combination another physical and/or chemical property of the non-polar composition, the method comprising
providing a host composition having a dielectric constant equal to or less than about 5;
providing at least one framing associative polymer substantially soluble in the host composition, the at least one framing associative polymer having a weight averaged molecular weight equal to or higher to 200,000 g/mol and equal to or lower than 2,000,000 g/mol the at least one framing associative polymer comprising
a linear, branched, or hyperbranched hydrocarbon polymer backbone comprising a polyolefin and having at least two ends; and
a functional group presented at two or more ends of the at least two ends of the linear, branched, or hyperbranched polymer backbone;
wherein a number of functional groups presented at the two or more ends of the at last one associative polymer is formed by associative functional groups each capable of undergoing an associative interaction with another associative functional group in the non-polar composition with an association constant (k) log 10 k≤14
the association constant (k) being provided by
k
(
M
-
1
)
≥
4
3
π
(
R
g
2
)
3
2
N
a
n
F
×
1
0
-
2
3
in which R g is the radius of gyration of the framing associative polymer in the non-polar composition in nanometers, Na is Avogadro's constant; and n F is the average number of the associative functional groups in the at least one framing associative polymer;
the method further comprising
combining the host composition and the at least one framing associative polymer at a concentration c being about 0.5 c* or less, depending on the weight averaged molecular weight and/or Radius of gyration of the at least one framing associative polymer and on a physical and/or chemical property to be controlled,
wherein
c
*
=
3
M
w
4
π
(
R
g
2
)
3
/
2
N
a
,
in which M w is the weight averaged molecular weight, R g is the radius of gyration, and N a is Avogadro's constant and
wherein the concentration of the at least one associative polymer is suitable to control resistance to flow and/or flow rate enhancement of the non-polar composition alone or in combination another physical and/or chemical property.
2. The method of claim 1 , wherein the association constant of the at least one framing associative polymer is between 7≤log 10 k≤14.
3. The method of claim 1 , wherein the at least one framing associative polymer has a weight averaged molecular weight 400,000<M w [g/mol]≤1,000,000.
4. The method of claim 1 , wherein the concentration c is about 0.1c* to 0.5c*.
5. The method of claim 1 , wherein the association constant of the at least one framing associative polymer is between 7≤log 10 k≤14.
6. The method of claim 1 , wherein the association constant of the at least one framing associative polymer is between 7≤log 10 k≤12.
7. The method of claim 1 , wherein the association constant of the at least one framing associative polymer is between 7≤log 10 k≤9.
8. The method of claim 1 , wherein the association constant of the at least one framing associative polymer is between 6.9≤log 10 k≤7.8.
9. The method of claim 1 , wherein the at least one framing associative polymer has a weight averaged molecular weight 500,000<M w [g/mol]≤2,000,000.
10. The method of claim 1 , wherein the at least one framing associative polymer has a weight averaged molecular weight 1,000,000<M w [g/mol]≤2,000,000.
11. The method of claim 1 , wherein the at least one framing associative polymer has a weight averaged molecular weight, 700,000<M w [g/mol]≤1,000,000.
12. The method of claim 1 , wherein the at least one framing associative polymer has a weight averaged molecular weight, 500,000<M w [g/mol]≤1,000,000.
13. The method of claim 1 , wherein the at least one framing associative polymer has a weight averaged molecular weight, 500,000<M w [g/mol]≤750,000.
14. The method of claim 1 , wherein the at least one framing associative polymer has a weight averaged molecular weight, 650,000<M w [g/mol]≤750,000.
15. The method of claim 1 , wherein the concentration c is from about 0.001c* to 0.1c*.
16. The method of claim 1 , wherein the concentration c is from about 0.001c* to 0.5c*.
17. The method of claim 1 , wherein the concentration c is from about 0.05c* to 0.1c*.
18. The method of claim 1 , wherein the concentration c is from about 0.02c* to 0.05c*.
19. The method of claim 1 , wherein the concentration c is from about 0.001c* to 0.02c*.
20. The method of claim 1 , wherein the at least one framing associative polymer has a weight averaged molecular weight 500,000<M w [g/mol]≤2,000,000, the association constant of the at least one framing associative polymer is between 6.9≤log 10 k≤12 and the concentration c is from about 0.001c* to 0.1c*.
21. The method of claim 1 , wherein the at least one framing associative polymer has a weight averaged molecular weight 500,000<M w [g/mol]≤1,000,000, the association constant of the at least one framing associative polymer is between 6.9≤log 10 k≤7.8 and the concentration c is from about 0.001c* to 0.05c*.
22. The method of claim 1 , wherein the at least one framing associative polymer has a weight averaged molecular weight 700,000<M w [g/mol]≤1,000,000, the association constant of the at least one framing associative polymer is between 7≤log 10 k≤9, and the concentration c is from about 0.001c* to 0.05c*.
23. The method of claim 1 , wherein the at least one framing associative polymer has a weight averaged molecular weight 1,000,000<M w [g/mol]≤2,000,000, the association constant of the at least one framing associative polymer is between 7.5≤log 10 k≤12, and the concentration c is from about 0.001c* to 0.1c*.
24. The method of claim 1 , wherein the associative functional groups of the at least one framing associative polymer comprise complementary associative functional groups, wherein the complementary associative functional groups comprise one or more of carboxylic acids with other carboxylic acids, carboxylic acids with amines, alcohols with amines, alcohols with carboxylic acids, diacetamidopyridine with thymine, the Hamilton Receptor with cyanuric acid, zinc sulfonate or palladated sulfur-carbon-sulfur (SCS) pincer with pyridine or primary, secondary or tertiary amines.
25. The method of claim 1 , wherein the host composition comprises a hydrocarbon composition, a fluorocarbon composition or a silicone composition.
26. The method of claim 1 , wherein the host composition comprises a mineral oil, a biofuel, pentane, hexane, cyclohexane, benzene, toluene, chloroform and diethyl ether, liquefied petroleum gas, liquid methane, butane, gasoline, kerosene, jet fuel and diesel fuel.
27. The method of claim 1 , wherein the host composition comprises crude oil or a refined fuel.
28. The method of claim 1 , wherein the host composition comprises a refined fuel selected from Jet-A, Jet-A1, kerosene, JP-8, gasoline and/or diesel.
29. The method of claim 1 , wherein the at least one framing associative polymer comprises one or more self-associative framing associative polymers.
30. The method of claim 1 , wherein the hydrocarbon polymer backbone of the framing associative polymer is a linear hydrocarbon polymer comprising the polyolefin.
31. The method of claim 1 , wherein the linear, branched, or hyperbranched hydrocarbon polymer backbone comprises a homopolymer and/or a copolymer.
32. The method of claim 1 , wherein the polyolefin in the linear, branched, or hyperbranched hydrocarbon polymer backbone of the framing associative polymer comprises a polyolefin copolymer.
33. The method of claim 32 , wherein the polyolefin copolymer comprises a poly(norbornene) chain and/or a poly(cyclooctadiene) chain.
34. The method of claim 1 , wherein the polyolefin is obtained by polymerizing one or more monomers comprising a substituted or unsubstituted cycloalkyl moiety, and/or a substituted or unsubstituted cycloalkenyl moiety.
35. The method of claim 34 , wherein the one or more monomers comprise one or more cyclic olefins.
36. The method of claim 35 , wherein the one or more cyclic olefins comprises one or more norbornene monomers.
37. The method of claim 35 , wherein the one or more cyclic olefins comprises one or more cyclooctadiene monomers.
38. The method of claim 35 , wherein the one or more cyclic olefins comprise a combination of norbornene monomers, and/or cyclooctadiene monomers.
39. The method of claim 33 , wherein the one or more monomers comprise an alkyl norbornene monomer in combination with or cyclooctadiene monomers.
40. The method of claim 1 , wherein the host composition comprises one or more of butanes, pentanes and hexanes.
41. The method of claim 1 , wherein the host composition comprises gasoline, kerosene or diesel.
42. The method of claim 1 , wherein the host composition comprises a crude oil.