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 system for controlling a physical and/or chemical property in a non-polar composition, the system comprising at least two between
at least one host composition having a dielectric constant equal to or less than 5, and
at least one framing associative polymer comprising
a linear, branched, or hyperbranched polymer backbone 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 the linear, branched, or hyperbranched polymer backbone is substantially soluble in the at least one host composition, and
wherein a number of the functional groups presented at the two or more ends is formed by associative functional groups each capable of undergoing an associative interaction with another associative functional group in the at least one host composition with an association constant (k) wherein
k
(
M
-
1
)
≥
4
3
π
(
R
g
2
)
3
2
N
a
n
F
×
10
-
2
3
in which R g is the radius of gyration of the framing associative polymer in the non-polar composition in nanometers, N a is Avogadro's constant; and n F is the average number of the associative functional groups in the framing associative polymer
the at least one host composition and at least one framing associative polymer for combined use to provide a non-polar composition in which the at least at a concentration c selected between from about 0.05c*to about 10c*,
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
depending on the weight averaged molecular weight and/or Radius of gyration of the at least one framing associative polymer and on the physical and/or chemical property to be controlled.
2. The system of claim 1 , wherein the at least one framing associative polymer has a weight averaged molecular weight equal to or lower than about 2,000,000 g/mol.
3. The system 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 system of claim 1 , wherein the association constant is 6≤log 10 k≤14.
5. The system of claim 1 , wherein the association constant is 6.9 log 10 k≤7.8.
6. The system of claim 1 , wherein the associative functional group is a carboxylic acid and the another associative functional group is a carboxylic acid, or the associative functional group is a carboxylic acid and the another associative functional group is an amine, or the associative functional group is an alcohol and the another associative functional group is an amine, or the associative functional group is an alcohol and the another associative functional group is a carboxylic acid, or the associative functional group is a diacetamidopyridine and the another associative functional group is a thymine, or the associative functional group is a Hamilton Receptor and the another associative functional group is a cyanuric acid, the associative functional group is zinc sulfonate or palladated sulfur-carbon-sulfur (SCS) pincer and the another associative functional group is selected from pyridine or primary, secondary and tertiary amines.
7. The system of claim 1 , wherein the another associative functional groups is presented at at least one end of a different associative polymer.
8. The system of claim 1 , wherein the at least one framing associative polymer is formed by at least two structure units having formula [[FG-chain [node] z (I) and optionally one or more structural units having formula node chain] (II), wherein:
FG is an associative functional group (FGa);
chain is a non-polar polymer substantially soluble in a non-polar composition, the polymer having formula:
R 1 -[A] n R 2 (III)
wherein:
A is a chemical and in particular an organic moiety forming the monomer of the polymer;
R 1 and R 2 are independently selected from any carbon based or organic group with one of R 1 and R 2 linked to an FG or a node and the other one of R 1 and R 2 linked to an FG or a node; and
n is an integer≥1;
z is 0 or 1;
node is a covalently linked moiety linking one of R 1 and R 2 of at least one first chain with one of the R 1 and R 2 of at least one second chain;
and wherein the FG, chain and node of different structural units of the polymer can be the same or different.
9. The system of claim 8 , wherein the associative functional group FGa is selected from diacetamidopyridine group, thymine group, Hamilton Receptor group, cyanuric acid group, carboxylic acid group, primary secondary or tertiary amine group, primary secondary and tertiary alcohol group, zinc sulfonate, palladated sulfur-carbon-sulfur (SCS) pincer pyridine or primary, secondary and tertiary amines.
10. The system of claim 8 , wherein A is a diene, olefin, styrene, acrylonitrile, methacrylate or acrylate, vinyl acetate, dichlorodimethylsilane, tetrafluoroethylene, acids, esters, amides, amines, glycidyl ethers, or isocyanates, siloxane.
11. The system of claim 8 , wherein n is equal to or greater than 200.
12. The system of claim 1 , wherein the at least one host composition comprises a hydrocarbon composition, a fluorocarbon composition or a silicone composition.
13. The system of claim 1 , wherein the at least one 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.
14. The system of claim 1 , wherein the at least one host composition comprises crude oil or a refined fuel.
15. The system of claim 1 , wherein the at least one host composition comprises a refined fuel selected from Jet-A, Jet-A1, kerosene, JP-8, gasoline and/or diesel.
16. The system of claim 1 , wherein when the at least one rheological property is selected from drag reduction, mist control, lubrication and/or viscoelastic properties.
17. The system of claim 8 , wherein n is equal to or greater than 800.