Associative polymers to control formation of particulate matter from ignitable compositions and related compositions, methods and systems
Described herein are associative polymers capable of controlling formation of particulate matter from a non-polar ignitable composition upon ignition of the non-polar ignitable composition, alone or in combination with control of a physical and/or chemical property of the 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 non-polar ignitable composition comprising:
a host ignitable composition having a dielectric constant equal to or less than about 5, and
at least one framing associative polymer, substantially soluble in the host ignitable composition, wherein the at least one framing associative polymer is comprised in the host composition in a concentration between from about 0.01 c* to about 2c* 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,
wherein the concentration is suitable to reduce formation of particulate matter from the ignitable host composition upon ignition of the ignitable composition, alone or in combination with control of at least one rheological property of the host ignitable composition, and
wherein the at least one framing associative polymer comprises:
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 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 non-polar composition with an association constant (k) wherein
k
(
M
-
1
)
≥
4
3
π
(
R
ℊ
2
)
3
2
N
a
n
F
×
10
-
23
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.
2. The non-polar ignitable composition of claim 1 , wherein the framing associative polymer has a weight averaged molecular weight equal to or lower than about 2,000,000 g/mol.
3. The non-polar ignitable composition of claim 1 , wherein the framing associative polymer has a weight averaged molecular weight 400,000≤M w [g/mol]≤1,000,000.
4. The non-polar ignitable composition of claim 1 , wherein the framing associative polymer has a weight averaged molecular weight 500,000≤M w [g/mol]≤2,000,000.
5. The non-polar ignitable composition of claim 1 , wherein the association constant is 6≤log 10 k≤14.
6. The non-polar ignitable composition of claim 1 , wherein the association constant is 6≤log 10 k≤10.
7. The non-polar ignitable composition of claim 1 , wherein the association constant is 6.9≤log 10 k≤7.8.
8. The non-polar ignitable composition 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.
9. The non-polar ignitable composition of claim 1 , wherein the another associative functional groups is presented at at least one end of a different associative polymer.
10. The non-polar ignitable composition of claim 1 , wherein the framing associative polymers are 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.
11. The non-polar ignitable composition of claim 10 , 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.
12. The non-polar ignitable composition of claim 10 , wherein A is a diene, olefin, styrene, acrylonitrile, methacrylate or acrylate, vinyl acetate, acids, esters, amides, amines, glycidyl ethers, or isocyanates.
13. The non-polar ignitable composition of claim 10 , wherein n is equal to or greater than 200 or equal to or greater than 800.
14. The non-polar ignitable composition of claim 1 , wherein when the at least one rheological property is selected from drag reduction, mist control, lubrication and/or viscoelastic properties.
15. The non-polar ignitable composition of claim 1 , wherein when the concentration of the at least one framing associative polymer is between 0.1 c* and 2.0 c*.
16. The non-polar ignitable composition of claim 1 , wherein when the concentration of the at least one framing associative polymer is between 0.1 c* and 1.0 c*.
17. The non-polar ignitable composition of claim 1 , wherein the at least one framing associative polymer comprises one or more pairs of telechelic polymers.
18. The non-polar ignitable composition of claim 17 , wherein the one or more pairs of telechelic polymers 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.
19. The non-polar ignitable composition of claim 1 , further comprising a capping associative polymer at a concentration up to 20 wt % of a total polymer concentration in the non-polar composition, wherein the capping associative polymer comprises:
a linear, branched, or hyperbranched polymer backbone having at least two ends and one associative functional groups presented at one end of the at least two ends of the backbone
wherein the linear or branched backbone is substantially soluble in the host composition, and the associative functional group is capable of undergoing an associative interaction with another associative functional group in the non-polar composition with an association constant (k) wherein
k (M −1 )≥4/3π(R g 2 ) 3/2 N a ×10 −23
in which Rg is the radius of gyration of the associative polymer in the non-polar composition in nanometer, and N a is Avogadro's constant.
20. The non-polar ignitable composition of claim 1 , wherein the host ignitable composition is a hydrocarbon composition.
21. The non-polar ignitable composition of claim 1 , wherein the host composition is a mineral oil, a biofuel, pentane, hexane, cyclohexane, benzene, toluene, diethyl ether, butane, gasoline, kerosene, jet fuel, or diesel fuel, or a combination thereof.
22. The non-polar ignitable composition of claim 1 , wherein the host composition is a gasoline, jet fuel, or diesel fuel, or a combination thereof.
23. The non-polar ignitable composition of claim 1 , wherein the host composition comprises crude oil or a refined fuel.
24. The non-polar ignitable composition of claim 1 , wherein the host composition comprise a refined fuel selected from Jet-A, Jet-A1, kerosene, JP-8, gasoline, or diesel, or a combination thereof.
25. A method to control formation of particulate matter from a non-polar ignitable composition upon ignition of the non-polar ignitable composition, alone or in combination with one or more physical and/or chemical properties, the method comprising:
providing a host ignitable composition having a dielectric constant equal to or less than about 5;
providing at least one framing associative polymer substantially soluble in the host ignitable composition; and
combining the host ignitable composition and the at least one framing associative polymer at a selected concentration c between from about 0.01 c* to 2.0 c*, depending on the weight averaged molecular weight and/or Radius of gyration of the at least one framing associative polymer and on the additional physical and/or chemical property to be optionally 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, wherein the at least one framing associative polymer comprises:
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 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 non-polar composition with an association constant (k) wherein
k
(
M
-
1
)
≥
4
3
π
(
R
ℊ
2
)
3
2
N
a
n
F
×
10
-
23
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; and
wherein the combining is performed at a concentration selected to reduce formation of particulate matter from the host ignitable composition upon ignition of the host ignitable composition.
26. A method to control formation of particulate matter from a non: polar ignitable composition upon ignition of the non-polar ignitable composition in combination with control of resistance to flow and/or flow rate enhancement of the non-polar ignitable composition alone or in combination another physical and/or chemical property of the non-polar ignitable composition, the method comprising
providing a host ignitable composition having a dielectric constant equal to or less than about 5;
providing at least one framing associative polymer substantially soluble in the host ignitable composition, the at least one framing associative polymer having a weight averaged molecular weight equal to or higher to 200,000 g/mol; and
combining the host ignitable composition and the at least one framing associative polymer at a concentration c selected between from about 0.01 c* to 1.0 c*, 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
wherein the at least one framing associative polymer comprises:
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 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 non-polar composition with an
k
(
M
-
1
)
≥
4
3
π
(
R
ℊ
2
)
3
2
N
a
n
F
×
10
-
23
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; and
wherein the combining is performed at a concentration selected to reduce formation of particulate matter from the host ignitable composition upon ignition of the host ignitable composition.
27. The method of claim 25 or 26 , wherein the association constant of the at least one framing associative polymer is between 7≤log 10 k≤14.
28. The method of claim 25 or 26 , wherein the at least one framing associative polymer has a weight averaged molecular weight 400,000<M w [g/mol]≤1,000,000.
29. The method of claim 25 or 26 , wherein the concentration c is about 0.1 c* to 0.5 c*.
30. The method of claim 25 or 26 , wherein the concentration c about 0.5c* to 1.0 c* and the another physical and/or chemical property is sizes, and/or distribution of sizes of the droplets of a fluid.
31. The method of claim 25 or 26 , wherein the concentration c is below or equal to about 1.0 c* and the another physical and/or chemical property is enhanced lubrication.
32. A method to control formation of particulate matter from a non-polar ignitable composition upon ignition of the non-polar ignitable composition in combination with control of sizes, and/or distribution of sizes, of the droplets of fluid in a non-polar ignitable composition alone or in combination with another physical and/or chemical property, the method comprising
providing a host ignitable composition having a dielectric constant equal to or less than about 5;
providing at least one framing associative polymer substantially soluble in the host ignitable composition, the at least one framing associative polymer having a weight averaged molecular weight equal to or higher to 400,000 g/mol; and
combining the host ignitable composition and the at least one framing associative polymer at a concentration c selected between from about 0.05 c* to about 2.0 c*, 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
wherein the at least one framing associative polymer:
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 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 non-polar composition with an
k
(
M
-
1
)
≥
4
3
π
(
R
ℊ
2
)
3
2
N
a
n
F
×
10
-
23
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; and
wherein the combining is performed at a concentration selected to reduce formation of particulate matter from the host ignitable composition upon ignition of the host ignitable composition.
33. The method of claim 32 , wherein the association constant of the at least one framing associative polymer is between 7≤log 10 k≤14.
34. The method of claim 32 , wherein the at least one framing associative polymer has a weight averaged molecular weight between 400,000 g/mol and 1,000,000 g/mol.
35. The method of claim 32 , wherein the concentration of the at least one framing associative polymer is between 0.5 c* and 1.0 c*.
36. The method of claim 32 , wherein the concentration c is about 0.5 c* or between about 0.5c* to 1.0 c* and the another physical and/or chemical property is drag reduction.
37. The method of claim 32 , wherein the concentration c is below or approximately equal 1.0 c* and the another physical and/or chemical property is enhanced lubrication.
38. A system for controlling formation of particulate matter from a non-polar ignitable composition upon ignition of the non-polar ignitable composition, alone or in combination with control of a physical and/or chemical property in an non-polar ignitable composition, the system comprising at least two between at least one framing associative polymer and at least one host ignitable composition having a dielectric constant equal to or less than 5,
wherein at least one framing associative polymer is substantially soluble in the host ignitable composition and
wherein the at least one framing associative polymer comprises:
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 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 non-polar composition with an association constant (k) wherein
k
(
M
-
1
)
≥
4
3
π
(
R
ℊ
2
)
3
2
N
a
n
F
×
10
-
23
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.
39. The non-polar ignitable composition of claim 1 , wherein when the concentration of the at least one framing associative polymer is between 0.05 c* and 0.1 c*.