U.S. patent application number 17/157589 was filed with the patent office on 2021-12-23 for associative polymers and related compositions, methods and systems.
The applicant listed for this patent is CALIFORNIA INSTITUTE OF TECHNOLOGY. Invention is credited to Simon JONES, Julia A. KORNFIELD, Virendra SAROHIA, Ming-Hsin WEI.
Application Number | 20210395491 17/157589 |
Document ID | / |
Family ID | 1000005807927 |
Filed Date | 2021-12-23 |
United States Patent
Application |
20210395491 |
Kind Code |
A1 |
KORNFIELD; Julia A. ; et
al. |
December 23, 2021 |
ASSOCIATIVE POLYMERS AND RELATED COMPOSITIONS, METHODS AND
SYSTEMS
Abstract
Described herein are associative polymers capable of controlling
one or more physical and/or chemical properties of non-polar
compositions and related compositions, methods and systems.
Inventors: |
KORNFIELD; Julia A.;
(PASADENA, CA) ; WEI; Ming-Hsin; (PASADENA,
CA) ; JONES; Simon; (WHITTIER, CA) ; SAROHIA;
Virendra; (ALTADENA, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CALIFORNIA INSTITUTE OF TECHNOLOGY |
PASADENA |
CA |
US |
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Family ID: |
1000005807927 |
Appl. No.: |
17/157589 |
Filed: |
January 25, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16566729 |
Sep 10, 2019 |
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17157589 |
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16120065 |
Aug 31, 2018 |
10494509 |
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16566729 |
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14217142 |
Mar 17, 2014 |
10087310 |
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16120065 |
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61799670 |
Mar 15, 2013 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 83/008 20130101;
C10L 1/1973 20130101; C10L 10/08 20130101; C10L 1/2366 20130101;
C10L 1/1976 20130101; C08L 101/02 20130101; C10L 1/198 20130101;
C10L 10/02 20130101; C08K 11/00 20130101; C10L 1/2368 20130101;
C10L 10/00 20130101 |
International
Class: |
C08K 11/00 20060101
C08K011/00; C10L 1/198 20060101 C10L001/198; C08G 83/00 20060101
C08G083/00; C08L 101/02 20060101 C08L101/02; C10L 1/197 20060101
C10L001/197; C10L 1/236 20060101 C10L001/236; C10L 10/00 20060101
C10L010/00; C10L 10/02 20060101 C10L010/02 |
Goverment Interests
STATEMENT OF GOVERNMENT GRANT
[0002] This invention was made with government support under Grant
Number 80NMO0018D0004, awarded by NASA (JPL). The government has
certain rights in the invention.
Claims
1. An 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 backbone; wherein the linear, branched, or
hyperbranched polymer backbone is substantially soluble in a
non-polar composition, and the functional groups is capable of
undergoing an associative interaction with another functional group
with an association constant (k) of from 0.1<log.sub.10
k<18.
2. The associative polymer of claim 1, in which the associative
polymer has a weight averaged molecular weight equal to or lower
than about 2,000,000 g/mol.
3. The associative polymer of claim 1, in which the associative
polymer has a weight averaged molecular weight is equal to or lower
than about 2,000,000 g/mol and/or a M.sub.w equal to or higher than
about 100,000 g/mol.
4. The associative polymer of claim 1, in which the associative
polymer has a weight averaged molecular weight is between about
100,000 g/mol and about 1,000,000 g/mol.
5. The associative polymer of claim 1, wherein the functional group
is a carboxylic acid and the other functional group is a carboxylic
acid, or the functional group is a carboxylic acid and the other
functional group is an amine, or the functional group is an
alcohols and the other functional group is an amine, or the
functional group is an alcohol and the another functional group is
a carboxylic acid, or the functional group is a diacetamidopyridine
and the another functional group is a thymine, or the functional
group is a Hamilton Receptor and the another functional group is a
cyanuric acid.
6. The associative polymer of claim 1, wherein the another
functional groups is presented at at least one end of the at least
two ends of a same associative polymer.
7. The associative polymer of claim 1, wherein the another
functional groups is presented at at least one end of a different
associative polymer.
8. The associative polymer of claim 1, having a structural unit of
formula [[FG-chain[node] (I) and optionally the structural unit of
formula -nodechain] (II) wherein: FG is a functional group, which
can comprise one or more associative moieties such that the
functional group are capable of undergoing an associative
interaction with another with an association constant (k) in a
range from 0.1<log.sub.10 k<18; chain is a non-polar polymer
substantially soluble in a non-polar composition, the polymer
having formula (III): R.sub.1-[A].sub.nR.sub.2 (III) wherein: A is
a chemical moiety; R.sub.1 and R.sub.2 are independently selected
from any carbon based or organic group; and n is an integer
.gtoreq.1; node is a covalently linked moiety linking one of
R.sub.1 and R.sub.2 of at least one first chain with one of the
R.sub.1 and R.sub.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 associative polymer of claim 8, wherein the functional group
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.
10. The associative polymer of claim 8, wherein A is be a diene,
olefin, styrene, acrylonitrile, methyl methacrylate, vinyl acetate,
dichlorodimethylsilane, tetrafluoroethylene, acids, esters, amides,
amines, glycidyl ethers, isocyanates.
11. The associative polymer of claim 8, wherein n is equal to or
greater than 200 or equal to or greater than 800.
12. The associative polymer of claim 11, wherein R.sub.1 and
R.sub.2 are independently substituted or unsubstituted methine or
methylene groups.
13. A non-polar composition comprising: a host composition having a
dielectric constant equal to or less than about 5 and at least one
associative polymer of claim 1, soluble in the host composition,
wherein the at least one associative polymer herein described is
comprised in the host composition in a concentration between from
about 0.1c* to about 10c* wherein c * = 3 .times. M w 4 .times.
.pi. .function. ( R g 2 ) 3 / 2 .times. N a , ##EQU00006## wherein
M.sub.w is the weight averaged molecular weight, R.sub.g is the
radius of gyration, and N.sub.a is Avogadro's constant.
14. The non-polar composition of claim 13, wherein the host
composition is a hydrocarbon composition, a fluorocarbon
compositions or a silicone composition.
15. The non-polar composition of claim 13, wherein the host
composition is pentane, hexane, cyclohexane, benzene, toluene,
chloroform and diethyl ether, liquefied petroleum gas, liquid
methane, butane, gasoline, kerosene, jet fuel and diesel fuel.
16. The non-polar composition of claim 13, wherein the
concentration is between 0.5c* to 2c*.
17. The non-polar composition of claim 13, wherein the
concentration is less than approximately c*.
18. The non-polar composition of claim 13, wherein the
concentration is between 0.1c* and 0.5c*.
19. The non-polar composition of claim 13, wherein the
concentration is below or approximately equal c*.
20. The non-polar composition of claim 13, wherein the
concentration is between 0.05c* to c*.
21. The non-polar composition of claim 13, wherein the
concentration is greater than c*.
22. The non-polar composition of claim 13, wherein the
concentration is between 2c* to 10c*.
23. A method to control a physical and/or chemical property in a
non-polar composition comprising providing a host composition
having a dielectric constant equal to or less than about 5;
providing at least one associative polymer of claim 1 soluble in
the host composition; determining an overlap concentration c* for
the at least one associative polymer; determining a concentration c
of the at least one associative polymer in the host composition,
the concentration c selected between from about 0.1c* to about 10c*
depending a physical and/or chemical property to be controlled; and
combining the host composition and the at least one associative
polymer herein described at the selected concentration c.
24. The method of claim 23 wherein the concentration c is between
0.5c* to 2c* and the physical and/or chemical property is mist
control.
25. The method of claim 23 wherein the concentration c is less than
approximately c* and the physical and/or chemical property is fuel
efficiency.
26. The method of claim 23 wherein the concentration c is between
0.1c* and 0.5c* and the physical and/or chemical property is fuel
efficiency.
27. The method of claim 23 wherein the concentration c is below or
approximately equal c* and the physical and/or chemical property is
drag reduction and/or enhanced lubrication.
28. The method of claim 23 wherein the concentration c is between
0.05c* to c* and the physical and/or chemical property is drag
reduction and/or enhanced lubrication.
29. The method of claim 23 wherein the concentration c is greater
than c* and the physical and/or chemical property is converting a
liquid into a gel.
30. The method of claim 23 wherein the concentration c is between
2c* to 10c* and the physical and/or chemical property is converting
a liquid into a gel.
31. A method to provide an associative polymer, the method
comprising providing a linear, branched or hyperbranched polymer
backbone substantially soluble in a non-polar composition having at
least two ends; and attaching at two or more ends of the at least
two ends of the linear, branched, or hyperbranched backbone a
functional group capable of undergoing an associative interaction
with another with an the association constant (k) of from
0.1<log.sub.10 k<18, so that the strength of each associative
interaction is less than that of a covalent bond between atoms.
32. A system or controlling a physical and/or chemical property in
an non-polar composition, the system comprising at least two
between at least one associative polymer of claim 1 and at least
one host composition having a dielectric constant equal to or less
than 5.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser.
No. 16/566,729 filed on Sep. 10, 2019 which is a continuation
application of U.S. application Ser. No. 16/120,065 filed on Aug.
31, 2018, which issued as U.S. Pat. No. 10,494,509 on Dec. 3, 2019,
which is a divisional application of U.S. application Ser. No.
14/217,142 filed on Mar. 17, 2014, now U.S. Pat. No. 10,087,310
issued on Oct. 2, 2018 which claims priority to provisional
application 61/799,670 entitled "Associative Polymers and related
Compositions Methods and Systems" filed on Mar. 15, 2013 the
contents of each of which is incorporated herein by reference.
FIELD
[0003] The present disclosure relates to associative polymers and
related compositions methods and systems. In particular, the
present disclosure relates to associative polymers suitable to be
used in connection with control of physical and/or chemical
properties of non-polar compositions.
BACKGROUND
[0004] Several non-polar compositions are known in the art for
which control of the related physical and/or chemical properties is
desired. For example, in hydrocarbon compositions which can be used
for combustion and energy production, control of properties such as
mist, drag, and combustion can be desirable.
[0005] Also in non-polar liquid hydrocarbon compositions suitable
to be used as ink, pesticide or fuel, control of properties such as
mist and drop breakup can be desirable.
[0006] However, despite development of several approaches, control
of those properties is still challenging.
SUMMARY
[0007] Provided herein are associative polymers which in several
embodiments can be used as additives in a non-polar composition,
and related compositions, methods, and systems. In particular
associative polymers herein described in several embodiments allows
control of physical and/or chemical properties, such as drag
reduction, mist control, lubrication, fuel efficiency, combustion
emissions, spreading and/or viscoelastic properties of the
composition.
[0008] According to a first aspect, a linear or branched
associative polymer is described, which comprises a linear,
branched, or hyperbranched polymer backbone having at least two
ends and functional groups presented at two or more ends of the at
least two ends of the backbone. In the associative polymer the
linear or branched backbone is substantially soluble in a non-polar
composition, and the functional groups are capable of undergoing an
associative interaction with another with an the association
constant (k) of from 0.1<log.sub.10 k<18, so that the
strength of each associative interaction is less than that of a
covalent bond between atoms and in particular backbone atoms. In
some embodiments the linear or branched associative polymer has an
overall weight average molecular weight, M.sub.w, equal to or lower
than about 2,000,000 g/mol, and/or a Mw equal to or higher than
about 100,000 g/mol.
[0009] According to a second aspect a modified non-polar
composition is described, the modified non-polar composition
comprising a host composition having a dielectric constant equal to
or less than about 5 and at least one associative polymer herein
described soluble in the host composition. In particular, in the
modified non polar composition the at least one associative polymer
herein described can be comprised in the host non polar composition
at a concentration from about 0.1c* to about 10c** with respect to
an overlap concentration c* for the at least one associative
polymer relative to the host composition.
[0010] According to a third aspect a method to control a physical
and/or chemical property in a non-polar composition is described.
The method comprises providing a host composition having a
dielectric constant equal to or less than about 5; providing at
least one associative polymer herein described soluble in the host
composition; determining an overlap concentration c* for the at
least one associative polymer relative to the host composition;
determining a concentration c of the at least one associative
polymer in the host composition, the concentration c selected
between from about 0.1c* to about 10c* depending on the physical
and/or chemical property to be controlled; and combining the host
composition and the at least one associative polymer herein
described at the selected concentration c.
[0011] According to a fourth aspect a method to provide an
associative polymer is described. The method comprises providing a
linear, branched or hyperbranched polymer backbone substantially
soluble in a non-polar composition and having at least two ends;
and attaching at two or more ends of the at least two ends of the a
linear, branched or hyperbranched backbone a functional group
capable of undergoing an associative interaction with another with
an association constant (k) in the range of from 0.1<log.sub.10
k<18, so that the strength of each associative interaction is
less than that of a covalent bond between backbone atoms.
[0012] According to a fifth aspect a system is described for
controlling a physical and/or chemical property in an non-polar
composition, the system comprising at least two between at least
one associative polymer herein described and at least one host
composition having a dielectric constant equal to or less than
5.
[0013] The associative polymers, and related material compositions,
methods and systems herein described can be used in connection with
applications wherein control of physical and/or chemical properties
of non-polar compositions is desired. Exemplary applications
comprise fuels, inks, paints, cutting fluids, lubricants,
pesticides and herbicides as well as synthetic blood, adhesive
processing aids, personal care products (e.g. massage oils or other
non-aqueous compositions) and additional applications which are
identifiable by a skilled person. Additional applications comprise
industrial processes in which reduction of flow resistance, mist
control, lubrication, and/or control of viscoelastic properties of
a non-polar composition and in particular a liquid non polar
composition is desired.
[0014] The details of one or more embodiments of the disclosure are
set forth in the accompanying drawings and the description below.
Other features, objects, and advantages will be apparent from the
description and drawings, and from the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The accompanying drawings, which are incorporated into and
constitute a part of this specification, illustrate one or more
embodiments of the present disclosure and, together with the
detailed description and the examples, serve to explain the
principles and implementations of the disclosure.
[0016] FIG. 1A and FIG. 1B show a schematic illustration of
supramolecular structures of associative polymers according to
embodiments herein described. In particular, FIG. 1A shows
schematics of telechelic donor/acceptor interaction. FIG. 1B shows
schematics of telechelic associating interactions.
[0017] FIG. 2A and FIG. 2B show a schematic illustration of end to
end association in associative polymers herein described. FIG. 2A
describes an exemplary donor acceptor association FIG. 2B describes
an exemplary self-association.
[0018] FIG. 3 shows an exemplary associative polymer according to
an embodiment herein described. In the illustration of FIG. 3 x and
y can be independently selected between any integer .gtoreq.1. The
sum of x and y can be between 1,000 and 10,000.
[0019] FIG. 4 shows exemplary functional groups and related
exemplary associative interactions according to embodiments herein
described.
[0020] FIG. 5 shows exemplary architectures of associative polymers
herein described. In particular in the illustration of FIG. 5, a,
b, c, d, n, and e are independently integers .gtoreq.1.
[0021] FIG. 6 shows exemplary block architectures of associative
polymers herein described and of an exemplary chain or backbone
moiety. In particular in the illustration of FIG. 6, a, b, c, d, n,
x, and y are independently integers .gtoreq.1.
[0022] FIG. 7 shows a schematic representation of a method to
provide an associative polymer of the disclosure according to
embodiments herein described.
[0023] FIG. 8 shows a schematic representation of a reaction
suitable to provide an associative polymer of the disclosure using
chain transfer agents according to embodiments herein
described.
[0024] FIG. 9 shows exemplary chain transfer agents suitable to be
used in the reaction illustrated in FIG. 8 according to embodiments
herein described, and in particular, chain transfer agents with
internal olefins based on benzyl ether dendrons.
[0025] FIG. 10 shows a schematic representation of an exemplary
method to produce associative polymers herein described using chain
transfer agents according to embodiments herein described.
[0026] FIG. 11 shows a diagram illustrating GPC traces of 430K
di-TE PB (di-TE PB also called octa tBu ester PB herein) and the
resulting polymer of its hydrolysis reaction (in THF). In
particular, FIG. 11, shows a diagram illustrating the GPC traces of
a telechelic 1,4-PB with a backbone length of 430,000 g/mol
(M.sub.w) and end groups having 4 tert-butyl ester groups on each
(denoted TE groups hereinafter; the polymer is denoted 430K di-TE
PB hereinafter) and the resulting polymer of its hydrolysis
reaction (in THF). The resulting end-groups with 4 acid groups and
the polymer are hereinafter denoted TA groups and 430K di-TA PB
(di-TA PB also called octa acid PB herein), respectively.
[0027] FIG. 12 shows a diagram illustrating viscosity in function
of shear rate of the 1 wt % Jet-A solutions of the 430K di-TE PB
and 430K diTA PB herein also indicated as di-TE PB and (430K
di-TA-PB).
[0028] FIG. 13 shows a diagram illustrating GPC traces of the 430K
octa chloro PB and the corresponding octa tertiary amine PB. In
particular, FIG. 13, shows a diagram illustrating the GPC traces of
telechelic 1,4-PB with a backbone length of 430,000 g/mol and
end-groups with 4 chloro groups on each and the corresponding
tertiary amine-terminated polymer (the end groups with 4 tertiary
amines are denoted TB groups, and the corresponding polymer is
denoted 430K di-TB PB hereinafter).
[0029] FIG. 14 shows a diagram illustrating viscosity in function
of shear rate of 1 wt % Jet-A solutions of 430K di-TE PB, di-TA PB,
di-TA PB, and 1:1 w/w di-TA PB/di-TB PB mixture herein also
indicated as 430K di-TE PB, di-TA PB, di-TB PB, and 1:1 w/w -di-TA
PB/di-TB PB mixture.
[0030] FIG. 15 illustrates properties of an exemplary hydrocarbon
composition according to the disclosure. In particular, Panel A
shows that the exemplary composition remains stable for months at
-30.degree. C. and Panel B shows that dewatering operations occur
as quickly and completely in the composition (right) as in an
untreated host (left).
[0031] FIG. 16 shows is a diagram illustrating the radius of
gyration of an exemplary backbone polymer (polystyrene) as a
function of its weight-average molecular weight (M.sub.w in g/mol)
in a representative theta solvent (cyclohexane) and in a
representative good solvent (toluene). In particular, FIG. 16 shows
an exemplary relationship between the radius of gyration R.sub.g of
a backbone polymer as a function of its weight average molecular
weight (M.sub.w in g/mol)
[0032] FIG. 17 shows a schematic representation of exemplary
interactions between conventional linear polymers of the
disclosure, in situation when the polymer concentration is equal to
the overlap concentration c*. The dotted lines represent the radius
of the single polymers (functional not shown). In particular the
schematic of FIG. 17, show an exemplary way polymer molecules can
pervade the entire solution when provided at their overlap
concentration c*.
[0033] FIGS. 18 and 19 show exemplary synthesis reactions for
exemplary CTAs suitable to make associative polymers in accordance
with embodiments herein described.
[0034] FIGS. 20 and 21 show exemplary covalent links linking node
to chain and node to FG according to embodiments herein
described.
[0035] FIG. 22 Shows a schematic illustration of the
self-association behavior of carboxyl-terminated telechelic 1,4-PBs
according to some embodiments herein described.
[0036] FIG. 23 shows a graph Specific viscosity of 1 wt % solutions
of test polymers in 1-chlorododecane (CDD) and tetralin (TL). FIG.
23, Panel (A) shows the effect of end functionality N=1, 2, 4, 8
for polymers with Mw .about.220,000 g/mol (Table 3.1). Data are not
available for octa-carboxyl end groups (N=8) due to insolubility of
the material in both in CDD and TL. FIG. 23, Panel (B) shows
results of N=4 at Mw=76, 230 and 430,000 g/mol. Graphs are on
different scales.
[0037] FIG. 24 shows the effect of number of chain-end functional
groups (N) on the concentration dependence of the specific
viscosity of solutions of telechelic associative polymers with Mw
.about.230,000 g/mol. FIG. 24, Panel (A) shows the effect in
1-chlorododecane (CDD). FIG. 24, Panel (B) shows the effect in
tetralin (TL). Graphs are on different scales.
[0038] FIG. 25 shows the concentration dependence of specific
viscosity of solutions of telechelic 1,4-PBs with non-associative
and associative chain ends (N=4) as a function of Mw: from left to
right, 76,000 g/mol, 230,000 g/mol, and 430,000 g/mol. The overlap
concentration of the tertbutyl ester form of each polymer is
indicated by the marks on the concentration axis, circles and
squares for tetralin (TL) and triangles for 1-chlorododecane (CDD);
for 76K di-TE in CDD c*=1.4 wt % (offscale). Solid lines indicate
linear regression from 0.2 wt % to 1.5c* for di-TE; dashed lines
correspond to the solid line vertically shifted to the linear
portion of the di-TA data: red for TL and blue for CDD.
[0039] FIG. 26A and FIG. 26B show graphs depicting shear-thinning
behavior of CDD solutions and TL solutions. FIG. 26A shows CDD
solutions of di-TA 1,4-PBs at three concentrations (0.4, 0.7 and
1.0 wt %) as a function of Mw: (a) 76,000 g/mol, (b) Mw=230,000
g/mol, and (c) 430,000 g/mol. FIG. 26B shows TL solutions of di-TA
1,4-PBs at three concentrations (0.4, 0.7 and 1.0 wt %) as a
function of Mw: (a) 76,000 g/mol, (b) Mw=230,000 g/mol, and (c)
430,000 g/mol.
[0040] FIG. 27 shows expanded .sup.1H NMR (500 MHz) spectra of
CDCl.sub.3 solutions of telechelic polymers that have a 10,000
g/mol 1,4-PB backbone with end groups. FIG. 27, Panel (a) shows the
THY (thymine) spectrum. FIG. 27, Panel (b) shows DAAP
(diacetamidopyridine). FIG. 27, Panel (c) shows the spectrum of a
mixture of the two polymers with a mass ratio of 1:2, which
represents a stoichiometric ratio of approximately 1:2. The
concentration of polymer in solution is approximate 1 wt %.
[0041] FIG. 28 shows expanded .sup.1H NMR (500 MHz) spectra of
CDCl.sub.3 solutions of telechelic polymers. FIG. 28, Panel (a)
shows the spectrum of 1,4-PB of M.sub.w=50,000 g/mol with CA
(cyanic acid) end groups FIG. 28, Panel (b) shows the spectrum of
1,4-PB of M.sub.w=24,000 g/mol with HR (Hamilton receptor) end
groups. FIG. 28, Panel (c) shows a mixture of the two polymers with
a mass ratio of 1:1.4, which represents a stoichiometric ratio of
CA:HR of approximately 1:2. The concentration of polymer in
solution is approximate 1 wt %.
[0042] FIG. 29 shows expanded .sup.1H NMR (500 MHz) spectra of
CDCl.sub.3 solutions of telechelic polymers. FIG. 29, Panel (a)
shows the spectrum of 1,4-PB of M.sub.w=22,000 g/mol with TB end
groups. FIG. 29, Panel (b) shows the spectrum of a mixture of
1,4-PB of M.sub.w=22,000 g/mol with TB end groups and 1,4-PB of
M.sub.w=22,000 g/mol with TA end groups two polymers with a mass
ratio of 1:1. The concentration of polymer in solution is
approximate 1 wt %.
[0043] FIG. 30 shows expanded .sup.1H NMR (500 MHz) spectra of
CDCl.sub.3 solutions of telechelic polymers. FIG. 30, Panel (a)
shows the spectrum of 1,4-PB of M.sub.w=288,000 g/mol with THY end
groups. FIG. 30, Panel (b) shows the spectrum of 1,4-PB of
M.sub.w=219,000 g/mol with DAAP end groups. FIG. 30, Panel (c)
shows the spectrum of a mixture of the two polymers with a mass
ratio of 1:2. The concentration of polymer in solution is
approximate 1 wt %.
[0044] FIG. 31 shows expanded .sup.1H NMR (500 MHz) spectra of
CDCl.sub.3 solutions of telechelic polymers. FIG. 31, Panel (a)
shows the spectrum of 1,4-PB of M.sub.w=200,000 g/mol with CA end
groups. FIG. 31, Panel (b) shows the spectrum of 1,4-PB of
M.sub.w=240,000 g/mol with HR end groups. FIG. 31, Panel (c) shows
the spectrum of a mixture of the two polymers with a mass ratio of
1:2. The concentration of polymer in solution is approximate 1 wt
%.
[0045] FIG. 32 shows expanded .sup.1H NMR (500 MHz) spectra of
CDCl.sub.3 solutions of telechelic polymers. FIG. 32, Panel (a)
shows the spectrum of 1,4-PB of M.sub.w=250,000 g/mol with TB end
groups. FIG. 32, Panel (b) shows the spectrum of a mixture of
1,4-PB of M.sub.w=250,000 g/mol with TB end groups and 1,4-PB of
M.sub.w=230,000 g/mol with TA end groups two polymers with a mass
ratio of 1:1. The concentration of polymer in solution is
approximate 1 wt %.
[0046] FIG. 33 shows a plot of specific viscosity (25.degree. C.)
of 1 wt % CDD solutions of 230K di-TE 1,4-PB, 230K di-TA 1,4-PB,
250K di-TB 1,4-PB, and the 1:1 (w/w) mixture of 230K di-TA 1,4-PB
and 250K di-TB 1,4-PB at shear rates 1-3000 s.sup.-1.
[0047] FIG. 34 shows a plot of specific viscosity (25.degree. C.)
of 1 wt % CDD solutions of 230K di-DE 1,4-PB, 230K di-DA 1,4-PB,
250K di-DB 1,4-PB, and the 1:1 (w/w) mixture of 230K di-DA 1,4-PB
and 250K di-DB 1,4-PB at shear rates 1-3000 s.sup.-1.
[0048] FIG. 35 shows a plot of specific viscosity (25.degree. C.)
of 1 wt % Jet-A solutions of 430K di-TE 1,4-PB, 430K di-TA 1,4-PB,
430K di-TB 1,4-PB, and the 1:1 (w/w) mixture of 430K di-TA 1,4-PB
and 430K di-TB 1,4-PB at shear rates 1-3000 s.sup.-1.
[0049] FIG. 36 shows GPC-LS (THF, 35.degree. C.) traces of 230K
di-TE 1,4-PB, 230K di-TA 1,4-PB and the resultant polymer of LAH
reduction of 230K di-TA 1,4-PB.
[0050] FIG. 37 shows a schematic illustration of a synthesis of
di-TE 1,4-PB via two-stage ROMP of COD as the benchmark reaction
for the influence of the purity of VCH-free COD.
[0051] FIG. 38 shows a plot of the viscosities of a non-associative
polymer in an appropriate host at varying concentrations using a
rheometer wherein at c* a deviation from linearity is observed in
the plot of viscosity versus polymer concentration. Linear
regression is performed on the data from both dilute and
concentrated regimes, and the crossover of the two linear fits
represents the overlap concentration, c*.
[0052] FIG. 39 shows an image of an experimental setup to test the
associative polymers herein described in the control of drag
reduction in compositions (see, e.g. Example 13).
[0053] FIG. 40 shows a plot of an exemplary relationship between c*
and M.sub.w that can be generalized to be used to select a desired
M.sub.w of a backbone in an associative polymer as herein described
based on the desired concentration of the associative polymer
relative to c*.
[0054] FIG. 41 shows a schematic illustration of a two-stage
synthesis of tert-butyl ester-terminated telechelic 1,4-PBs. Step
(a): 50-100 equiv of COD, 1/30 equiv of second-generation of Grubbs
Catalyst, anhydrous dichloromethane (DCM), 40.degree. C., 30-60
min. Step (b): 1000-2000 equiv of COD for target Mw <300,000
g/mol, anhydrous dichloromethane (DCM), 40.degree. C., 16 h; 10000
equiv of COD for target Mw >400,000 g/mol, anhydrous
dichloromethane (DCM), 40.degree. C., <10 min.
[0055] FIG. 42 shows a schematic illustration of TFA hydrolysis of
tert-butyl ester polymer end groups.
[0056] FIG. 43 shows graphs of specific viscosity (25.degree. C.)
of 1 wt % 1-chlorododecane (CDD) and dodecane solutions of 288K
di-THY 1,4-PB, 219K di-DAAP 1,4-PB, and 1:2 (w/w) mixture of 288K
di-THY 1,4-PB and 219K di-DAAP 1,4-PB.
[0057] FIG. 44 shows a graph of Specific viscosity (25.degree. C.)
of 1 wt % 1-chlorododecane (CDD) and Jet-A solutions of 240K di-HR
1,4-PB, 200K di-CA 1,4-PB, and 1:2 and 2:1 (w/w) mixtures of 240K
di-HR 1,4-PB and 200K di-CA 1,4-PB.
[0058] FIG. 45 shows a schematic illustration of a synthesis of
di-DB and di-TB 1,4-PBs via two-stage, post-polymerization
end-functionalization reaction.
[0059] FIG. 46A and FIG. 46B show a schematic representation of a
synthesis of bis-dendritic, tert-butyl ester-terminated chain
transfer agents (CTA). FIG. 46A shows a synthesis of a CTA with
only one tert-butyl ester on each side (compound 3). FIG. 46B shows
a synthesis of a CTA with only one tert-butyl ester on each side
(compound 10), with the conditions being: (a) 2.2 eq. of 2 or 2',
K.sub.2CO.sub.3, N,N-dimethylformamide (DMF), 80.degree. C., 5 h;
(b) 4 eq. of LiAlH.sub.4, THF, R.T., overnight; (c) 6 eq. of 2 or
2', 6 eq. of PPh.sub.3, 6 eq. of DIAD, THF, 0.degree. C. then
40.degree. C., overnight; (d) 8 eq. of LiAlH.sub.4, THF, R.T.,
overnight; (c) 12 eq. of 3, 12 eq. of PPh3, 12 eq. of DIAD, THF,
0.degree. C. then 40.degree. C., overnight.
DETAILED DESCRIPTION
[0060] Associative polymers, and related materials, compositions,
methods, and systems are described, which based in several
embodiments, allow control of physical and/or chemical properties,
of a non-polar composition.
[0061] "Chemical and/or physical properties" in the sense of the
present disclosure comprise properties that are measurable whose
value describes a state of a physical system and any quality that
can be established only by changing a substance's chemical
identity.
[0062] The term "non-polar compositions" in the sense of the
present disclosure indicate compositions having a dielectric
constant equal to or lower than 5 which can comprise compositions
of varying chemical nature. In particular, a non-polar composition
can comprise hydrocarbon compositions, fluorocarbon compositions or
silicone compositions. A hydrocarbon composition is a composition
in which the majority component is formed by one or more
hydrocarbons. A fluorocarbon composition is a composition in which
the majority component is formed by one or more fluorocarbons. A
silicone composition is a composition in which the majority
component is formed by one or more silicones.
[0063] In embodiments herein described, associative polymers are
provided which can be added to a non-polar composition to control
at least one physical and/or chemical property of the composition
as illustrated in the present disclosure. In particular, chemical
and/or physical properties that can be controlled by associative
polymers herein described include drag reduction, mist control,
lubrication, fuel efficiency and/or viscoelastic properties of a
non-polar composition.
[0064] In particular, the term "drag reduction" as used herein
refers to the reduction of the resistance to flow in turbulent flow
of a fluid in a conduit (e.g. a pipe) or pipeline thereby allowing
the fluid to flow more efficiently. A skilled person would realize
that drag reduction can be described in terms that include, for
example, a reduction in the friction factor at high Reynolds
number, a reduction in the pressure drop required to achieve a
given volumetric flow rate, or a reduction in hydraulic resistance.
In particular, drag reduction can be measured by methods
identifiable to a skilled person, for example measurement of the
flow rate of a fluid though a conduit and/or by measurement of the
change in pressure of a fluid flowing through a conduit.
[0065] In particular, the term "mist control" as used herein refers
to the control of the properties of a fluid mist. In particular,
the properties that can be controlled can include the sizes, and/or
distribution of sizes, of the droplets of fluid comprising the
fluid mist. In some embodiments, control of the sizes, and/or
distribution of sizes, of the droplets can control the flammability
of the mist of a fluid (e.g., to reduce the propagation of a flame
through the fuel mist in the event of an accident). In other
embodiments, control of the sizes, and/or distribution of sizes, of
the droplets can increase the deposition of a fluid on an intended
surface (e.g., to reduce pesticide wasted by convection away from
the field to which it is being applied). In particular, mist
control can be measured by techniques identifiable to a skilled
person, such as measurement of the sizes and size distribution of
droplets when a fluid is converted to a mist.
[0066] In particular, the term "lubrication" as used herein refers
to the reduction of wear and/or inhibition of movement between two
surfaces separated by a non-polar composition as herein described.
In particular, in some embodiments, the lubrication properties of a
non-polar composition can be controlled to improve the
wear-resistance and/or movement of the surfaces with respect to
each other when the non-polar composition is introduced as a
lubricant between the two surfaces (e.g. improving the
wear-resistance and/or movement of ball bearings in a ball bearing
structure, or improving the wear resistance and/or movement of a
piston in an engine). In particular, lubrication of a fluid can be
measured by techniques identifiable to a skilled person, such as
rheological measurements (e.g. measuring the coefficient of
friction when two surfaces with the fluid between them are slid
past each other).
[0067] In particular, the term "fuel efficiency" as used herein,
refers to the thermal efficiency with which the potential energy of
a fuel is converted to kinetic energy and/or work in the chemical
transformation undergone by the fuel (e.g. combustion of the fuel
in an engine). In particular, fuel efficiency can be measured by
techniques identifiable to a skilled person, such as measurement of
the amount of work performed by the chemical transformation of the
fuel (e.g. measuring the number of miles of travel an engine can
provide when combusting a given volume of fuel).
[0068] In particular, the term "viscoelastic properties" as used
herein refers to the manner in which a non-polar composition reacts
to external stresses such as deformation, in which the non-polar
fluid exhibits a combination of viscous response (e.g. production
of a permanent strain of the non-polar composition once it has been
distorted by the applied stress) and elastic response (deformation
of the non-polar composition during application of the stress, and
return to the original shape upon removal of the stress). In
particular, viscoelastic properties can be measured by methods
identifiable to a skilled person, such as rheological measurements
(e.g. measurement of the storage and loss moduli of the non-polar
composition).
[0069] In the associative polymer the linear or branched backbone
is substantially soluble in the non-polar composition. The term
"substantially soluble" as used herein with reference to a polymer
and a nonpolar composition indicates the ability of the polymer
backbone to dissolve in the non-polar liquid. Accordingly, the
backbone of the associative polymers as herein described can be
substantially soluble in a nonpolar composition when the polymer
backbone and nonpolar composition have similar Hildebrand
solubility parameters (.delta.) which is the square root of the
cohesive energy density:
.delta. = .DELTA. .times. .times. H v - RT V m ##EQU00001##
wherein .DELTA.H.sub.v is equal to the heat of vaporization, R is
the ideal gas constant, T is the temperature, and V.sub.m is the
molar volume. In particular, similar solubility parameters between
a polymer and a nonpolar composition can be found when the absolute
value of the difference between their solubility parameters is less
than about 1 (cal/cm.sup.3).sup.1/2 (see also Tables 3-5 herein). A
skilled person will realize that the ability of the backbone to
dissolve in the non-polar composition can be verified, for example,
by placing an amount of the homopolymer or copolymer to be used as
the backbone of the associative polymer in a host liquid as herein
described, and observing whether or not it dissolves under
appropriate conditions of temperature and agitation that are
identifiable to a skilled person.
[0070] In some embodiments, the backbone of associative polymers as
herein described can be substantially soluble in a nonpolar
composition when the difference in solubility parameters gives rise
to a Flory-Huggins interaction parameter (.chi.) of about 0.5 or
less. In particular, .chi. can be determined by the following
empirical relationship:
= s + H .apprxeq. 0.34 + v 0 RT .times. ( .delta. 1 - .delta. 2 ) 2
##EQU00002##
[0071] where .chi..sub.s is the entropic part of the interaction
between the associative polymer and nonpolar composition (generally
assigned an empirical value of 0.34, as would be apparent to a
skilled person), .chi..sub.H is the enthalpic part of the
interaction, v.sub.0 is the molar volume of the nonpolar
composition, .delta..sub.1 is the solubility parameter of the
polymer, and .delta..sub.2 is the solubility parameter of the host.
Additional exemplary empirical solubility parameters are
identifiable by a skilled person (see, e.g., [Ref 1] and other
available references known or identifiable by one skilled in the
art) An exemplary solubility determination of the backbone of an
associative polymer according to the disclosure with an exemplary
non-polar composition is reported in Example 12. Similarly, a
skilled person can determine if other associative polymer backbones
would be substantially soluble in other non-polar compositions by
applying the same calculations using the particular solubility
parameters for the particular non-polar composition.
[0072] In embodiments herein described, associative polymers are
polymers having a non-polar backbone and functional groups
presented at ends of the non-polar backbone and in particular at
two or more ends of the non-polar backbone.
[0073] In the associative polymer, the functional groups able to
associate with each other and/or corresponding functional groups in
other associative polymers to be added to a same non-polar
composition can associate with an association constant (k) of from
0.1<log.sub.10 k<18, so that the strength of each associative
interaction is less than that of a covalent bond between backbone
atoms.
[0074] The term "functional group" as used herein indicates
specific groups of atoms within a molecular structure that are
responsible for the characteristic physical and/or chemical
reactions of that structure and in particular to physical and/or
chemical associative interactions of that structure. As used
herein, the term "corresponding functional group" or "complementary
functional group" refers to a functional group that can react, and
in particular physically or chemically associate, to another
functional group. Thus, functional groups that can react, and in
particular physically or chemically associate, with each other can
be referred to as corresponding functional groups. In some
embodiments herein described functional end groups of polymers to
be added to a same non-polar compositions are corresponding
functional groups in the sense of the present disclosure.
[0075] In particular, exemplary functional groups can include such
groups as carboxylic acids, amines, and alcohols, and also
molecules such as, for example, diacetamidopyridine, thymine, the
Hamilton Receptor (see, e.g. [Ref 2]), cyanuric acid, and others
identifiable to a skilled person. In particular, some of the
exemplary functional groups can form pairs of complementary
functional groups, for example, 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, and others
identifiable to a skilled person (see, e.g., FIG. 4).
[0076] In particular, in some embodiments, functional groups as
herein described can be synthesized by installation of other
functional groups onto the backbone of the associative polymers at
a plurality of appropriate ends as herein described and transformed
according to methods identifiable to a skilled person (see, e.g.
[Ref 3]). In particular, in some of those embodiments the
installation can be performed in at least two ends of the
associative polymers. More particularly, installation at an end of
the polymer can be performed by installation of the functional
group on the terminal monomer of the polymer backbone, or on an
internal monomer within a range of approximately 1 to 100 monomers
from the terminal monomer.
[0077] In particular, in some embodiments, the at least two ends of
the associative polymers herein described identify at least two
positions in the linear branched or hyperbranched polymer backbone
of the associative polymer that are separated by an internal span
that has a length of at least 2,000 backbone bonds, or an internal
span between functional groups with a weight average molar mass not
less than 100,000 g/mol. In embodiments herein described
installation is performed so that the functional groups are
presented on the polymer.
[0078] The terms "present" and "presented" as used herein with
reference to a compound or functional group indicates attachment
performed to maintain the chemical reactivity of the compound or
functional group as attached. The term "attach" or "attached" as
used herein, refers to connecting or uniting by a bond, link, force
or tie in order to keep two or more components together, which
encompasses either direct or indirect attachment where, for
example, a first molecule is directly bound to a second molecule or
material, or one or more intermediate molecules are disposed
between the first molecule and the second molecule or material.
[0079] In particular, groups presented "at an end" of the polymer
backbone can comprise groups attached to the terminal monomer of a
polymer or to a monomer less than 100 monomers from a terminal
monomer of the polymer.
[0080] In various embodiments, functional end groups of associative
polymers herein described are able to associate in a donor/acceptor
association and/or in a self-to-self association (FIG. 1A, FIG. 1B
and FIG. 2A, FIG. 2B). In the donor/acceptor association the donor
and acceptor can be stoichiometric (e.g. equal numbers of donor and
acceptor functional groups) or non-stoichiometric (e.g. more donor
groups than acceptor groups or vice versa).
[0081] In various embodiments, the self-associative polymers, the
backbone can be linear or branched and following association of the
functional end groups the self-associating polymer can form various
supramolecular architectures (see Example 1). In particular in some
embodiments the backbone length can be such that the backbone has a
weight-averaged molecular weight of 250,000 g/mol and more for
individual chains.
[0082] More particularly, in various embodiments, the backbone can
be a nonpolar linear, branched or hyperbranched polymer or
copolymer (e.g. substituted or unsubstituted polydienes such as
poly(butadiene) (PB) and poly(isoprene), and substituted or
unsubstituted polyolefins such as polyisobutylene (PIB) and
ethylene-butene copolymers, poly(norbornene), poly(octene),
polystyrene (PS), poly(siloxanes), polyacrylates with alkyl side
chains, polyesters, and/or polyurethanes) providing a number of
flexible repeat units between associative functional end groups. In
some embodiments, the weight average molar mass (M.sub.w) of the
associative polymer can be equal to or lower than about 2,000,000
g/mol and in particular can be between about 100,000 g/mol and
about 1,000,000 g/mol.
[0083] In particular, in some embodiments, the backbone and
functional end groups can be selected to have a ratio of carbon
atoms to heteroatoms greater than about 1000:1 in the associative
polymers. For example, in some embodiments, a skilled person can
ensure that the heteroatom content is so low (e.g. greater than
10,000:1) as to not affect burning (e.g. the emissions produced by
burning a fuel composition that contains some associative
polymers). In some embodiments, the associative polymer can
comprise functional groups within the backbone as shown
schematically in FIG. 6 and, therefore, in a location not limited
to the functional groups at one or more end of the polymer backbone
while still maintaining a ratio of carbon atoms to heteroatoms
greater than about 1000:1.
[0084] In particular embodiments, associative polymers herein
described can have structural unit of formula [[FG-chain-[node] (I)
and optionally the structural unit of formula nodechain] (II)
wherein: [0085] FG is a functional group, which can comprise one or
more associative moieties such that the functional group are
capable of undergoing an associative interaction with each other
with an the association constant (k) in a range from
0.1<log.sub.10 k<18, so that the strength of each associative
interaction is less than that of a covalent bond between backbone
atoms; [0086] chain is a non-polar polymer substantially soluble in
a non-polar composition, the polymer having formula:
[0086] R.sub.1-[A].sub.nR.sub.2 (III) [0087] wherein: [0088] A is a
chemical and in particular an organic moiety; [0089] R.sub.1 and
R.sub.2 are independently selected from any carbon based or organic
group; and [0090] n is an integer .gtoreq.1; [0091] node is a
covalently linked moiety linking one of R.sub.1 and R.sub.2 of at
least one first chain with one of the R.sub.1 and R.sub.2 of at
least one second chain; [0092] and wherein [0093] the FG, chain and
node of different structural units of the polymer can be the same
or different.
[0094] In some embodiments herein described, FG indicates a
functional group that is capable of undergoing an associative
interaction with another suitable functional group whereby the
association constant (k) for an interaction between associating
functional groups is in the range 0.1<log.sub.10 k<18, and in
particular in the range 4<log.sub.10 k<14 so that the
strength of each individual interaction is less than that of a
covalent bond between backbone atoms. In particular, in some
embodiments, the FG can be chosen to have an association constant
that is suitable for a given concentration of the associative
polymer in the non-polar composition relative c*, as described
herein. For example, a skilled person will realize that if the
concentration of the associative polymer is high (e.g. greater than
3c*), a lower log.sub.10 k value (e.g. about 4 to about 6) can be
suitable, as can a higher log.sub.10 k value (e.g. about 6 to about
14). Additionally, a skilled person will also realize that if the
concentration of associative polymer is low (e.g. less than 0.5c*)
a higher log.sub.10 k value (e.g. about 6 to about 14) can be
suitable.
[0095] Exemplary FGs comprise those that can associate through
homonuclear hydrogen bonding (e.g. carboxylic acids, alcohols),
heteronuclear hydrogen bond donor-acceptor pairing (e.g. carboxylic
acids-amines), Lewis-type acid-base pairing (e.g. transition metal
center-electron pair donor ligand such as palladium (II) and
pyridine, or iron and tetraaceticacid, or others identifiable to a
skilled person as moieties that participate in metal-ligand
interactions or metal-chelate interactions), electrostatic
interactions between charged species (e.g.
tetraalkylammonium-tetraalkylborate), pi-acid/pi-base or quadrupole
interactions (e.g. arene-perfluoroarene), charge-transfer complex
formation (e.g. carbazole-nitroarene), and combinations of these
interactions (e.g. proteins, biotin-avidin). More than one type of
FG may be present in a given polymer structure.
[0096] In some embodiments, FG can selected among a
diacetamidopyridine group, thymine group, Hamilton Receptor group
(see, e.g. [Ref 2]), cyanuric acid group, carboxylic acid group,
primary secondary or tertiary amine group, primary secondary and
tertiary alcohol group, and others identifiable to a skilled
person.
[0097] In the structural unit of Formulas (I) and (II) a chain can
be a polymer backbone that is substantially soluble in a liquid
host that has a dielectric constant equal to or less than 5. Such
chains can comprise for example polydienes such as poly(butadiene),
poly(isoprene), polyolefins such as polyisobutlyene, polyethylene,
polypropylene and polymers of other alpha olefins identifiable to a
skilled person, poly(styrene), poly(acrylonitrile), poly(vinyl
acetate), poly(siloxanes), substituted derivatives thereof, and
copolymers of these.
[0098] In the structural unit of Formulas (I) and (II) a node can
be a connecting unit between one or more and in particular two or
more [FG-chain] units such that the total molecular structure is
substantially terminated by FG species (e.g., a plurality of the
chain ends have a FG less than 100 repeat units from the chain
end). In some embodiments, the simplest such polymer is a linear
telechelic: two [FG-chain] units with their chains connected
end-to-end at a node: [FG-chain]-node-[chain-FG] or FG-chain-FG.
Alternative branched, hyperbranched, star, brush, partially-cross
linked or other multi-armed polymer structures can also be used,
provided that ends and/or other regions of the polymer chain are
functionalized according to the present disclosure. In particular,
a skilled person will understand from a reading of the present
disclosure the term "functionalized" according to the present
disclosure can be understood to mean that the functional groups can
be at the end of the polymer chains or other polymer structures, or
at different regions within the polymer chain (see, e.g., FIGS.
5-6).
[0099] In particular, in certain cases, the nodes can comprise one
or more FG units such that some degree of associative functionality
is present in the internal polymer structure. A node is formed by
any covalently bound group such as organic, siloxane, and
additional group identifiable by a skilled person. In particular, a
node can link two or more chains through suitable covalent bonds
and more particularly form branched polymers wherein a node can
link two to 10 chain nodechain] (II) (see e.g. FIG. 5). More than
one type of nodes may be present in a given polymer structure.
[0100] In particular in some embodiments, the chain can have a
formula R.sub.1[A].sub.n-R.sub.2 (III) in which A is a chemical
moiety suitable to be used as monomer and n can be an integer equal
to or greater than 200 and, in particular, equal to or greater than
800. In some embodiments particular A can be a diene, olefin,
styrene, acrylonitrile, methyl methacrylate, vinyl acetate,
dichlorodimethylsilane, tetrafluoroethylene, acids, esters, amides,
amines, glycidyl ethers, isocyanates and additional monomers
identifiable by a skilled person. In particular, a skilled person
will realize that the particular moieties used as monomers can give
rise to polymer backbones that are suitable for combination with
particular types of nonpolar compositions. For example, styrene
monomers, olefin monomers, and in particular diene monomers can
form polymers for very non-polar compositions (e.g. compositions
with a dielectric constant of 1.5-2.5); amide, ester, epoxy, and
urethanes can form polymers for nonpolar compositions that have
somewhat greater dielectric constants (e.g., in the range 2.5-5);
and fluorocarbon monomers and silicone monomers can form polymers
for fluorous media. A skilled person will understand that
additional types of monomers would be suitable for other types of
nonpolar compositions.
[0101] In some embodiments. A in Formula (III) can be a moiety of
formula (IV):
##STR00001##
wherein R.sup.a-R.sup.m are independently selected from hydrogen,
C.sub.1-C.sub.12 substituted or unsubstituted alkyl, cycloalkyl,
alkeneyl, cycloalkenyl, alkynyl, cycloakynyl, and aryl groups and n
is in the range 200-20,000 and, in particular, in the range from
1000-10,000.
[0102] In some embodiments, A in formula (III) can be a moiety of
formula (V)-(VIII):
##STR00002##
wherein R.sup.a-R.sup.j are independently selected from the group
consisting of hydrogen, C.sub.1-C.sub.12 substituted or
unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,
cycloakynyl, and aryl groups and n is 1000-20,000.
[0103] In some embodiments, A in formula (III) can be a moiety of
formula (IX):
##STR00003##
wherein R.sup.a-R.sup.d are independently selected from the group
consisting of hydrogen, C.sub.1-C.sub.12 substituted or
unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,
cycloakynyl, and aryl groups and n is 1000-40,000.
[0104] In some embodiments, A in formula (III) can be a moiety of
formula (X):
##STR00004##
wherein R.sup.a-R.sup.h are independently selected from the group
consisting of hydrogen, C.sub.1-C.sub.12 substituted or
unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,
cycloakynyl, and aryl groups and n is 1000-20,000.
[0105] In some embodiments, A in formula (III) can be a moiety of
formula (XI):
##STR00005##
wherein R.sup.a-R.sup.e are independently selected from the group
consisting of hydrogen, C.sub.1-C.sub.12 substituted or
unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,
cycloakynyl, and aryl groups and n is 1000-20,000.
[0106] In embodiments of the nodes of Formula (III) R.sub.1 and
R.sub.2 can be chemical moieties independently selected and capable
of forming a covalent bond. In some embodiments, a node can
comprise functional groups such as arenes, perfluoroarenes, groups
containing oxygen, groups containing nitrogen and groups containing
phosphorus and sulfur all identifiable by a skilled person. In
particular, functional groups suitable for nodes can comprise a
carboxylic acid, amine, triarylphosphine, azide, acetylene,
sulfonyl azide, thio acid and aldehyde. In particular, for example,
in forming covalent links between node and chain and possibly
between node and functional group a first chemical moiety and a
second corresponding chemical moiety can be selected to comprise
the following binding partners: carboxylic acid group and amine
group, sulfonyl azide and thio acid, and aldehyde and primary
amine. Additional chemical moieties can be identified by a skilled
person upon reading of the present disclosure. Reference is also
made to the exemplary nodes of Example 11.
[0107] In some embodiments, R.sub.1 and/or R.sub.2 can be
independently a substituted or unsubstituted methine or methylene
group.
[0108] In some embodiments where A is a moiety of formula
(IV)-(VIII), (X), or (XI), R.sub.1 and/or R.sub.2 can be a moiety
of formula (XII):
##STR00006##
wherein:
[0109] q is 1 to 18;
X is selected from the group consisting of CH.sub.2, O, and S; and
R.sup.a and R.sup.b are independently hydrogen and/or a moiety of
formula XIII-XVIII:
##STR00007##
provided that at least one of R.sup.a and/or R.sup.b is not
hydrogen.
[0110] In some embodiments where A is a moiety of formula
(IV)-(VIII), (X), or (XI), R.sub.1 and/or R.sub.2 can be a moiety
of formula (XX):
##STR00008##
wherein: q is 1 to 18; X is selected from the group consisting of
CH.sub.2, O, and S; and R.sup.a and R.sup.b are independently a
moiety of formula (XIII)-(XVIII) as described herein.
[0111] In some other embodiments where A is a moiety of formula
(IV)-(VIII), (X), or (XI), R.sub.1 and/or R.sub.2 can be a moiety
of formula (XX):
##STR00009##
wherein: q is 1 to 18; X.sup.1, X.sup.2, and X.sup.3 are
independently selected from the group consisting of CH.sub.2, O,
and S; and R.sup.a-R.sup.d are independently hydrogen and/or a
moiety of formula (XIII)-(XVIII) as described herein; provided that
at least one of R.sup.a, R.sup.d, R.sup.c, and/or Rb is not
hydrogen.
[0112] In some other embodiments where A is a moiety of formula
(IV)-(VIII), (X), or (XI), R.sub.1 and/or R.sub.2 can be a moiety
of formula (XXI):
##STR00010##
wherein: q, r and s are independently 1 to 18; X.sup.1, X.sup.2,
and X.sup.3 are independently selected from the group consisting of
CH.sub.2, O, and S; and R.sup.a-R.sup.d are independently hydrogen
and/or a moiety of formula (XIII)-(XVIII) as described herein;
provided that at least one of R.sup.a, R.sup.b R.sup.c, and/or
R.sup.d is not hydrogen.
[0113] In some embodiments nodes can also present additional groups
for binding with FG which can be introduced at the node according
to some embodiments. In some embodiments nodes comprise an organic
moiety, in some embodiments nodes comprise non organic moieties
such as Si--O and additional moieties identifiable by a skilled
person.
[0114] In some embodiments where A is a moiety of formula (IX)
R.sub.1 and/or R.sub.2 can be a moiety of formula (XXII):
##STR00011##
wherein: q is 1 to 18; X is selected from the group consisting of
CH.sub.2, O, and S; and R.sup.a and R.sup.b are independently H
and/or a moiety of formula (XIII)-(XVIII) as described herein,
provided that at least one of R.sup.a and/or R.sup.b is not H.
[0115] In some embodiments where A is a moiety of formula (IX)
R.sub.1 and/or R.sub.2 can be a moiety of formula (XXIII):
##STR00012##
wherein: q is 1 to 18; X is selected from the group consisting of
CH.sub.2, O, and S; and R.sup.a and R.sup.b are independently a
moiety of formula (XIII)-(XVIII) as described herein.
[0116] In some other embodiments where A is a moiety of formula
(IX) R.sub.1 and/or R.sub.2 can be a moiety of formula (XXIV):
##STR00013##
wherein: q is 1 to 18; X.sup.1, X.sup.2, and X.sup.3 are
independently selected from the group consisting of CH.sub.2, O,
and S; and R.sup.a-R.sup.d are independently H and/or a moiety of
formula (XIII)-(XVIII) as described herein; provided that at least
one of R.sup.a, R.sup.b, R.sup.c, and/or R.sup.d is not H.
[0117] In some other embodiments where A is a moiety of formula
(IX) R.sub.1 and/or R.sub.2 can be a moiety of formula (XXV):
##STR00014##
wherein: q, r and s are independently 1 to 18; X.sup.1, X.sup.2,
and X.sup.3 are independently selected from the group consisting of
CH.sub.2, O, and S; and R.sup.a-R.sup.d are independently H and/or
a moiety of formula (XIII)-(XVIII) as described herein; provided
that at least one of R.sup.a, R.sup.b, R.sup.c, and/or R.sup.d is
not H.
[0118] In some other embodiments where A is a moiety of formula
(IX) R.sub.1 and/or R.sub.2 can be a moiety of formula (XXVI):
##STR00015##
wherein: q is 1-18; R.sup.a-R.sup.b are independently H and/or a
moiety of formula (XIII)-(XVIII) as described herein; and R.sup.c
is hydrogen or C.sub.1-C.sub.12 substituted or unsubstituted alkyl;
provided that at least one of R.sup.a, R.sup.b, and/or R.sup.c is
not H.
[0119] In some other embodiments where A is a moiety of formula
(IX) R.sub.1 and/or R.sub.2 can be a moiety of formula (XXVII):
##STR00016##
wherein: q is 1 to 18; R.sup.a-R.sup.d are independently H and/or a
moiety of formula (XIII)-(XVIII) as described herein; and
R.sup.f-R.sup.g are independently hydrogen or C.sub.1-C.sub.12
substituted or unsubstituted alkyl; provided that at least one of
R.sup.a, R.sup.b, R.sup.c, and/or R.sup.d is not H.
[0120] In particular in some embodiments the [chain-node] segments
have average molar mass equal to or greater than 10,000 g/mol. In
some embodiments the span of [chain-node].sub.m between FGs has
average molar mass >50,000 g/mol (in particular when dispersion
in the host composition despite the "solvent-phobic" FGs is
desired). In some embodiments, the largest span of the molecule can
be equal to or less than 500,000 g/mol (for example, when
resistance to shear degradation is desired). In some embodiments
the largest span of the molecule, expressed as weight average
molecular weight can be equal to or less than 1,000,000 g/mol.
[0121] In some embodiments associative polymers herein described
can be telechelic.
[0122] In some embodiments associative polymers herein described
have a total polymer molecular weight is M.sub.w<2,000,000 g/mol
and in particular can be between 100,000 g/mol and 1,000,000 g/mol.
In some embodiments the largest span between nodes is less than
500,000 g/mol in particular when the associative polymers are
branched polymers. In some embodiments associative polymers herein
described can have an atomic composition with heteroatoms (i.e.,
other than C or H) present at less than 1 heteroatom per 1000
carbons. In some embodiments, heteroatoms are placed predominantly
in correspondence of the functional groups.
[0123] In some embodiments associative polymers herein described
can have a significant level of unsaturation (e.g. with a ratio of
H to C less than 1.8), which can improve low temperature liquid
behavior. However, fully-saturated chains can also be considered
effective and are included in the scope of the current
disclosure.
[0124] In various embodiments herein described, the associative
polymers of the disclosure can interact to form supramolecular
structures following interactions of the FG having association
constant (k) of from 0.1<log.sub.10 k<18.
[0125] In particular, in embodiments of supramolecular structures,
FG associations can be due to, for example reversible noncovalent
interaction between the associative polymers that enables a
discrete number of molecular subunits or components to be
assembled, typically with an individual interaction strength less
than that of a covalent bond. Exemplary interactions include, for
example, self-associative hydrogen bonds (H-bonds), donor-acceptor
H-bonds, Bronsted or Lewis acid-base interactions, electrostatic
interactions, pi-acid/pi-base or quadrupolar interactions, charge
transfer complex formation, or other supramolecular
interactions.
[0126] In various embodiments herein described, the associative
polymers of the disclosure can be used in connection with a
non-polar composition to control physical and/or chemical
properties of the composition. In particular, in some embodiments,
the non-polar compositions comprise a host composition and at least
one associative polymer herein described.
[0127] The terms "host" and "host composition", as used herein,
refer to a majority component in a non-polar composition in which
the physical and/or chemical properties are sought to be
controlled. In particular, the host or host composition can be a
single substance such as a solvent like hexane or benzene, or the
host or host composition can be a substance which is a mixture such
as gasoline, diesel, olive oil, or kerosene. The host or host
composition can also be a mixture such as a paint or ink.
[0128] In particular, in non-polar compositions herein described a
range of hosts can have dielectric constant less than 5, with hosts
having dielectric constant less than 2.5 being particularly well
suited to applications herein described as will be understood by a
skilled person upon reading of the disclosure. Non-polar
compositions with the above mentioned dielectric constants
encompasses a wide range of liquids that are relevant to
applications that comprise, fuels (such as gasoline, kerosene, jet
fuel and additional fuels identifiable by a skilled person), foods
and pharmaceuticals (such as olive oil, linseed oil, castor oil and
additional foods identifiable by a skilled person), solvents used
as cleaning fluids (such as turpentine, toluene and additional
solvents identifiable by a skilled person), and adhesive
formulations (such as pinene and additional formulations
identifiable by a skilled person).
[0129] In embodiments of non-polar composition of the present
disclosure, the dielectric constant of a given host will vary with
temperature, which can be taken into account by one skilled in the
art.
[0130] Exemplary non-polar compositions, and in particular host
liquids, with a dielectric constant less than 5 are illustrated in
the table below (Table 1A). The table also provides exemplary hosts
that can be recognized as unfavorable for the modified non-polar
compositions herein described (see Table 1B).
TABLE-US-00001 TABLE 1A Dielectric Entry Fluid Temperature/.degree.
C. constant .di-elect cons. Exemplary Favorable Hosts 1 Benzene 20
2.3 2 Carbon disulfide 2.64 3 Carbon tetrachloride 20 2.23 4 Castor
oil 15.6 4.7 5 Chloroform 20 4.8 6 Cotton seed oil 3.1 7 Cumene 20
2.4 8 Decane 20 2 9 Dodecane 20 2 10 Ether 20 4.3 11 Fluorine
refrigerant R-12 25 2 12 Fluorine refrigerant R-22 25 2 13 Furan 25
3 14 Gasoline 21.1 2 15 Heptane 20 1.9 16 Hexane -90 2 17 Jet fuel
21.1 1.7 18 Kerosene 21.1 1.8 19 Linoleic acid 0 2.6-2.9 20 Linseed
oil 3.2-2.5 21 Naphthalene 20 2.5 22 Octane 20 2 23 Olive oil 20
3.1 24 Palmitic acid 71.1 2.3 25 Pentane 20 1.8 26 Phenol 10 4.3 27
Pinene 20 2.7 28 Styrene 25 2.4 29 Terpinene 21.1 2.7 30 Toluene
2.0-2.4 31 Turpentine (wood) 20 2.2 32 Vacuum (by definition) 1
32.1 Cyclohexane 2.0 32.2 Liquid methane -280 1.7 32.3 Liquid
Butane -1 1.4 32.4 Heavy oil 3 32.5 Petroleum oil 2.1 32.6 Liquid
asphalt 2.5-3.2
TABLE-US-00002 TABLE 1B Dielectric Entry Fluid Temperature/.degree.
C. constant .di-elect cons. Exemplary Unfavorable Hosts 33 Acetone
25 20.7 34 Alcohol, ethyl (ethanol) 25 24.3 35 Alcohol, methyl
(methanol) 20 35.1 36 Alcohol, propyl 20 21.8 37 Ammonia (aqua) 20
15.5 38 Aniline 20 7.3 39 Cresol 17.2 10.6 40 Ethylamine 21.1 6.3
41 Ethylene glycol 20 37 42 Furfural 20 42 43 Glycerine 47.68 44
Glycerol 25 42.5 45 Hexanol 25 13.3 46 Hydrazine 20 52 47 Pyridine
20 12
[0131] In particular, in some embodiments, host composition that
have dielectric constant equal to or less than about 5 are pentane,
hexane, cyclohexane, benzene, toluene, chloroform and diethylether.
In some embodiments, which can be used for fuel applications host
composition can also have dielectric constant less than 5,
including liquified petroleum gas, liquid methane, butane,
gasoline, kerosene, jet fuel and diesel fuel.
[0132] In embodiments, herein described polymer dielectric
constants can further provide an indication of their compatibility
with a chosen non-polar composition that is in the range indicated
in above. Reference is made for example to the exemplary list
provided in the table below (Table 2).
TABLE-US-00003 TABLE 2 Dielectric Plastic Material Constant -
.di-elect cons. - Acetal 3.7-3.9 Acrylic 2.1-3.9 ABS* 2.9-3.4
Polybutadiene approximately 2 Polycarbonate 2.9-3.8 Polyester, TP
3.0-4.5 Polypropylene 2.3-2.9 Polysulfone 2.7-3.8
Polydimethylsiloxane (Silicone Rubber) 3.0-3.2 Polyphenylene
sulfide 2.9-4.5 Polyacrylate 2.6-3.1 *ABS is Acrylonitrile
Butadiene Rubber
[0133] In particular, in some embodiments, for a given host
determined to have a dielectric constant within the threshold
herein disclosed, at least one associative polymer herein described
is selected that is substantially soluble in the host in accordance
with the present disclosure.
[0134] In particular, appropriate associative polymers for a given
host can be identified by a skilled person in view of the present
disclosure. For example the backbone substantially soluble in the
host composition can be identified by comparison of the solubility
parameters (.delta.) of the polymer backbone and host composition,
as well as by determining the Flory-Huggins interaction parameter
(.chi.) from the solubility parameters according to calculations
described herein. In an exemplary embodiment, one or more
polymer-solvent pairs can have silicone backbones for use in one or
more fluorocarbon liquids.
[0135] In particular, an exemplary reference providing solubility
parametes is the website
www.sigmaaldrich.com/etc/medialib/docs/Aldrich/General_Information/polyme-
r_solutions.Par.0001.File.tmp/polymer_solutions.pdf at the time of
filing of the present disclosure (see Tables 3-5). More
particularly, a skilled person will know that Sigma-Aldrich and
other chemical companies provide exemplary tables showing exemplary
solubility parameter values for various non-polar compositions and
polymers. A skilled person can also refer to sources such as the
Polymer Handbook to find solubility parameter values [Ref 1].
TABLE-US-00004 TABLE 3 Table II: Solubility Parameters for
Plasticizers and Solvents (Alphabetical sequence) .delta. H-Bonding
.delta. H-Bonding Solvent (cal/cm.sup.3)F Strength.sup.3 Solvent
(cal/cm.sup.3).sup.1/2 Strength.sup.3 Acetone 9.9 m Dioctyl
sebacate 8.6 m Acetonitrile 11.9 p 1,4-Dioxane 10.0 m Amyl acetate
8.5 m Di(propylene glycol) 10.0 s Aniline 10.3 s Di(propylene
glycol) 9.3 m Benzene 9.2 p monomethyl ether Butyl acetate 8.3 m
Dipropyl phthalate 9.7 m Butyl alcohol 11.4 s Ethyl acetate 9.1 m
Butyl butyrate 8.1 m Ethyl amyl ketone 8.2 m Carbon disulfide 10.0
p Ethyl n-butyrate 8.5 m Carbon tetrachloride 8.6 p Ethylene
carbonate 14.7 m Chlorobenzene 9.5 p Ethylene dichloride 9.8 p
Chloroform 9.3 p Ethylene glycol 14.6 s Cresol 10.2 s Ethylene
glycol diacetate 10.0 m Cyclohexanol 11.4 s Ethylene glycol diethyl
ether 8.3 m Diamyl ether 7.3 m Ethylene glycol dimethyl ether 8.6 m
Diamyl phthalate 9.1 m Ethylene glycol monobutyl ether 9.5 m
Dibenzyl ether 9.4 m (Butyl Cellosolve .RTM.) Dibutyl phthalate 9.3
m Ethylene glycol monoethyl ether 10.5 m Dibutyl sebacate 9.2 m
(Cellosolve .RTM.) 1,2-Dichlorobenzene 10.0 p Furfuryl alcohol 12.5
s Diethyl carbonate 8.8 m Glycerol 16.5 s Di(ethylene glycol) 12.1
s Hexane 7.3 p Di(ethylene glycol) monobutyl 9.5 m Isopropyl
alcohol 8.8 m ether (Butyl Carbitol .RTM.) Methanol 14.5 s
Di(ethylene glycol) monoethyl 10.2 m Methyl amyl ketone 8.5 m ether
(Carbitol .RTM.) Methylene chloride 9.7 p Diethyl ether 7.4 m
Methyl ethyl ketone 9.3 m Diethyl ketone 8.8 m Methyl isobutyl
ketone 8.4 m Diethyl phthalate 10.0 m Propyl acetate 8.8 m
Di-n-hexyl phthalate 8.9 m 1,2-Propylenecarbonate 13.3 m Diisodecyl
phthalate 7.2 m Propylene glycol 12.6 s N,N-Dimethylacetamide 10.8
m Propylene glycol methyl ether 10.1 m Dimethyl ether 8.8 m
Pyridine 10.7 s N,N-Dimethylformamide 12.1 m
1,1,2,2-Tetrachloroethane 9.7 p Dimethyl phthalate 10.7 m
Tetrachloroethylene 9.3 p Dimethylsiloxanes 4.9-5.9 p
(perchloroethylene) Dimethyl sulfoxide 12.0 m Tetrahydrofuran 9.1 m
Dioctyl adipate 8.7 m Toluene 8.9 p Dioctyl phthalate 7.9 m Water
23.4 s .sup.2"Polymer Handbook", Eds. Brandrup, J.; Immergut, E.
H.; Grulke, E. A, 4th Edition, John Wiley, New York, 1999,
VII/675-711, Aldrich Catalog Number Z41.247.3. .sup.3H-Bonding: p =
poor; m = moderate; s = strong
TABLE-US-00005 TABLE 4 Table III: Solubility Parameters (.delta.)
for Plasticizers and Solvents (Increasing .delta. value sequence)
.delta. H-Bonding Solvent (cal/cm.sup.3).sup.1/2 Strength.sup.4
Dimethylsiloxanes 4.9-5.9 p Diisodecyl phthalate 7.2 m Hexane 7.3 p
Diamyl ether 7.3 m Diethyl ether 7.4 m Dioctyl phthalate 7.9 m
Butyl butyrate 8.1 m Ethyl amyl ketone 8.2 m Ethylene glycol
diethyl ether 8.3 m Butyl acetate 8.3 m Methyl isobutyl ketone 8.4
m Methyl amyl ketone 8.5 m Amyl acetate 8.5 m Ethyl n-butyrate 8.5
m Ethylene glycol dimethyl ether 8.6 m Carbon tetrachloride 8.6 p
Dioctyl sebacate 8.6 m Dioctyl adipate 8.7 m Isopropyl alcohol 8.8
m Diethyl carbonate 8.8 m Propyl acetate 8.8 m Diethyl ketone 8.8 m
Dimethyl ether 8.8 m Toluene 8.9 p Di-n-hexyl phthalate 8.9 m Ethyl
acetate 9.1 m Diamyl phthalate 9.1 m Tetrahydrofuran 9.1 m Dibutyl
sebacate 9.2 m Benzene 9.2 p Tetrachloroethylene 9.3 p
(perchloroethylene) Di(propylene glycol) 9.3 m monomethyl ether
Chloroform 9.3 p Dibutyl phthalate 9.3 m Methyl ethyl ketone 9.3 m
Dibenzyl ether 9.4 m Ethylene glycol monobutyl ether 9.5 m (Butyl
Cellosolve .RTM.) Di(ethylene glycol) monobutyl 9.5 m ether (Butyl
Carbitol .RTM.) Chlorobenzene 9.5 p Methylene chloride 9.7 p
Dipropyl phthalate 9.7 m 1,1,2,2-Tetrachloroethane 9.7 p Ethylene
dichloride 9.8 p Acetone 9.9 m 1,2-Dichlorobenzene 10.0 p Diethyl
phthalate 10.0 m Ethylene glycol diacetate 10.0 m Di(propylene
glycol) 10.0 s Carbon disulfide 10.0 p 1,4-Dioxane 10.0 m Propylene
glycol methyl ether 10.1 m Di(ethylene glycol) monoethyl 10.2 m
ether (Carbitol .RTM.) Cresol 10.2 s Aniline 10.3 s Ethylene glycol
monoethyl 10.5 m ether (Cellosolve .RTM.) Pyridine 10.7 s Dimethyl
phthalate 10.7 m N,N-Dimethylacetamide 10.8 m Cyclohexanol 11.4 s
Butyl alcohol 11.4 s Acetonitrile 11.9 p Dimethyl sulfoxide 12.0 m
Di(ethylene glycol) 12.1 s N,N-Dimethylformamide 12.1 m Furfuryl
alcohol 12.5 s Propylene glycol 12.6 s 1,2-Propylenecarbonate 13.3
m Methanol 14.5 s Ethylene glycol 14.6 s Ethylene carbonate 14.7 m
Glycerol 16.5 s Water 23.4 s .sup.4H-Bonding: p = poor; m =
moderate; s = strong Carbitol and Cellosolve are registered
trademarks of Union Carbide Corp.
TABLE-US-00006 TABLE 5 Table IV: Solubility Parameters for
Homopolymers.sup.5 Repeating Unit .delta.(cal/cm.sup.3).sup.1/2
Repeating Unit .delta.(cal/cm.sup.3).sup.1/2 (Alphabetical
Sequence) (Increasing .delta. Value Sequence) Acrylonitrile 12.5
Tetrafluoroethylene 6.2 Butyl acrylate 9.0 Isobutyl methacrylate
7.2 Butyl methacrylate 8.8 Dimethylsiloxane 7.5 Cellulose 15.6
Propylene oxide 7.5 Cellulose acetate (56% Ac groups) 27.8
Isobutylene 7.8 Cellulose nitrate (11.8% N) 14.8 Stearyl
methacrylate 7.8 Chloroprene 9.4 Ethylene 8.0 Dimethylsiloxane 7.5
1,4-cis-Isoprene 8.0 Ethyl acrylate 9.5 Isobornyl methacrylate 8.1
Ethylene 8.0 Isoprene, natural rubber 8.2 Ethylene terephthalate
10.7 Lauryl methacrylate 8.2 Ethyl methacrylate 9.0 Isobornyl
acrylate 8.2 Formaldehyde (Oxymethylene) 9.9 Octyl methacrylate 8.4
Hexamethylene adipamide (Nylon 6/6) 13.6 n-Hexyl methacrylate 8.6
n-Hexyl methacrylate 8.6 Styrene 8.7 Isobornyl acrylate 8.2 Propyl
methacrylate 8.8 1,4-cis-Isoprene 8.0 Butyl methacrylate 8.8
Isoprene, natural rubber 8.2 Ethyl methacrylate 9.0 Isobutylene 7.8
Butyl acrylate 9.0 Isobornyl methacrylate 8.1 Propyl acrylate 9.0
Isobutyl methacrylate 7.2 Propylene 9.3 Lauryl methacrylate 8.2
Chloroprene 9.4 Methacrylonitrile 10.7 Tetrahydrofuran 9.4 Methyl
acrylate 10.0 Methyl methacrylate 9.5 Methyl methacrylate 9.5 Ethyl
acrylate 9.5 Octyl methacrylate 8.4 Vinyl chloride 9.5 Propyl
acrylate 9.0 Formaldehyde (Oxymethylene) 9.9 Propylene 9.3 Methyl
acrylate 10.0 Propylene oxide 7.5 Vinyl acetate 10.0 Propyl
methacrylate 8.8 Methacrylonitrile 10.7 Stearyl methacrylate 7.8
Ethylene terephthalate 10.7 Styrene 8.7 Vinylidene chloride 12.2
Tetrafluoroethylene 6.2 Acrylonitrile 12.5 Tetrahydrofuran 9.4
Vinyl alcohol 12.6 Vinyl acetate 10.0 Hexamethlene adipamide(Nylon
6/6) 13.6 Vinyl alcohol 12.6 Cellulose nitrate (11.8% N) 14.8 Vinyl
chloride 9.5 Cellulose 15.6 Vinylidene chloride 12.2 Cellulose
acetate (56% Ac groups) 27.8 .sup.5Values reported are for
homopolymers of the Repeating Unit. Reported .delta. values vary
with the method of determination and test conditions. Averaged
values are given in this table.
[0136] In particular, in some embodiments, the associative polymer
can be selected depending on the particular physical and/or
chemical properties of the non-polar composition to be controlled.
In particular, in some embodiments, the chemical and/or physical
property can be controlled by controlling concentration of one or
more associative polymers in the host composition relative to the
overlap concentration c* of the one or more associative polymers in
the host concentration. Accordingly one or more associative
polymers can be comprised in the host in a concentration of a
fractional or integer multiple of the overlap concentration
(c*).
[0137] The terms "overlap concentration", or "c*", as used herein
refer to the concentration at which molecules of a non-associative
form of the associative polymer (e.g. obtained from literature
sources on the backbone of interest or from experimental methods
described herein using the polymer of interest modified to
inactivate the functional groups to prevent association, for
example by esterifying carboxylic acids) dissolved in the host
begin to overlap each other, as opposed to being separated as they
would be in a more dilute solution. In particular, c* for
particular polymers in particular hosts can be identified by
methods and calculations identifiable to a skilled person (see,
e.g. [Ref 4] and Example 23).
[0138] In particular, the chain length of the backbone can be
chosen such that the backbone is long enough to ensure that a small
concentration of the polymer will suffice to produce a desired
effect using relationships between chain length and the c* of the
associative polymer described herein. For example, a polymer that
is effective at concentrations less than 1% by weight can be
obtained by choosing a backbone length that gives c* less than or
approximately equal to 1% by weight. In particular, the
relationship between chain length (e.g., expressed as the weight
averaged molecular weight) and c* can be determined from references
identifiable by a skilled person or determined by calculations as
described herein.
[0139] In particular, for a non-associative polymer chain, the
overlap concentration is given by:
c * = 3 .times. M w 4 .times. .pi. .function. ( R g 2 ) 3 / 2
.times. N a , ##EQU00003##
wherein M.sub.w is the weight averaged molecular weight, R.sub.g is
the radius of gyration, and N.sub.a is Avogadro's constant. The
overlap concentration represents a concentration equal to one
polymer molecule per spherical volume of radius R.sub.g, as
illustrated for example in the exemplary schematic of FIG. 17.
Throughout this disclosure, reference is made to c* when describing
the concentration of associative polymer required to achieve each
type of desired chemical or physical property. Generally the
pairings of polymer and host represent good solvent (e.g. a solvent
in which the polymer-solvent interactions are more
thermodynamically favorable than polymer-polymer interactions; see
e.g. [Ref 5]) conditions for the polymer backbone. In good solvent
conditions, R.sub.g increases approximately as the 2/3 power of
M.sub.w, so the expression for c* above shows that c* decreases as
M.sub.w increases. For a specific choice of polymer backbone and
host liquid, c* scales approximately as 1/M.sub.w. For example,
doubling the length of the polymer backbone approximately reduces
by half the concentration of associative polymer required to
achieve a given effect.
[0140] In several exemplary embodiments, many polymers' data
relating R.sub.g to M.sub.w are available for commonly used
solvents [Ref 6]. When experimental values are not available, an
indicative estimate can be made using a theoretical chain model as
herein described. For example, the estimate of R.sub.g using the
ideal chain model provides a conservative estimate c* of the
concentration of polymer required to achieve a desired effect. A
skilled person will realize upon a reading of the present
disclosure that the polymer backbone is in a good solvent condition
when dissolved in the host, so the actual c* of the polymer in the
host can be less than the value of c* estimated using the ideal
chain model.
[0141] For the purpose of selecting the degree of polymerization to
use for the span of the polymer (which is the backbone length in
the simple case of a linear telechelic structure), an equivalent
expression can be written that refers to tabulated parameters,
including e.g. parameters available for many polymers. In
particular, tabulated values of the characteristic ratio,
c.sub..infin., and the length and equivalent mass of a "Kuhn
segment" (b and M.sub.o) can be used to estimate the chain length
that will confer a desired effect with a selected concentration.
For example, for mist control, the polymer can be present at its
overlap concentration. In applications in which a polymer
concentration is desired to be at most c.sub.max, a chain can be
used that has sufficiently many Kuhn segments, N, so that the
polymer begins to overlap when its concentration is approximately
c.sub.max or less. Such chain can be given by:
N 3 / 2 = 9 .times. 6 2 .times. n .times. b 3 .times. c max
##EQU00004##
where N is the number of Kuhn segments and corresponds to a linear
polymer (or span of a branched polymer) having molar mass NM.sub.o,
where M.sub.o is the mass per Kuhn segment. Therefore, one can
synthesize for example a polymer that has a span of molar mass
NM.sub.o (and functional groups, selected with guidance below) and
introduce the synthesized polymer to a composition at a
concentration c* to provide mist control. A skilled person will
realize that when using approximate expressions for c*, mist
control is expected to improve by increasing or decreasing the
concentration relative to the estimated value of c*. In particular,
in experiments that examine the extent of mist control with
associative polymer, concentrations of associative polymer of 0.5c*
and 2c* can be suitable. Similar reasoning can be applied for other
effects herein described as will be understood by a skilled
person.
[0142] A list of exemplary tabulated parameters is indicated below
(Table 6; [Ref 7], p. 53):
TABLE-US-00007 TABLE 6 Characteristic ratios, Kuhn lengths, and
molar masses of Kuhn monomers for common polymers at 413 K Polymer
Structure C.sub..infin. b (.ANG.) .rho. (gcm.sup.-3) M.sub.0
(gmol.sup.-1) 1,4-Polyisoprene (PI)
--(CH.sub.2CH.dbd.CHCH(CH.sub.3))-- 4.6 8.2 0.830 111
1,4-Polybutadiene (PB) --(CH.sub.2CH.dbd.CHCH.sub.2)-- 5.3 9.6
0.826 105 Polypropylene (PP) --(CH.sub.2CH.sub.2(CH.sub.3))-- 5.9
11 0.791 180 Poly(ethylene oxide) (PEO) --(CH.sub.2CH.sub.2O)-- 6.7
11 1.064 137 Poly(dimethyl siloxane) (PDMS)
--(OSi(CH.sub.3).sub.2)-- 6.8 13 0.895 381 Polyethylene (PE)
--(CH.sub.2CH.sub.2)-- 7.4 14 0.784 150 Poly(methyl methacrylate)
(PMMA) --(CH.sub.2C(CH.sub.3)(COOCH.sub.3))-- 9.0 17 1.13 655
Atactic polystyrene (PS) --(CH.sub.2CHC.sub.6H.sub.5)-- 9.5 18
0.969 720
[0143] In addition, a skilled person can also identify the
relationship between chain length and c* by experimental
measurement, e.g. by measuring the shear viscosity of the host
composition including the non-associative form of the polymer as a
function of the concentration of the polymer.
[0144] In particular, the overlap concentration of the backbone can
be determined from conventional shear viscosity measurements of
solutions containing various concentrations of the non-associative
form of the polymer. Alternatively, it can be evaluated using the
weight average molecular weight of the longest span of the polymer,
which is often characterized as part of the synthesis and
purification of a synthetic polymer.
[0145] In particular, c* can be determined at a given temperature
by measuring the viscosities of a non-associative polymer in an
appropriate host at varying concentrations using a rheometer
wherein at c* a deviation from linearity is observed in the plot of
viscosity versus polymer concentration. Linear regression is
performed on the data from both dilute and concentrated regimes,
and the crossover of the two linear fits represents the overlap
concentration, c* (see, e.g. [Ref 7, 8] and FIG. 38).
[0146] In particular, in some embodiments, a way to identify a
"desired overlap concentration" is to consider the type of
beneficial effect that is needed. For example, for a desired effect
of mist control, a concentration of polymer can be used that is
approximately equal to the overlap concentration. For example a
concentration range suitable for mist control can be between 0.5c*
to 2c*. In embodiments in which a desired effect is enhancing fuel
efficiency, a polymer concentration can be used in the non-polar
compositions herein described that is less than c*, and in
particular can be between 0.1c* and 0.5c*. In embodiments in which
the desired effects are drag reduction and enhanced lubrication, a
polymer concentration can be a concentration below or approximately
equal c*, and in particular can be between 0.05c* to c*. In
embodiments in which a desired effect is converting a liquid into a
gel, a concentration greater than c* can be provided and in
particular a concentration from 2c* to 10c*.
[0147] Selection of one or more specific associative polymers that
can be comprised within the composition at a concentration relative
to the c* selected to control a set of one or more chemical and/or
physical properties can be performed in view of the characteristics
of functional groups, chain structures, and weight average
molecular weight of associative polymers herein described
[0148] In some embodiments, the functional groups described herein
at the ends of the backbone of the associative polymer can be
selected to ensure association occurs with the range of the polymer
concentrations selected. In conjunction with the selection of
functional groups, the synthetic chemistry is selected to be
appropriate for introduction of such groups.
[0149] A skilled person will realize that characteristics of the
host that influence the selection of functional groups include, for
example, its dielectric constant and whether or not it contains
protic species or species that offer a lone pair of electrons.
Non-polar liquids generally contain molecules made mainly of atoms
with similar electronegativities, such as carbon and hydrogen (for
example, hydrocarbons that dominate fuels and many lubricants).
Bonds between atoms with similar electronegativities lack partial
charges, making the molecules non-polar. A common way of
quantifying this polarity is the dielectric constant. A skilled
person will also realize that another characteristic of components
in the host liquid is whether or not they have O--H or N--H bonds
that can participate in hydrogen bonding. A skilled person would
recognize these as protic molecules. Examples of protic species
that may be present in host liquids in the disclosed ranges of
dielectric constants include, for example secondary amines with
substantial hydrocarbon content (e.g., Diisobutylamine, which has
dielectric constant 2.7; dipropylamine, which has dielectric
constant 2.9; Methylbenzylamine, which has dielectric constant
4.4), carboxylic acids with substantial hydrocarbon content (e.g.,
palmitic acid, which has dielectric constant 2.3; linoleic acid,
which has dielectric constant 2.6; oleic acid, which has dielectric
constant 2.5), and alcohols with substantial hydrocarbon content
(e.g., hexadecanol, which has dielectric constant 3.8). In
addition, a skilled person will also realize that other protic
species (e.g., protic species that in their pure state can have a
dielectric constant greater than 5, such as aniline and phenol) can
be present as minor species in a host liquid that has dielectric
constant less than 5.
[0150] A skilled person will realize that another relevant
characteristic of components in the host liquid is whether or not
they present a lone pair of electrons that can participate in
hydrogen bonding. Examples of species with lone pairs that may be
present in host liquids in the disclosed ranges of dielectric
constants include alkyl-quinoxalines (e.g.,
2,3-Dimethylquinoxaline, which has dielectric constant 2.3),
tertiary amines (e.g., triethylamine, which has dielectric constant
2.4) and nonconjugated esters (e.g., isoamylvalerate, which has
dielectric constant 3.6). In addition, a skilled person will also
realize that other lone-pair species (that in their pure state
might have a dielectric constant greater than 5, such as pyridine
and methylethylketone) can be present as minor species in a host
liquid that has dielectric constant less than 5. In addition, a
skilled person will realize that components that are used as
additives when the host liquid is formulated can also be present.
For example, metal chelating agents (e.g.,
N,N-Disalicylidene-1,2-propanediamine) can be present in a host
liquid that is a fuel. A skilled person will realize that the
presence of these constituents influences the selection of
functional groups depending on the presence of protic species or
species that offer a lone pair of electrons as described
herein.
[0151] A skilled person will also realize the presence of protic
species can, in some circumstances, interfere with FG association
mediated by hydrogen bonding. The skilled person will realize that
one way to overcome the interference is to increase the number of
hydrogen bond moieties at the chain ends. The skilled person will
also realize that another way to overcome the interference is to
reduce the concentration of protic species in the host. A skilled
person would recognize that these two approaches can be used
together. IN addition, a skilled person will also realize that, all
other factors being equal, increasing the dielectric constant of
the host weakens the interaction (e.g., conventional hydrogen
bonds, charge-assisted hydrogen bonds, charge transfer interaction,
metal-ligand interactions). For example, increasing the dielectric
from 2.4 (toluene) to 4.8 (chloroform) decreases the association
constant for the Hamilton-receptor and cyanuric acid by an order of
magnitude. Accordingly, FGs that provide a stronger association
(e.g., charge assisted hydrogen bonding or a metal-ligand
interaction) are expected to be beneficial when the dielectric
constant is greater than 2.5. A skilled person would realize that
the selection of FGs that provide strong association can be used
together with increasing the number of associative groups at the
chain ends and with reducing the concentration of host components
that have high dielectric constants.
[0152] In particular, in some embodiments, the value of the
concentration of the associative polymer relative to overlap
concentration c* can be governed by the selection of chain-host
pair and can be insensitive to the specific choice of FG. A skilled
person will understand that the overlap concentration can vary with
temperature, in a manner that is particular to a specific
chain-host pair. For example, the selection of polymer backbone and
host governs the solvent quality; and, for a given solvent quality,
the degree of polymerization is chosen to adjust c* once the
chain-host pair is selected. In this connection selecting a greater
degree of polymerization, provides a greater R.sub.g and,
consequently, a reduced c* as will be understood by a skilled
person.
[0153] In some embodiments herein described, the chain structure
between the nodes (e.g. the chain being a polyolefin, polydiene, or
other structure identifiable to a skilled person upon a reading of
the present disclosure) can be chosen such that it interacts
favorably with the host, the state of the backbone can be estimated
using good solvent (e.g. a solvent in which the polymer-solvent
interactions are more thermodynamically favorable than
polymer-polymer interactions; see e.g. [Ref 5]) scaling for its
pervaded volume. Over most of the molar mass range of interest, the
ideal chain approximation (e.g. approximation of the polymer chain
as a random walk and neglecting any kind of interactions among
monomers; see e.g. [Ref 7]) can also be useful: it provides a lower
bound on R.sub.g that is usually within a factor of 2 of the good
solvent chain dimensions, as shown in FIG. 16 for the case of
polystyrene for a good solvent such as toluene, and a theta solvent
(e.g. a solvent in which the polymer-solvent interactions are
approximately as equally thermodynamically favorable as
polymer-polymer interactions; see e.g. [Ref 5]) such as
cyclohexane. In particular, the value of the radius of gyration can
be used to estimate the concentration at which polymer molecules
would begin to overlap one another: the overlap concentration c*
corresponds to the value that gives approximately one polymer
molecular per R.sub.g{circumflex over ( )}3.
[0154] Additional factors related to applications of the resulting
compositions (e.g. distribution through a pipeline, storage for a
certain time period and other factors identifiable by a skilled
person), can also be taken into account in the selection of the
specific associative polymer or combination thereof and/or in the
selection of the related concentration in the host composition
relative to c* within a range associated to control of one or more
chemical and/or physical properties.
[0155] In embodiments in which a low concentration of polymer is
desired, a reduction in the concentration of the associative
polymer relative to c* can be obtained by selecting a polymer with
high degree of polymerization. In some of those embodiments, the
degree of polymerization of the polymer is low enough that the
polymers do not degrade during necessary handling. For example, in
embodiments in which the non-polar compositions are fuel or other
liquid and the liquid is intended to travel through a distribution
system, minimization of the degradation of the polymer upon passage
through pumps and filters, and/or minimization of degradation
during turbulent flow in transport pipelines or hoses can be
desirable. In this connection, in exemplary embodiments in which
the polymers comprise linear chains, keeping the weight-average
molar mass below 1,000,000 g/mol can give adequate stability with
respect to shear degradation. In exemplary embodiments in which the
polymer comprises lightly branched molecules, having
node-chain-node segments that are individually greater than 10,000
g/mol, the longest span of the molecule can be kept below the
threshold for shear degradation (typically less than 1,000,000
g/mol).
[0156] In embodiments wherein conversion of liquid to gel is
desired, a solution or gel that has dielectric constant less than 5
and comprises a polymer that has weight average molar mass between
100,000 g/mol and 1,000,000 g/mol, can comprise the polymer at a
concentration that is between 0.1c* and 10 c*. The specific
concentration can be determined based on the measured length and
backbone composition of the polymer, and the polymer molecules
manifestly associate with one another as evidenced by shear
viscosity that is anomalously enhanced relative to a
non-associative polymer of the same molar mass and backbone
structure or by light scattering showing structures that are much
larger than a non-associative polymer of the same molar mass and
backbone structure. The latter measurements can be performed for
example by removing the polymer from the composition and
reconstituting them in a solvent that has a dielectric constant
that is close to that of the composition (plus or minus 20%) at a
concentration of c* based on the weight-average molar mass
determined by GPC equipped with light scattering.
[0157] In embodiments in which the composition comprise liquid
fuels, such as gasolines, diesel fuels, kerosene and jet fuels,
such compositions can comprise polymers with molar mass between
100,000 g/mol and 1,000,000 g/mol having backbones that, as bulk
polymers, have dielectric constant less than 3 and are present in
the composition at a concentration that is between 0.1c* and 10c*,
based on the measured weight averaged molar mass and backbone
composition of the polymer, and the polymer molecules manifestly
associate with one another as evidenced by shear viscosity that is
enhanced relative to a non-associative polymer of the same molar
mass and backbone structure or by light scattering showing
structures that are much larger than a non-associative polymer of
the same molar mass and backbone structure. The latter measurements
can be performed for example by removing the polymer from the
composition and reconstituting them in toluene at a concentration
of c* based on the weight-average molar mass determined by GPC
equipped with light scattering. In several examples of the current
disclosure toluene is indicated as a reference host because it has
a dielectric constant of approximately 2.2, which is at the upper
range of diverse fuels and, therefore, gives a conservative
diagnostic of association. That is, a polymer that forms
intermolecular associations in toluene will form intermolecular
associations in gasoline, diesel, kerosene and jet fuel, among
others.
[0158] In some embodiments, polymer for improving fuel efficiency
can be effective at 10000 ppm or less with weight average molecular
weight below 1,000,000 g/mol, possibly after more than 10 passages
of the fuel through a fuel pump. In some embodiments, associative
polymers can remain uniformly dissolved for at least 2 weeks or
even months even at -30.degree. C.
[0159] In some embodiments, with weight average molecular weight
400,000 g/mol chains, droplet behavior of non-polar composition
comprising associative polymers herein described is expected to
match 4,200,000 g/mol (weight average) polyisobutylene, a commonly
used standard material to achieve mist control effect using high
molecular weight polymer, compared at the same, concentration of
0.3%.
[0160] In some embodiments, if for a particular application the
polymer concentration is desired to be kept low, this can be
achieved by increasing the length of the polymer chain between
associative groups. The reason for this is that polymers tend to
adopt compact conformations in isolated clusters when the
concentration is far below their overlap concentration; increasing
the length of the polymer between associative groups decreases the
overlap concentration, thereby allowing desired properties to be
achieved with a lower concentration of polymer.
[0161] In some embodiments, if for a particular application the
polymer additive is desired to survive passage through pumps and
turbulent pipe flow, this can be achieved by keeping the length of
the polymer below the threshold at which chain scission occurs in
intense flows. For a number of polymers, the literature provides
values of the chain length above which chains scission occurs (e.g.
polyisobutylene) For any choice of polymer backbone structure, the
threshold length (or equivalently, degree of polymerization or
molar mass) above which chain scission occurs upon passage through
pumps or turbulent pipe flow can be determined as will be
understood by a skilled person,
[0162] In some embodiments, for the purpose of creating additives
that deliver valuable effects at low polymer concentration, use of
chain segments having molar mass between 100,000 g/mol and 500,000
g/mol between FG and node can be desired. This range of structures
can associate at low concentrations to give desired properties. For
example, in the context of fuels, the resulting polymers can
inhibit misting in order to reduce the risk of post-crash fires;
can control atomization to increase fuel efficiency and/or reduce
emissions; can confer drag reduction that reduces pumping costs and
improves throughput through existing pipelines; and improve
lubrication. In particular, polymers of the present disclosure can
survive prolonged, severe shear with little degradation; the
polymers do not interfere with filtering fuel; the polymers do not
interfere with dewatering fuel.
[0163] According to the above indication and to the additional
indication provided in the disclosure, in some embodiments, one
skilled in the art can identify whether or not a host of interest
(e.g., a particular lubricant oil) is suitable for application of
the associative polymers based on the dielectric constant of the
host, and the skilled person can identify suitable monomer
structures using knowledge of the dielectric constant or solubility
parameter of the resulting polymer, and thus select the degree of
polymerization (e.g. by synthesizing a polymer backbone of a
particular weight-averaged molecular weight) to achieve a desired
c*.
[0164] In some embodiments herein described once the suitability of
a potential host is determined, as well as the selection of the
monomer and the selection of the degree of polymerization are made,
functional groups can be selected that are able to associate
according to the indicated association constant. In particular, in
some embodiments when the host has a relatively low dielectric
constant (e.g. .epsilon.<2) and little or no participation in
hydrogen bonds, there are many associative groups that are
effective as will be understood by a skilled person. Therefore,
secondary considerations can be applied to narrow down the
selection (such as cost, sensitivity to ionic species, nature of
combustion products, and other considerations identifiable to a
skilled person). For example, in some instances, with increasing
dielectric constant of the host, many of the useful interactions
(hydrogen bonding, charge transfer, acid-base, and others
identifiable to a skilled person) become progressively weaker.
Therefore, clusters of functional groups may be required to confer
adequate association. Consequently, for solvents that have
dielectric constant greater than 2.5, dendrimeric FG can be used
that include multiple associative groups (examples are shown for FG
that each present four or eight copies of a chosen associative
group).
[0165] For example, if drag reduction (e.g. the flow resistance of
a non-polar composition through a conduit such as an oil pipeline
or fuel line in a vehicle) is the property sought to be controlled,
a skilled person can identify the solubility parameter of the
fluid, and then can identify polymer backbones that are
substantially soluble in the fluid (e.g. by comparing the
solubility parameters and/or using the solubility parameters to
determine the Flory-Huggins interaction parameter as described
herein). The selection of particular polymers for the backbone of
the associative polymer suitable to be included at a concentration
relative to c* below c* can be further refined based on, for
example, on the cost of the polymers, or the ease and/or expense of
the polymerization chemistry, as would be identifiable to a skilled
person.
[0166] In particular, for drag reduction, a skilled person would
realize it is desirable to minimize the amount of polymer used for
two reasons: to minimize cost and to avoid undue increase in the
shear viscosity of the mixture. Accordingly, the length (expressed
as the weight-averaged molecular weight) of the backbone of the
associative polymer can be near the threshold imposed by shear
degradation, which a skilled person would understand to be in the
range of approximately 500,000 g/mol for hydrocarbon polymers such
as polyisobutylene, polybutadiene, polyolefins, and others
identifiable to a skilled person.
[0167] In particular, a skilled person can verify that the chain
length selected resists shear degradation by performing analyses
known to the skilled person. For example, the viscosity of a
non-polar composition comprising the associative polymers described
herein can be measured before and after recirculation through a
conduit (e.g. by using a fuel pump to recirculate a sample of the
non-polar composition) and determining if there is a difference in
viscosity between the two time points (e.g., if the viscosity
decreases after recirculation, the associative polymer can be
considered to have undergone shear degradation).
[0168] As another example, if mist control is the property of the
nonpolar composition desired to be controlled, the polymer backbone
selection among the possible polymers to be included at a
concentration relative to c* between 0.5c* to 2c* can be based on
solubility of the in nonpolar composition as described herein (e.g.
solubility parameters and/or Flory-Huggins interaction parameter),
with the additional consideration of the associative polymer having
negligible effect on the calorific value of the nonpolar
composition in which mist control is desired, as would be
identifiable to a skilled person (e.g. by using the calorimetric
method ASTM D240-09). The functional groups described herein at the
ends of the backbone of the associative polymer can be chosen to
ensure that association occurs at desired concentration such that
heteroatom content is so low as to not affect burning. For example,
association can be measured using titration techniques identifiable
to a skilled person (see, e.g., [Ref 9]). Using the titration
methods, the skilled person can identify a concentration at which
the particular associative polymers (with a given number of end
groups containing heteroatoms) associate; if the concentration is
suitable based on c* considerations (e.g. the particular
concentration of the associative polymer relative to c* to control
a particular property such as mist control) the skilled person can
then measure the calorific value using ASTM D240-09. If the
concentration is not suitable, the number of end groups can be
changed accordingly (e.g. by increasing the number for greater
association at a given concentration, or by decreasing the number
for lesser association), the titration re-performed, and the
calorific value re-measured.
[0169] In various embodiments, associative polymers herein
described can be made with methods in which a backbone polymer is
provided which is then functionalized with suitable FGs.
[0170] In some embodiments, in which the backbone has a structural
unit of formula nodechain] (II), wherein [0171] chain is a
non-polar polymer substantially soluble in a non-polar composition,
the polymer having formula
[0171] R.sub.1-[A].sub.nR.sub.2 [0172] in which [0173] A is an
organic moiety; [0174] R.sub.1 and R.sub.2 are independently
selected from any carbon based or organic group; and [0175] n is an
integer .gtoreq.1; and [0176] node is a chemical moiety covalently
linking one of R.sub.1 and R.sub.2 of at least one first chain with
one of the R.sub.1 and R.sub.2 of at least one second chain; [0177]
and wherein the chain and node of different structural units of the
polymer can be the same or different and the polymer presents two
or more terminal R.sub.1 and R.sub.2 groups the method can
comprise: providing the polymer having structural unit of formula
node.sctn. chain] (II) and attaching functional groups FG herein
described to terminal R.sub.1 and/or R.sub.2 groups of the
polymer.
[0178] In some embodiments, an associative polymer can be provided
by forming a polymer chain through a method of polymerization of a
suitable monomer such as those described in "Polymer Handbook",
4.sup.th edition; Brandrup, J.; Immergut, Edmund H.; Grulke, Eric
A.; Abe, Akihiro; Bloch, Daniel R. (eds.), J. Wiley and Sons (New
York), 1999) so that the desired architecture (linear, branched,
star, and other architectures identifiable to a skilled person) is
generated and individual polymer chains are substantially
terminated by chemical groups that are amenable to
functionalization. The end groups can already be functionalized by
FGs or formed by precursors that are converted to FGs (e.g., by
deprotection or functional groups that are suitable for covalent
attachment of FGs). This prepolymer can then be reacted with a
molecule containing the desired FG, so that FGs are introduced to
the polymer chain through chemical transformations commonly
described as functional group interconversions. Thus, in some
embodiments the desired polymer composition can be achieved in a
two-step process, in which after the first step reaction of the
monomer gives a polymer that does not substantially include the
desired FG or FGs, which are introduced in the second step. For
example, the prepolymer may be synthesized as substantially
terminated with functional groups known in the art to be "leaving
groups" such as halide, triflate or tosylate, and the desired FG or
FGs introduced to the polymer chain through nucleophilic
substitution reaction.
[0179] In some embodiments, suitable monomers comprise dienes,
olefins, styrene, acrylonitrile, methyl methacrylate, vinyl
acetate, dichlorodimethylsilane, tetrafluoroethylene, acids,
esters, amides, amines, glycidyl ethers, isocyanates, and mixtures
of these.
[0180] The association polymers described herein can be synthesized
by methods known to a skilled person. For example, the backbone can
be synthesized by Ring-Opening Metathesis Polymerization (ROMP)
chemistry and functionalized at the ends of the backbone using
appropriate chain transfer agents (see, e.g., Examples section
herein and [Ref 10]). In addition, anionic polymerization,
Atom-transfer Radical-Polymerization (ATRP), Reversible
Addition-Fragmentation chain Transfer polymerization (RAFT) and
other polymerization techniques identifiable to a skilled person
(including an alternative overview of metathesis techniques) can be
used to synthesize several types of backbones (e.g. block, star,
branched and other architectures) and introduce of many different
types of functional groups at the ends of the polymer chain (or
elsewhere if desired) (see, e.g. [Ref 11, 12]).
[0181] In certain embodiments, an associative polymer in accordance
with the present disclosure can be provided by forming a polymer
chain such that the desired architecture is generated, and
individual polymer chains are substantially terminated by the
desired FG, in situ. Thus, in some embodiments the desired polymer
composition can be achieved in a single step process, and reaction
of the monomer affords a polymer that includes the desired FG or
FGs. In yet other embodiments, the desired FGs can be introduced to
the polymer chain in a form such that the ultimate function of such
FGs is masked by a chemical substitution (e.g. the FGs feature one
or more "protecting groups"), and the desired functionality of the
FGs can then be enabled for example through removal of such a
"protecting group" through chemical transformation in subsequent
steps. However, in some embodiments, the desired polymer
composition can still be achieved in a single step process, and the
polymer as synthesized includes the desired FG or FGs in protected
form. In some of those embodiments, suitable monomers include
cyclic olefins and acyclic .alpha.,.omega.-dienes.
[0182] Suitable methods of polymerization in accordance with some
embodiments herein described, comprise ring-opening metathesis
polymerization (ROMP) and acyclic diene metathesis polymerization
(ADMET), in the presence of suitable chain transfer agent (CTA)
typically consisting of the FG suitably disposed about a reactive
olefinic functionality (e.g. cis-double bond). The FG or FGs can be
in their ultimate functional form in this CTA, or can be in
"protected" form such that unmasking of the ultimate functional
form may be achieved through removal of this "protecting group"
through chemical transformation.
[0183] Suitable "protecting groups" in accordance with some
embodiments herein described, comprise those described in "Greene's
Protective Groups in Organic Synthesis, 4.sup.th edition"; Wuts P.
G. M. and Green, T. W., J. Wiley and Sons (New York), 2006.
[0184] For example, in some embodiments where the polymer backbone
is made by a ROMP polymerization (e.g. using cyclooctadiene to
synthesize a backbone of repeating
.dbd.CHCH.sub.2CH.sub.2CH.dbd.CHCH.sub.2CH.sub.2CH.dbd. units), the
ends of the polymer backbone can be functionalized with appropriate
chain transfer agents to provide functionalized ends of the
backbone which can be further transformed to provide functional
groups capable of being corresponding functional groups, as shown
for example in Examples 1-3 where carboxylic acid functional groups
are installed. A skilled person will realize upon a reading of the
present disclosure that analogous reactions can be performed to
synthesize other backbones such as poly(vinylacetate) (e.g. RAFT
polymerization as shown, for example in [Ref 13]; or free radical
polymerization of vinyl acetate using a free radical initiator
comprising FG groups as shown, for example, in [Ref 14]).
[0185] In particular, as exemplified in Example 3, chain transfer
agents can be used to attach moieties substituted with chloro
groups, which can then be displaced with azide groups (e.g. using
trimethylsilyl (TMS) azide by methods identifiable to a skilled
person). A moiety comprising attached alkyne groups can then be
reacted with the azide groups via reactions such as the
azide-alkyne Huisgen cycloaddition (e.g. click reaction) to attach
the moiety to thereby attach the FG to the backbone (see, e.g.
Example 3).
[0186] In yet further embodiments, an associative polymer in
accordance with the present disclosure can be provided by
metathesis applied to a high molecular weight (M.sub.w
>5,000,000 g/mol) poly(diene) such as poly(butadiene) in the
presence of suitable CTA and metathesis catalyst to give a shorter
poly(diene) substantially terminated by FG, with the diene:CTA
ratio chosen to afford the desired molecular weight for the product
telechelic polymer. In particular methods of these particular
embodiments, the starting high molecular weight poly(diene) can be
linear and substantially free of 1,2-vinyl groups in the polymer
backbone.
[0187] In exemplary methods to make a polymer of the present
disclosure, the polymer can be made by ROMP in a continuous
process. In particular, methods of these particular embodiments the
continuous process can use reactions in series (FIG. 10). In
relation to compositions that are used as liquid fuels the
continuous production of the associative polymers herein described
can be performed near or inside a petrochemical refinery and
incorporated into a product continuously.
[0188] In exemplary methods to make a polymer of the present
disclosure, the polymer can be made by ring-opening metathesis
polymerization (ROMP) to obtain desired end-functional telechelic
polymers of weight averaged molecular weight 100,000 to 1,000,000
g/mol.
[0189] In exemplary methods to make a polymer of the present
disclosure, the polymer can be made by related polymerization
and/or functionalization methods to make functional telechelics of
molecular weight 100,000 to 1,000,000 g/mol.
[0190] In various embodiments, associative polymers herein
described can be used in methods and systems to control physical
and/or chemical properties of a non-polar composition herein
described.
[0191] In particular in some embodiments, in which associative
polymers herein described are resistant to shear degradation (e.g.
chain scission upon passage through pumps, during prolonged
turbulent flow in pipelines, tubes or hoses, during passage through
filters), the associative polymer of the present disclosure can be
introduced at early steps in the preparation of non-polar host
compositions. In many applications the host composition can be
itself a mixture.
[0192] In particular in exemplary embodiments in which a modified
non polar composition comprising associative polymers herein
described is provided in connection with production of inks or
paints that can comprise a carrier liquid, pigments, stabilizers
and other components, the associative polymer can be added to the
carrier liquid prior to incorporation of the remaining components,
with the possibility that a central depot of carrier liquid can
feed production lines for diverse colors or grades of ink or paint.
In some of these embodiments, the efficacy of the polymer can be
retained after pumping, filtering, mixing and other processing
steps.
[0193] Similarly, in exemplary embodiments in which a modified non
polar composition comprising associative polymers herein described
is provided in connection with lubricant applications, the
associative polymers herein described can be incorporated into the
base oil that is subsequently combined with diverse additive
packages. At concentrations up to c*, the associative polymers are
expected to survive and are expected to not interfere with
processes that include but are not limited to filtering,
dewatering, pumping and mixing operations.
[0194] In exemplary embodiments in which a modified non polar
composition comprising associative polymers herein described is
provided in connection with fuel applications (e.g. use as drag
reducing agents, enhancers of fuel efficiency, emission reducing
agents, or mist control agents), the ability to incorporate the
associative polymer herein described at any point along the
distribution system allows for example incorporation at the
refinery; or in the intake line of a storage tank; or in the intake
line of a tanker ship, railway tank car, tank of a tanker truck; or
in the intake line to a major site of use, such as an airport or a
military depot; or in the transfer line from a storage tank into a
vehicle; or as a solution added to the tank of a vehicle at the
time of fueling.
[0195] In exemplary embodiments in which a modified non polar
composition comprising associative polymers herein described is
provided in connection with drag reducing agents in the transport
of petrochemicals (especially crude oil) through very long
pipelines, the present polymers resist shear degradation upon
passage through pumps; therefore, fewer injection stations are
required. In some cases, introduction of the associative polymer at
a single location prior to the intake of the pipeline will provide
drag reduction throughout the entire length of the pipeline.
[0196] In some embodiments herein described associative polymers
are not interfacial agents, so that such polymers can be added
prior to dewatering operations (including but not limited to fuel
handling) and defoaming operations (including but not limited to
production of paints and inks); at concentrations up to c*, the
associative polymers do not interfere with these essential
processing steps and the processing steps have a minimal effect on
the associative polymers.
[0197] In some embodiments, associative polymers herein described
can be used as a fuel additive with one or more of the following
features: i) effective at low concentrations (acceptable
viscosity), ii) introduced at the refinery; iii) resistant to
non-intentional degradation; iv) soluble over wide temperature
range (-50.degree. C. to 50.degree. C.); v) permit dewatering and
filtering, vi) permit optimization in engine combustion chamber;
vii) clean burning, and viii) affordable.
[0198] As disclosed herein, the associative polymers and non-polar
composition herein described can be provided as a part of systems
to control physical and/or chemical properties herein described,
including any of the methods described herein. The systems can be
provided in the form of kits of parts.
[0199] In a kit of parts, polymers (e.g. backbone polymers,
associative polymers or precursor thereof), compositions and other
reagents to perform the methods can be comprised in the kit
independently. One or more polymers, precursors, compositions and
other reagents can be included in one or more compositions alone or
in mixtures identifiable by a skilled person. Each of the one or
more polymers, precursors, compositions and other reagents can be
in a composition alone or together with a suitable vehicle.
[0200] Additional reagents can include molecules suitable to
enhance reactions (e.g. association of one or more associative
polymers herein described with a related host composition)
according to any embodiments herein described and/or molecules
standards and/or equipment to facilitate or regulate the reaction
(e.g. introduction of the associative polymer to the host)
[0201] In particular, the components of the kit can be provided,
with suitable instructions and other necessary reagents, in order
to perform the methods here described. The kit can contain the
compositions in separate containers. Instructions, for example
written or audio instructions, on paper or electronic support such
as tapes or CD-ROMs, for carrying out reactions according to
embodiments herein described (e.g. introduction of associative
polymer in a host composition), can also be included in the kit.
The kit can also contain, depending on the particular method used,
other packaged reagents and materials.
[0202] Further advantages and characteristics of the present
disclosure will become more apparent hereinafter from the following
detailed disclosure by way of illustration only with reference to
an experimental section.
EXAMPLES
[0203] The associative polymers, materials, compositions, methods
system herein described are further illustrated in the following
examples, which are provided by way of illustration and are not
intended to be limiting.
[0204] In particular, the following examples illustrate exemplary
associative polymers and related methods and systems. A person
skilled in the art will appreciate the applicability and the
necessary modifications to adapt the features described in detail
in the present section, to additional associative polymers,
compositions, methods and systems according to embodiments of the
present disclosure.
Example 1: Exemplary Associative Polymer and Architectures
[0205] Exemplary associative polymers and related exemplary
architectures are illustrated in FIGS. 3 to 6.
[0206] In particular in the illustration of FIG. 3 a linear polymer
backbone of 1,4-polybutadiene is illustrated in which end groups
are <1 wt % of the polymer and contain <0.2 wt % heteroatoms.
When added to fuel, polymers of this type burn cleanly and maintain
the caloric content of the fuel.
[0207] The illustration of FIG. 4 provides exemplary functional
groups which can be used with the backbone of FIG. 3 or other
backbones as will be understood by a skilled person. The
illustration of FIGS. 5 and 6 shows exemplary branched
architectures (FIG. 5) and exemplary block-polymer architecture
(FIG. 6) which can be created with the backbone of and/or other
backbones as will be understood by a skilled person. When the
associative polymer is added to a host composition the FGs form
physical associations according to their nature (e.g. self to self,
donor-acceptor, pairwise, or multidentate). The illustration of
FIGS. 1 and 2 show exemplary types of supramolecular structures
thus formed.
Example 2: Methods of Making Associative Polymers and Related
Architectures
[0208] A schematic illustration of exemplary reactions and methods
suitable to make associative polymers herein described is provided
in FIGS. 7 to 10.
[0209] In particular FIG. 7 shows a schematic of an exemplary
method to provide an associative polymer herein described
illustrated making specific reference to embodiments where a
corresponding non-polar composition is a fuel.
[0210] FIGS. 8 and 9 show an exemplary ROMP+Chain Transfer Agent
(CTA) reaction (FIG. 8) and exemplary chain transfer agents (FIG.
9). This exemplary reaction allows in several cases precise control
of the number of associating groups. It will be appreciated by a
skilled person that it can be straightforward to synthesize and
purify at large scale associative polymers compatible with
non-polar compositions, with the backbone and associative groups
chosen for a particular application as described in the
specification (see, e.g., [Ref 10-12]).
[0211] FIG. 10 shows a schematic of an exemplary method to
synthesize an associative polymer using CTAs.
Example 3: Synthesis of High Molecular Weight Di-TE PB by ROMP
[0212] 6.7 mg of octa-functional tert-butyl ester CTA is loaded
into a 50 ml Schlenk flask (charged with a magnetic stir bar). The
flask is later sealed with a septum. The content is then
deoxygenated by 5 times of pulling vacuum/filling argon. 0.5 ml of
deoxygenated DCM is added to dissolve the CTA. 0.13 ml of 1 mg/ml
DCM solution of Grubbs II catalyst is injected into the flask, and
then 0.03 ml of freshly vacuum distilled, purified COD 50 eq.
w.r.t. CTA) is immediately injected.
[0213] The mixture is stirred at 40.degree. C. for 33 minutes to
allow complete incorporation of CTA into the polymer. Another 0.13
ml of freshly prepared 1 mg/ml DCM solution of Grubbs II catalyst
is then injected, followed by 5.6 ml of freshly vacuum distilled,
purified COD 10,000 eq.) in 12 ml of deoxygenated DCM. The reaction
is stopped by adding 30 ml of oxygen-containing DCM as the mixture
turns viscous enough to completely stop the motion of magnetic stir
bar. The diluted mixture is precipitated into 400 ml of acetone at
room temperature. The resulting polymer is collected and dried in
vacuo at room temperature overnight. GPC results of the polymer:
M.sub.w=430,000 g/mol, PDI=1.46.
##STR00017##
Example 4: Deprotection of the Acid End Groups
[0214] 1 g of the aforementioned polymer is loaded into a 50 ml
Schlenk flask (charged with a magnetic stir bar), and degassed by 5
times of pulling vacuum/filling argon). 30 ml of deoxygenated is
then syringe-transferred into the flask. The mixture is homogenized
at room temperature. Once complete homogenization is achieved, 1.25
ml of deoxygenated trifluoroacetic acid (TFA) is
syringe-transferred into the flask. The mixture is then stirred at
room temperature overnight.
[0215] Upon the completion of TFA hydrolysis, the mixture is
diluted with 20 ml of DCM, and the resulting solution is
precipitated into 400 ml of acetone at room temperature. The
resulting polymer is further purified by 2 times of
re-precipitation from THF into acetone.
##STR00018##
Example 5: Synthesis of High Molecular Weight Di-TB PB by ROMP
[0216] Synthesis of high M.W di-TB PB by ROMP is performed
according to the following steps:
[0217] Step 1: Prepolymer Synthesis
[0218] 5 mg of octa-functional chloro CTA is loaded into a 50 ml
Schlenk flask (charged with a magnetic stir bar). The flask is
later sealed with a septum. The content is then deoxygenated by 5
times of pulling vacuum/filling argon. 0.5 ml of deoxygenated DCM
is added to dissolve the CTA. 0.13 ml of 1 mg/ml DCM solution of
Grubbs II catalyst is injected into the flask, and then 0.03 ml of
freshly vacuum distilled, purified COD 50 eq. w.r.t. CTA) is
immediately injected. The mixture is stirred at 40.degree. C. for
33 minutes to allow complete incorporation of CTA into the polymer.
Another 0.13 ml of freshly prepared 1 mg/ml DCM solution of Grubbs
II catalyst is then injected, followed by 5.6 ml of freshly vacuum
distilled, purified COD 10,000 eq.) in 12 ml of deoxygenated DCM.
The reaction is stopped by adding 30 ml of oxygen-containing DCM as
the mixture turns viscous enough to completely stop the motion of
magnetic stir bar. The diluted mixture is then precipitated into
400 ml of acetone at room temperature. The resulting polymer is
collected and dried in vacuo at room temperature overnight. GPC
results of the polymer: M.sub.w=430,000 g/mol, PDI=1.46.
##STR00019##
[0219] Step 2: End-Azidation of Prepolymer
[0220] 1 g of the aforementioned chloro-terminated prepolymer is
loaded into a 50 ml Schlenk flask, and dissolved into 30 ml of
anhydrous THF. Upon complete homogenization, 0.73 g of
azidotrimethylsilane 1200 eq w.r.t. polymer) and 1.57 g of
tetrabutylammonium fluoride 1200 eq w.r.t. polymer) are added into
the flask. The resulting mixture is degassed by 2 freeze-pump-thaw
cycles to prevent crosslinking by dissolved oxygen. Then, the
mixture is stirred at 60.degree. C. overnight. The mixture is
precipitated into 300 ml of methanol at room temperature. The
resulting polymer is further purified by 2 more times of
reprecipitation from THF into acetone. The resulting polymer is
dried in vacuo at room temperature overnight.
##STR00020##
[0221] Step 3: Attachment of Tertiary Amine Groups to Polymer Chain
Ends
[0222] 0.68 g of the aforementioned azido-terminated prepolymer is
loaded into a 50 ml Schlenk flask, and dissolved into 25 ml of
anhydrous THF. Once homogenization is complete, 0.23 g of
3-Dimethylamino-1-propyne (.ident.1,200 eq. w.r.t. the polymer),
along with 0.02 g of N,N,N',N',N''-pentamethyldiethylenetriamine
(PMDETA, .ident.50 eq. w.r.t. the polymer) are added into the
flask. The mixture is then deoxygenated by 2 freeze-pump-thaw
cycles. Later it is frozen and pumped again, and then 0.016 g of
copper (I) bromide (.ident.50 eq. w.r.t. the polymer)) is added
into the flask under the protection of argon flow when the mixture
is still frozen. After thawing the mixture and filling the flask
with argon, the mixture is stirred at room temperature for 20
minutes in order to homogenize the copper (I) catalyst. The mixture
is stirred at 50.degree. C. overnight. 2 ml of methanol is slowly
injected into the mixture in order to remove copper from the amine
end groups. The mixture is precipitated into 300 ml of methanol at
room temperature. The resulting polymer is further purified by 2
more times of reprecipitation from THF into methanol. It is later
dried in vacuo at room temperature overnight.
##STR00021##
Example 6: Effect of Self-Association in Exemplary Associative
Polymers
[0223] Proof of effect of self-association in exemplary associative
polymers herein described is illustrated in FIG. 11 and FIG. 12. In
the exemplary associative of Example 5 the aforementioned method of
recovering the end acid groups does not crosslink the polybutadiene
backbone, as proved in the superposition of GPC traces of 430K
di-TE PB and the resulting polymer of its hydrolysis reaction (in
THF) illustrated in FIG. 11
[0224] In the illustration of FIG. 11, the slight increase in the
population of high molecular weight species is due to the weak
self-association of chain-end acid clusters. The apparent M.sub.w
increases by 20% after TFA hydrolysis.
[0225] A further confirmation is provided by the illustration of
FIG. 12. In particular, FIG. 12 shows the rheology data of the 1 wt
% Jet-A solutions of the 430K di-TE PB and 430K di-TA PB
respectively. The viscosities of 1 wt % Jet-A solution of 430K
di-TA PB are significantly higher than those of the ester
prepolymer. Since the GPC results show the extent of backbone
crosslinking during removal of tert-butyl groups is negligible, it
is reasonable to say that the self-association of acid clusters
accounts for the increase in viscosities.
Example 7: Effect of End-to-End Donor Acceptor Association in
Exemplary Associative Polymers
[0226] A proof of the effect of end-to-end donor/acceptor
association is provided in FIG. 13 and FIG. 14. In particular FIG.
13, shows the superposition of GPC traces of the 430K octa chloro
PB and the corresponding octa tertiary amine PB.
[0227] In the illustration of FIG. 13, the polybutadiene backbone
is mainly intact after two end-functionalization reactions.
[0228] FIG. 14 shows the rheology data of 1 wt % Jet-A solutions of
430K di-TE PB, di-TA PB, di-TB PB, and 1:1 w/w di-TA PB/di-TB PB
mixture. In the illustration of FIG. 14, the 1:1 mixture shows
significantly higher viscosities than the other solutions. Since
none of the two polymer components are crosslinked, it suggests
that the end-to-end acid/base interaction results in the formation
of supramolecular species.
Example 8: Effect of an Exemplary Associative Polymer on Fuel
Compositions
[0229] Effect of di-TA PB synthesized according to Example 5, was
tested in Jet A fuel. In particular a composition comprising 0.5%
of di-TA PB with a backbone length of 264,000 g/mol (denoted 264K
di-TA PB) in jet A fuel has been provided as illustrated in FIG.
15.
[0230] In the illustration of FIG. 15 is shown that the exemplary
associative di-TA PB of Example 5 showed no phase separation and
was able to stay in solution (crystal clear) even at -30.degree. C.
for months (see FIG. 15A).
[0231] Additionally, dewatering operations appeared to occur as
quickly and completely in the composition with associative di-TA PB
of Example 5, as in the untreated host Jet A (see FIG. 15B left
vial v. right vial)
Example 9: High-Speed Impact/Flammability Test
[0232] To demonstrate the effect of exemplary polymers on the
mist-control of kerosene, a series of high-speed
impact/flammability test were conducted at California Institute of
Technology. The high-speed impact test is designed to simulate a
scenario in which fuels can be atomized into droplets due to
impact, whereas the continuously provided ignition sources are used
to obtain an indication of the flammability of resulting droplets.
The following samples were loaded into 50 ml aluminum cans, fixed
on a stage, and impacted by a 5 cm.times.3 cm steel cylinder
travelling at 200 km/hr (three continuously burning propane torches
were set up along the path of splashed samples): Jet-A, 0.35 wt %
Jet-A solutions of 4.2 M polyisobutylene (PIB) with and without
recirculation by a Bosch 69100 In-line turbine fuel pump for 1
minutes, 0.3 wt % of Jet-A solutions of 430K di-TA PB with and
without recirculation by a Bosch 69100 In-line turbine fuel pump
for 1 minutes. The results for each sample are described below:
Jet-A: Significant amount of fine droplets was generated upon
impact. The fine droplets travelling along the path of the
projectile were ignited by the burning torches within 50
milliseconds, and then evolved into a propagating fire ball.
[0233] 0.35 wt % Jet-A solution of 4.2M PIB, without shear: Large
droplets and filaments were generated by the impact. Sparkles were
observed as the fluid elements passed over the torches, but they
failed to propagate.
[0234] 0.35 wt % Jet-A solution of 4.2M PIB, with 1 min. of shear:
Fine droplets were generated by the impact. The fine droplets
travelling along the path of the projectile were ignited by the
burning torches within 50 milliseconds, and then evolved into a
propagating fire ball.
[0235] 0.3 wt % Jet-A solution of 430K di-TA PB, without shear:
Droplets were generated by the impact. Sparkles were observed as
the fluid elements passed over the torches, but they failed to
propagate.
[0236] 0.3 wt % Jet-A solution of 430K di-TA PB, with 1 min. of
shear: Droplets were generated by the impact. Sparkles were
observed as the fluid elements passed over the torches, but they
failed to propagate.
Example 10: Synthesis of Octa Functional CTAs
[0237] Reaction schemes for exemplary Octa functional CTAs in
accordance with the present disclosure are shown in the
illustration of FIG. 18 and FIG. 19.
Example 11: Exemplary Node to Chain and Node to FG Interactions
[0238] Exemplary pairs of reactive groups that are useful at end
positions such as R.sub.1 or R.sub.2 in the structure of formula
(III) or in di- or multi-valent crosslinkers and the product of
their reaction, which can be used for covalently linking a chain
and a FG, or linking chains to a node or attaching FG to a node in
accordance with the present disclosure, are shown in the
illustration of FIG. 20 and FIG. 21.
Example 12: Polymer-Composition Solubility Determination
[0239] Solubility of an exemplary polymer 1,4-polybutadiene (PB) in
a non-polar composition has been determined. The nonpolar
composition is kerosene, which can be considered to be a mixture of
hydrocarbons that contain 6-16 carbon atoms per molecule, the
v.sub.0 of octane (160 cm.sup.3/mol) can be chosen as a
representative value for kerosene.
[0240] Accordingly, when 1,4-polybutadiene (PB) is used as the
backbone of invented associative polymers, the value of
.delta..sub.1 is .about.8 (cal/cm.sup.3).sup.0.5 (see, e.g. [Ref 1,
15]). To evaluate .delta..sub.2 for kerosene, the following
relationship (dispersive Hansen parameter) can be used:
.delta.=9.55n.sub.D-5.55
where n.sub.D is the refractive index of the host, and n.sub.D can
be well-approximated by the square root of the dielectric constant
(.epsilon.) of the host. Given .epsilon..sub.kerosene is 1.8 at
20.degree. C., .delta..sub.2 is
.about.9.55.times.(1.8).sup.0.5-5.55=7.26.
[0241] Accordingly, the interaction parameter for the associative
polymer with a 1,4-polybutadiene backbone in kerosene at ambient
temperature can be estimated as follows:
.apprxeq. 0.34 + 1 .times. 6 .times. 0 1 . 9 .times. 8 .times. 7
.times. 2 .times. 9 .times. 8 . 1 .times. 5 .times. ( 8 - 7 . 2
.times. 6 ) 2 = 0 .times. .49 . ##EQU00005##
[0242] The calculated value of .chi. of 0.49 indicates that the PB
associative polymer with a 1,4-polybutadiene backbone would be
expected to be substantially soluble in a non-polar composition of
kerosene.
[0243] A skilled person can determine based on the above Example if
other associative polymer backbones would be substantially soluble
in other non-polar compositions by applying the same calculations
using the particular solubility parameters for the particular
non-polar composition.
Example 13: Drag Reduction Test
[0244] 0.2 grams of telechelic 1,4-PB of M.sub.w 630,000 g/mol,
terminated by 2 acid groups (denoted 630K di-DA PB) and 0.2 grams
of telechelic 1,4-PB of M.sub.w 540,000 g/mol, terminated by 2
tertiary amine groups (denoted 540K di-DB PB) were dissolved in
39.6 grams of Jet-A at room temperature over 16 hours.
[0245] The resulting 1 wt % Jet-A solution of 1:1 w/w 630K di-DA
PB/540K di-DB PB was further diluted with 1293 grams of Jet-A to a
concentration of 300 ppm (.about.0.1c* of the non-associative
backbone). A Bosch 69100 In-line turbine fuel pump with its outlet
connected to a piece of TYGON.RTM. tubing (inner diameter=6.34 mm;
length=40 cm) and inlet outlet connected to a piece of TYGON.RTM.
tubing (inner diameter=3.17 mm; length=2.14 m) was used to transfer
the fuel sample from its reservoir to a collecting jar over a
period of 20 seconds (FIG. 39).
[0246] The pump was primed with .about.200 mL of the sample before
the test. The collecting jar was weighed before and after the
transfer in order to determine the amount of fuel collected. The
same procedure was also performed on the unmodified host Jet-A. The
measured mass flow rate of unmodified Jet-A was 24.17 g/s, which
corresponded to a Reynolds number of 6458. As for the Jet-A sample
with 300 ppm of 1:1 donor/acceptor polymer pair, the measured mass
flow rate was 24.92 g/s. Hence, an increase of 3.2% in mass flow
rate was achieved, indicating that the presence of 1:1 (w/w)
mixture of 630K di-DA PB and 540K di-DB PB at 300 ppm in Jet-A
reduced the effect of turbulent drag on flow rate.
[0247] A skilled person will realize that the above test can be
applied to other associative polymers in order to determine the
extent of drag reduction.
Example 14: Detection of Rheological Properties of Solutions
[0248] The methods presented in Examples 2-5 to synthesize
telechelic 1,4-PBs with M.sub.w up to 430,000 g/mol capped at each
end with well-defined tert-butyl ester-terminated dendrons (FIG.
41) provides facile access to matched pairs of non-associative and
associative telechelic 1,4-PBs (FIG. 42). In this example, these
model polymers were used to study the relationship between
molecular properties (e.g., polymer molecular weight and the number
of carboxyl groups on chain ends) and association behavior,
particularly its effects on the rheological properties in solution.
The present study of the self-association behavior of
carboxyl-terminated telechelic 1,4-PBs provides a foundation for
comparative studies of complementary association illustrated in
FIG. 22.
[0249] The following materials and methods were used: Solvents
1-chlorododecane (CDD) and tetralin (TL) were both obtained from
Aldrich in 97% and 99% purity, respectively. All tert-butyl
ester-terminated telechelic 1,4-PBs and their corresponding
carboxyl-terminated telechelic 1,4-PBs were prepared as described
herein. Four values of the number of functional groups on polymer
chain ends, N, and three polymer backbone lengths (in terms of
M.sub.w by GPC-LS) were selected for the present study: A series of
polymers with approximately matched backbone length (nominally
220,000 g/mol) were prepared with N=1, 2, 4 and 8; and a series of
polymers with N=4 was prepared with three backbone lengths of
76,000, 230,000, and 430,000 g/mol. (Table 3.1). To simplify the
nomenclature of materials, polymer end-groups with N=1, 2, 4, and 8
tert-butyl ester groups are denoted ME, DE, TE, and OE (for mono-,
di-, tetra-, octa-ester end groups, respectively), respectively.
Similarly, polymer end-groups with N=1, 2, 4, and 8 carboxyl groups
are denoted MA, DA, TA, and OA (for mono-, di-, tetra-, octa-acid
end groups, respectively), respectively
[0250] Procedure for Sample Preparation: Solutions of tert-butyl
ester terminated polymers for viscosity measurements were prepared
by combining polymer and solvent in clean 20 mL scintillation vials
or larger 50 mL glass jars which were placed on a Wrist-Action
Shaker (Burrell Scientific) for up to 24 h to allow complete
homogenization.
[0251] Solutions of carboxyl-terminated polymers were prepared as
follows: To 150 to 200 mg of carboxyl-terminated polymer in a 50-mL
Schlenk flask was added necessary amount of solvent for 1 wt %
stock. The contents of the Schlenk flask were degassed by 3
freeze-pump-thaw cycles, and then stirred overnight at 70.degree.
C.
[0252] Viscosity Measurements: Steady shear viscosity was measured
in a cone-plate geometry (60 mm diameter aluminum, 1.degree. cone,
29 .mu.m truncation) using an AR1000 rheometer from TA Instruments
(temperature controlled at 25.degree. C.). Solutions of tert-butyl
ester terminated polymers were probed in the shear rate range 1-200
s.sup.-1 logarithmically (5 shear rates per decade). The range was
extended to 3000 s.sup.-1 for carboxyl-terminated polymers to
better capture shear-thinning behavior. All viscosity data were
reported in terms of specific viscosity (.eta..sub.sp,
.ident.(.eta..sub.solution-.eta..sub.solvent)/.eta..sub.solvent,
where .eta..sub.solvent=2.72 mPas for CDD and 2.02 mPas for TL at
25.degree. C.) which reflects the contribution of the polymer to
the viscosity [Ref 16].
Example 15: Dissolution Behavior
[0253] All six tert-butyl ester-terminated 1,4-PBs (Table 7) were
found readily soluble in both CDD and TL. With increasing carboxyl
content, it became more difficult to dissolve carboxyl-terminated
polymers: For N=1, the corresponding polymer (226K di-MA 1,4-PB)
was found soluble in both CDD and TL at room temperature; at N=2
and 4, the corresponding polymers (230K di-DA 1,4-PB; 76K, 230K,
and 430K di-TA 1,4-PBs) were not soluble in either model solvent at
room temperature, but they dissolved into CDD and TL when heated at
70.degree. C. and remained in solution thereafter. At N=8, the
polymer 207K di-OA 1,4-PB did not dissolve completely into either
solvent even when heated at elevated temperatures (>110.degree.
C.) overnight. The difficulty of dissolving 207K di-OA 1,4-PB is
not due to crosslinking: The polymer dissolves readily in THF, it
passes easily through filters, and GPC-LS analysis showed that 207K
di-OA 1,4-PB has a unimodal distribution similar to the other
polymers in the series of similar M.sub.w (near 220,000 g/mol; see
Table 7, which shows molecular weight (M.sub.w) and number of
chain-end functional groups (N) of tert-butyl ester- and
carboxyl-terminated telechelic 1,4-PBs).
TABLE-US-00008 TABLE 7.sup.a Nominal M.sub.w N 76 220 430 1 226
(1.4) 2 230 (1.5) 4 76 (1.5) 230 (1.4) 430 (1.5) 8 207 (1.5)
.sup.aGPC was performed for in THF for 35.degree. C. for the
tert-butyl ester form; results are shown for M.sub.w in kg/mol
followed by PDI in parentheses.
Example 16: Steady-Flow Shear Viscosity of 1 wt % Polymer
Solutions
[0254] Specific viscosity (.eta..sub.sp) of 1 wt % polymer
solutions averaged over shear rates from 10-100 s.sup.-1 show that
all solutions of carboxyl-terminated 1,4-PBs had higher
.eta..sub.sp than their tert-butyl ester-terminated (i.e.,
protected) counterparts, but the highest increase was observed in
the case of N=4 (FIG. 23). The lack of .eta..sub.sp data for
carboxyl-terminated 1,4-PB with N=8 is due to the poor solubility
of the polymer in both solvents. While .eta..sub.sp for all of the
non-associative .about.230K tert-butyl ester-terminated polymers
was the same, the deprotection of carboxyl groups on polymer chain
ends produced a threefold increase in specific viscosity in both
CDD and tetralin for N=4, whereas at N=1 and 2 only marginal
increases were observed after deprotection of carboxyl groups (FIG.
23). Thus, there appears to be a minimum number of carboxyl groups
on polymer chain ends to achieve the intermolecular association
suitable for viscosity modification (N>2) and a maximum number
imposed by the solubility limit (N<8). The effect of solvent
quality on .eta..sub.sp was also observed in FIG. 23. Increasing
the length of 1,4-PB backbone, for identical TA end groups (N=4)
increases the specific viscosity strongly (FIG. 23): In tetralin,
for the 76,000 g/mol polymer, deprotection of carboxyl groups only
increases the specific viscosity by 90%, whereas the increase is
more than 320% for the 430,000 g/mol polymer. For each polymer,
.eta..sub.sp of its 1 wt % tetralin solution was found nearly twice
as high as that of its 1 wt % 1-chlorododecane solution.
Example 17: Concentration Dependence of Specific Viscosity
[0255] While the values of .eta..sub.sp of three tert-butyl
ester-terminated polymers in both CDD and TL showed a nearly linear
dependence on polymer concentration, the CDD and TL solutions of
the three carboxyl-terminated polymers (76K, 230K and 430K di-TA
1,4-PBs) exhibited nonlinear increases of .eta..sub.sp with
concentration, and the extent of such non-linearity was found
positively correlated with the M.sub.w of polymer backbone (FIG.
24). In accord with the observation that associative polymers with
1 and 2 carboxyl groups at their ends have less effect on
viscosity, comparison of the three 230K carboxyl-terminated 1,4-PBs
with N=1, 2 and 4 shows that the non-linear increase of
.eta..sub.sp with polymer concentration was obvious only in the
case of N=4 (FIG. 25).
Example 18: Shear-Thinning Behavior of Solutions of
Carboxyl-Terminated Polymers
[0256] The onset and magnitude of shear-thinning can depend on the
molecular weight and concentration of polymer. Solutions of 76K
di-TA 1,4-PB showed negligible shear-thinning (up to 3000 s.sup.-1)
(in either CDD or TL, FIGS. 33 and 34, respectively). In the case
of 230K di-TA 1,4-PB, its CDD and TL solutions showed
shear-thinning at 1 wt %, with onsets in the range 10-100 s.sup.-1.
With decreasing concentration, the magnitude of shear thinning
decreased and the shear rate required to elicit it increased (e.g.,
relative to the 1 wt % solution, at 0.7 wt %, the extent of
shear-thinning observed in both CDD and TL was less significant and
the onset shifted to >100 s.sup.-1) (FIGS. 33 and 34). Similar
trends were observed for solutions of 430K di-TA 1,4-PBs, with
greater extent of shear-thinning and onset of shear-thinning at
lower shear rates compared to their 76K and 230K counterparts (in
both CDD and TL, FIGS. 33 and 34, respectively).
[0257] An interesting shear-thickening feature followed by further
shear-thinning was observed for 430K di-TA 1,4-PB at 1 wt % in CDD
and 0.7 wt % in TL (see FIGS. 26A and 26B). The shear-thickening
appeared at a higher shear rate in CDD than in TL (shear rates
between 250 and 1000 s.sup.-1 in FIG. 26, compared to 160 and 630
s.sup.-1 in FIG. 26B).
Example 19: .sup.1H NMR Study on Complementary End-Association in
Deuterated Chloroform
[0258] .sup.1H NMR spectroscopy has been widely used to study the
association of hydrogen-bonding-based hetero-complementary
associative motifs in non-polar deuterated solvents (e.g.,
CDCl.sub.3) because the resultant hydrogen bonds can cause
significant changes in electron environments surrounding protons
participating complementary associations; consequently, measurable
changes in chemical shifts of those protons can be observed as the
results of such complementary associations [Ref 17-23]. This
technique was adopted to investigate if the three pairs of
hetero-complementary associative groups (THY/DAAP, HR/CA, and
TA/TB) can perform complementary association in CDCl.sub.3 at room
temperature when attached to chain ends of 1,4-PB of
M.sub.w.about.10,000-50,000 g/mol, which was chosen to keep signals
of end-groups recognizable.
[0259] .sup.1H NMR Study of Hetero-Complementary End-Association.
.sup.1H NMR study of hetero-complementary end-association of
telechelic 1,4-PB chains was carried out at a total polymer
concentration of .about.1 wt % in deuterated chloroform
(CDCl.sub.3) at room temperature. .sup.1H NMR samples of individual
telechelic associative polymers were prepared by combining polymer
and CDCl.sub.3 at a polymer concentration .about.1 wt % in 20 mL
scintillation vials, which were placed on a Wrist-Action Shaker
(Burrell Scientific) for up to 16 h to allow the polymer to
completely dissolve. .sup.1H NMR samples of complementary polymer
pairs were prepared by mixing .about.1 wt % CDCl.sub.3 solutions of
their corresponding polymers in 20 mL scintillation vials in
desired end-group ratios, except for the 1:1 (w/w) mixture of 24K
di-TA/22K di-TB 1,4-PBs, of which the .sup.1H NMR sample was
prepared by combining the two polymers at a 1:1 weight ratio and
CDCl.sub.3 at a total polymer concentration .about.1 wt % in a 20
mL scintillation vial that was placed on a Wrist-Action Shaker
(Burrell Scientific) for 16 h at room temperature.
[0260] The investigation of hetero-complementary end-association by
.sup.1H NMR spectroscopy was carried out by measuring the .sup.1H
NMR spectra of individual telechelic associative polymers and those
of complementary polymer pairs, followed by comparing signals of
protons participating hetero-complementary end-association in
.sup.1H NMR spectra of individual polymer solutions to those of the
same protons in the spectra of corresponding polymer mixtures. Due
to the inherent detection limit of .sup.1H NMR spectroscopy, either
changes in chemical shifts or the disappearance of the signals of
protons participating hetero-complementary association of polymer
end-groups were followed as the evidence of end-association,
depending on the sizes of polymer backbones. For telechelic
associative polymers of M.sub.w.ltoreq.50,000 g/mol, characteristic
shifts of signals of associative end-groups were followed; for
those of M.sub.w .gtoreq.200,000 g/mol, the focus was whether the
mixing of complementary partners caused the disappearance of the
signals of protons participating hetero-complementary association
of polymer end-groups.
[0261] .sup.1H NMR spectra were obtained using a Varian Inova 500
spectrometer (500 MHz); all spectra were recorded in CDCl.sub.3,
acetone-d.sub.6, and DMSO-d.sub.6 at ambient temperature. Chemical
shifts were reported in parts per million (ppm, .delta.) and were
referenced to residual solvent resonances. Polymer molecular weight
measurements were carried out in tetrahydrofuran (THF) at
35.degree. C. eluting at 0.9 mL/min (pump: Shimadzu LC-20AD
Prominence HPLC Pump) through four PLgel 10-.mu.m analytical
columns (Polymer Labs, 10.sup.6 to 10.sup.3 .ANG. in pore size)
connected in series to a DAWN EOS multi-angle laser light
scattering (MALLS) detector (Wyatt Technology, Ar laser,
.lamda.=690 nm) and a Waters 410 differential refractometer
detector (.lamda.=930 nm).
[0262] The results of each pair are described as follows:
[0263] THY (thymine)/DAAP (diacetamidopyridine): FIG. 27 shows the
expanded .sup.1H NMR spectra (500 MHz, CDCl.sub.3) of 10K di-THY
1,4-PB 5, 10K di-DAAP 1,4-PB 14, and the mixture of 5 and 14 in a
1:2 wt ratio. In the absence of its complementary unit, the signal
of the imide proton of THY end groups was observed at 8.05 ppm
(FIG. 27). Upon addition of .about.2 eq of DAAP end groups, a large
downfield shift to 11.05 ppm accompanied by signal broadening was
observed (FIG. 27). Similar shift was also observed for the signal
of the amide protons of DAAP end groups (from 7.58 to 8.42 ppm, (b)
and (c) in FIG. 27). The observed association-induced shift
(.about.2.9 ppm) of the imide proton signal of THY end groups is in
good agreement with the literature [Ref 18, 19, 21], and it
indicates that THY and DAAP end groups could find and associate
with each other in CDCl.sub.3.
[0264] HR (Hamilton receptor)/CA (cyanuric acid): FIG. 28 shows the
expanded .sup.1H NMR spectra (500 MHz, CDCl.sub.3) of 50K di-CA
1,4-PB, 24K di-HR 1,4-PB, and the mixture of 50K di-CA 1,4-PB and
24K di-HR 1,4-PB in a 1:1.4 wt ratio. In the absence of its
complementary unit, the signal of the imide protons of the CA end
group was observed at 7.75 ppm (FIG. 28). A very large downfield
shift to 12.90 ppm accompanied by peak broadening was observed
(FIG. 28) as .about.2 eq of HR end groups were added. Similar to
the case of THY/DAAP pair, the observed association-induced shift
(.about.5.2 ppm) of the signal of the imide protons of CA units
indicates that CA and HR end groups could also find and associate
with each other in CDCl.sub.3. The magnitude of the observed shift
is in good agreement with the literature [Ref 24-29].
[0265] TA/TB: Due to the fact that 24K di-TA 1,4-PB is not soluble
in CDCl.sub.3, .sup.1H NMR study was only performed on 22K di-TB
1,4-PB and its 1:1 (w/w) mixture with 24K di-TA 1,4-PB and
monitored the association by tracking the shifts of the signals of
the tertiary amine end group (H.sub.1 and H.sub.2, see FIG. 29).
The results are shown in FIG. 29. It was found that the presence of
22K di-TB 1,4-PB assisted the dissolution of 24K di-TA 1,4-PB in
CDCl.sub.3 and thus rendered the .sup.1H NMR experiment possible.
The signals of H.sub.1 and H.sub.2 were observed at 2.28 and 3.60
ppm respectively in the absence of 24K di-TA 1,4-PB (FIG. 29). The
addition of 24K di-TA 1,4-PB resulted in shifts of both signals:
The signals of H.sub.1 and H.sub.2 shifted from 2.28 and 3.60 to
2.46 and 3.85 ppm, respectively. The observed shifts indicate the
association of TA and TB end groups.
[0266] In order to determine if the three pairs of complementary
associative groups were still effective when attached to chain ends
of 1,4-PBs of M.sub.w.about.200,000-300,000 g/mol, .sup.1H NMR
analysis of the corresponding polymers and the complementary pairs
was performed at .about.1 wt % in CDCl.sub.3 at room temperature.
It was found that in this case, signals of polymer end groups were
barely recognizable due to their low contents in the test samples.
In addition, association-induced signal broadening could cause
signals of protons involved in complementary association to appear
vanished. Nevertheless, evidence of end-association was observed in
all three pairs of telechelic associative polymers of
M.sub.w.about.200,000 g/mol. In the case of the THY/DAAP pair, the
signal of the imide proton of THY end group of 288K di-THY 1,4-PB
was observed at 8.05 ppm with a very low intensity (FIG. 30), and
it was found disappeared in the .sup.1H NMR spectrum of the 1:2
(w/w) mixture of 288K di-THY and 219K di-DAAP 1,4-PBs. The
disappearance of the signal indicates that THY and DAAP end groups
could find and bind with each other in CDCl.sub.3, even when
attached to chain ends of polymers of M.sub.w.about.200,000 g/mol.
Likewise, the signal of imide protons of the CA end groups of 200K
di-CA 1.4-PB, along with those of the amide protons of the HR end
groups of 240K di-HR 1,4-PB, were not observable in the .sup.1H NMR
spectrum of the 1:1 (w/w) mixture of 200K di-CA and 240K di-HR
1,4-PBs (FIG. 31). Signals of the TB end groups of 250K di-TB
1,4-PB were also found disappeared after the polymer was mixed with
230K di-TA 1,4-PB in a 1:1 wt ratio (FIG. 32). These results
suggest that all three complementary associative pairs can provide
sufficient strength of end-association for telechelic 1,4-PB chains
of M.sub.w.about.200,000 g/mol to form supramolecular aggregates
stable at least on the time scale of .sup.1H NMR spectroscopy.
Example 20: Shear Viscometric Study of Complementary
End-Association
[0267] Shear viscometry was used as a complementary measure of
.sup.1H NMR study to evaluate the strength of hetero-complementary
pairs. 1-Chlorododecane (CDD) was chosen as the solvent due to its
low interference with hydrogen bonding, low volatility at room
temperature, high solvency for 1,4-PB backbones, and being a pure
solvent. For all of the four hetero-complementary pairs (THY/DAAP,
HR/CA, DA/DB, and TA/TB), telechelic polymers of
M.sub.w.about.200,000 g/mol were used. In addition to CDD, dodecane
and Jet-A were also used in shear viscometric study of THY/DAAP and
HR/CA pairs, respectively. Except for di-DA and di-TA 1,4-PBs,
polymer solutions in 1-chlorododecane were prepared by combining
polymer and solvent at a weight fraction of polymer=1 wt % in clean
20 mL scintillation vials, which were placed on a Wrist-Action
Shaker (Burrell Scientific) at room temperature for up to 16 h to
allow complete dissolution of polymers. 1 wt % CDD solutions of
di-DA and di-TA 1,4-PBs of M.sub.w.about.200,000 g/mol were
prepared according to the procedure described in Examples 2-5. For
each hetero-complementary associative pair, 1 wt % solutions of
polymer mixture were prepared by mixing 1 wt % solutions of the
individual polymers in desired weight ratios in 20 mL scintillation
vials at room temperature. Shear viscosity of polymer solutions
were measured according to the procedure described herein (see,
e.g. Examples 16-17).
[0268] Steady-flow shear viscometry at 25.degree. C. was used in
parallel with .sup.1H NMR spectroscopy to investigate the ability
of OHB-based and CAHB-based hetero-complementary associative pairs
to afford supramolecular aggregates of telechelic 1,4-PBs of
M.sub.w.gtoreq.200,000 g/mol that are stable enough at low-moderate
shear rates to provide modulation of rheological properties. In
other words, it is expected that at the same concentrations, the
solution of complementary polymer pair would be more viscous than
those of individual components. To avoid possible complications
arising from the multi-component nature of fuels, 1-chlorododecane
(CDD) was chose as the model solvent, and prepared all polymer
solutions at 1 wt % in CDD. In both THY/DAAP and HR/CA
complementary polymer pairs, none of them showed the expected
enhancement in shear viscosity due to complementary end-association
(FIGS. 43 and 44). To find out if the comparatively polar CDD
(dielectric constant=4.2 at 25.degree. C.) interferes with THY/DAAP
and HR/CA complementary interactions, the experiments were repeated
in less polar solvents: Dodecane (dielectric constant=2.0 at
20.degree. C.) and Jet-A (dielectric constant=1.8 at 20.degree. C.)
were used for THY/DAAP pair and HR/CA pair, respectively. As shown
in FIGS. 43 and 44, the expected enhancement in shear viscosity was
still absent in both cases when less polar solvents were used.
[0269] Different results were observed in the case of TA/TB pair.
The 1:1 (w/w) mixture of 1 wt % CDD solutions of 230K di-TA and
250K di-TB 1,4-PBs was found considerably more viscous than both
solutions (FIG. 33), and the observed enhancement in viscosity
illustrated that the strength of TA/TB complementary
end-association was sufficient to drive the formation of
supramolecules stable at shear rates investigated in the present
study. As discussed in above, strong self-association of 230K di-TA
1,4-PB resulted in significant difference in shear viscosity
between the 1 wt % CDD solution of 230K di-TA 1,4-PB and that of
the non-associative pre-polymer 230K di-TE 1,4-PB (FIG. 33). It was
observed that the addition of equal amount (by weight) of 250K
di-TB 1,4-PB further enhanced the shear viscosity. What is also
worth noting is the shear-thinning behavior observed in the 1 wt %
CDD solution of 1:1 mixture of 230K di-TA and 250K di-TB 1,4-PBs,
which is a feature shared by aqueous solutions of water-soluble
telechelic associative polymers [Ref 30-33]. As for the 1 wt % CDD
solution of 250K di-TB 1,4-PB, even though GPC-LS analysis
confirmed no crosslinking of polymer backbone took place during
end-functionalization with tertiary amine groups, it was found that
it was more viscous than that of the non-associative 230K di-TE
1,4-PB. Aggregation of triazole units resulting from the
end-functionalization reaction (FIG. 45) may contribute to the
above difference in shear viscosity [Ref 34].
[0270] With the positive results of the pair of 230K di-TA/250K
di-TB 1,4-PBs, the viscometric study was extended further to the
complementary DA/DB association as an attempt to approach the limit
of the strength of carboxyl/tertiary amine association. FIG. 34
shows the results of 1 wt % CDD solutions of the corresponding
polymers (230K di-DE, 230K di-DA, and 250K di-DB 1,4-PBs) and the
1:1 (w/w) DA/DB mixture. Surprisingly, strong enhancement in shear
viscosity induced by complementary DA/DB association was still
observed in the 1:1 mixture. While only insignificant difference in
shear viscosity was observed between the 1 wt % CDD solution of
230K di-DA 1,4-PB and that of the non-associative 230K di-DE
1,4-PB, the considerable increase in viscosity due to DA/DB
complementary end-association reaffirmed the promising strength of
carboxyl/tertiary amine interaction.
[0271] The final part of the shear viscometric study of
carboxyl/tertiary amine pairs was to investigate if the TA/TB
complementary end-association was effective in Jet-A when the
M.sub.w of the 1,4-PB backbone increased to 430,000 g/mol, and the
results are shown in FIG. 35. Strong enhancement in shear viscosity
due to TA/TB complementary association was observed: At 1 wt %, the
1:1 mixture of 430K di-TA and 430K di-TB 1,4-PBs in Jet-A was found
significantly more viscous than the Jet-A solutions of the
individual polymers. These results indicate that when used in
dendritic configurations, carboxyl/tertiary amine pair is suitable
for building complementary pairs of telechelic associative polymers
as mist-control additives for fuels.
Example 21: A.1 Measurements of Polymer Molecular Weights
[0272] The determination of molecular weight and molecular weight
distribution is of central interest in polymer analysis, as the
molecular weight of a polymer directly relates to its physical
properties. [Ref 35] Take telechelic associative polymers as
mist-control additives for kerosene for example, their efficacy in
providing fire protection and resistance to shear degradation rely
on proper choice of backbone length, which falls in the range
M.sub.w=5.times.10.sup.5-10.sup.6 g/mol. Table 8, which shows
molecular weight measurement methods, summarizes common
characterization methods for determining different average
molecular weights (MWs) and molecular weight distributions (MWDs)
of polymers [Ref 16, 35, 36].
TABLE-US-00009 TABLE 8 Abso- Rela- Method lute tive M.sub.n M.sub.w
Range (g/mol) Proton NMR end-group x x M.sub.n < 2.5 .times.
10.sup.4 analysis Vapor pressure x x M.sub.n < 3 .times.
10.sup.4 osmometry Ebulliometry x x M.sub.n < 3 .times. 10.sup.4
Light Scattering (LS) x x 10.sup.4 < M.sub.w < 10.sup.7
Intrinsic Viscosity x M < 10.sup.6 GPC.sup.a with concen- x x x
10.sup.3 < M.sub.w < 10.sup.7 tration detectors GPC.sup.a
with concen- x x x 10.sup.4 < M.sub.w < 10.sup.7 tration and
LS detectors MALDI-TOF-MS.sup.b x x x M < 3 .times. 10.sup.4
.sup.aGPC, gel permeation chromatography. .sup.bMALDI-TOF-MS,
matrix-assisted laser desorption/ionization time-of-flight mass
spectroscopy
[0273] Among the methods in Table 8, GPC with concentration and LS
(light scattering) detectors (referred to as "GPC-LS" herein) was
chosen in the present study for determining MW and the MWD of
telechelic associative 1,4-PBs due to the following reasons: (1) it
allows measurements of absolute weight-average MWs and
corresponding MWDs; (2) it has a wide applicable range
(10.sup.4-10.sup.7 g/mol) which covers the MW range of interest
(5.times.10.sup.5-10.sup.6 g/mol) for mist-control applications;
(3) it is comparatively easy to implement. Although MALDI-TOF-MS is
capable of measuring absolute MWs and MWDs of polymers with more
accuracy than GPC-LS, it is not as useful in analyzing polymers of
MW >30,000 g/mol [Ref 37]; selection of matrix compounds, sample
preparation and interpretation of the mass spectra become difficult
in the case of synthetic polymers of MW >30,000 g/mol and thus
detract from the benefits associated with the unrivalled accuracy
provided by MALDI-TOF-MS [Ref 35, 36, 38]. Given that many
associative polymers as herein described are telechelic 1,4-PBs of
MW >>30,000 g/mol, it is clear that GPC-LS can be a better
option to measure MWs than MALDI-TOF-MS in the present study. The
same rationale also applies to the other competing method, proton
NMR end-group analysis, which has been widely used in determining
number-average MWs (i.e., M.sub.n) of synthetic polymers via
comparing the integration values of signals of backbone protons to
those of the end-group protons [Ref 35, 39, 40]. The implementation
of proton NMR end-group analysis can be straightforward: the
M.sub.n value of a polymer can be derived from its .sup.1H NMR
spectrum without any additional experimental work. However, the
determination of M.sub.n by proton NMR end-group analysis for
polymers of MW >25,000 g/mol loses its accuracy due to a
diminished resolution resulting from the inherent detection limit
of proton NMR spectroscopy, and the uncertainty in the M.sub.n
values becomes greater for polymers of higher MWs [Ref 35]. The
other issue of this method is that it lacks the ability to measure
molecular weight distributions (MWDs) of polymers. These
shortcomings render proton NMR end-group analysis a less effective
method to characterize high-MW (i.e., MW >100,000 g/mol)
telechelic 1,4-PBs as potential mist-control additives for
kerosene.
[0274] In the case that associative groups are attached onto the
chain ends of telechelic 1,4-PBs, measuring of MWs and MWDs of such
polymers by GPC-LS becomes challenging, since the associative chain
ends could possibly interact with the column packing, or drive the
formation of supramolecular aggregates in THF, leading to false
reading of MWs and MWDs. It was found that compared to the
non-associative 230K di-TE 1,4-PB, the apparent M.sub.w of 230K
di-TA 1,4-PB was found to be higher by 63% (see Table 9, which
shows molecular weight and PDI (polydispersity index) data of
tert-butyl ester- and carboxyl-terminated telechelic 1,4-PBs, and
FIG. 23).
TABLE-US-00010 TABLE 9 N = 1 N = 2 N = 4 N = 8 N = 4 Before TFA
M.sub.w 226 230 230 207 430 Hydrolysis (kg/mol).sup.a PDI.sup.b
1.43 1.53 1.50 1.43 1.49 After TFA M.sub.w 276 299 375 304 510
Hydrolysis (kg/mol).sup.a PDI 1.56 1.73 1.72 1.51 1.61 Increase in
22.12 30.00 63.04 46.86 18.60 M.sub.w (%) .sup.a,bdetermined by
GPC-LS
[0275] It was hypothesized that the apparent increase in M.sub.w
resulted from the aggregate of associative TA end groups in THF,
rather than crosslinking of 1,4-PB backbone during TFA hydrolysis
of tert-butyl ester groups. To test the hypothesis, 230K di-TA
1,4-PB was treated with LiAlH.sub.4 in THF so as to reduce the
highly associative carboxyl groups to less associative hydroxyl
groups. The GPC-LS result of the resultant hydroxyl-terminated 230K
telechelic 1,4-PB, as shown in FIG. 36, virtually overlaps with
that of 230K di-TE 1,4-PB, although the former seems slightly
broadened compared to the latter. Comparison of the three GPC-LS
traces in FIG. 36 verified the hypothesis: the apparent increase in
M.sub.w after TFA hydrolysis of 230K di-TE 1,4-PB was due to
aggregation of associative TA end groups, since the increase in
M.sub.w disappeared after the carboxyl groups on polymer chain ends
were reduced to hydroxyl groups. It also suggests that the mild
condition of TFA hydrolysis does not cause appreciable amount of
crosslinking of 1,4-PB backbone. As for the broadening of GPC-LS
trace of hydroxyl-terminated 230K telechelic 1,4-PB, it is thought
to result from interaction of hydroxyl-terminated chain ends with
column packing. The results in FIG. 36 also reveal the importance
of interpreting GPC-LS results of telechelic associative polymers
with scrutiny, since association of chain ends and chain-end/column
interaction can both result in false reading of MWs and MWDs. In
other words, using the non-associative forms of telechelic
associative polymers in GPC-LS analysis yields more accurate
information concerning the MWs and MWDs of polymer backbones on the
condition that the transformation of associative chain ends to
non-associative counterparts does not damage the backbones.
Example 22: Effect of COD Purity on the Proceeding of ROMP with
CTAs
[0276] It was found that the purity of VCH
(4-vinylcyclohexene)-free COD has a profound effect on the
synthesis of telechelic 1,4-1,4-PBs via ROMP of COD using Grubbs
II: peroxides and n-butanol (introduced during BH.sub.3.THF
treatment of COD according to the Macosko protocol) can also
adversely affect the metathetical activity of Grubbs II by reacting
with it and irreversibly transforming it into inactive species. In
response to the issues associated with peroxides and n-butanol, a
multi-stage process (Section 2.2.3) was developed to rigorously
purify COD.
[0277] In particular, in an exemplary purification procedure,
redistilled cis,cis-1,5-cyclooctadiene (COD, 72.3 g, 0.67 mol) was
syringe-transferred to a 250 ml Schlenk flask in an ice bath at
0.degree. C. under argon atmosphere. Under argon flow, 1M
borane-THF complex in THF (BH.sub.3.THF, 108 mL, 0.11 mol) was then
slowly added into the flask over a 10-min period. The flask was
taken out of the ice bath, and left to stir under argon atmosphere
at room temperature for 2 h. THF was evaporated under reduced
pressure at room temperature to an extent that the concentration of
residual THF in the mixture was below 300 ppm (verified by .sup.1H
NMR analysis). The monomer was vacuum distilled from the mixture at
40.degree. C., 100 mTorr into a 100 mL Schlenk flask (loaded with 9
g of MAGNESOL.RTM. xl and a magnetic stir bar) in a dry-ice tub.
The mixture was stirred under argon atmosphere at room temperature
overnight. The monomer was vacuum distilled again at 45.degree. C.
and 100 mTorr from the mixture into a 100 mL Schlenk flask (loaded
with 10 g of calcium hydride (CaH.sub.2) and a stir bar) in a
dry-ice tub in order to remove moisture introduced by MAGNESOL.RTM.
xl. After stirring at room temperature for 3 h under argon flow,
the monomer was once again vacuum distilled (45.degree. C., 100
mTorr) from the mixture into a 100 mL Schlenk flask in a dry-ice
tub. After warmed to ambient temperature, the flask was sealed with
a SUBA-SEAL.RTM. rubber septum while argon stream was flowing, and
placed in a freezer at -30.degree. C. for storage of purified COD
(40.0 g, 55.3% yield). The purified monomer was vacuum-distilled
again at 35.degree. C. prior to use.
[0278] To illustrate the influence of the purity of VCH-free COD on
the preparation of telechelic 1,4-PBs via ROMP of COD, the
synthesis of di-TE 1,4-PB via the two-stage ROMP of COD with
octa-functional tert-butyl ester-terminated bis-dendritic CTA
(compound 8 in FIG. 46B) was chosen as the benchmark reaction (FIG.
37). Two different batches of VCH-free COD were prepared: the first
(i.e., the control, COD I) was afforded via purification according
to only the Macosko protocol, whereas the second one (COD II) was
prepared according to the purification procedure described above.
The implementation of two-stage ROMP using both batches of COD was
the same as the purification procedure described above, in which
the total monomer:CTA ratio was 2000:1, and 100 eq of COD was used
in the first stage of ROMP; the load of Grubbs II was 1/30 eq of
the CTA. Here the following properties to quantitate the effect of
the purity of COD were chosen: (1) the period of time during which
the reaction mixture develops enough viscosity to stop the magnetic
stir bar from moving after the addition of 1900 eq of COD (t.sub.v)
(2) the overall conversion of COD (X.sub.f, measured by .sup.1H NMR
analysis of the aliquot of reaction mixture) (3) the cis/trans
ratio of the polymeric species in the aliquot (measure by .sup.1H
NMR analysis) (4) M.sub.w of the resultant polymer (measured by
GPC-LS). The results for COD I and COD II were summarized in Table
10, which shows the results of synthesis of di-TE 1,4-PB via ROMP
of batch 1 and batch 2 VCH-free COD.
TABLE-US-00011 TABLE 10 COD I COD II t.sub.v(min) 40.0 1.5 X.sub.f
(mol %) 85.0 97.6 cis/trans ratio 2.20 1.73 M.sub.w (kg/mol) 264
142 PDI 1.58 1.43
[0279] Table 10 shows that the second stage of ROMP of COD II
proceeded significantly faster (t.sub.v=1.5 min) compared to that
of COD I (t.sub.v=40 min); the conversion of COD II was nearly
quantitative (X.sub.f=97.6%), whereas the reaction stopped at
X.sub.f=85% in the case of COD I. In addition, .sup.1H NMR analysis
of aliquots taken in the end of polymerization reactions also
revealed that the use of COD II led to a lower cis/trans ratio
(1.73) compared to the case of COD I (2.20). The M.sub.w of the
resultant polymer of ROMP of COD II (142,000 g/mol), as revealed by
GPC-LS analysis, was found significantly lower than that of ROMP of
COD I (264,000 g/mol). When considered as a whole, these results
indicate that Grubbs II possesses a higher metathetical activity
(or a higher turnover number) when impurities in VCH-free COD that
can interfere with Grubbs II are removed. This explains the much
faster reaction rate of the second stage of ROMP of COD II.
Similarly, Grubbs II in the presence of COD II can perform more
cycles of metathesis reactions compared to in COD I, and thus a
nearly quantitative X.sub.f=97.6% was achieved in the case of COD
II. The low cis/trans ratio (1.73) and M.sub.w (142,000 g/mol)
resulting from ROMP of COD II suggest that a considerable fraction
of ruthenium complexes on polymer chain ends remained
metathetically active when COD II was mostly consumed, and as a
result they continued to react with available C.dbd.C bonds present
in the reaction mixture (in this case, C.dbd.C on polymer
backbones) till they reached their maximum turnover number. The
consumption of backbone by active ruthenium centers on chain ends
(i.e., back-biting) led to the decreases in cis/trans ratio and
M.sub.w.
[0280] In sum, the enhanced activity of Grubbs II observed above
validates the multi-stage purification procedure of COD described
above.
Example 23: Example of Controlling Drag Reduction
[0281] In some embodiments, the associative polymers described
herein can be used to provide a composition in which the property
controlled is drag reduction. In particular, using the methods
described herein, the composition can have a more than 10%
reduction in the pressure drop required to drive a given volumetric
flow rate through a given pipeline.
[0282] In particular, a skilled person can identify the non-polar
host to be transported in which the drag is desired to be
reduced.
[0283] The skilled person can then use published solubility
parameters to estimate the solubility parameter of the identified
non-polar host, or in the alternative, the skilled person can use
literature on polymer solubility in similar liquids, and use this
information to identify polymers that would be expected to dissolve
in the non-polar host, for use as backbones of the associative
polymers. The solubility can be confirmed by the skilled person by
using techniques identifiable to the skilled person, for example by
dissolving a sample of the polymer in the host and determining if
it is homogeneous (e.g., by performing light-scattering
measurements).
[0284] The skilled person can then use published dielectric
constants to estimate the dielectric constant of the host liquid,
and determine the kind of associative interaction of the FGs would
be most suitable. For example, if the dielectric constant is less
than or approximately 2, there are a wide range of suitable
associative groups, including ordinary hydrogen bonding moieties
(e.g. Hamilton receptor/cyanuric acid pairs,
thymine/diacetamidopyridine pairs, and other identifiable to a
skilled person) and charge transfer complexing moieties (e.g.
dinitrophenyl/carbazole pairs and other identifiable to a skilled
person). As the dielectric constant increases, the range of viable
associative moieties decreases. For example, in chlorododecane
(dielectric constant of 4.2 at 25.degree. C.), charge-assisted
hydrogen bonding moieties perform better than ordinary
hydrogen-bond moieties. If there are organic acids (such as,
Butyric acid, isobutyric acid, valeric acid, isovaleric acid,
Heptanoic acid, and others identifiable to a skilled person) or
organic bases (trimethylamine, diethylamine, diisopropylamine,
Triethylamine, Diisobutylamine, diisoamylamine, diphenylamine, and
others identifiable to a skilled person) present in the host
composition, ionic interactions or ligand-metal interactions (a
type of Bronsted/Lewis acid/base interaction) can be more suitable
than charge-assisted hydrogen bond association. Therefore, some
additional optimization can be performed as described below.
[0285] The additional optimization can be performed by preparing
several telechelic polymers with backbone degree of polymerization
of at least 200 and with candidate associative groups at their ends
(e.g. ordinary hydrogen bonding moieties and/or charge transfer
complexing moieties), and dissolving them in the host liquid using
polymer concentration approximately equal to the overlap
concentration for the backbone polymer and length used in the trial
polymers (e.g., by calculating c* as described herein). The
polymers that do not dissolve can be identified, and their
corresponding associative end groups can be designated as being
unsuitable, to thereby identify the suitable associative groups. If
the viscosity of the non-polar composition is not greater than it
would be for a solution of a non-associative polymer of the same
backbone, length and concentration, the associative end groups can
be modified by increasing the number of associative moieties in
each group (i.e., increase the strength of association using
polyvalent interactions).
[0286] Using one or more of the combinations of polymer backbone
structure and end-group structure identified above, the skilled
person can then estimate the backbone length that is compatible
with a desirable or acceptable polymer concentration in the host.
For example, if the backbone is determined to be polybutadiene, and
the associative polymer concentration needs to be kept down to 0.8%
or less (the "x" marked on the vertical axis of FIG. 40), then the
minimum polybutadiene backbone can be read off a graph of the
relationship between the overlap concentration and the
weight-average molecular weight (as shown by the horizontal line
from the "x" on the vertical axis to the corresponding point on the
c* vs M.sub.w relationship for polybutadiene and the vertical line
from that point down to the horizontal axis in FIG. 40), leading to
a value of M.sub.w of about 400,000 g/mol.
[0287] A skilled person can then use experiments to refine the
choice of backbone, backbone length, and FGs by preparing candidate
polymers with the most promising backbone, backbone length, and
FGs, then subjecting them to a limited set of experiments to
validate their performance in both reducing turbulent drag (e.g.,
measuring the flow rate of the non-polar composition though a
conduit, or measuring the change in pressure of the non-polar
composition flowing through a conduit) and, if desired, resisting
degradation due to turbulent flow (e.g. by measuring changes in
viscosity of the non-polar composition after transportation through
a conduit). If the required concentration is found by the skilled
person to be too high (e.g. the amount of polymer required would be
too costly), then the skilled person can prepare another polymer
with the same, but longer, backbone and repeat the process until
the polymer shows efficacy at an acceptably low concentration. This
exemplary procedure is expected to give a drag reduction in
turbulent pipe flow of at least 10%. If the extent of drag
reduction is less than 30%, the skilled person can improve drag
reduction up to 30% by increasing the strength of association, for
example by increasing the number of associative moieties per
associative group (e.g., using end groups with four carboxyl groups
rather than two) or by using a stronger type of association (e.g.,
using charge-assisted hydrogen bonding--that is, a hydrogen bond
formed between a hydrogen bond donor and hydrogen bond acceptor
where the hydrogen bond donor is more acidic than the conjugate
acid of the hydrogen bond acceptor by at least about 4 pKa
units-rather than ordinary hydrogen bonding--that is, a hydrogen
bond formed between a hydrogen bond donor and hydrogen bond
acceptor where the hydrogen bond donor is less acidic than the
conjugate acid of the hydrogen bond acceptor).
Example 24: Use of Associative Polymers in a Fuel in an Engine
while Maintaining Engine Performance
[0288] In this example, an exemplary self-associative polymers were
incorporated in fuel at a level that is appropriate for drag
reduction and/or mist control for improved fire safety. 430K di-TA
PB was selected as the test polymer along with diesel as the base
fuel; a polymer concentration of 0.1 wt % in diesel was
subsequently chosen. A concentrated 1 wt % stock solution of the
exemplary associative polymer was prepared by mixing the polymer
with diesel under oxygen-free condition at 120.degree. C. for 12
hours, and two identical 0.1 wt % diesel solutions of the polymer
with a volume of 1.3 liters were prepared by diluting the 1 wt %
stock solution with the same base fuel at room temperature. Test
samples comprised the two 0.1 wt % solutions and two 1.3-liter
bottles of unmodified base fuel as controls. A 3.75 kW diesel
generator connected to a Simplex Swift-e load bank and a Fluke 434
Series II Energy Analyzer was used as the test apparatus, and the
tests were performed at the Vehicle Emission Research Laboratory
(VERL) of the Center for Environmental Research & Technology
(CE-CERT), University of California at Riverside. A sequence of
generator load/operating time comprising the following stages was
used to carry out the tests: 2000 Watts (.about.53% of its rated
power)/9 min, 3000 Watts (.about.80% of the rated power)/9 min,
3500 Watts (.about.93% of the rated power)/6 min, 3000 Watts/9 min,
and 2000 Watts/9 min. Between samples the fuel supply to the engine
was switched to a reservoir filled with the reference fuel (the
same diesel fuel that was used to prepare the samples with
inventive polymer) to keep the generator operating. The AC output
from the generator was recorded continuously by the Energy
Analyzer, and the emissions were analyzed using gas analysis of an
isothermal stream of precisely calibrated dilution of the exhaust
gas; quantitative values for carbon dioxide (CO.sub.2), carbon
monoxide (CO), mono-nitrogen oxide (NO.sub.x), methane (CH.sub.4)
and total hydrocarbons (THC) were continuously monitored. Samples
were run in a blind randomized sequence and the results were
quantitatively analyzed prior to unmasking the sample
identification. The results show no decrease in power output at any
of the three loads to within the uncertainty of the power
measurement. The results showed no adverse effects on engine
emissions (Table 11). For the composition used in this example, it
was not possible to identify the time at which the fuel supply to
the engine was switched between the reference fuel, since none of
the measured quantities changed at or near the time the valve was
switched. The emissions of CO and THC were reduced (11), while the
power output was the same (to within the uncertainty of the
measurement) as for untreated diesel.
TABLE-US-00012 TABLE 11 % change Condition A #29.sup.a CO.sub.2
Sample-Diesel 2 kW 2.03 Sample-Diesel 3 kW -0.09 Sample-Diesel 3.5
kW 0.43 Sample-Diesel 3 kW 1.56 Sample-Diesel 2 kW 1.46 CO
Sample-Diesel 2 kW 5.63 Sample-Diesel 3 kW -4.34 Sample-Diesel 3.5
kW -10.20 Sample-Diesel 3 kW -1.93 Sample-Diesel 2 kW 8.87 THC
Sample-Diesel 2 kW -15.54 Sample-Diesel 3 kW -13.04 Sample-Diesel
3.5 kW -11.54 Sample-Diesel 3 kW -8.73 Sample-Diesel 2 kW -0.68
NO.sub.x Sample-Diesel 2 kW 4.30 Sample-Diesel 3 kW 2.81
Sample-Diesel 3.5 kW 3.76 Sample-Diesel 3 kW 4.13 Sample-Diesel 2
kW 5.96 .sup.aA#29 is diesel treated with 0.1 wt % di-TA PB
Example 25: Reduction of Emissions in Fuels Comprising Associative
Polymers
[0289] In this example, exemplary donor-acceptor polymers are
incorporated in fuel at a level that is appropriate for drag
reduction and/or mist control for improved fire safety, with the
additional benefit that emissions from the engine are reduced. A
1:1 (w/w) mixture of 630K di-DA PB and 540K di-DB PB was selected
as an exemplary donor-acceptor polymer pair along with diesel as
the base fuel; a total polymer concentration of 0.1 wt % in diesel
was subsequently chosen. A concentrated 1 wt % stock solution of
the donor-acceptor pair was prepared by mixing the pair with diesel
at room temperature for 12 hours and at 70.degree. C. for 7 hours,
and two identical 0.1 wt % diesel solutions of the pair with a
volume of 1.3 liters were prepared by diluting the 1 wt % stock
solution with the same base fuel at room temperature. Test samples
comprised the two 0.1 wt % solutions and two 1.3-liter bottles of
unmodified base fuel as controls. The Same apparatuses, procedures,
and characterizations described in Example 24 were used in this
example. Samples were run in a blind randomized sequence and the
results were quantitatively analyzed prior to unmasking the sample
identification. The results showed no decrease in power output at
any of the three loads to within the uncertainty of the power
measurement. For the composition used in this example, the
emissions of CO and THC were reduced (Table 12), while the power
output was the same (to within the uncertainty of the measurement)
as for untreated diesel.
TABLE-US-00013 TABLE 12 % change Condition AB #90.sup.a AB #8.sup.a
AB averaged CO.sub.2 Sample-Diesel 2 kW 0.68 0.95 0.81
Sample-Diesel 3 kW -1.74 1.40 -0.17 Sample-Diesel 3.5 kW 0.71 0.92
0.82 Sample-Diesel 3 kW 0.19 -0.43 -0.12 Sample-Diesel 2 kW 0.09
1.09 0.59 CO Sample-Diesel 2 kW -13.89 -10.99 -12.44 Sample-Diesel
3 kW -15.81 -12.52 -14.16 Sample-Diesel 3.5 kW -14.36 -16.31 -15.33
Sample-Diesel 3 kW -10.79 -14.91 -12.85 Sample-Diesel 2 kW -11.79
-12.49 -12.14 THC Sample-Diesel 2 kW -25.12 -23.83 -24.47
Sample-Diesel 3 kW -14.39 -16.65 -15.52 Sample-Diesel 3.5 kW -10.13
-12.63 -11.38 Sample-Diesel 3 kW -11.75 -12.50 -12.12 Sample-Diesel
2 kW -12.27 -13.37 -12.82 NO.sub.x Sample-Diesel 2 kW -1.29 0.77
-0.26 Sample-Diesel 3 kW -3.16 -0.35 -1.76 Sample-Diesel 3.5 kW
-2.17 -0.59 -1.38 Sample-Diesel 3 kW -1.95 -0.43 -1.19
Sample-Diesel 2 kW 0.77 2.70 1.73 .sup.aAB #90 is a first sample of
0.1 wt % 1:1 di-DA PB/di-DB PB; AB #90 is a second sample of 0.1 wt
% 1:1 di-DA PB/di-DB PB
[0290] Based on the observed reductions of THC and CO, a
corresponding increase in fuel efficiency occurred.
Example 26: Improvement of Fuel Efficiency with Self-Associative
Polymers
[0291] The emissions data discussed for Example 24 (0.1 wt % diesel
solution of 430K di-TA PB) show a reduction in THC and CO emissions
compared to the diesel reference sample, indicating a more
efficient burning of the fuel.
Example 27: Improvement of Fuel Efficiency with Donor-Acceptor
Associative Polymers
[0292] The emissions data discussed for example 25 (0.1 wt % diesel
solution of 630K di-DA PB/540K di-DB PB 1:1 mixture) show a
reduction in THC and CO emissions compared to the diesel reference
sample, indicating a more efficient burning of the fuel.
Example 28: Additional Improvement of Fuel Efficiency with
Donor-Acceptor Associative Polymers
[0293] The exhaust gas temperatures for untreated diesel and the
sample described in Example 25 (0.1 wt % diesel solution of 630K
di-DA PB/540K di-DB PB 1:1 mixture) were measured by a thermal
couple immediately after the exhaust was diluted with an isothermal
stream of carrier gas (hence, the temperature of the actual exhaust
gas was considerably higher that reported here after dilution). The
results revealed a 5.degree. C. reduction for the exhaust
corresponding to example 25, indicating a more efficient burning
and conversion of fuel energy to useful power in the engine for
this example.
[0294] The examples set forth above are provided to give those of
ordinary skill in the art a complete disclosure and description of
how to make and use the embodiments of the associative polymers,
materials, compositions, systems and methods of the disclosure, and
are not intended to limit the scope of what the inventors regard as
their disclosure. All patents and publications mentioned in the
specification are indicative of the levels of skill of those
skilled in the art to which the disclosure pertains.
[0295] The entire disclosure of each document cited (including
patents, patent applications, journal articles, abstracts,
laboratory manuals, books, or other disclosures) in the Background,
Summary, Detailed Description, and Examples is hereby incorporated
herein by reference. All references cited in this disclosure are
incorporated by reference to the same extent as if each reference
had been incorporated by reference in its entirety individually.
However, if any inconsistency arises between a cited reference and
the present disclosure, the present disclosure takes
precedence.
[0296] The terms and expressions which have been employed herein
are used as terms of description and not of limitation, and there
is no intention in the use of such terms and expressions of
excluding any equivalents of the features shown and described or
portions thereof, but it is recognized that various modifications
are possible within the scope of the disclosure claimed Thus, it
should be understood that although the disclosure has been
specifically disclosed by preferred embodiments, exemplary
embodiments and optional features, modification and variation of
the concepts herein disclosed can be resorted to by those skilled
in the art, and that such modifications and variations are
considered to be within the scope of this disclosure as defined by
the appended claims.
[0297] It is also to be understood that the terminology used herein
is for the purpose of describing particular embodiments only, and
is not intended to be limiting. As used in this specification and
the appended claims, the singular forms "a," "an," and "the"
include plural referents unless the content clearly dictates
otherwise. The term "plurality" includes two or more referents
unless the content clearly dictates otherwise. Unless defined
otherwise, all technical and scientific terms used herein have the
same meaning as commonly understood by one of ordinary skill in the
art to which the disclosure pertains.
[0298] Unless otherwise indicated, the term "alkyl" as used herein
refers to a linear, branched, or cyclic saturated hydrocarbon group
typically although not necessarily containing 1 to about 15 carbon
atoms, or 1 to about 6 carbon atoms, such as methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and
the like, as well as cycloalkyl groups such as cyclopentyl,
cyclohexyl and the like. Generally, although again not necessarily,
alkyl groups herein contain 1 to about 15 carbon atoms. The term
"cycloalkyl" intends a cyclic alkyl group, typically having 4 to 8,
or 5 to 7, carbon atoms. The term "substituted alkyl" refers to
alkyl substituted with one or more substituent groups, and the
terms "heteroatom-containing alkyl" and "heteroalkyl" refer to
alkyl in which at least one carbon atom is replaced with a
heteroatom. If not otherwise indicated, the terms "alkyl" and
"lower alkyl" include linear, branched, cyclic, unsubstituted,
substituted, and/or heteroatom-containing alkyl and lower alkyl,
respectively.
[0299] Unless otherwise indicated, the term "hydrocarbyl" as used
herein refers to any univalent radical, derived from a hydrocarbon,
such as, for example, methyl or phenyl. The term "hydrocarbylene"
refers to divalent groups formed by removing two hydrogen atoms
from a hydrocarbon, the free valencies of which may or may not be
engaged in a double bond, typically but not necessarily containing
1 to 20 carbon atoms, in particular 1 to 12 carbon atoms and more
particularly 1 to 6 carbon atoms which includes but is not limited
to linear cyclic, branched, saturated and unsaturated species, such
as alkylene, alkenylene alkynylene and divalent aryl groups, e.g.,
1,3-phenylene, --CH.sub.2CH.sub.2CH.sub.2-propane-1,3-diyl,
--CH.sub.2-methylene, --CH.dbd.CH--CH.dbd.CH--. The term
"hydrocarbyl" as used herein refers to univalent groups formed by
removing a hydrogen atom from a hydrocarbon, typically but not
necessarily containing 1 to 20 carbon atoms, in particular 1 to 12
carbon atoms and more particularly 1 to 6 carbon atoms, including
but not limited to linear cyclic, branched, saturated and
unsaturated species, such as univalent alkyl, alkenyl, alkynyl and
aryl groups e.g. ethyl and phenyl groups.
[0300] Unless otherwise indicated, the term "heteroatom-containing"
as in a "heteroatom-containing alky group" refers to a alkyl group
in which one or more carbon atoms is replaced with an atom other
than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon,
typically nitrogen, oxygen or sulfur. Similarly, the term
"heteroalkyl" refers to an alkyl substituent that is
heteroatom-containing, the term "heterocyclic" refers to a cyclic
substituent that is heteroatom-containing, the terms "heteroaryl"
and "heteroaromatic" respectively refer to "aryl" and "aromatic"
substituents that are heteroatom-containing, and the like. It
should be noted that a "heterocyclic" group or compound may or may
not be aromatic, and further that "heterocycles" may be monocyclic,
bicyclic, or polycyclic as described above with respect to the term
"aryl." Examples of heteroalkyl groups include alkoxyaryl,
alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the
like. Examples of heteroaryl substituents include pyrrolyl,
pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl,
imidazolyl, 1,2,4-triazolyl, tetrazolyl, and others known to a
skilled person, and examples of heteroatom-containing alicyclic
groups are pyrrolidino, morpholino, piperazino, piperidino, and
other known to a skilled person.
[0301] Unless otherwise indicated, the term "alkoxy" as used herein
intends an alkyl group bound through a single, terminal ether
linkage; that is, an "alkoxy" group may be represented as --O-alkyl
where alkyl is as defined above. A "lower alkoxy" group intends an
alkoxy group containing 1 to 6 carbon atoms. Analogously,
"alkenyloxy" and "lower alkenyloxy" respectively refer to an
alkenyl and lower alkenyl group bound through a single, terminal
ether linkage, and "alkynyloxy" and "lower alkynyloxy" respectively
refer to an alkynyl and lower alkynyl group bound through a single,
terminal ether linkage.
[0302] Unless otherwise indicated, the term "alkylamino" as used
herein intends an alkyl group bound through a single terminal amine
linkage; that is, an "alkylamino" may be represented as --NH--
alkyl where alkyl is as defined above. A "lower alkylamino" intends
an alkylamino group containing 1 to 6 carbon atoms. The term
"dialkylamino" as used herein intends two identical or different
bound through a common amine linkage; that is, a "dialkylamino" may
be represented as N(alkyl).sub.2 where alkyl is as defined above. A
"lower dialkylamino" intends an alkylamino wherein each alkyl group
contains 1 to 6 carbon atoms. Analogously, "alkenylamino", "lower
alkenylamino", "alkynylamino", and "lower alkynylamino"
respectively refer to an alkenyl, lower alkenyl, alkynyl and lower
alkynyl bound through a single terminal amine linkage; and
"dialkenylamino", "lower dialkenylamino", "dialkynylamino", "lower
dialkynylamino" respectively refer to two identical alkenyl, lower
alkenyl, alkynyl and lower alkynyl bound through a common amine
linkage. Similarly, "alkenylalkynylamino", "alkenylalkylamino", and
"alkynylalkylamino" respectively refer to alkenyl and alkynyl,
alkenyl and alkyl, and alkynyl and alkyl groups bound through a
common amine linkage.
[0303] Unless otherwise indicated, the term "aryl" as used herein,
and unless otherwise specified, refers to an aromatic substituent
containing a single aromatic ring or multiple aromatic rings that
are fused together, directly linked, or indirectly linked (such
that the different aromatic rings are bound to a common group such
as a methylene or ethylene moiety). Aryl groups can contain 5 to 24
carbon atoms, or aryl groups contain 5 to 14 carbon atoms.
Exemplary aryl groups contain one aromatic ring or two fused or
linked aromatic rings, e.g., phenyl, naphthyl, biphenyl,
diphenylether, diphenylamine, benzophenone, and the like.
"Substituted aryl" refers to an aryl moiety substituted with one or
more substituent groups, and the terms "heteroatom-containing aryl"
and "heteroaryl" refer to aryl substituents in which at least one
carbon atom is replaced with a heteroatom, as will be described in
further detail infra.
[0304] Unless otherwise indicated, the term "arene", as used
herein, refers to an aromatic ring or multiple aromatic rings that
are fused together. Exemplary arenes include, for example, benzene,
naphthalene, anthracene, and the like. The term "heteroarene", as
used herein, refers to an arene in which one or more of the carbon
atoms has been replaced by a heteroatom (e.g. O, N, or S).
Exemplary heteroarenes include, for example, indole, benzimidazole,
thiophene, benzthiazole, and the like. The terms "substituted
arene" and "substituted heteroarene", as used herein, refer to
arene and heteroarene molecules in which one or more of the carbons
and/or heteroatoms are substituted with substituent groups.
[0305] Unless otherwise indicated, the terms "cyclic", "cyclo-",
and "ring" refer to alicyclic or aromatic groups that may or may
not be substituted and/or heteroatom containing, and that may be
monocyclic, bicyclic, or polycyclic. The term "alicyclic" is used
in the conventional sense to refer to an aliphatic cyclic moiety,
as opposed to an aromatic cyclic moiety, and may be monocyclic,
bicyclic or polycyclic.
[0306] Unless otherwise indicated, the terms "halo", "halogen", and
"halide" are used in the conventional sense to refer to a chloro,
bromo, fluoro or iodo substituent or ligand.
[0307] Unless otherwise indicated, the term "substituted" as in
"substituted alkyl," "substituted aryl," and the like, is meant
that in the, alkyl, aryl, or other moiety, at least one hydrogen
atom bound to a carbon (or other) atom is replaced with one or more
non-hydrogen substituents.
[0308] Examples of such substituents can include, without
limitation: functional groups such as halo, hydroxyl, sulfhydryl,
C1-C24 alkoxy, C2-C24 alkenyloxy, C2-C24 alkynyloxy, C5-C24
aryloxy, C6-C24 aralkyloxy, C6-C24 alkaryloxy, acyl (including
C2-C24 alkylcarbonyl (--CO-- alkyl) and C6-C24 arylcarbonyl
(--CO-aryl)), acyloxy (--O-acyl, including C2-C24 alkylcarbonyloxy
(--O--CO-alkyl) and C6-C24 arylcarbonyloxy (--O--CO-aryl)), C2-C24
alkoxycarbonyl (--(CO)--O-alkyl), C6-C24 aryloxycarbonyl
(--(CO)--O-aryl), halocarbonyl (--CO)--X where X is halo), C2-C24
alkylcarbonato (--O--(CO)--O-alkyl), C6-C24 arylcarbonato
(--O--(CO)--O-aryl), carboxy (--COOH), carboxylato (COO.sup.-),
carbamoyl (--(CO)--NH.sub.2), mono-(C1-C24 alkyl)-substituted
carbamoyl (--(CO)--NH(C1-C24 alkyl)), di-(C1-C24 alkyl)-substituted
carbamoyl (--(CO)--N(C1-C24 alkyl).sub.2), mono-(C5-C24
aryl)-substituted carbamoyl (--(CO)--NH-aryl), di-(C5-C24
aryl)-substituted carbamoyl (--(CO)--N(C5-C24 aryl)2),
di-N--(C1-C24 alkyl), N--(C5-C24 aryl)-substituted carbamoyl,
thiocarbamoyl (--(CS)--NH2), mono-(C1-C24 alkyl)-substituted
thiocarbamoyl (--(CO)--NH(C1-C24 alkyl)), di-(C1-C24
alkyl)-substituted thiocarbamoyl (--(CO)--N(C1-C24 alkyl).sub.2),
mono-(C5-C24 aryl)-substituted thiocarbamoyl (--(CO)--NH-aryl),
di-(C5-C24 aryl)-substituted thiocarbamoyl (--(CO)--N(C5-C24
aryl)2), di-N--(C1-C24 alkyl), N--(C5-C24 aryl)-substituted
thiocarbamoyl, carbamido (--NH--(CO)--NH.sub.2),
cyano(--C.ident.N), cyanato (--O--C.ident.N), thiocyanato
(--S-C.ident.N), formyl (--(CO)--H), thioformyl ((CS)--H), amino
(--NH2), mono-(C1-C24 alkyl)-substituted amino, di-(C1-C24
alkyl)-substituted amino, mono-(C5-C24 aryl)-substituted amino,
di-(C5-C24 aryl)-substituted amino, C2-C24 alkylamido
(--NH--(CO)-alkyl), C6-C24 arylamido (--NH--(CO)-aryl), imino
(--CR.dbd.NH where R=hydrogen, C1-C24 alkyl, C5-C24 aryl, C6-C24
alkaryl, C6-C24 aralkyl, and others known to a skilled person),
C2-C20 alkylimino (CR.dbd.N(alkyl), where R=hydrogen, C1-C24 alkyl,
C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, and others known to a
skilled person), arylimino (--CR.ident.N(aryl), where R=hydrogen,
C1-C20 alkyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, and
others known to a skilled person), nitro (--NO2), nitroso (--NO),
sulfo (--SO2-OH), sulfonato (--SO2-O.sup.-), C1-C24 alkylsulfanyl
(---S-alkyl; also termed "alkylthio"), C5-C24 arylsulfanyl
(--S-aryl; also termed "arylthio"), C1-C24 alkylsulfinyl
(--(SO)-alkyl), C5-C24 arylsulfinyl (--(SO)-aryl), C1-C24
alkylsulfonyl (--SO.sub.2-alkyl), C5-C24 arylsulfonyl
(--SO.sub.2-aryl), boryl (--BH2), borono (--B(OH)2), boronato
(--B(OR).sub.2 where R is alkyl or other hydrocarbyl), phosphono
(--P(O)(OH).sub.2), phosphonato (--P(O)(O.sup.-).sub.2),
phosphinato (--P(O)(O.sup.-)), phospho (--PO.sub.2), phosphino
(--PH.sub.2), silyl (--SiR.sub.3 wherein R is hydrogen or
hydrocarbyl), and silyloxy (--O-silyl); and the hydrocarbyl
moieties C1-C24 alkyl (e.g. C1-C12 alkyl and C1-C6 alkyl), C2-C24
alkenyl (e.g. C2-C12 alkenyl and C2-C6 alkenyl), C2-C24 alkynyl
(e.g. C2-C12 alkynyl and C2-C6 alkynyl), C5-C24 aryl (e.g. C5-C14
aryl), C6-C24 alkaryl (e.g. C6-C16 alkaryl), and C6-C24 aralkyl
(e.g. C6-C16 aralkyl).
[0309] Unless otherwise indicated, the term "acyl" refers to
substituents having the formula --(CO)-alkyl, --(CO)-aryl, or
--(CO)-aralkyl, and the term "acyloxy" refers to substituents
having the formula --O(CO)-alkyl, --O(CO)-aryl, or --O(CO)-aralkyl,
wherein "alkyl," "aryl, and "aralkyl" are as defined above.
[0310] Unless otherwise indicated, the term "alkaryl" refers to an
aryl group with an alkyl substituent, and the term "aralkyl" refers
to an alkyl group with an aryl substituent, wherein "aryl" and
"alkyl" are as defined above. In some embodiments, alkaryl and
aralkyl groups contain 6 to 24 carbon atoms, and particularly
alkaryl and aralkyl groups contain 6 to 16 carbon atoms. Alkaryl
groups include, for example, p-methylphenyl, 2,4-dimethylphenyl,
p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl,
3-ethyl-cyclopenta-1,4-diene, and the like. Examples of aralkyl
groups include, without limitation, benzyl, 2-phenyl-ethyl,
3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl,
4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl,
4-benzylcyclohexylmethyl, and the like. The terms "alkaryloxy" and
"aralkyloxy" refer to substituents of the formula --OR wherein R is
alkaryl or aralkyl, respectively, as just defined.
[0311] When a Markush group or other grouping is used herein, all
individual members of the group and all combinations and possible
subcombinations of the group are intended to be individually
included in the disclosure. Every combination of components or
materials described or exemplified herein can be used to practice
the disclosure, unless otherwise stated. One of ordinary skill in
the art will appreciate that methods, device elements, and
materials other than those specifically exemplified can be employed
in the practice of the disclosure without resort to undue
experimentation. All art-known functional equivalents, of any such
methods, device elements, and materials are intended to be included
in this disclosure. Whenever a range is given in the specification,
for example, a temperature range, a frequency range, a time range,
or a composition range, all intermediate ranges and all subranges,
as well as, all individual values included in the ranges given are
intended to be included in the disclosure. Any one or more
individual members of a range or group disclosed herein can be
excluded from a claim of this disclosure. The disclosure
illustratively described herein suitably can be practiced in the
absence of any element or elements, limitation or limitations which
is not specifically disclosed herein.
[0312] A number of embodiments of the disclosure have been
described. The specific embodiments provided herein are examples of
useful embodiments of the disclosure and it will be apparent to one
skilled in the art that the disclosure can be carried out using a
large number of variations of the devices, device components,
methods steps set forth in the present description. As will be
obvious to one of skill in the art, methods and devices useful for
the present methods can include a large number of optional
composition and processing elements and steps.
[0313] In particular, it will be understood that various
modifications may be made without departing from the spirit and
scope of the present disclosure. Accordingly, other embodiments are
within the scope of the following claims.
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References