REDUCING ALUMINOSILICATE SCALE IIS THE BAYER PROCESS
Cross-Reference to Related Applications
This application is a continuation in part of pending application 12/567116 filed
on September 25, 2009.
Statement Regarding Federally Sponsored Research or Development
Not Applicable.
Background of the Invention
This invention relates to compositions of matter and methods of using them to
treat scale in various industrial process streams, in particular certain silane based small molecules
that have been found to be particularly effective in treating aluminosilieate scale in a Bayer
process stream.
As described among other places in US Patent 6,814,873 the contents of which are
incorporated by reference in their entirety, the Bayer process is used to manufacture alumina
from Bauxite ore. The process uses caustic solution to extract soluble alumina values from the
bauxite. After dissolution of the alumina values from the bauxite and removal of insoluble waste
material from the process stream the soluble alumina is precipitated as solid alumina trihydrate.
The remaining caustic solution known as "liquor" and / or "spent liquor" is then recycled back to
earlier stages in the process and is used to treat fresh bauxite, It thus forms a fluid circuit. For
the purposes of this application, this description defines the term "liquor". The recycling of
liquor within the fluid circuit however has its own complexities.
Bauxite often contains silica in various forms and amounts. Some of the silica is
unreactive so it does not dissolve and remains as solid material within the Bayer circuit. Other
forms of silica (for example clays) are reactive and dissolve in caustic when added into Bayer
process liquors, thus increasing the silica concentration in the liquor. As liquor flows repeatedly
through the circuit of the Bayer process, the concentration of silica in the liquor further increases,
eventually to a point where it reacts with aluminum and soda to form insoluble aluminosilieate

particles, Aluminosilicate solid is observed in at least two forms, sodalite and catiorinite. These
and other forms of aluminosilicate are commonly referred to, and for the purposes of this
application define, the terms "desilication product" or "DSP".
DSP can have a formula of 3(Na2O-Al2O32SiO20-2 H2O) 2NaX where X
represents OH-, Cl-, CO3 -, SO4 -. Because DSP has an inverse solubility (precipitation
increases at higher temperatures) and it can precipitate as fine scales of hard insoluble crystalline
solids, its accumulation in Bayer process equipment is problematic. As DSP accumulates in
Bayer process pipes, vessels, heat transfer equipment, and other process equipment, it forms flow
bottlenecks and obstructions and can adversely affect liquor throughput. In addition because of
its thermal conductivity properties, DSP scale on heat exchanger surfaces reduce the efficiency of
heat exchangers.
These adverse effects are typically managed through a descaling regime, which
involves process equipment being taken offline and the scale being physically or chemically
treated and removed. A consequence of this type of regime is significant and regular periods of
down-time for critical equipment. Additionally as part of the descaling process the use of
hazardous concentrated acids such as sulfuric acid are often employed and this constitutes an
undesirable safety hazard.
Another way Bayer process operators manage the buildup of silica concentration
in the liquor is to deliberately precipitate DSP as free crystals rather than as scale. Typically a
"desilication" step in the Bayer process is used to reduce the concentration of silica in solution by
precipitation of silica as DSP, as a free precipitate. While such desilication reduces the overall
silica concentration within the liquor, total elimination of all silica from solution is impractical
and changing process conditions within various parts of the circuit (for example within heat
exchangers) can lead to changes in the solubility of DSP, resulting in consequent precipitation as
scale.

Previous attempts at controlling and/or reducing DSP scale in the Bayer process
have included adding polymer materials containing three atkyloxy groups bonded to one silicon
atom as described in US patent 6,814,873 332, US published applications 2004/0162406 Al,
2004/0011744 Al, 2005/0010008 A2, international published application WO 2008/045677 Al,
and published article Max HTTM Sodalite Scale Inhibitor: Plant Experience and Impact on the
Process, by Donald Spitzer et. al.. Pages 57-62, Light Metals 2008. (2008) all of whose contents
are incorporated by reference in their entirety.
Manufacturing and use of these trialkoxysilane-grafted polymers however can
involve unwanted degrees of viscosity, making handling and dispersion of the polymer through
the Bayer process liquor problematic. Other previous attempts to address fbulant buildup are
described in US Patents 5,650,072 and 5,314,626 both of which are incorporated by reference in
their entirety.
Thus while a range of methods are available to Bayer process operators to manage
and control DSP scale formation, there is a clear need for, and utility in, an improved method of
preventing or reducing DSP scale formation on Bayer process equipment- The urt described in
this section is not intended to constitute an admission that any patent, publication or other
information referred to herein is "prior art" with respect to this invention, unless specifically
designated as such. In addition, this section should not be construed to mean that a search has
been made or that no other pertinent information as delined in 37 C.F.R. § 1.56(a) exists.
Brief Summary of the Invention
At least one embodiment is directed towards a method for reducing siliceous scale
in a Bayer process comprising the step of adding to a Bayer liquor an aluminosilicate scale
inhibiting amount of reaction product between an amine-containing molecule and an amine-
reactive molecule containing at least one amine-reaetive group per molecule and at least one -
Si(QR)„ group per molecule , where n = 1, 2, or 3, and R - H, C1-C12 Alkyl, Aryl, Na, K, Li, or
NH4, or a mixture of such reaction products.

Another embodiment is directed towards a method for reducing siliceous scale in
a Bayer process comprising the step of adding to a Bayer liquor an efficacious amount of reaction
product between: 1) an amine-containing small molecule, and 2) an amine-reactive small
molecule containing at least one amine-reactive group per molecule and at least one - Si(OR)n
group per molecule, where, n - 1,2, or 3, and R= H, C1-C12 Alkyl, Aryl, Na, K, Li, orNH4, or a
mixture of such reaction products, and 3) a non-polymeric amine reactive hydrophobic
hydrocarbon.
At least one embodiment is directed towards a method of reducing DSP in a Bayer
process comprising the step of adding to the Bayer process stream an aluminosilicate scale
inhibiting amount of a mixture of products as defined above.
Brief Description of the Drawings
A detailed description of the invention is hereafter described with specific
reference being made to the drawings in which:
FIG. 1 is a graph illustrating a batch reaction profile of the invention.
FIG. 2 is a graph illustrating a semi-batch reaction profile of the invention.
Detailed Description of the Invention
For purposes of this application the definition of these terms is as follows:
"Polymer" means a chemical compound comprising essentially repeating
structural units each containing two or more atoms. While many polymers have large molecular
weights of greater than 500, some polymers such as polyethylene can have molecular weights of
less than 500. Polymer includes copolymers and homo polymers.
"Small molecule" means a chemical compound comprising essentially non-
repeating structural units. Because an oligomer (with more than 10 repeating units) and a
polymer are essentially comprised of repeating structural units, they are not small molecules.
Small molecules can have molecular weights above and below 500. The terms "small molecule"
and "polymer" are mutually exclusive.

"Foulant" means a material deposit that accumulates on equipment during the
operation of a manufacturing and/or chemical process which may be unwanted and which may
impair the cost and/or efficiency of the process. DSP is a type of foulant.
"Amine" means a molecule containing one or more nitrogen atoms and having at
least one secondary amine or primary amine group. By this definition, monoamines such as
dodecylamine, diamines such as hexanediamine, and triamines such as diethylenetriamine, are all
amines.
"GPS" is 3-glycidoxypropyltrimethoxysilane,
"Alkyloxy" means having the structure of OX where X is a hydrocarbon and O is
oxygen. It can also be used interchangeably with the term "alkoxy". Typically in this
application, the oxygen is bonded both to the X group as well as to a silicon atom of the small
molecule. When X is C1 the alkyloxy group consists of a methyl group bonded to the oxygen
atom. When X is C2 the alkyloxy group consists of an ethyl group bonded to the oxygen atom.
When X is C3 the alkyloxy group consists of a propyl group bonded to the oxygen atom. When
X is C4 the alkyloxy group consists of a butyl group bonded to the oxygen atom. When X is C5
the alkyloxy group consists of a pentyl group bonded to the oxygen atom. When X is C6 the
alkyloxy group consists of a hexyl group bonded to the oxygen atom.
"Monoalkyloxy" means that attached to a silicon atom is one alkyloxy group.
"Dialkyloxy" means that attached to a silicon atom are two alkyloxy groups.
"Trialkyloxy" means that attached to a silicon atom are three alkyloxy groups.
"Synthetic Liquor" or "Synthetic Spent Liquor" is a laboratory created liquid used
for experimentation whose composition in respect to alumina, soda, and caustic corresponds with
the liquor produced by recycling through the Bayer process.
"Bayer Liquor" is actual liquor that has run through a Bayer process in an
industrial facility.

In the event that the above definitions or a description stated elsewhere in this
application is inconsistent with a meaning (explicit or implicit) which is commonly used, in a
dictionary, or stated in a source incorporated by reference into this application, the application
and the claim terms in particular are understood to be construed according to the definition or
description in this application, and not according to the common definition, dictionary definition,
or the definition that was incorporated by reference. In light of the above, in the event that a term
can only be understood if it is construed by a dictionary, if the terra is defined by the Kirk-
Othmer Encyclopedia of Chemical Technology, 5th Edition, (2005), (Published by Wiley, John &
Sons, Inc.) this definition shall control how the term is to be defined in the claims.
In the Bayer process for manufacturing alumina, bauxite ore passes through a
grinding stage and alumina, together with some impurities including silica, are dissolved in
added liquor. The mixture then typically passes through a desilication stage where silica is
deliberately precipitated as DSP to reduce the amount of silica in solution. The slurry is passed
on to a digestion stage where any remaining reactive silica dissolves, thus again increasing the
concentration of silica in solution which may vsubsequently form more DSP as the process
temperature increases. The liquor is later separated from undissolved solids, and alumina is
recovered by precipitation as gibbsite. The spent liquor completes its circuit as it passes through
a heat exchanger and back into the grinding stage. DSP scale accumulates throughout the Bayer
process but particularly at the digestion stage and most particularly at or near the heat exchanger,
where the recycled liquor passes through.
In this invention, it was discovered that dosing of various types of silane-based
products can reduce the amount of DSP scale formed.
In at least one embodiment of the invention, an effective concentration of a silane-
based small molecule product is added to some point or stage in the liquor circuit of the Bayer
process, which minimizes or prevents the accumulation of DSP on vessels or equipment along
the liquor circuit.

In at least one embodiment, the small molecule comprises the reaction product
between an amine and at least one amine-reactive silane, the silicon of the silane can be
monoalkyloxy, dialkyloxy, trialkyloxy or trihydroxy.
In at least one embodiment the small molecule is a reaction product between an
amine-eontaining small molecule and an amine-reacttve molecule containing at least one amine-
reactive group per molecule and at least one - Si(OR)R group per molecule , where n - 1, 2, or 3,
and R = H, C1-C12 Alkyl, Aryl, Na, K, Li, or NH4, or a mixture of such reaction products.
In at least one embodiment the method for the reduction of aluminosilicate
containing scale in a Bayer process comprises the steps of:
adding to the Bayer process stream an aluminosilicate scale inhibiting amount of a
composition comprising at least one small molecule, the at least one small molecule comprising
of at least three components, one being an R1 component, one being an R2 component and one
being an R3 component, the components within the small molecule arranged according to the
general formula:

wherein the small molecule may be at least one of: carbonates, bicarbonates, carbamates, ureas,
amides and salts thereof and:
(i) R1 is selected from the group consisting of: H, alkyl, amine,
structure (A) and structure (B);


(ii) R2 is independent!)' selected from the group consisting of: H,
alkyl, amine, G and E,
G being one item selected from the group consisting of: 3-
glyeidoxypropyltrimethoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-
glycidoxypropylalkyldiaikoxysilane.S-glycidoxypropyldialkyimonoalkoxysilane^-
isoeyanatopropyltrialkoxysilane, 3-isocyanatopropylalkyldialkoxysilane, 3-
isocyanaiopropyldialkylmonoalkoxysilane, 3-chloropropyltrialkoxysilanc, 3-
chloropropylalkyidialkoxysilane, and 3-chloropropyldialkylmonoalkoxysilane;
E being 2-ethylhexyl glycidyl ether, C3-C22 glycidyl ether, C3-C22 isocyanate, C3-C22
chloride, C3-C22 bromide, C3-C22 iodide, C3-C22 sulfate ester, C3-C22 phenolglycidyl ether, and
any combination thereof,
(iii) R3 is independently selected from the group consisting of: H,
alkyl, amine, G and E and
(iv) n. is an integer from 2 to 6.
In at least one embodiment the R1 is independently selected from the group
consisting of: monoisopropanol amine, ethylene diamine, diethylene triamine, tetraethylene
pentamine, isophoronediamine, xylenediamine, bis(aminomethyl)cyclohexane, hexanediamine,
C,C,C"trimethylhexanediamine, methylene bis(arninocydohexane), saturated fatty amines,
unsaturated fatty amines such as oleylamine and soyarnine, .N-fatty-1,3-propanediarnine such as
coeoalkylpropanediamine, oleylpropanediamine, dodecylpropanediamine, hydrogenized tallow
alkylpropanediamine, and tallow alkylpropanediamine and any combination thereof,

In at least one embodiment said small molecule is selected from the group
consisting of: (I), (II), (III), (IV), (V), (VI), (VII), (VIII), and (IX):

In at least one embodiment the small molecule is selected from the group
consisting of: (X) (XI), (XII), (XIII), (XIV), (XV), (XVI), (XVII), (XVIII), and (XIX);

In at least one embodiment the small molecule is selected from the group
consisting of: (XX), (XXI), and (XXII):



In at least one embodiment the small molecule is selected from the group
consisting of: (XXIII), (XXIV), (XXV), (XXVI), (XXVII), (XVIII), and (XIX):



In at least one embodiment the small molecule is selected from the group
consisting of: (XXVIII), (XXIX), (XXX). (XXXI), (XXX11) and combinations thereof:

In at least one embodiment the small molecule is selected from the group
consisting of; (XXXIII), (XXXIV), (XXXV), (XXXVI), (XXXVII), (XXXVIII), (XXXIX),
(XL), (XLI), aad (XLII):

In at least one embodiment the small molecule is selected from the group
consisting of: (XLIII), (XLIV), (XLV), (XLVI), (XLVII), (XLVII), (XLIX), (L), (LI), and
(LII):

In at least one embodiment the small molecule is selected from the group
consisting of: (LII), (LIV), and (LV):



In at least one embodiment the small molecule is selected from the group
consisting of: (LVI), (LVII), (LVIII), (LIX), (LX), (LI), and (LII):

In at least one embodiment the smaJl molecule is selected from the group
consisting of: (LXI), (LXII), (LXIII), and (LXIV):

In at least one embodiment the small molecule is present in a solution in an
amount ranging from about 0.01 to about 100 wt%. The composition may further comprise one
item selected from the list consisting of: amines, activators, antifoaming agents, co-absorbents,
corrosion inhibitors, coloring agents, and any combination thereof. The composition may
comprise a solvent, the solvent is selected from the group consisting of: water, alcohols, polyols,
other industrial solvents, organic solvents, and any combination thereof. The components may
be isolated from the reaction in the form of a solid, precipitate, salt and/or crystalline material in
p'H's ranging from 0 to 14,
Although some of these small molecules have been mentioned in various
references, their uses are for entirely unrelated applications and their effectiveness in reducing
Bayer Process scale was wholly unexpected. Some places where these or similar small
molecules have been mentioned include: US Patent 6,551,515, scientific papers: Ethyhnediamine
attached to silica as an efficient, reusable nanocatalystfor the addition ofnitromethane to
cyclopentenane* By DeOliveira, Edimar; Prado, Alexandre G. S., Journal of Molecular Catalysis
(2007), 271 (1-2), 6369, Interaction of divalent copper with two diaminealkyl hexagonal
mesoporous silicas evaluated by adsorption and thermochemical data, By Sales, Jose; Prado,
Alexandre; and Airoldi, Claudio, Surface Science, Volume 590, Issue 1, pp. 51-62 (2005), and
Epoxide silyant agent ethylenediamine reaction product anchored on silica gel-thermodynamics

of cation-nitrogen interaction at solid/liquid interface, Journal of Noncrvsialine Solids. Volume
330, Issue 1-3, pp. 142-149 (2003), international patent applications: WO 2003002057 A2, WO
2002085486, WO 2009056778 A2 and WO 2009056778 A3, French Patents: 2922760 Al and
2922760 Bl, European Patent: 2214632 A2, and Chinese patent application: CN 101747361.
The effectiveness of these small molecules was unexpected as the prior art teaches
that only high molecular weight polymers are effective. Polymer effectiveness was presumed to
depend on their hydrophobic nature and their size. This was confirmed by the fact that cross-
linked polymers are even more effective than single chain polymers. As a result it was assumed
that small molecules only serve as building blocks for these polymers and are not effective in
their own right. (WO 2008/045677 [0030]), Furthermore, the scientific literature states "small
molecules containing" ... "[an] S1-O3 grouping are not effective in preventing sodalite
scaling".... because ... "[tjhe bulky group" ,.. "is essential [in] keeping the molecule from being
incorporated into the growing sodalite," Max HTm Sodalite Scale Inhibitor: Plant Experience
and Impact on the Process, by Donald Spitzer et. al., Page 57, light Metals 2008. (2008).
However it has recently been discovered that in fact, as further explained in the provided
examples, small molecules such as those described herein are actually effective at reducing DSP
scale.
It is believed that there are at least three advantages to using a small molecule-
based inhibitor as opposed to a polymeric inhibitor with multiple repeating units of silane and
hydrophobes. A first advantage is that the smaller molecular weight of the product means that
there are a larger number of active, inhibiting moieties available around the DSP seed crystal
sites at the DSP formation stage. A second advantage is that the lower molecular weight allows
for an increased rate of diffusion of the inhibitor, which in turn favors fast attachment of the
inhibitor molecules onto DSP seed crystals. A third advantage is that the lower molecular weight
avoids high product viscosity and so makes handling and injection into the Bayer process stream
more convenient and effective.

EXAMPLES
The foregoing may be better understood by reference to the following examples,
which are presented for purposes of illustration and are not intended to limit the scope of the
invention.
I, Example of a Synthesis Reaction A, E and G.
In a typical synthesis reaction the three constituents: A (e.g., hexane diamine), G
(e.g. 3-glycidoxypropyltrimethoxysilane) and E (e.g. ethyl hexyl glyeidyl ether) are added to a
suitable reaction vessel at a temperature between 23-40 °C and allowed to mix. The reaction
vessel is then warmed to 65-70 C during which time the reaction begins and a large exotherm is
generated. The reaction becomes self-sustaining and depending on the scale of the reaction, can
reach temperatures as high as 125 to 180 °C. (see FIG. 1), Typically the reaction is complete
after 1 to 2 hours and then the mixture is allowed to cool down. As an aspect of this invention
this un-hydrolyzed product mixture can be isolated as a liquid or gel or a solid in a suitable
manner. Alternatively, the reaction product mixture can be hydrolyzed, via a number of
methods, to prepare a solution of the hydrolyzed product mixture in water. The hydrolysis of the
alkoxysilane groups in the component G results in the formation of the corresponding alcohol
(e.g methanol, ethanol etc., depending on the akloxysilane used in the synthesis).
It is common to those skilled in the art to conduct the ring opening of an epoxide
with a reactive amine in a batch mode (where the components are mixed together), heated to an
initiation temperature above room temperature (e.g. 50-65 °C) with the reaction temperatures
allowed to reach as high as 125 to 180 *C. This can cause internal cross-linking and side reactions
to occur - which is often desired in the resin manufacturing processes.
However, at least one embodiment involves the use of a continuous or semi-batch
synthesis method which provides several advantages over the batch process commonly used.

This involves adding only a portion of the G and E constituents either together or sequentially or
individually in a form of a slow feed to initiate the primary epoxide ring opening reaction,
followed by the slow continuous feeding of the two constituents G and E (either together or
separately and at the same time or sequentially). This method allows for a much better control
over the overall reaction, the reaction temperature and provides a better overall yield of the active
compounds in the product also avoiding the undesired side reactions, (see FIG. 2),
In at least one embodiment the synthesis reaction utilizes constituent G:::i 3-
glycidoxypropyltrimethoxysilane. Prolonged exposure at high temperatures above 120 "C can
result in internal coupling reactions and multiple substitutions with the reactive amine groups
such as hexane diamine or ethylene diamine. The resulting un-hydrolyzed reaction products will
turn to a gel over shorter time period accompanied by an increase in the reaction product
viscosity. Use of a semi-batch process or continuous or separate or slow sequential or individual
or combined feed of the E and G epoxides into the reaction mixture allows better control of the
reaction temperature thereby reducing the amount of methanol that is generated and isolated
during the reaction. Furthermore the reaction mixture has a lower viscosity and accounts for
fewer undesired side reactions (see Table l).

Examples of the relative DSP scale inhibition of various A:G:E small molecules formed
during the synthesis reaction disclosed above.

The scale inhibition performance of the small molecule is typically performed as follows:
1) A small amount of sodium silicate (0.25 - 1.5 g/L as Si02) is added to a Bayer refinery
spent liquor at room temperature to raise the silica concentration in the liquor.
2) Portions of this liquor sample are dosed with varying amounts of the new scale inhibitor
compound or mixture.
3) Dosed and untreated (or Blank) liquor samples are subjected to elevated temperatures
between 96 to 105 °C for 4 to 6 hours.
4) Samples are then cooled and the amount of DSP scale formed in each of the dosed liquors
samples are measured and compared to that formed in the untreated or blank samples.
As an example, Table II shows the relative DSP Scale Inhibition for several A:G:E synthesized
mixtures using the synthesis reaction disclosed earlier, with various amine constituents as the
core.
Table II. Relative DSP Scale Inhibition for Various A:G:E Synthesized Reaction
Mixtures, where
A - Amine
G ::: Glycidoxypropyltrimethoxysilane
E = 2-Ethylhexyl glycidyl ether

While this invention may be embodied in many different forms, there are shown
in the drawings and described in detail herein specific preferred embodiments of the invention.
The present disclosure is an exemplification of the principles of the invention and is not intended
to limit the invention to the particular embodiments illustrated. All patents, patent applications,
scientific papers, and any other referenced materials mentioned herein are incorporated by

reference in their entirety. Furthermore, the invention encompasses any possible combination of
some or all of the various embodiments described herein and incorporated herein.
'The above disclosure is intended to be illustrative and not exhaustive, This
description will suggest many variations and alternatives to one of ordinary skill in this art. All
these alternatives and variations are intended to be included within the scope of the claims where
the term "comprising" means "including, but not limited to". Those familiar with the art may
recognize other equivalents to the specific embodiments described herein which equivalents are
also intended to be encompassed by the claims.
All ranges and parameters disclosed herein are understood to encompass any and
all subranges assumed and subsumed therein, and every number between the endpoints. For
example, a stated range of "1 to 10" should be considered to include any and all subranges
between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all
subranges beginning with a minimum value of 1 or more, (e.g. 1 to 6.1), and ending with a
maximum value of 10 or less, (e.g. 2.3 to 9.4, 3 to 8,4 to 7), and finally to each number 1,2, 3,4,
5, 6. 7, 8, 9, and 10 contained within the range.
This completes the description of the preferred and alternate embodiments of the
invention. Those skilled in the art may recognize other equivalents to the specific embodiment
described herein which equivalents are intended to be encompassed by the claims attached
hereto.

We Claim:
1. A method for the reduction of aluminosilicate containing scale in a Bayer process
comprising the steps of:
adding to the Bayer process stream an aluminosilicate scale inhibiting amount of a
composition comprising at least one small molecule, the at least one small molecule comprising
of at least three components, one being an R1 component, one being an R2 component and one
being an R3 component, the components within the small molecule arranged according to the
general formula:

wherein the small molecule may be at least one of: carbonates, bicarbonates, carbamates, ureas,
amides and salts thereof and:
R1 is selected from the group consisting of: H, alkyl, amine, structure (A) and
structure (B);

R2 is independently selected from the group consisting of: H, alkyl, amine, G and
E,
G being one item selected from the group consisting of; 3-
glycidoxypropyltrimethoxysilane, 3-glycidox.ypropyltrialkoxysilane, 3-
glycidoxypropylalkyldiaikoxysilane,3-glycidoxypropyldiaIkylmonoalkoxysilane, 3-

isocyanatopropyltrialkoxysilane, 3-isocyanatopropylalkyldialkoxysilane, 3-
isocyanatopropyldialkylmonoalkoxysilane, 3-chloropropyltrialkoxysilane, 3-
chloropropylalkyldialkoxysilane, and 3-chloropropyldia!ky)monoalkoxysilane and wherein G is
optionally hydrolyzed;
E being 2-ethylhexyl glycidyl ether, C3-C22 glycidyl ether, C3-C22 isocyanate, C3-
C22 chloride, C3-C22 bromide, C3-C22 iodide, C3-C22 sulfate ester, C3-C22 phenolglycidyl ether,
and any combination thereof
R3 is independently selected from the group consisting of: H, alkyl, amine, G and
E and
n is an integer from 2 to 6.
2. The method of Claim 1, wherein the R1 is independently selected from the group
consisting of: monoisopropanol amine, ethylene diamine, diethylene iriamine, tetraethylene
pentamine, isophoronediamme, xylenediamine, bis(aminomethyl)cyclohexane, hexanediamine,
C,C,C-trimethylhexanediatnine, methylene bis(aminocyelohexane), saturated fatty amines,
unsaturated fatty amines such as oleylamine and soyamine, N-fatty-l,3-propanediamine such as
cocoalkylpropanediamine, oleylpropanediamine, dodecylpropanediamine, hydrogenized tallow
alkylpropanediamine, and tallow alkylpropanediamine and any combination thereof.
3. The method of Claim 1, wherein G is hydrolyzed and said small molecule is selected
from the group consisting of: (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and any
combination thereof:

4. The method of Claim 1, wherein G is hydrolyzcd and the small molecule is selected from
the group consisting of: (X) (XI), (XII), (XIII), (XIV), (XV), (XVI), (XVII), (XVIII), (XIX), and
any combination thereof:

5. The method of Claim 1, wherein G is hydrolyzed and the small molecule is selected from
the group consisting of: (XX), (XXI), (XXII), and any combination thereof:



6. The method of Claim 1, wherein G is hydrolyzcd and the small molecule is selected from
the group consisting of: (XXIII), (XXIV), (XXV), (XXVI), (XXVII), (XVIII), (XIX), and any
combination thereof:

7. The method of Claim 1, wherein G is hydrolyzed and the small molecule is selected from
the group consisting of: (XXVIII), (XXIX), (XXX), (XXXI), (XXXII), and any combination
thereof:



8. The method of Claim 1, wherein G is not hydrolyzed and the small molecule is selected
from the group consisting of; (XXXIII), (XXXIV), (XXXV), (XXXVI), (XXXVII), (XXXVIII),
(XXXIX), (XL), (XLI), (XLII), and any combination thereof:

9. The method of Claim 1, wherein G is not hydrolyzed and the small molecule is selected
from the group consisting of: (XLIII), (XLIV), (XLV), (XLVI), (XLVII), (XLVIII), (XLIX),
(L), (LI), (LII), and any combination thereof:

10. The method of Claim 1, wherein G is not hydrolyzed and the small molecule is selected
from the group consisting of: (LIII), (LIV), (LV), and any combination thereof:



11. The method of Claim 1, wherein G is not hydrolyzed and the small molecule is selected
from the group consisting oft (LVI), (LVD), (LVIII), (LIX), (LX), (LI), (LII) and any
combination thereof:

12. The method of Claim 1, wherein G is not hydrolyzed and the small molecule is selected
from the group consisting of: (LXI), (LXII), (LXIII), (LXIV) and any combination thereof: