NZ794050A - Charge-bearing cyclodextrin polymeric materials and methods of making and using same - Google Patents
Charge-bearing cyclodextrin polymeric materials and methods of making and using sameInfo
- Publication number
- NZ794050A NZ794050A NZ794050A NZ79405020A NZ794050A NZ 794050 A NZ794050 A NZ 794050A NZ 794050 A NZ794050 A NZ 794050A NZ 79405020 A NZ79405020 A NZ 79405020A NZ 794050 A NZ794050 A NZ 794050A
- Authority
- NZ
- New Zealand
- Prior art keywords
- cdp
- fibers
- groups
- cyclodextrin
- present disclosure
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 150
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- 125000000129 anionic group Chemical group 0.000 claims abstract description 37
- 125000005647 linker group Chemical group 0.000 claims description 57
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- 125000003118 aryl group Chemical group 0.000 claims description 36
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- 125000002091 cationic group Chemical group 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 9
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 8
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- 238000002360 preparation method Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000005551 pyridylene group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001172 regenerating Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000002470 solid-phase micro-extraction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960005404 sulfamethoxazole Drugs 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 1
- 238000004808 supercritical fluid chromatography Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 230000001550 time effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical class CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- HFHDHCJBZVLPGP-RWMJIURBSA-N α-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
- GDSRMADSINPKSL-HSEONFRVSA-N γ-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 1
Abstract
The present disclosure relates to charge-bearing polymeric materials and methods of their use for purifying fluid samples from micropollulants, such as anionic micropollutants.
Description
The present disclosure relates to charge-bearing ric materials and methods of their use for
purifying fluid samples from micropollulants, such as anionic micropollutants.
NZ 794050
WO 68104
CHARGE—BEAEMNG CYCLGDEXTRlN PGL‘thERlC h/lATERlALS AND
h/lli'l‘lrlGDS 0F hlAKlNG AND USlNG SAhllij
Racheround
mmnmunmm
{twill} Organic niicropollutants (MPs) are present in water resources at ng L“1 to pg L—1
concentrations as a consequence of human activitiesl’2 Concerns about their negative effects on
human health3“7 and the environmentg‘m motivate the development of technologies that remove
lvll?’s more effectively.”16 MPs span a wide variety of physiocheniical properties including
surface charge, size, and chemical functionality. Charged Ml’s can he cationic, anionic, or
zwitterionic and are typically difficult to remove in the presence of complex matrix constituents
like natural organic matter (NOM) using conventional adsorption methods like activated carbon.
Of the anionic h/lPs, PFASs present a particular nmental prohleni because of their
resistance to hiodegradation and correlation to negative health effects. PFASs have been used in
the formulations of thousands of consumer goodsl and are present in aqueous foam formulations
used to suppress aviation fires in training scenarios. ”“9 As a result, they have contaminated
surface and ground waters near thousands of airports and, military installations.20 ln 2016, Hu and
coworkers showed that at least 6 million Americans were served ng water contaminated
with PFASS at or above the US EPAs 20l6 health ry limit for pertluorooctanoic acid
(PFOA) and pertluorooctanesulfonic acid (PFOS) of 70 ng liil.21 PFASs have been linked to
cancers,3 liver damage,4 thyroid disease5 and other health problems.6
‘tZ} Contaminated water s are typically rernediated with granular activated carbon
(GAG), but its modest affinity for PFASS, particularly short chain tives, makes it an
expensive and stop~gap solution.”24 in recent reports, 14’13 it was discovered that noncovalent
ctions and the ostatics of functional groups influence PFAS affinity to adsorbents, For
example, a combination of philic interactions of the crosslinlter and a lower tration
of anionic charged functional groups in decafluorohiphenyldinlred CDPs led to high PFOA and
PFOS removal from water. in contrast, CDPs crosslinked by epichlorohydrin exhibited inferior
FFAS removal.25
{(3893} Adsorption processes can be employed to remove specific contaminants or contaminant
classes from fl uids like air and water. ted carbons (A (Is) are the most read sorhents
used to remove organic pollutants, and their efficacy derives primarily from their high surface
areas, nanostructured pores, and hydrophobicity. However, no single type ofAC s all
contaminants well, ularly anionic h/ll’s. Because of their poorly defined structure and
binding site variation, optimal adsorption selectivities require empirical screening at new
installations, precluding rational design and, improvement. Furthermore, regenerating spent AC is
energy intensive (heating to Siltlngt‘it‘i“ C or other energy intensive procedures) and does not
restore full performance. AC also has a slow pollutant uptake rate, achieving its uptake
equilibrium in hours to days, such that more rapid contaminant removal requires excess sorbent.
y, AC can perform poorly for many emerging contaminants, particularly those that are
relatively hilic.
{Wild} An alternative adsorbent material can he made from polymeric cyclodextrin materials
produced from insoluble polymers of B—cyclodextrin (B—CD), which are toroidal macrocyeles
comprised of seven glucose units whose al cavities are capable of binding organic
compounds. Ei—CD is an inexpensive and sustainably produced monomer derived from cornstarch
that is used extensively to formulate and stabilize pharmaceuticals, flavorants, and fragrances, as
well as within chiral chromatography stationary phases. lnsoluhle fi—CD polymers have been
formed by crosslinlsing with epichlorohydrin and other ve compounds, and feature well
defined binding sites and high association nts, lnsoluhle Ei—CD polymers crosslirtked with
epichlorohydrin have been investigated as alternatives to AC for water purification, hut their low
surface areas result in interior sorhent performance relative to ACs.
} Thus there is a need for new sorbents that address the deficiencies ofAC and the like
and which will provide more effective sorption and/or sequestration properties for MPs (such as
anionic MPs). Th ere is a need for an adsorbent that provides rapid anionic MP extraction, high
total , and facile ration and reuse procedures. This invention meets those needs,
Summary
{dildo} in some ments, the present disclosure es a porous polymeric material
comprising a plurality of cyclodextrins crosslinlred with a plurality of crosslinlss comprising
formula (l):
WO 68104
wherein
A is an aiyl or neteioaryl nieiety;
each R1 is. independently selected from the group cdnsisting ofH C1—C6 alkyl, C1—C3
halnalkyh aryl, lietei‘daiyl? ~CF3, —SOiH, —CN, “N02, ~NH2 ~NCOfi ~C(O)2R3, —C(O)N(R3)2, and —
halogen;
each R2 is independently H, —0H, tai cation, al,kyl., aryi, netematyl, ~SHfi —S—nietal
catidn, —S~aikyl, “C(OhH, er ~C(O)NH2;
each R3 is. independently —H, —C1'C6 allay}? —C1'C3 haloalliyi, —atyle —C(O)N(Ra)(Rb),
—C(O)R“, —C02RC, —SOzN(R"‘)(RbL or —SOR‘, and each Ra and Rb is independently H or C1—C6
alkyl.
each W is independently a, bond, an alkylene group, an arylene greup, a hetemarylene
gmup, —O-eiylene-, ~(Cl-{23a—aiylene—, —SO2—erylene~, ~Nlri-erylene~, letie—, —O~
neteioeiylene-, ~(Cl-{23a—hetemaryleneg —SQ2—heteraeen/letie-, ieteroeiylene-, ~S—
AK J-k
N 0””(CHzla‘Z‘
neteieeiylene-, -O»—--(CH2)a—--)x---, ---t---NH—--(Cl-12)) »---(»-—S»—-—(Ci—igi), , c c H
A.\N/LN—utcnzni'
_ .
or H H wherein a 15 0-100 and x. is. l—lOtl, and each e 0t heteroai’ylene
tneiety can be substituted or unsubstituted;
each Z is a, eatieiue moiety or an anionic moiety;
each L is independently a linking moiety selected from the group consisting of MO -—S-—-
—N—, C1-C6 substituted or unsubstituted alkylene, C1—C3 lialoalkyleiie, O Q
O C} O 8
. O G AK JLx /* A'\, [J‘K /* /L\ X
fi 0 G E RAG/‘2‘ *, {i .Jk A A
a a and E g
a 7 3 7 ,
A’ is a covalent bond to A;
Z’ is a covalent bond; to Z;
* is a nt bond to g;
‘3 is a point of attachment to the plurality of cyclodextrin carbon atoms;
X is GUS;
y: is lnzflj,
yz is lull; and
ys is 04.
{NEW} in some embodiments, the crosslinks of the porous polymeric material comprise
formula (ll):
wherein
yz is l or 2; and
X is l or 2.
{titlllS} in some embodiments, the porous ric material of the present disclosure
comprises a plurality of linkers of formula (ill);
%) H H
N N
.. . 0%?!“
R4 ' R4 03
(iii)
WO 68104
wherein one R4 is ---l-l and one R4 is v--—Me.
{M1399} in some embodiments, the present disclosure provides a supported porous polymeric
material comprising porous particles affixed to a solid substrate, wherein said porous particles
comprise a plurality of cyclodextrin moieties with a plurality of inks comprising formula
(u (in, or out
{Wild} in some embodiments, the t sure provides a method of purifying a fluid
sample comprising one or more pollutants, the method comprising contacting the fluid sample
with the porous polymeric al or the supported porous polymeric material of the present
disclosure whereby at least 50 wt. % of the total amount of the one or more pollutants in the fluid
sample is adsorbed by the porous polymeric material.
lilllllll ln some embodiments, the present disclosure provides a method of removing one or
more compounds from a fluid sample or determining the presence or absence of one or more
compounds in a fluid sample comprising: a) contacting the sample with the porous polymeric
material or the supported porous polymeric material of the present sure for an incubation
period; b) separating the porous polymeric material or supported porous polymeric material after
the tion period from the ; and c) heating the porous polymeric material or supported
porous polymeric material separated in step b), or ting the porous polymeric material or
supported porous polymeric material separated in step b) with a. t, thereby releasing at
least a portion of the compounds from the porous polymeric material or ted porous
polymeric material; and d l) optionally isolating at least a portion of the compounds released in
step c); or d2) determining the ce or absence of the compounds released in step c} wherein
the presence of one or more compounds correlates to the ce of the one or more compounds
in the sample.
{@912} ln some embodiments, the present disclosure provides an article of manufacture
comprising the porous polymeric material or the supported porous polymeric material of the
present disclosure
Briefflescrl tion of the Brawin s
{Wlft} Fig. l shows a comparison of PFAS uptalre capability of polymers of the present
disclosure at 0.5 hours (top) and 48 hours (bottom).
{WM} Fig. 2 shows a comparison between two choline chloride—modified 'l‘FNuCDF polymers
and a {3—CD—l‘Dl polymer for PFOA uptalre (top) and PFGS uptake (bottoni).
{8815} Fig. 3 shows a 1H NMR um for B—(iD—TDl polymer (top) and fluCD (bottom).
{W16} Fig. 4 shows the change in the 1H NMR spectrum of fiatCDu'l‘Dl polymer upon addition
ofTth).
{W17} Fig. 5 shows a comparison of various BuCD~'l"l)l polymers made with different p—
CDYFDE molar equivalents.
{W18} Fig. 6 shows a comparison of choline chloride—modified BuCD—E‘Dl rs made
with ent molar equivalents of choline de.
{W19} Fig. 7 shows choline—chloride modified B—CD—TFN uptake studies performed with
methylene blue (top) and methyl orange (bottom).
{W20} Fig. 8 shows MO uptake rms for modified 'l‘FNucDF polymers with l5 (top) and
3.0 (middle) equivalents of choline chloride, and unmodified 'l‘F‘NuCDF (bottom). Dots represent
the experimental data points and straight lines are the fitted curves using a Langmuir model.
{8821} Fig. 9 shows EPA uptake isotherms for modified 'l‘FNuCDF polymers with l5 (top) and
3.0 (middle) equivalents of e chloride, and unmodified ’lFN~CDl’ (bottom). Dots represent
the experimental data points and straight lines are the fitted curves using a Langmuir model.
{W22} Fig. l0 shows a 1H NMR spectrum of a choline chloride—modified fluCD—TDE polymer
made with l:6:l molar equivalents of fi—CD:TDl:choline chloride.
{W23} Fig. ll shows a comparison of a choline chlorideumodified ButjDu'l‘Dl polymer and a ll"
CDJI‘Dl polynier.
{W24} Fig. l2 shows a comparison between three choline chloride—modified p—(ID—TDl
rs with different choline chloride loading s.
{W25} Fig. l3 shows FFOA uptake of choline de—modified TDI polymers.
{9926} All documents cited herein are incorporated by reference in their entirety for all
purposes to the same extent as if each individual document was specifically and individually
indicated to be incorporated by reference.
{(130327} As used above, and throughout this disclosure, the ing terms, unless otherwise
indicated, shall be understood to have the following meanings. If a term is missing, the
conventional term as lrnown to one slrilled in the art controls.
{9928} As used herein, the terms “including,” “containing,” and “comprising” are used in their
open, nonmliniiting sense.
{8829} The articles ”a“ and “an” are used in this disclosure to refer to one or more than one
t: 1'.c to at least one) of the grammatical obj ect of the article. By way of example, "an element"
means one element or more than one element.
{(130330} The term ”and/or" is used in this disclosure to mean either "and" or ”or” unless
indicated otherwise.
31} To provide a more concise ption, some of the quantitative expressions given
herein are not qualified with the term “about”. lt is understood that, whether the term ” is
used explicitly or not, every quantity given herein is meant to refer to the actual given value, and
it is also meant to refer to the approximation to such given value that would reasonably be
inferred based on the ry slrill in the art, including equivalents and approximations due to
the experimental and/or ement conditions for such given value. Whenever a yield, is given
as a percentage, such yield refers to a mass of the entity for which the yield is given with respect
to the m amount of the same entity that could he obtained under the particular
stoichioinetric conditions. Concentrations that are given as percentages refer to mass ratios,
unless indicated ently.
{(3932} The term, adsorbent or adsorh is used to refer to compositions or s of the present
disclosure to refer to solid materials as described herein which remove contaminants or
pollutants, typically but not exclusively organic molecules, from a fluid medium such as a. liquid
(eg, water) or a gas (eg, air or other commercially useful gases such as nitrogen, argon,
WO 68104
helium, carbon dioxide, anesthesia gases, etc). Such terrns do not imply any specific physical
mechanism (e.g adsorption vs. absorption).
{8833} The term dextrin" includes any of the lrnown cyclotlextrins such as unsubstituted
cyclodextrins containing from six to twelve glucose units, especially, alphaucyclodextrin, beta~
cyclodextrin, gamniaucyclodextrin and/or their derivatives and/or mixtures thereof. The alpha—
cyclodextrin consists of six glucose units, the hetaucyclodextrin consists of seven e units,
and the gamma—cyclodextrin consists of eight glucose units arranged in donut-shaped rings. The
specific coupling and conformation of the glucose units give the extrins rigid, conical
molecular structures with hollow interiors of specific volumes. The ”lining" of each internal
cavity is formed by en atoms and glycosidic bridging oxygen atoms, therefore, this
surface is fairly hydrophobic. The unique shape and physicalnchernical properties of the cavity
enable the cyclodextrin les to ahsorb (form ion complexes with) organic molecules
or parts of organic molecules which can fit into the cavity.
{0934} Unless otherwise stated, the terms “crosslinlrer” or “crosslinlr” or “linker” refer to a
monomer capable of reacting with or forming a covalent linkage between one or more
cyclodextrins or polymers, For example, if the crosslinher reacts at the end of a polymer chain, it
may covalently react with one cyclodextrin moiety of the polymer (eg. via the glycosiilic oxygen
of the l extrin), The crosslinlrer may or may not, further react with other monomers or
cyclorlextrin units or polymer chains to, for example, extend a r chain or link two or more
polymer chains together, For example the crosslinker may he hound to l, 2, 3, or 4+ monomers
or cyclodextrin units or polymers,
{9935} The term "cationic moiety" refers to a group which carries a ve charge (eg, +l
+2, etc), for example, ammonium, mono~, di— or triallrylamrnonium, diallrylsulfonium and
triallrylphosphonium,
{9936} The term "anionic moiety” refers to a group which carries a negative charge (eg —l
, ~2,
etc), for example, phosphate, carhoxylate, alkoxide, and sulfate.
{(3937} As used herein, “alkyl” means a ht chain or branched saturated chain having from
1 to ill carbon atoms. Representative saturated alkyl groups include, but are not d to,
methyl, ethyl, n-propyl, pyl, Z-niethyl-l ~propyl, 2-methyl~2-propyl, 2-methyl~l ~hutyl, 3—
methyl—l—hutyl, 2-methyl~3~hutyl, 2,2-dimethyld l, 2~inethyl—l ~pentyl, 3-methyl~l ~pentyl,
llamethylulupentyl, Emmethyl—Zupentyl, 3—inethyl~2—pentyl, 4uniethyl—2uperi'tyl, 2,2—dimethyl—l_
hutyl, 3,3—dimethylulubutyl, Zuetliyl—l—butyl, hutyl, isobutyl, t—hutyl, n—pentyl, isopentyl,
neopentyl, n—hexyl and the like, and longer alkyl , such as lieptyl, and oetyl and the like.
An allryl group can be unsubstituted or substituted. Allryl groups containing three or more carbon
atoms may be straight, or ed. As used , “lower alhyl” means an alkyl having from l
to 6 carbon atoms.
{Wild} The term ene” refers to straight~ and branched~chain alltylene groups. Typical
alkylene groups include, for example, methylene ("CHz—L ethylene ("Cl'elzCHM , propylene (~
CH2CH2CH2-) n— hutylene (—CHzCH2CH2CH2n)
, isopropylene ("CHtZCHfiCHH , , seo~butylene
(—CH(CH2CH3)CH2U) and the like.
{9&39} The term “hydroxyl” or “hydroxy” means an OH group;
{9949} It should also he noted that any carbon as well as heteroatorn with unsatisfied valences
in the text, schemes, examples and Tables herein is d to have the sufficient number of
hydrogen atom(s) to satisfy the yalenees.
{hilt-ll} The term “halo” or “halogen” refers to fluorine, chlorine, bromine, or iodine.
{9942} The term “oyano” as used herein means a substituent having a carbon atom joined to a
nitrogen atom by a triple bond, in, GEN.
{@943} The term “amine” or “amino” as used herein means a tuent containing at least one
nitrogen atom. Specifically, NH; —NH(allryl) or all<ylarnino, "NtZallrylh or lamino, amide,
oarboxainide, urea, and sulfarnide suhstituents are ed, in the term “aniino”.
{tilled} Unless otherwise specifically defined, the term “aryl“ refers to cyolio, aromatic
arbon groups that have l to 3 aromatic rings, including monooyelic or hicyclic groups
such as phenyl, biphenyl or naphthyl. Where containing two aromatic rings (bioyelic, eta), the
aromatic rings of the aryl group may be joined at a single point (eg, biphenyl), or fused (gig,
hyl). Furthermore, in the context of the present disclosure, the term aryl is taken to refer to
two aryl rings joined by a short linker suelt as —CH2—, CR2— (where R can be H, ,
etc), 4302—, —SO~, ~NR— (where R can be H, alkyl, etc), or —O—; for example, aryl may refer to
methylene diphenyl or oxybisphenyl respectively). The aryl group may be optionally substituted
by one or more substituents, eg, l to 5 substituents, at any point of attachment. The substituents
can themselves be optionally substituted. Furtherinere when containing twe fused rings the aryl
groups herein defined may have an unsaturated er partially saturated ring fused with a fully
saturated ring. Exemplary ring systems all these aryl groups include, hut are net limited to,
phenyl, hiphenyl, naphthyl, anthraeenyl, phenalenyl, threnyl, l, indenyl,
tetrahydrenaphthalenyl, tetrahydrobenzeannulenyl, and the like.
{8345} Unless otherwise specifically defined, “heternaryl” means a nionoyalent nioneeyclie er
clic aromatic l nf 5 to 18 ring atoms or a polycyclic aromatic radical, containing one
or more ring hetereaterns selected, from N, 0, er S, the ing ring atonis being C.
aryl as herein defined also means a polycyclic (eg, ic) aromatic group
wherein the heternatorn is selected from N, O, or S. The aromatic radical is optionally
substituted independently with one or more substituents descrihed herein. The suhstituents can
themselves be optinnally substituted. Examples include, but are not limited to, benzethiophene,
furyl, thienyl, pyrrelyl, pyridyl, pyrazinyl, pyrazelyl, pyridazinyl, pyrimidinyl, iinidazelyl,
isexazelyl, exazelyL exadiazolyl, pyrazinyl, indnlyl, tliieplieri~2~ylfi quinelyl, yranyl,
isothiazolyl, thiazolyl, thiadiazolyl, thieneEfi,2—blthinphene? triazelyl, triazinyl, ofi ,2-
hjpyrazelyl, furanfi~clpyridinyl? iniidazofl ,2malpyridinyl, in,daznlyl., pyrroloflfi—e]pyridinyl,
pyrrolofi,2melpyridinyl, pyrazele[3,4~e]pyridinyl, midazelyl, thi,eno{3.,2—tt]pyridinyl,
thienanfi~c}pyridinyl., thieneflfi~blpyridinyl, henzethiazolyl, indolyl, indolinyl, indolinonyl,
dihydrobenzethiophenyl, nbenzefuranyl, benzoi’uran, chromanyl, thinehromanyl,
tetrahydrnquinulinyl, dihydrnbenzothiazine, dihydrohenzoxanyl, quinolinyl, ianmnolmyl? if»
napl'ithyridinyl, henmlde}isequinolmyl, pyridoEdfihHl filnaphthyridmyl, thieneQfil3h3yrazinyl
, quinazolinyl, lell,5~a}pyridinyl, [l 72,4]triazololélfi—a]pyridinyl, isoindolylg
pyrreloflfi—h}pyridinyl, pyrrolofi,4—hlpyridinyl, pyrrolofiQ—blpyridinyl, imidaznlfi,4~
hlpyridinyl, pyrrololl ,Z—alpyrimidinyl, tetrahydropyrrololl ,Z—alpyrimidinyl, 3,4—dihydrn—ZH~
lAZ-pyrrelopgl—hlpyrirnidme? dihenzeEhfl}thiophene, pyridirnzone, ,Z—cjpyridinyl,
l‘urelZfinelpyridmyl, illupyridQESAuhjlLilithiazmyl, henzeexazelyl, henzeisexazelyl, furanfi—
hjpyridinyl, benzothiephenyl, l,5—naphthyridinyl, fure[3,2—hlpyridine, E:l,2,4}triazele{l,5~
ailpyridinyl, henzo [1,2,3]triazolyl, irnidazoll,Zualpyrimidinyl, {l,2,4:Etriazele{4,3—hjpyridazinyl,
benzele] { l ,2,5 lthiadiazolyl, henzole}{1,2,5}oxadiazele, l ,3 —dihydrta—2ll~lien;:ta{idliniidazoluflone
3,4—dihydro—Zl-lupyrazolol:l ,Sub} [: l ,2] exazinyl, 7_tetrahydropy razeloll ,S—alpyridinyl,
thiazelel5,4—djthiazolyl, iniidazolefiuhlll ,3,4:§thiadiazelyl, thierio[2,3— jpyrrelyl, 3l-luindolyl,
and derivatives thereof. Furthermore when containing two fused rings the heteroaryl groups
herein defined may have an unsaturated or partially saturated ring fused with a fully saturated
ring.
{8346} Numerical ranges, as used herein, are intended to include sequential rs unless
indicated otherwise. For e, a range expressed as “from O to 5” would include 0, l, 2, 3, 4
and 5.
{8847} The present disclosure provides porous t: e. g. niicroporous or mesoporous), typically
high surface area cyclodextrin polymeric materials (PuCDPs), as well as methods of making and
using these materials. The P—CDPs are comprised of insoluble polymers of cyclodextrin, which is
an inexpensive, sustainably produced macrocycle of e. The cyclodextrin rs are
crosslinked with linking groups as described . The polymers of cyclodextrin are
comprised of cyclodextrin es that are derived from cyclodextrins. The cyclodextrin
nioiety'(s) can he derived from naturally ing cyclodextrins (eg, Cir, 33-, and 7—, comprising
6, 7, and 8 glucose units, respectively) or synthetic cyclodextrins. The cyclodextrin moiety has at
least one —0— bond derived from an —OH group on the cyclodextrin from which it is derived.
The cyclodextrin moieties can comprise 3—20 e units, including 3, 4, 5, 6, ‘7, 8, 9, l0, ll,
l2, l3, l4, l5, l6, l7, 18, l9, and 20 glucose units, inclusive of all ranges therehetween, In, many
embodiments, the cyclodextrin moieties are derived from starch, and comprise 6—9 glucose units,
The polymeric materials may comprise two or more different cyclodextrin moieties. ln particular
embodiments, the P—CDP is comprised of insoluble polymers of ll~cyclodextrin (BED),
lull/43} The P—CDP can also comprise cyclodextrin tives or modified cyclodextrins, The
derivatives of cyclodextrin t mainly of les wherein some of the OH groups are
converted to OR groups, The cyclodextrin derivatives can, for example, have one or more
additional moieties that provide additional functionality, such as desirable solubility behavior and
affinity characteristics, es of suitable cyclodextrin derivative materials include
methylated cyclodextrins (eg, RAMEB, randomly methylated ll—cyclodextriris),
hydroxyalkylated extrins (e, g, hydroxypropyl—ll—cyclodextrin and hydroxypropyl—y—
cyclodextrin), acetylated cyelodextrins (e, g, acetyl—y—cyclodextrin), reactive extrins (eg,
chlorotriaziriyh{tCD}, branched cyclodextriris (eg, glucosyl~B~cyelodextrin and maltosyl-fi—
cyclodextrin), sulfohutyl—ll—cyclodextrin, and sulfated cyclodextrins. For example, the
cyclodextrin nioiety r comprises a moiety that binds (eg, with specificity) a metal such as
arsenic, cadrhium, copper, or lead.
{111149} The P—CDP can also comprise cyclodextrin derivatives as disclosed in US Pat. No.
712 including, e.g., cyclodextrin derivatives with short chain alkyl groups such as
methylated cyclodextrihs, and ethylated cyclodextrihs, wherein R is a methyl or an ethyl group;
those with hy droxyalhyl tuted , such as hydroxypropyl cyclodextrihs and/or
hydroxyethyl cyclodextrins, wherein R is a —CH2—CH{OH)—CF13 or a “CH2CHz—0H group;
branched extrins such as inaltose—honded cyclodextrins; cationic cyclodextrins such as
those containing 2—hydroxyn3n(dimethylarnino)propyl ether, wherein R is CH2—CH(OH)—
CH2—N(CH3)2W’thl’l is cationic at low pH; quaternary ammonium, e.g, 2nhydroxy—3~
(trinrethylannnonio)propyl ether chloride groups, wherein R is CH2—CH(OH)—CH22—
Cl"; anionic extrins such as carboxyniethyl cyclodextrins, cyclodextrin es,
and cyclodextrin succinylates; ainphoteric cyclodextrins such as carhoxyniethyl/quaternary
ammonium cyclodextrins; cyclodextrins n at least one glucopyranose unit has a 3—6—
anhydro—cyclonialto structure, eg, the mono~3~6~anhydrocyclodextrins, as disclosed in “Optimal
Performances with Minimal Chemical Modification of Cyclodextriris”, 1:7. DiedainivPilard and B,
Perly, The 7th International Cyclodextrin Symposium Abstracts, April 1994, p, 49 said references
being incorporated herein by reference; and mixtures thereof. Other cyclodextrin derivatives are
disclosed in US. Pat. No. 3,426,011, Parnierter et a1, issued Fe‘o~ 4, 1969; US Pat. Nos.
3,453,257; 3,453,258; 3,453,259; and 3,453,260, all in the names ot‘l’arnierter et al, and all
issued Jul. 1, 1969; US. Pat. No. 3,459,731, Gramera et al, issued Aug. 5, 1969; US. Pat, No.
3,553,191, Parrnerter eta1., issued Jan. 5, 1971; US. Pat. No. 887, Parrnerter et al, issued
Feb, 23, 1971; US. Pat. No, 152, Szeitli et a1, issued Aug~ 13, 1985; US Pat. No~
4,616,008, Hirai et al, issued Oct. 7, 1986', US. Pat. No, 4,678,598, Ogino eta1., issued Jul. 7,
1987; US. Pat. No. 4,638,058, Brandt et a1, issued Jan 20, 1987; and US Pat. No~ 4,746,734,
'l‘sucliiyania et a1, issued May 24, 1988, all of said s heing incorporated herein hy
reference.
{1111511} In some embodiments, the present disclosure provides a porous polymeric material
comprising a plurality of cyclodextrins crossliiil<ed with a plurality of crosslinl-(s comprising
formula (:1):
wherein
A is an aiyl or neteioaryl nieiety;
each R1 is. independently selected from the group cdnsisting ofH C1—C6 alkyl, C1—C3
halnalkyh aryl, lietei‘daiyl? ~CF3, —SOiH, —CN, “N02, ~NH2 ~NCOfi ~C(O)2R3, (R3)2, and —
halogen;
each R2 is independently H, —0H, —O~nietai cation, al,kyl., aryi, netematyl, ~SHfi —S—nietal
catidn, —S~aikyl, “C(OhH, er ~C(O)NH2;
each R3 is. independently —H, —C1'C6 allay}? —C1'C3 haloalliyi, —atyle —C(O)N(Ra)(Rb),
—C(O)R“, —C02RC, —SOzN(R"‘)(RbL or —SOR‘, and each Ra and Rb is ndently H or C1—C6
alkyl.
each W is independently a, bond, an alkylene group, an arylene greup, a hetemarylene
gmup, lene-, ~(Cl-{23a—aiylene—, —SO2—erylene~, ~Nlri-erylene~, ~S—aiyletie—, —O~
neteioeiylene-, ~(Cl-{23a—hetemaryleneg —SQ2—heteraeen/letie-, —NH-l’ieteroeiylene-, ~S—
AK J-k
N 0””(CHzla‘Z‘
neteieeiylene-, ---(---O»—--(CH2)a—--)x---, ---t---NH—--(Cl-12)) »---(»-—S»—-—(Ci—igi), , c c H
A.\N/LN—utcnzni'
_ .
or H H wherein a 15 0-100 and x. is. l—lOtl, and each e 0t heteroai’ylene
tneiety can be substituted or unsubstituted;
each Z is a, eatieiue moiety or an anionic moiety;
each L is independently a g moiety selected from the group consisting 015me -—S-—-,
A'\ /u\ /*
—N—, C1-C6 substituted or unsubstituted ne, C1—C3 kylene, O Q
O C}
a a: 0
AFN” /* Al\, /*
O d ,
J Gsia sis:
i a MA ii: i i i
, we
A’ is a covalent bond to A;
Z’ is a covalent bond to Z;
* is a covalent bond to g;
‘3 is a point of attachment to the ity of cyclodextrin carbon atoms;
X is GUS;
yi is lnzflj,
yz is lull, and
y3 is Quail.
l} Each Z is a cationic moiety or an anionic moiety. For example, in some embodiments,
each Z is a cationic moiety. in certain embodiments, each cationic moiety is independently —
N(R3)3+, —l3‘(R3)3+, —S(R3)z+, oi~ —Hetei'oai'yl+ wherein each R3 is ndently —H, —Ci-Cs alkyl,
—CinC3 haloalkyl, —aiyl, —C(O)N(Ra)(Rb), —C(O)Rf, , —802N(Ra)(Rb), or —SORC, and
each Ra and Rb is independently H, or Ci—Cs alkyl. For example, in some embodiments, each
cationic moiety is —N(R3)3+ where each R3 is H or C1—C6 alkyl. Accordingly, in some
embodiments, each cationic moiety is is —l**vl(l‘ide)3+ or is —NH3+, In some embodiments, eacli
cationic moiety is is —N(Me)3+. in some embodiments, each cationic moiety is independently ~
Heteroaryll‘. A variety of charged lieteroaryls are contemplated in the context of the present
disclosure and are readily apparent to a skilled artisan, For example, in some embodiments, —
Heteroaryll' may refer to pyridininm, pyriolidininni, zolium, triazolium, tetrazolium, and
the like. in some embodiments, each Z is an anionic moiety. in certain embodiments, each
p033 Ool""_/Ei,\ \\ O
i Gui—Oioggigg0 li a;
. . l . 9kg R3 anionic inciety is OR3 ,3 Q C) hi; or
7 9 a a 3 3 7
%_€>O ~
wherein each R3 is as defined above, i .
{8852} ln accordance with certain embodiments of the present disclosure, each W is
independently a bond, an allrylehe group (e g. 3:14:10, Gin—{720, or (infirm), an arylene group, a
heteroarylene group, uO—arylene—, —((Ill2)a—arylene~, —S()2_arylene—, uNl-l—aryleneu, lene_, ~
Ouheteroarylene—, —(Cliz)a~heteroarylene~, —S()2_heteraoarylene—, heteroarylene—, —S—
heteroarylene—, ( G (CHM ). , ( NH (Cflzh )a or
, ( S (CHM ). whereinais 0—100
and X is l—lOO, and each arylene or heteroarylene moiety can be substituted or unsubstituted. The
term “arylene” refers to a bivalent group derived from an aryl group (as described herein,
ing phenyl, hiphenyl, naphthyl, etc.) by removing hydrogen atoms from two ring carbons
For e, an arylene can include a phenyl in which the two valencies are situated in an orthon
or para- orientation. For polycyclic arylenes, the two valencies can be on the same ring,
, meta:
or on different rings. Arylenes can be derived from any aromatic rings described herein, and, can
be substituted or unsubstituted. Similarly, the term oarylene” refers to a bivalent group
derived from a heteroaryl group (as described herein, including furyl, pyridyl, etc.) by removing
hydrogen atoms from two ring atoms (whi ch can be carbon or heteroatoms). The valencies can
be on the same ring or ditt‘erent rings (in the case of polycyclic heteroaromatics) and can be on
any two ring atoms. Heteroarylenes can be derived from any aromatic rings described
herein, and can be substituted or unsubstituted. Thus in some embodiments, each W is a bond
(re, a covalent bond). In other embodiments, each W is an alliylene group. For example, each
W may be, methylene {*CE‘IT‘), ethylene (—CllzCl-lz—)
, propylene (~Cll2{:ll2(:ll2—) , isopropylene
(—ClfiQCl-lfiCl-lr) n— butylene (—CHzCl-lgCl:lzCl-l2—) and the
, , tylene (—Cl-l2(Cl-l2Cl—ls)CH2—)
like, in some ments, each ’W is methylene (—Cl—lr), ln some embodiments, each W is an
arylene group (phenylene). in some embodiments, each W is a arylene group ,
pyridyl). in some embodiments, each W is ~O—arylene— (-Q—phenylene), In some embodiments,
each W is —(Cl5l2)a—arylene— (—Cliz—phenylene). in some ments, each W is —S{)2uaryleneu (~
SQzuplienylene). lh some embodiments, each W is "NH—arylene (—Nl—luphenylene). ln some
embodiments, each W is —S~arylene~ (:uSuplienylene). lh some embodiments, each W is a
hetei'oarylene group (furylene, pyridylene). in some embodiments, each W is ~0uheteroarylene—
yridinylene:i. ln some embodiments, each W is —(Cl-lgh—heteroarylene— (—Cl-lz—
nylene}. ln some embodiments, each W is SOz—heteroarylehe— (—SQz—pyridinylene). in
some embodiments, each W is uNl-l—heteroaryleneu (éNli—pyi‘idinylene). in some embodiments,
each W is nS—heteroarylene~ ("S—pyridinylene). ln some embodiments, Wis —(O—CH2—CH2)x—.
. . \N/Ekomtmizla"?
ln some ments, Wis --—O-—-~Cl-l2-—-Cl-l2-—-~._ _ _ , ,
in some embodiments, W is H
where A" is a covalent bond to A and Z’ is a covalent bond to 2;. ln some emhcdimehts, Wis
AKN/LLOAV, 2’
{(3853} In some embodiments, each instance of uW-Z is talten together to form ---O»---Cl-l'2---CHz—--
hel(R)3+~ In some embodiments, each instance of ---W»—--Z is talten together to form »-—O»---Cl-l2---Cl-lzm-
NtMelf. lh some ments, each instance of —-—Z is taken together to form
{<2 Omii
N Me‘( )3
{@1954} In some emhodiments, each L is a g moiety. ln some embodiments, each L is
independently a linking moiety selected from the group consisting ell-Om, -S-, --N»--,
o o o
it a Nhe» notN fit it JL a
,, , i N N
O O H H Ai 4:) O * H H and
7 7 :1 7 7 7
sNiNa 3‘
H H where A’ is a covalent bond to A and * is a nt hand to 3 (which as descrihed
herein represents a point of attachment to the plurality of cyclodextriri carbon atoms). In some
embodiments, eacli L is independently "O"- ln certain embodiments, when each L is
Q A\N’Jl\O/k Q
A'\ /U\ /* )L» I’ll
independently O Q H AF 0 or --,--—O the oxygen atom maybe a
, ,
glycosidic oxygen from the plurality of cyclodextrins of the porous polymeric material or" the
present disclosure. For example, in some embodiments, when each L is independently "0 the
oxygen atom is a glycosidic oxygen atom from the plurality of cyclodextrins of the porous
polymeric material of the present disclosure.
{9955} ln some embodiments, A is an aryl or heteroaryl . in some embodiments, A is an
aryl moiety. For example, A may be phenyl, hiphenyl, naplithyl, anthracenyl, phehalenyl,
tlireriyl, indanyl, indenyl, tetrahydronaphthalehyl, or tetrahydrobenzoannulenyl. in some
embodiments, A is a heterearyl moiety. For example, A may be benzethmphene, furyl, thieiiyl,
yl, pyridyl, pyrazmyl, pyrazolyl, pyridezinyl, pyrimidiriyl, imidazelyl, isoxazelyl,
exazolyl, exadiezelyl, pyreziiiyl, indelyl, thiephenuZuyl, quinolyl, benzopyranyl, isothiazelyl,
thiazolyl, tliiadiazelyl, thiene{3,2~b}thi0phene, triazolyl, triazinyl, imidazell,Z—blpyrezelyl,
furolZfinelpyridmyl, imidazofl,Z—alpyridinyl, indezolyl, pyi'relo{2,3—clpyridiiiyl, pyrrolol’fifin
clpyridinyl, pyramleBAnclpyridii‘iyl, benzeimidazolyl, tliienol’i,2nelpyridmyl, thienolZfin
ejpyi'idinyl, thienollfinblpyridiiiyl, benzethiazelyl, indelyl, indolinyl, indoliiionyl,
dihydrobenzethiophenyl, diliydi'ehenzofuranyl, benzofuran, nyl, thieehremanyl,
tetrahyquuinelmyl, (lihydi'ebenzothiazme, dihydrobenzoxanyl, quiriolinyl, isequmolmyl, 1,6“
iiaphthyridmyl, benzeldefisequmolmyl, pyridoHfi—blll,6lnaplithyridmyl, thiene[2,3—
blpyrazinyl, quinazolmyl, tetrazelell,SUaEpyridinyl, [l,2,4]triazolo[4,3"alpyridmyl, isomdolyl,
pyrmloflfi~blpyridiiiyl, pyrmlolS,sil—bjpyridmyl, pyrrolofi,2—33}pyridinyl, imidazelidm
blpyridinyl , pyrrel cl l yrimidinyl, ydropyrrol0[ l ,Z—alpyrimldmyl , 3 ,4—diliydi‘0—2H~
lVapyrmlofl,l-bjpyrimidme, di,ben,zo[b,d}thiophene, n~2~one, ,2—ttlpyridiriyl,
furo[2,3—c}pyridmyl, lH~pyrid0[3,4—b}{l ,d-lthiazmyl, benzooxazelyl, benzeisexazolyl, ful‘£)[2,3'
blpyridinyl, beiizothmpheiiyl, LS-nephthyridinyl, furo[3,2—b}pyridine, [l,2,4]triazole{l,5~
idinyl, benze [1,2,3]trlazolyl, imldazofi,Z—ajpyrimldiriyl, {l,2,4}triazolo[4,3—blpyi‘idazinyl,
benzeEeHl liiatliazolyl, [1,2,5]0xadiazole, hydre-2H~benze[dfimidazelflwne
3,4—dihyer—erl~pyi'eml0il,SJD} [l ,2} oxazinyl, 4,5,6,7—tetral’iydmpyrazeloEl ,S-alpyridinyl,
tl’iiamlol5,4—dlthiazolyl, imidazelll—b}{l,3,4}thiediazelyl, thienoEZS~lijpyrmlyl, or 3l-l—indolyl.
In some embodiments, A is selected from the group eensisting of , riaplitliyl, pyridyl,
l3enzol'iii'ei'iyl, pyrazinyl, pyridazmyl, pyrin'iiclinyl, triazinyl, quinoline, benzexemle,
bei'imtl’iiamle, lH-benzimidazole, isequmeline, oline, quirioxeline, pyrrole, indele,
bipheiiyl, pyrenyl, and anthracenyl. in some embedimen‘ts, A is phenyl. in some embodiments,
A is an aryl er lieterearyl ring system as described in US Patent No. 9,855,545, which is hereby
incorporated by reference in its entirety.
{8356} En some embodiments, A is the pelymerizatiori preduct 0f commercially ble
cliiseeyanates. For example, in some embedimen‘ts, A is the pelymerizatien product of
commercially available eryl diiseeyenates including but net limited to 2,4—toluene diisecyariete,
2,6—t0luene cliiseeyanate, 4,4’~metliylene diphenyl cliiseeyanate, 2,4’umethylene yl
diisocyanete, l,3—bis(iseeyanatemetliylflienzene, l ,3—bis(l misocyanetoul arnetliyletliyl)benzene,
3,3’udichiore—4,4"—diisocyanatou1,1’uhiphenyi, inrethyimlifi‘—hiphenyiene diisocyanate, 4,45
oxyhisiphenyi isocyanate), 1,3—phenyiene diisocyanate, 1,4—phenyiene diisocyanate, 4—chioro—6_
methy1u1,3~phenylene diisecyanate, and l"chlorornethyi—Z,4ndiisocyanatohenzene. in some
embodiments, A is
where the wavy hne represents any of the suhstituents attached to A as d herein. In sonre
©/O\.m<n§ >140
embodiments? A is or
where the wavy hne represents any of the substituents attached to A as defined herein. In some
the Me
where the wavy hne
represents any of the substituents ed to A as defined, herein, the —Me, —C1, and l
groups bound to the aryl ring in the preceding structures corresponds to R} groups, and the —
CEL— and —C(Me)2— groups hound to the aryi ring correspond to L groups. In some
where the wavy hne represents any of the substituents attached to A as defined , and the
Me and ---CE groups bound to the aryE ring in the preceding structures corresponds to R1 groups.
{@857} The porous polymeric material of the present discios ure comprises a phrrahty of
cyeiodextrins with a pturality of crosshnks comprising formula (I). The ty of
cyciodextrins of the present disclosure may he any cyeiodextrin containing from six to twelve
e units. For example, in some embodiments, the plurality of cyclodextrins of the present
disclosure are selected from the group consisting of u—cyclodextrin, B—cyclodextrin, y—
cyclodextrin, and combinations thereof In some embodiments, each cyclodextrin is a it
cyclodextrin.
{8858} The R‘1 groups of the plurality of crosslinks comprising formula (I) are each R1 is
independently ed from the group consisting of H, C1—C6 alkyl, (ii—Ca haloalkyl, aryl,
heteroaiyl, (To, -S()3l-l, ---CN, ~NO2, ~Nl-l2, —NCO, —C(0)2R3, —C(O)N(R3)z, and »---halogen. In
certain embodiments, each R] is independently selected from the group consisting ofl-l, (Ii—Cs
, CiuCi lialoalkyl, aryl, heteroaryl, 4:? ’3, "803E, —--CN, —N{)2, uNl-lz, —NCO, —C(0)2R3, u
C(O)N(R3)2, and --——lialogen. ln certain embodiments, 0—8 R1 groups are present on the plurality of
iiilrs comprising formula (l). For example, 0, l, 2, 3, 4, 5, 6, 7, or 8 R} groups are present
on each of the individual crosslinlrs sing formula (1). lt is understood that any positions of
A not substituted with R], R3, uW—Z or ML" will be unsubstituted or have one or more H atoms as
required to satisfy the valency of that position. As will be appreciated by a skilled artisan, the
number of R1 groups on each of the individual crosslinlrs of a (i) may vary hout the
porous polymeric material of the present disclosure. For example, when Rl is —l§' and the
polymerized porous material of the present invention is exposed to reactants e of
substitution (eg. choline chloride), the —F groups on some crosslinks will be substituted, s
in other crosslinlrs, the —F groups may be effectively shielded from the reactants and thus not
react. Accordingly, a porous polymeric material of the present disclosure may have multiple
linking groups of formula (I) present, and each individual linlring group may independently have
0—8 (eg. l, 2, or 3) R1 groups.
{@939} ln some ments, the porous polymeric material of the present disclosure may be
characterized as having, on average, a fractional number of R1, R2, JWnZ or —L— groups in each
crosslmking group This fractional number of substituents can be calculated by dividing the total
number of such groups by the total number of crosslinhs in the porous ric material. For
example, if half of the crosslinlring groups are functionalized with a —O—CH2—CH2—N(Me)3l
group (e.g where W is a —0—CH2—CHz— and Z is —N(Me)3), then the average number (or
fraction) of —O—CH2—CH2—N(Me)il groups corresponding to ~W—Z per inking group is 05.
For R1, the fractional number of such groups includes values of about 0, about 0. l, about 0.2,
WO 68104 2020/018149
about 0.3, about 04, about 0.5, about 0.6, about 07, about 08, about 09, about 1.0, about 1.1,
about 1.2, about 1.3, about 14, about 1.5, about 1.6, about 17, about 1.8, about 1.9, about 2.0,
about 2.1, about 22, about 2.3, about 2.4, about 25, about 2.5, about 27, about 2.8, about 2.9,
about 3.0, about 3.1, about 3.2, about 3.3, about 3.4, about 35, about 3.6, about 3.7, about 38,
about 3.9, about 4.0, about 4.1, about 4.2, about 4.3, about 44, about 4.5, about 4.6, about 4.7,
about 4,8. about 4.9, about 5.0, about 5.1, about 5.2, about 5.3, about 5.4, about 5.5, about 5.6,
about 5.7, about 5.8, about 5.9, about 6.0, about 6.1, about 6.2, about 6.3, about 6.4, about 6.5,
about 6.6, about 6.7, about 6.8, about 6.9, about 7.0, about 7.1, about 7.2, about 7.3, about 7.4,
about 7.5, about 7.6, about 7.7, about 7.8, about 7.9, or about 8.0, inc1usive of a11 ranges between
any of these va1ues. For R2, the fractiona1 number of such groups ino1ut1es va1ues of about 0,
about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9,
about 1.0, about 11, about 1.2, about 1.3, about 14, about 1.5, about 1.6, about 1.7, about 1.13,
about 1.9, about 2.0, about 2.1, about 2.2, about 2.3, about 24, about 25, about 2.5, about 2.7,
about 2.8, about 29, about 3.0, about 3.1, about 32, about 3.3, about 34 about 3. 5, about 3.6,
about 3.7, about 313, about 3.9, or about 4.0, ino1usive of a11 ranges between any ot‘tbese va1ues.
For ~W—Z, the fractiona1 number of such groups ino1udes va1ues of about 10, about 11, about
1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 113, about 1.9, about 2.0, about
2.1, about 22, about 2.3, about 2.4, about 25, about 2.5, about 2.7, about 28, about 2.9, about
, about 3.1, about 32, about 33, about 3.4, about 35, about 3.6, about 3.7, about 38, about
3.9, or about 4.0, ine1usive of a11 ranges between any of these va1ues. For »---1...~, the fractionaE
number of such groups es va1ues of about 1.0, about 11, about 1 .2, about 1.3, about 14,
about 1.5, about 16, about 1.7, about 1.8, about 19, about 2.0, about 21, about 22, about 2.3,
about 24, about 2.5, about 25, about 27, about 2.8, about 29, about 3.0, about 3.1, about 3.2,
about 3.3, about 34, about 3.5, about 3.6, about 37, about 3.8, about 3.9, or about 4.0, ino1usive
of a11 ranges between any of these va1ues.
{0060} Each R3 is independenfly 11, —()1-1, "()umeta1 cation, a11<y1, ai'y1, betei'oary1, —S1-1, “Sn
meta1 cation, a11<y1, —C(0)211, or —C(0)N1—12. 1n some embodiments, each 13.2 is 1:1. to some
embodiments, each R3 is 431-1. 1n some embodiments, each R2 is ~0umeta1 cation. 1n some
embodiments, each 132 is a11ty1. 1n some embodiments, each R2 is and (eg, substituted or
unsubstituted bbeny1 or naphtbyl). 1n some embodiments, each 13.2 is betei'oaryE (e.g., substituted
or unsubstituted 5— or berec1 heteroary1 rings with one, two, or three ring beteroatoms
selected from the group consisting of O, S, or N). in some embodiments, each R3 is —SH. in
some embodiments, each R2 is --——Sumetal cation. in some embodiments, each R3 is "Smallryl. in
accordance with embodiments of the present disclosure, there may he l, 2, 3, or 4 Kg .
For example, 0, l, 2, 3, or 4 R) groups are present on the plurality of crosslinks comprising
a (l). As will be appreciated by a skilled artisan, the number of R) groups on each of the
individual plurality of linking groups sing formula (l) may vary by each individual linking
group throughout the porous polymeric material of the t disclosure. Accordingly, a porous
polymeric material of the present disclosure may have multiple linking groups of formula (l)
present, and each individual g group may independently have eg. 0, l, 2, 3, or 4 R3 groups.
When there are more than one R2 groups on the plurality of linlring groups of formula (I), the R2
groups may be the same or different. For example, in some embodiments, one or more R2 group
is al cation and one or more R2 group is —0H.
{earn} Each R3 is independently —H, —Cl-C6 alhyl, —Ci—C3 haloall<yl, —aryl, —C(O)N(Ra)(Rb),
—C(O)RC, —C02Rc, -SOzN(Ra)(Rb), or —SORC, and each R3 and Rh is independently H, or Ci—C6
alkyl. in some embodiments, each R3 is Me, In some embodiments, each R3 is H. When R3 is
aryl, the aryl may be, for example, a substituted or unsubstituted phenyl or naphthyl,
{6962} in certain embodiments, x, is L4. For example, x may be l, 2, 3, or I—‘l. in some
embodiments, x, is l or 2 and R1 is —l:7.
{6963} in certain embodiments, yi is L4, For example, y i may be l, 2, 3, or 4. in some
embodiments, yi is l~2.
{6964} in certain ments, yz is l or 2.
{0965} in n embodiments, ys is O or l.
{9966} in certain embodiments, the porous polymeric material of the present disclosure
comprises a plurality of cyclodextrins crossliiilred with a ity of crosslinks comprising
formula (ll):
WO 68104
wherein
yz is l or 2; and
x is l or 2. in some embodiments, yz is 2 and x is l. In some embodiments, each
cyclodextrin is B—cyclotlextrin.
{(130367} in certain embodiments, the porous polymeric material of the present disclosure
comprises a plurality of linlrers of a (Ill):
l—o H
N . N OVA, l /
Y N
o 0 lg) 9
R4 . R4 Cl
(ill)
{sues} wherein one R4 is 4H and one R4 is —Me. in some ments, each
cyclodextrin is B—cyclodextrin.
{W69} in various embodiments, the porous polymeric material of the present disclosure is
prepared by crosslinlring cyclodextrins of the same structure with crosslinkers of the same
structure. in some embodiments, the porous polymeric material of the present disclosure is
prepared by crosslinlring cyclodextrins of the same ure with two, three, four, or more
different crosslinlrers, In various embodiments, the porous polymeric material of the present
disclosure is prepared by crosslmlring two, three, or four different cyclodextrins (ie, having
different structures) with crosslinlrers of the same structure In some embodiments, the porous
polymeric material of the present disclosure is prepared by crosslinlring two, three, or four
different cyclodextrins with two, three, four, or more different crosslinkers.
{(3979} lo some embodiments, some of the crosslinlrs of the porous polymeric al do not
include a cationic or anionic moiety (re, corresponding to group “Z” of formula (1)). In such
embodiments, the porous polymeric material comprises a plurality of erosslinkers of formula (I)
and a plurality of crosslinlrers haying a ure r to that of formula (l), except that there is
no cationic or anionic moiety corresponding to group “Z”. So, for e, such crosslinlrers
g a cationic or c moiety can have any of the crosslinlrer structures described in US
Patent No. l0,086,360, herein incorporated by nce for all purposes, including, for example
a plurality of crosslinkers of the following structure (a):
regime/i
\ structure l:a ll
or the following ure (b):
ure (b),
or a combination of structures (a) and (b) (where X in structure (h) is 0,, l, 2, 3, or 4). In such
embodiments of porous polymeric materials having crosslihlrers of structure (a) arid/or structure
(b), such materials also include charged crosslmlrers of formula (l) as described herein,
{9971} In still other embodiments, the porous ric materials of the present disclosure
comprise a plurality of cationic crosslihlrers of the ing structure (c):
structure (c)
(where X' is a pharmaceutically able anionic oounterion such as C l ).
{9972} In still other embodiments, the porous polymeric materials of the present disclosure
comprise a plurality of cationic crosslihlrers of the following structure (cl):
structure (d)
(where x in structure (cl) is 0, l, 2, 3, or 4; and; X” is a pharniaceutically acceptable anionic
counterion such as Cl“).
{(130373} ln still other embodiments, the porous polymeric materials of the present disclosure
comprise a plurality of cationic inkers of structure (c) and a plurality of cationic
crosslinkers of structure (cl). As described herein, any crosslinkers of the present disclosure
having an aromatic halide group can be modified to proyide a charged moiety, for example by
reaction with e chloride under suitable conditions as described .
{8874} In other embodiments, the porous polymeric materials of the present disclosure
comprise a ity of anionic crosslirrkers of the following ure (e):
fiat; i :2 2
at yo «3
structure (e).
Ellll’75l 'l'he cationic counterion for structure (e) (depicted as Na? can alternatively be
any other pharmaceutically acceptable cationic counterion such as, t limitation, H+ or
{0076} ln yet other embodiments the porous polymeric materials of the present
disclosure se a plurality of anionic crosslinkers of the following structure (f2):
structure (f)
(where x in structure (f) is Oa l2 2., 3 or 4)”
WO 68104
{0077} In still other embodiments, the porous polymeric materials of the present disclosure
comprise a ity of cationic crosslinlrers of structure (e) and a plurality of cationic
crosslinlrers of structure (itm
{0078} in some embodiments, the present disclosure provides a porous polymeric material
comprising a plurality of cyclodextrin es crosslinlced by one or more polyisocyanates. in
some embodiments, the plurality of cyclodextrins are fi—cyclodextrin. lii some embodiments, the
one or more polyisocyanates are aiyl diisocyanates including but not d to SEA—toluene
diisocyanate, 2,6—toluerie diisocyanate, 4,4’~methylerie iyl diisocyanate, 2,4’~methylerie
diphenyl diisocyanate, 1,3"his(isocyanatomethyl)benzene, 1,3-bis(l—isocyanato—l _
methylethyDbenzene, 3,3’“dichloronit-A’—diisocyanato~l,l’m‘oiphenyl, 3,3'mdimethy1nclfl’n
biphenylene diisocyanate, 4,4’—oxybis(phenyl isocyanate), 1,3—phenylene diisocyanate, L4"
ene diisocyanate, 4—ch1oro—6—methy1nl,3—plienylene diisocyanate, and orornethylmléln
diisocyanatobenzene, and combinations thereof. ln some embodiments, the aryl diisocyanate is
2,4-toluene diisocyanate in some embodiments, the one or more polyisoeyanates are aliphatic
diisocyanates including but not limited to 4,4"—diisocyanato—methylenedicyclohexane (Hlvl‘fll),
hexamethylene diisocyanate (EDI), isopliorone diisoeyanate (lPDl), l_.~lysine diisocyanate (LEI),
trimethylhexametliylene diisocyanate (TREE, l,3—bis(i,soeyanatomethyl)cyclohexane, 1,4—
diisocyanatobutane, trimethyl—l ,6~diisocyanatohexane, 1,6—dii socyanato—2,2,4—trimethylhexane,
transd ,4—cyelohexylene yanate, l,8-diisocyanatooctane, 1,12—diisocyana‘tododecane, and
combinations thereof in some en'ibodiinents, the plurality of cyclodextrins are B-cyclodextrin
and the one or more ocyanates are Z,4~toluene diisocyanates, in some embodiments, the
porous polymeric material has a Brunauer—Emmetb’l‘eller (BET) surface area of about 10 mz/g
to 2000 rnz/g. For example, in some embodiments, the porous polymeric material has a BET
surface area of about l0 m2.«’g, 20 m2/g, 30 in2/g, 40 , 50 ir12/’g, 75 inZ/g, 100 mz/g, 150 nil/g,
zoo ng, 250 ng, soo mW’g, 350 mW/g, 400 nit/g, 450 ng soc ng, 550 ng one ng, 650
m2/’g, 700 rnz/g, 750 rh2/’g, 800 inZ/g, 850 mQ/g, 900 mZ/g, 950 Mg, lOOO rnz/g, 1050 rh2/’g, 1100
inZ/g, l150 inZ/g, 1200 mQ/g, 1250 mZ/g, l300 m2,/g,', 1350 mz/g, 1400 inZ/g, 1450 mQ/g, 1500
m2/’g, 1550 rnz/g, 1600 inZ/g, 1650 in2/'g, l700 mZ/g, 1750 mZ/g, l 800 rnz/g, 1850 in2/’g, 1900
inz/g, 1950 mZ/g to about 2000 mQ/g, including all integers and ranges tlierebetween. ln some
embodiments, the porous polymeric material has an amine t from about 0 mmol/g to about
1.0 minol/g. ln some ments, the porous polymeric material has an amine content from
about 0.1 mniol/g to about 1.0 nimol/g. in some embodiments, the porous polymeric material
has an amine content from about 0.15 mmo1/g to about 0.35 mmol/g. For examp1e, in some
embodiments, the amine content may be about 0.15 nimol/g, about 0.16 mmol/g, about 0.17
mmo1/g, about 0.18 mmol/g, about 0.19 mmol/g, about 0.20 mmol/g, about 0.21 nimol/g, about
.22 mmol/g, about 0.23 , about 0.24 mmol/g, about 0.25 , about 0.26 mmol/g,
about 0. 27 mmol/g, about 0.28 mmol/g, about 0.29 mmol/g, about 0.30 mmol/g, about 0.31
mmol/g, about 0.32 mmol/g, about 0.33 , about 0.34 , and about 0.35 mmol/g
including all ranges therebetween Without being bound by any ular theory, it was
discovered that by using asnis CD (re. undrietl) in the polymer synthesis, the resulting polymer
had a higher amine content than similar polymers described in the prior art, which lerl to higher
affinity for some micropollutants such as PFASs.
{00791 In certain embodiments, the molar ratio of extrin to linking groups of formula (1),
(11), or (111) ranges from about 1:1 to about 1:31, wherein X is three times the e number of
glucose subunits in the cyelodextrin. 1n certain embodiments, the molar ratio of oyclodextrin to
linking groups of formula (I), (11), or (111) is about 1:6. 1n certain embodiments, the molar ratio
of oyolodextrin to linking groups of formula (1) (11,), or (111) is about 1:5, 1n certain
embodiments, the molar ratio of cyclodextrin to linking groups of formula (1), (11), or (111) is
about 1:11. 1n eertain embodiments, the molar ratio of oyelodextrin to linking groups of formula
(1), (11), or (111) is about l :3. in certain embodiments, the molar ratio of cyelodextrin to g
groups of a (1), (11), or (111) is about 1:2. 1n various embodiments, the molar ratio of
cyclodextrin moieties to aryl eross1inl<ing moieties is about 1:1 to about 1:24, including about
1:1, about 115, about 1:2, about 1:25, about 1:3, about l :35, about 1:4, about 1 :45, about
1:5, about 1:55, about 1:6, about 1 :65, about 1 :7, about 1:75, about 1:8, about 1:85, about 1:9,
about 1:95, about 1:10, about 1:105, about 1:11, about 1:115, about 1:12., about 1:125, about
1:13, about 1:135, about 1:14, about 1:145, about 1:15, about 11155, about 1:16, about 1:165,
about 1:17, about 1:175, about 1:18, about 1:185, about 1:19, about 1:195, about 1:20, about
1:205, about 1:21, about 1:215, about 1:22, about 1:225, about 1:23, about 1:235, or about
1:24, ing a1l ranges of ratios therebetween. in an embodiment, the molar ratio ot"
cyclodeirtrin moieties to aryl crosslinlring moieties is about 122.5 to about 1:10.
{0080} 1n some embodiments, a composition according to the present disclosure comprises one
or more porous ric materials of the present disclosure and one or more support materials,
where the porous polymeric material is bound (e.g covalently, adhesively, or mechanically
bonded as described herein) to the support material. For example, in some embodiments, the
composition comprises porous polymeric materials sing a plurality of cyclodestrins
crosslinlred with a plurality of crosslinlrs sing formulatl), and/or (ll), and/or (ill).
es of support materials include cellulose (eg, cellulose fibers), carbon—based materials
such as activated carbon, graphene oxide, and oxidized carbon materials, silica, alumina, natural
or synthetic polymers, and natural or synthetic polymers modified to include surface hydroxyl
groups. One of shill in the art will recognize that any material with mechanical or other
properties suitable to act as a support, which can covalently bond to the porous polymeric
material, or can serve as a suitable support material if the porous polymeric al is
adhesively bonded to the support via a suitable binder material. In an embodiment, the
composition is in the form a membrane or a column packing al. In an ment, the
t is a fiber (eg a cellulose, nylon, polyolet‘in or polyester fiber). to an embodiment, the
support is a porous particulate al (eg, porous silica and porous alumina} In an
embodiment, the support is a woven or non~woven fabric. In an embodiment, the support is a
garment (such as a protective garment) or a surgical or l drape, dressing, or sanitary
article.
{(3981} in some embodiments, the P~CDP may be grafted or bonded (eg chemically or
ically bonded) onto a support to provide an adsorbent where the particle size and
morphology are well-controlled to give ideal flow characteristics The term "mechanical bonc "
refers to a bond formed n two materials by re, ultrasonic ment, and/or other
mechanical bonding process without the intentional application of heat, such as mechanical
entanglement. The physical entanglement and wrapping of mi rils to hold in place micron—
sized particulate matter is a prime example of a mechanical bond. The term mechanical bond
does not comprise a bond formed using an adhesive or chemical grafting. ln some embodiments,
the PuCDl’ may be grafted or bonded {eg or mechanically bonded) onto a support to
/ 5 chemically
provide an adsorbent where the particle size and morphology are further engineered (e.g by
granulation or g) to provide particles with a wellucontrolled size and morphology to give
ideal flow characteristics.
{8882} The P—CDP—support complex may be prepared by a variety of methods, ing
conventional grafting methods. As used herein, the term “grafting” refers to covalently attaching
lLCDl’s to a substrate surface through coupling ons between one or more functional groups
on the ECU? and one or more functional groups on the substrate. in some embodiments,
grafting includes an “in situ” process as described herein in which cyclodextrins, linking groups
of the present disclosure, and a substrate having surface bound nucleophiles (eg, hy dross/ls) are
reacted together such that the linking groups of the t disclosure reacts with the hydroxyl
groups of the cyclodextrins and the surface nucleophiles of the substrate, forming a P—CDP
which is partially bonded via one or more linking groups of the present disclosure to the
substrate. The substrate having surface hound nucleophiles e, but are not limited to
hydroxyls (such as niicrocrystalline cellulose), amines, ines, and thiols.
{9983} In some embodiments, “grafted” P—CDl’~support complexes are prepared by first
sizing the l’~CDPs in a dedicated al reactor with te control of the reaction
conditions and material purification to produce optimized P-CDP les. The PnCDPs are then
chemically reacted with a suitably onalized substrate. For example, a ate
functionalized with carboxylic acid groups (or activated fornis thereof such as acid halides,
anliydrides, etc. known in the art) can react with one of more yls on the P—CD‘P to form an
ester bond with the ate. Alternatively, the P~CDP can be appropriately functionalized (eg,
by selection of a functionalized cyclodextrin as described herein) of by a subsequent
modification of the P—CDP such that it can react with suitable functional groups on the substrate.
Any suitable reaction chemistries can be contemplated, such as reactions between ylic
acids (and derivatives thereof) and hydroxyls to form ester bonds, reactions between carboxylic
acids (and derivatives th ereof) and amine groups to form amide bonds, reactions between
isocyanates and alcohols to make urethanes, reactions between nates and amines to make
ureas, reactions between cyclic carbonates and amines to make urethanes, reactions between
thiols and alhenes or alkynes to make tl'iioethers, reactions between epoxides and amine groups,
photochemical reactions between acrylates, niethacrylates, thiols etc, and olefins, and so forth.
The reactive functional groups described herein can be on either of the 9—510? or substrate
provided the reaction forms a covalent bond between the substrate and the PACE? For example,
of the reactive functional groups are hydroxyls and carboxylic acids (forming an ester bond after
on), the hydroxyl groups can be t on the PuCDP and the carbonyl groups on the
substrate or viceuversa.
{8884} in other embodiments, the substrate can be coated with a r” having reactive
functional groups as described above. The primer s to the surface of the substrate, and
under suitable conditions can react with a suitably functionalized P433? to for a covalent bond
between the P—CDP and the primer.
{8885} The P—CDP les may be engineered to achieve specific particle sizes. in some
embodiments, the P—CDP is produced in the form of crosslinlred particles which may require
r reduction in size leg, for the purposes of forming stable dispersions or slurries, or in
providing optimal flow teristics). A variety of means that are readily apparent to a skilled
artisan can be employed to reduce the particle size of the l’nCDP such as grinding or milling.
Grinding and milling can be employed to create smaller particles with sizes less than l micron.
Typical milling operations can be used by a skilled n and include both wet and dry milling.
Milling can be employed through a variety of methods including, but not d to: ball mill,
autogeneous mill, SAG mill, pebble mill, rod mill, Buhrstone mill, tower mill, vertical shaft
impactor mill, and the like. g media includes, but is not limited to: metals, silicates, and
other inorganic materials in s form factors including, rods, balls, and irregular shapes. In
some embodiments, the milling is performed on dry RC1")? powder material in a dry process to
produce a finer dry powder or on wet aqueous slurries of the P—CDP powder with or without
emulsifying agents to produce a finer particulate dispersion. Eniulsifying agents may be used
and are readily apparent to a d artisan, including, but not limited to: small le and
polymeric surfactant compounds with nonionic, anionic, or cationic ter. A skilled artisan
will appreciate that using fine ulate form factors will enable a variety ofbenefits, such as
( l) more stable aqueous dispersions that remain homogeneous over time by resisting separation,
(2) enable a high loading of material by weight in the dispersion with values of 50% by weight or
higher, (3) produce particulate matter that can be evenly coated or applied to various substrates,
surfaces, fibers, yarns, fabrics and the like to produce a finished material with minimal
perceptible changes in “hand,” and (4) produce sions that are stable to dilution and
blending with other emulsions or solutions such as binders, surfactants, wetting agents, or
softeners. in some embodiments, the final le diameter includes <l micron, lufi micron, 5—
l0 micron, l0~l 5 micron, and lS—ZO micron, or ranges therehetween.
{8886} lf larger particle sizes are desired, the composition may be ated to form
agglomerates of larger particle size. Thus, in some embodiments, granules (eg, self~supporting
granules) are ed from PuCDP particle s of various sizes. Broadly, this process will
transform P—CDP particle powders in the size regimes ranging from lu30 s to granules in
excess or" lot} microns, 200 microns, 300 microns, and larger. This process may be achieved via
granulation techniques common to the pharmaceutical industry {1721;152:500}; omenai’crrion
logy, Ed. Parilrh, D. 1%, 2005, Taylor & Francis Group) in which the powders are bound
together via physical and/or chemical means in batch or continuous modes. ln the simplest form,
particles of the P—CDP are blended mechanically with a fluid (cox, aqueous) e containing
an adhesive hinder — typically a synthetic, seminsynthetic, or natural r. Suitable semi"
synthetic polymers that can be used include cellulose etheis, specifically ethylcellulose,
cellulose. hydroxypropylcellulose, carboxymethylcellulose, starch and starch tives,
and others. le fully synthetic polymers such as polyvinylpyrrolidone or polyethylene
glycol can be used. Other suitable s include sizes and other coatings used in the textile
industry and paper industries including polyamide amine epichlorohydrin (FAB) or polymeric
glyoxal crosslinlcers, polyvinylalcoliol, and starch~hased sizes. ln order to create robust granules
which are resistant to dissolution in water or other solvents, further nt crosslinking may he
facilitated via the addition of small molecule crosslinhers such as glyoxal, formaldehyde,
diisocyanate, and/or diepoxide onalities. in addition to covalent crosslinlring electrostatic
agglomeration of polyelectrolytes can also be utilized as a binding motif in which cationic
polyelectrolytes form suitable adl'iesiye properties when blended with anionic ectrolytes in
the presence of P-CDP powders and/or support structures. ‘tions can comprise those
commonly used for flocculation including, but not limited to polydiallyldimethylarnmonium
chloride (polyDADh/lAC), acidic polyethyleneimine, and polyacrylamides. Polyanions can
comprise those commonly used for flocculation including, but not limited to sodium
polyacrylate, sodium polystyrene sulfonate, and polyvinylsulfonate.
{(3887} Mechanical blending during the granulation may he achieved via low shear processes
such as rotary drum mixing or ad mechanical stirring. As will be readily apparent to a
slrilled artisan, the stirring rate and total length of stirring time effects the granule size.
ation may also he conducted in fluidized beds or via spray drying techniques. ln each
case, the ECU? particle are combined with the aqueous or t borne mixture containing the
binder compounds and the mechanical or physical agitation is conducted at a specified shear for
a determined number of cycles. The resultant particles will display a step growth change in their
average diameters and can also display a changed polydispersity. The physical properties of
these granules depend on the binder selected, the crosslinlring chemistry, and the physical
process used in their granulation. These larger granular particles will be suitable for packed bed
column filtration commonly employed for water filtration and industrial separations.
{8888} ln some ments, the present disclosure provides a stable aqueous dispersion
comprising P—CDP particles. ln some embodiments, the 1’—CDP particles of the t
disclosure, which can be used in such stable aqueous dispersions are from about l pm to about
150 urn. For example, the PCB? particles are from about l, 2, 3, 4, 5, 6, 7, 8, 9, l0: ll, l2, 13,
14515,l6,l7,l8,19,20,2l,22523,24,25,26,27,28,29,3O,3l§32,33,34,35,36,37,38,39,
40,41,42,43,44,45,46,47,48,49,50,Sl,52,53,54,55,56,57,58,59,6u,ol,62,63,64,65,
66:67,6$,69,70,7l,72,73,74,75,76,77,78,79,80,8l,82,83,84,85,86,87,88,89,9u,9l,
92,93,94,95,96§97,98,99,l00,101,192,l03,104,105,l06,107,108,l99,llu,lll,ll2,
4,l15,llo,ll7,118,119,120,12l,l22,123,124,l25,l26,127,128,l29,130,13h
132,133,l34,l35,136,l37,l38,l39,l40,l4l,142,143,l44,l45,l46,l47,l48,149,n3
about lSO pm A stable aqueous dispersion may be used in “grafting” applications. For
example, the stable aqueous dispersion may be used in applications with chemical binders or
fibrillating fibers for mechanical loading and binding, and incorporation into thermally—bonded
particulate pressed forms and into solution processed polymer form factors.
{9989} The P—CDP materials of the present disclosure can also be prepared on a support
material natively termed a “substrate”), for example covalently bonded, adliesiyely bonded,
or mechanically attached to a support such as a s substrate. The support material can be
any material that has one or more groups (e. g, hydroxyl or amino, thiol, or ine, or other
group as described herein) that can form an interaction (e,g a covalent or mechanical bond) with
a inlring agent or cyclodextrin. For example, one end ofa inking agent (e.g the
linking groups of Formulas (1), (11), and/or (111)) is covalently bound to the substrate material and
another end of the crosslinking agent is covalently bound to a cyclodextrin glucose unit or a
reactive center on modified cyclodextrin (such as an acid halide or ted ester bound to the
cyclodextrin). lt is desirable that the support material not dissolve (e.g to an observable extent
by, for e, visual inspection, gravimetric s, or spectroscopic methods) under use
conditions, for example in aqueous media. Examples of support materials include, but are not
limited to, microcrystalline cellulose, cellulose nanocrystals, polymer als (e.g acrylate
WO 68104
materials, methacrylate materials, styrenic als (eg, polystyrene), polyester materials,
nylon materials, and combinations thereof or inorganic materials (eg, silicates, silicones, metal
oxides such as alumina, a, zirconia, and hafnia, and combinations thereof). ln various
examples, the polymer materials are hornopolymers, copolymers, or resins (eg, resins
comprising ric materials). The support material may be hydroxyl or amino containing
polymer beads or irregular particles. The support material can be in the form a fiber (cg, pulps,
short cut, staple fibers, and continuous filaments), fiber bundles (e.g., yarn — both spun and
uous filament), fiber mats (eg, nonwovens — both staple and continuous filament), fabrics
(eg, lrnits, woven, nonwovens), membranes tog, films, spiral wound, and hollow fibers, cloth,
particulate leg, a powder), or a solid surface. in some embodiments, the fibrous substrate is a
osic substrate. osic substrates can comprise any suitable form of cellulose, such as
cellulose derived from plant sources such as wood pulp (eg, paper or paper fibers), cotton,
regenerated cellulose, ed cellulosics such ose esters and/or , and the like,
starch, polyvinyl alcohols and derivatives thereof. The cellulosic substrate can be in the form of a
fabric, such as a woven or nonwoven fabric, or as fibers, films, or any other le shape,
particularly shapes that provide high surface area or porosity. In a particular embodiment, the P—
CDP materials of the present sure are bonded to fibers, for example, a cellulosic fiber or a
fabric, such as cotton.
{(3899} In addition to the substrates listed in the preceding paragraph, the substrate may include
any of the ing: polyvinylamine, hylenimine, proteins, proteirnbased fibers (cg,
wool), chitosan and amine-bearing cellulose derivatives, polyarnide, vinyl chloride, vinyl acetate,
polyurethane, melamine, polyirnide, polystyrene, polyacryl, polyamide, acrylate butadiene
styrene (ABS), Barnox, PVC, nylon, EVA, PET, cellulose nitrate, cellulose acetate, mixed
cellulose ester, lfone, polyether sulfone, polyvinylidene fluoride (PVDF) or
polytetrafluoroethylene (PFTE or Teflon R), polyethylene, polypropylene, polycarbonate,
phosphine or thiol functional materials, and silicone or combinations f. The substrate may
also consist of silicon or silicon oxide, or glass leg. as inicrofibres). Suitable materials further
include textiles or synthetic or natural fiberubased materials. The material may exhibit any form
or shape and may for instance be in the form of a sheet, bead, granule, rod, fiber, foam or tube,
and may be rigid, flexible or elastic.
{$091} If ary, the material surface may be activated by any method known in the art,
such as known surface activation techniques, including for instance corona treatment, oxygen
plasma, argon plasina, selective plasma hromination, al grafting, allyl try, chemical
vapour deposition (CVD) of reactive groups, plasma activation, sputter coating, etching, or any
other known technique. For instance in the case of a glass surface, such an activation is usually
not required as such a surface is herein considered already activated. The purpose of the
activation of the surface is to provide for a surface suitable for the covalent attachment of a
surface—modifying functionality or (directly) of a primer polymer. Following its optional
activation, the e may he r functionalized. The e of the functionalization of the
surface is to provide for functional group suitable for the covalent ment of a prencoat
polymer.
{9992} The skilled artisan is well aware of the various possibilities of ing polymers
to optionally activated surfaces. These techniques generally involve the introduction of
amino, silane—, thiol—, hydroxyl~ and/or functionalities to the surface, and the
subsequent attachment thereto of the polymer.
[9993} The onalizati on may also comprise the introduction of spacers or linker to the
surface for the ment of the primer polymer to the surface at a predetermined distance. A
suitable spacer is for instance an alkylation by reacting the surface with for instance
aininoalkylsilane.
[9994} The P—Cf)? may he hound to the substrate via the linking groups of the present
sure (eg. via a hydroxyl or amino group of the linking group). A c‘linlrer moiety” refers to
the intervening atoms between the P—CDP and substrate. The terms “linker” and “linking moiety”
herein refer to any moiety that connects the substrate and PCT)? to one another, The linking
moiety can he a nt bond or a chemical functional group that directly connects the P—CDP
to the substrate. The linking moiety can contain a series of covalently bonded atoms and their
substituents which are collectively referred to as a linlting group. in some embodiments, linking
moieties are characterized by a first covalent bond or a al functional group that bonds the
P~CDP to a first end of the linlter group and a second covalent bond or chemical functional group
that bonds the second end of the linker group to the substrate. The first and second functionality,
which independently may or may not be present, and the linker group are collectively referred to
as the linker moiety. The linker moiety is d by the linking group, the first functionality if
present and the second functionality if present. In certain embodiments, the linker moiety
contains atoms interposed between the P—CDP and substrate, independent of the source of these
atoms and the reaction sequence used to synthesize the coniugate. In some embodiments, the
linker moiety is an aryl moiety as described herein. In some embodiments, the linker has one or
more of the following onalities: multifunctional isocyanate (cg, a diisocyanate), epoxy,
carboxylic acid, ester, ted ester, cyanuric chloride, cyanuric acid, acid chloride, halogen,
liydroxyl, amino, thiol, and phosphine
{0095} In some embodiments, the ECU? is grafted or bonded onto microcrystalline cellulose
(CMC). CMC is available in a variety of median particles sizes from about l0 — about 500 um
including about l0 pin, 20 um, 45 ttm, 50 pm, 65 pm, 75 um, l00 uni, lSO um, l80 itin, l90
pm, 200 pm, 225 um, 250 pm, 275 pm, 300 pm, 325 um, 350 um, 375 pm, 400 um, 42:3 pm,
450 pm, 475 um, and about 500 um and all particle sizes tlierebetween, In some embodiments,
I’uCDP is grafted or bonded onto CMC having a median particle size of about 50 um. In one
example, CMC is commercialized as Avicelm, In other embodiments, the P—CDP is grafted or
bonded onto a ric substrate other than cellulose, as described herein, in which the surface
is treated to produce e onal groups as disclosed herein, such as hydroxyl groups.
{00%} In some embodiments, the P~CDP—substrate complex (eg, a P—CDP crosslinked with
an aryl linker of formula (l)~CMC substrate complex) has a polymer thickness tie, the thickness
of the porous P—CDP particles on the surface of the substrate) of between about l nm to about
2000 nm. For e, P—CDP—substrate complex has a polymer ess of about l, 2, 3, 4, 5,
6, 7, 8, 9, l0, 20, 30, 40, 50, 60, 70 , 80, 90, l00, l50, 200, 250, 300, 350, 400, 450, 500, 550,
600, 650, 700, 750, 800, 850, 900, 950, l000, l050, ll00, ll50, L200, l250, I300, I350, l400,
l450, l500, l550, l600, l650, l700, l750, l300, l850, l900, l950, to about 2000 nm. In some
embodiments, P—CDP—substrate complex has a polymer thickness or" less than 1000 nrn. In some
ments, P—CDP—substrate complex as a polymer ess of about 800 nm. As will be
readily apparent to a skilled artisan, a having a lower thickness (eg, less than l000 nm} will
allow for faster kinetics to absorb inants, for e aqueous contaminants.
{0097} In some embodiments, the PuCDP—substrate complex (eg a P—CDP crosslinked with
an aryl linker or" formula (1)4)th substrate complex) has a contaminant adsorption capacity of
up to 500 mg contaminant/g CD. For example, the adsorption capacity may be up to about l, 2,
3,4,5,6,7,8,9,10,15,20,25,30,35,40,45,SO,55,60,65,70,75,80,85,90,95,100,lOS,
ll0,ll5,120,125,130,l35,l40,l45,l50,155,160,165,l70,l75,180,l85,190,195,200,
0,230,24o,250,260,270,zso,2ao,300,310,320,330,34o,350,3eo,37o,3so,390,
400, till), 420, 430, 440, 45G, 460, 470, 480, 490, to about 590 mg contaminant/g Cl). in some
embodiments, the adsorption capacity is up to about 200 mg contaminant/g Cl). ln some
embodiments, the contaminant is an c mieropollutant (eg. PFASS). In some embodiments,
the cyclodextrin is B—cyclodextrin. ln some embodiments, the linking groups are the linking
groups of Formulas (I), (ll), and/or (Ill).
{9998} ln some embodiments, the lLCDP—substrate complex (eg, a P—CDP crosslinked with
an aryl linlter of formula (l)~Cl\/lC substrate complex) has an brium contaminant adsorption
capacity of up to Sill) mg contaminant/g Cl). For example, the equilibrium adsorption ty
maybe up to about l, 2, 3, 4, 5, 6, 7, 8, 9, ll), l5, 20, 25, 30, 35, 40, 45, 5t), 55, 60, 65, '70, '75,
so,ss,9o,95,ioo,ios,iio,iis,izo,i25,iso,135,14o,i45,iso,155,ieo,165,17o,i75,
iso,iss,ieo,i95,200,2io,220,230,2ao,250,260,27o,2so,290,3oo,sio,320,330,340,
sso,3eo,370,3so,390,aoo,4io,420,430,44o,450,4eo,47o,4so,490,aiaeautsooing
contaminant/g CD. In some embodiments, the equilibrium adsorption capacity is up to about
200 mg contaminant/g Cl?~ In some embodiments, the contaminant is an anionic- micropollutant
(eg~ PFASs). ln some embodiments, the cyclodextrin is lodextrin. in some diinents,
the lii'ikiiig groups are the linking groups of Formulas (l), (ll), arid/or (lll).
} In some embodiments, the P~CDP—substrate complex (eg, a P—CDP crosslinked with
an aryl linlter of formula (DEB/h: substrate complex) has a relaxation time of less than 2
minutes, As will be appreciated by a skilled n, where processes with high tion times
slowly reach equilibrium, while processes with small tion times adapt to equilibrium
quickly. ln some embodiments, the contaminant is an anionic i'nicropolhitai'it (eg. . ln
some embodiments, the cyclodextrin is B-cyclodextrin. ln some embodiments, the linking
groups are the linking groups of Formulas (I), (ll), or (ill).
{lllllllll} ln some embodiments, any of the P-CDP materials disclosed herein are grafted or
bonded onto CMC directly or via a linlter group as defined herein. ln some einhodin'ients, the P-
CDP is homogenously distributed on the CMC surface. in some embodiments, the aryl linker is
an aryl linker of formula (l). ln some embodiments, the aryl linker is a linking groups of
Formula (ll). in some embodiments, the aryl linker is a linking groups ot‘li'ormula (ill). ln some
embodiments, the median particle size is about 50 pm. hi other embodiments, the median
le size is from about 1 about 250 am.
} CMC can also be distinguished by a particle shape known to impact flow characteristics
among other things. A nonulimiting list of particle shapes includes spherical —shaped), rod—
shaped, and needle—like. Particles can also be described as flat, flat and elongated, or be
characterized by their aspect ratio. ln some ments, the CMC has a spherical particle
shape. In some embodiments, the CMC is present in the form of agglomerates of smaller CMC
particles. Such CMC agglomerates can have particle sizes in the range of 200 um up to about 2
mm. For example, the particle sizes of CMC agglonierates can be about 200 um, about 300 um,
about 400 pm, about 500 pm, about 600 urn, about 700 um, about 800 um, about 900 um, about
1 mm, about 1.2 mm, about l3 mm, about 'l.4 mm, about l5 mm, about 1.6 mm, about l7 mm,
about 1.8 mm, about l9 mm, or about 2 mm, inclusive of all ranges therebetween.
litltlllliZl ln some embodiments, the ECU? is d or bonded onto CMC via a linking groups
of Formula (1). ln some embodiments, the ECU? is grafted or bonded onto CMC via a linking
groups of Formula (la). ln some embodiments, the P—CDP is grafted or bonded onto CMC via a
linking groups ot‘Formula (ll). In some embodiments, the RC1")? is grafted or bonded onto
CMC via a linking group of Formula (Ill),
{@9193} ln some embodiments, P~CDP of the present sure is grafted or bonded onto CMC
via an aryl linker, and the aryl linker is hoinogen ously distributed on the CMC crystal In some
embodiments, the median particle size is about 100 nm,
lttttll‘ldl In addition to the use of CMC as illustrated herein, examples of other potential t
materials include those materials described above, such as activated carbon, graphene oxide, as
well as silica and alumina.
{99195} ln some embodiments, it is desirable that the supported P~CDP materials disclosed
herein (e,g a P—CDP crosslinked with an aivl linker of formula (ll—CMC substrate complex) are
in the form of les having a narrow dispersity of particle sizes. ln some embodiments, the
particle size distribution has a low relative span of about 5 or less, where relative span is defined
by the ratio (D90—DiG}/’D50, where D90, D50, and Die are, respectively the diameters at which 90%,
50%, and 10% of the particles in the bution have a smaller diameter. le spans are no
more than 5, 4.5, 4, 3.5, 3, 2.5, 2, l, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.l, including all
ranges between.
{00106} In other various embodiments, the PuCDP may be grafted or bonded onto cellulose
nanocrystais (CN Cs). CNCs are the crystalline regions of ose mici'ofibrils obtained after
mechanical, chemical, and enzyme treatments. Depending on the source and, preparation
method, CNCs are available with lengths ranging front about lml000 nni and, widths ranging
from about 3-50 nm, inclusive of all values therehetween. For example, the CNCs have a length
of about l, 2, 3, 4, 5, 6, 7, 8, 9, l0, l5, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, '70, '75, 80, 85, 90,
95, ion, l50, zoo, 250, 3m, 350, 400, 450, soc, 550, eon, 6.50, 700, 750, see, 850, sec, 95a, to
about 1000 nrn. The CNCS have a Width of about 3, 4, 5, 6, '7, 8, 9, l0, ll, l2, 13, 14, l5, l6, l7,
is, 19, 20, 2t, 22, 23, 24, 25, 2e, 27, 2s, 29, so, 31, 32, 33, 34, 35, 36, 37 3s, 39, 40, 41, 42, 43,
44, 45, 46, 47, 48, 49, or about 50, In some embodiments, the P~CDP~CNC substrates may he 2-
3 times the size (length, and width) as the unbound CNCs. The CNCs are further characterized
by aspect ratio values (LCD) ranging from about 2~l 00 (George, J, et at, Cellulose nanoorystals:
synthesis, tirnctional properties, and applications, .Z‘v’anotechnofogu Science andApplications.
206045—54). For example, the CNCs have an aspect ratio of about 2, 5, l 0, 15, 20, 25, 30, '35,
40, 45, so, 55, no, 65, 7o, 75, so, as, so, 95, too, 105, no, its, 120, i25, l30, i35, 140, MS,
150, L55, ieo, res, i7o, i75, iao, 135, l90, l95,01‘l00.
{00107} In some embodiments, the P~CDP is grafted or bonded onto (INC via the linking groups
are the linking groups offinmulas (l), (ll), and/oi (ill) as described herein. ln some
ments, the P-CDP is grafted or bonded onto CMC via a linking groups of Formula (I). In
some embodiments, the P~CDP is gratted or bonded onto CMC via a linking groups of a
(II). in some embodiments, the P—CDP is grafted or bonded onto CMC via a linking groups of
Formula (111).
{00108} In some embodiments, P~CDP is grafted or bonded onto CNC via a linker, and the
linker is homogenously buted on the CNC crystal. In some ments, the median
particle size is about 100 nm.
{@8199} (INC can also be distinguished by particle shape known to impact flow characteristics
among other things. A nonulimiting list of particle shapes includes spherical (round—shaped), rod—
shaped, and —like. Particles can also be bed as flat, flat and elongated, or be
characterized by their aspect ratio. In some embodiments, the CNC has an aspect ratio of
between about 5 to about lQQ. For examples, the aspect ratio may be about 5, l0, l5, 20, 25, 30,
, 40, 45, 50, 55, 60, 65, '70, 75, 80, 85, 9t), 95 to about lt‘it‘i. In some embodiments, the CNC
aspect ratio is about 20—25. In some ments, the CNCs are needle—like. In some
embodiments, the CNC is present in the form of agglomerates of smaller CNC particles. Such
CNC agglomerates can have particle sizes which are 5400 times larger than the sizes of the
individual particles, depending on the sizes and number of the particles constituting the
aggregates.
} In some embodiments, the substrate is a fabric or fiber. 'I‘hus, in some embodiments,
the t disclosure provides a composition sing a I’nCDP grafted or bonded (e. g,
chemically or mechanically) to a fiber. In some embodiments, the PCB? is grafted or bonded
onto a fiber yia the linker of formulas (I), (II), and/or (III), as described herein. In some
embodiments, the fiber is a nonwoyen fiber. In some embodiments, the present disclosure
provides a composition comprising a P—CI)P grafted or bonded (eg chemically, adhesively, or
mechanically) to a fabric. In some embodiments, the P—CDP is grafted or bonded onto a fabric
via the linker of formulas (I), (II), or (III),
lll Fibers suitable for use include, but are not limited to fibers comprising any of the
polyi'ners disclosed herein, for example fibers made from highly oriented polymers, such as gel—
spun ultrahigh molecular weight polyethylene fibers (e.g, SPECTRA® fibers from Honeywell
Advanced Fibers of Morristowri, Nl and DYNEMA® fibers from DSIVI High Performance
Fibers Co of the Netherlands), melt-spun polyethylene fibers (eg, CERTRANG?) fibers from
Celanese Fibers of Charlotte, NC), melt~spun nylon fibers (eg, high tenacity type nylon 6,6
fibers from a of Wichita, Kans), melt—spun polyester fibers (e.g high ty type
polyethylene terephthalate fibers from lnyista of Wichita, , and sintered polyethylene
fibers (eg, ’l‘ENSYLONfii‘) fibers from l'l‘S of Charlotte, NC). Suitable fibers also include those
made from rigidurod polymers, such as lyotropic rigid~rod polymers, heterocyclic rigid~rod
rs, and thermotropic liquid—crystalline polymers. Suitable fibers also include those made
from regenerated cellulose ing ve wet spun Viscose rayon (Viscose from Birla of
lndia or Lenzing of Austria}, cuproaniinoniurn based ray on (Cupro® Bernberg,‘ from Asahi Kasei
of Japan), or air gap spun froni Nit/{MO solvent ('l'encelfi's) from Lenzing of Austria). Suitable
fibers made from lyotropic rigidurod polymers e araniid fibers, such as polylpu
leneterephthalainide) fibers (egg, KE’VLARGE fibers from DuPont of Wilmington, Del. and
’l‘WARONd‘) fibers from 'l‘eijin of Japan) and fibers made from a l:l copolyterephthalaniide of
3,4’“dianiinodiphenylether and pnphenylenedianiine (cg, 'l'ECHNORA® fibers front 'l'eiiin of
. Suitable fibers made from heterocyclic rigidmrod polymers, such as pnphenylene
lieterocyclics, include poly(pnphenylenen2,6-benzobisoxazole) fibers (PEG fibers) (cg.
ZYLON® fibers from 'l'oyobo of Japan), polytpnphenylenenf/l,ombenzobisthiazole) fibers (PBZT
fibers), and, polylZfi—diimidazold,5—b:4",5’—e}pyridinylene—l,4—(2,5nrliliydroxy)phenylene} fibers
(PIPE) fibers) (ego, M5® fibers from DuPont of Wilmington, Del). Suitable fibers made from
therinotropic liquidmcrystalline polymers e poly(o—hydroxy~2~napthoic acid—coalit—
hydroxybenzoic acid) fibers (erg, VECTRAN® fibers from Celanese of Charlotte, NC).
Suitable fibers also include carbon fibers, such as those made from the high temperature
pyrolysis of rayon, polyacrylonitrile (eg, OPF® fibers from Dow of Midland, Mich), and
orphic hydrocarbon tar (eg, THORNEL® fibers from Cytec of Greenville, SC). In
n possibly red embodiments, the yarns or fibers of the textile layers comprise fibers
selected from, the group consisting of un ultrahigh molecular weight hylene fibers,
rnelt~spun polyethylene fibers, melt—spun nylon fibers, melt—spun polyester fibers, sintered
polyethylene fibers, aramid , PEG fibers, PBZT fibers, PIPE) fibers, poly'(6—hydroxy—2—
napthoic acid—co—d—hydroxybenzoic acid) fibers, carbon fibers, and combinations thereof~
{$49112} The P—CDP materials of the present disclosure can be adhered to such fibers by means
of a suitable binder polymer as described herein, or chemically bonded to such fibers by
functional izing the surface of the fibers as described herein (cg, e oxidation to e
surface hydroxyl groups) and either forming the P—CDP in situ on the fiber surface, or by
reacting a suitably functionalized P—CDP directly with the functionalized fiber surface, or
indirectly Via a linlrer moiety as described herein.
{98113} The fibers may be converted to nonwoyens (either before or after attachment of the P—
010?) by ent bonding methods. uous fibers can be formed into a web using industry
standard spunbond type technologies while staple fibers can be formed into a web using ry
standard carding, airlaid, or wetlaid technologies. Typical bonding methods include: calendar
(pressure and heat), ir heat, mechanical entanglement, hydrodynamic entanglement, needle
punching, and chemical bonding and/or resin bonding. The calendar, thru—air heat, and chemical
bonding are the red bonding methods for the starch polymer fibers. lly bendable
fibers are required for the pressurized heat and ir heat bonding methods.
{Mill/l} The fibers of the present invention may also be bonded or combined with other
synthetic or natural fibers to make nonwoven articles. The synthetic or natural fibers may be
blended, together in the forming process or used in discrete layers. Suitable synthetic fibers
include fibers made from polypropylene, polyethylene, polyester, polyacrylates, and, mers
thereof and mixtures thereof. Natural fibers include cellulosic fibers and tives f.
le cellulosic fibers include those derived from any tree or vegetation, including hardwood
fibers, softwood fibers, hemp, and, . Also included are fibers made from processed natural
cellulosic resources such as rayon.
lfil The fibers of the present invention may be used to make nonwovens, among other
suitable articles. Nonwoven articles are defined as articles that contains greater than l5% of a
plurality of fibers that are continuous or non—continuous and physically and/or chemically
attached to one another. The nonwoyen may be combined with additional noriwoyens or films to
produce a layered product used either by itself or as a component in a complex, combination of
other materials. Preferred articles are disposable, en articles. The resultant products may
find use in filters for air, oil and water; textile fabrics such as rniero fiber or breathable fabrics
having improved moisture and odor absorption and softness of wear; electrostatieally charged,
ured webs for collecting and removing dust and pollutants, medical textiles such as surgical
drapes, wound ng, es, dermal patches, textiles for absorbing water and oil for use in
oil or water spill clean—up, etc” The articles of the present invention may also include disposable
ens for hygiene and medical applications to absorb off~odors Hygiene applications
include such items as wipes; diapers, particularly the top sheet or baclr sheet; and feminine pads
or products, particularly the top sheet.
{lllll 16} The yarns or fibers of the textile layers can have any suitable weight per unit length
(cg denier). Typically, the fibers have a weight per unit length of about l to about 50 denier per
filament (l to about 50 g per 9000 meters). The yarns n a plurality of filaments from l0 to
about 5000.
{98117} ln some embodiments, the PuCDP is adhesively bound to a substrate such as a fiber or
fabric Via a binder. ln some embodiments, the P—CDP is coated on a substrate such as a fiber or
fabric via a binder. in some embodiments, the P—CDP is bound to or coated on a substrate such
as a fiber or fabric via a binder by introducing the e to stable s dispersions of the P—
CDP particles in conjunction with binders. 'l'he P—CDP particle dispersion may be l~50% by
weight and a polymeric binder material may be present in an emulsion or solution in l~50% by
weight. For example, the P—CDP particle dispersion may be present at about 1, 2, 3, 4, 5, 6, 7, 8,
9,10,ll,12,13,l4,l5,l6,l7,l8,l9, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 3l, 32, 33, 34,
, 36, 3'7, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or about 50% by . The polymeric
binder material may be present in an emulsion or solution at about l, 2, 3, 4, 5, 6, 7, 8, 9, l0, ll,
12, i3, l4, l5, l6, 17, is, l9, 2o, 21, 22, :23 :24, 25, 2e, 27, 2s, 29, 3o, 31, 3:2 33, 34, 35, 36,, 37,
38, 39, 40, 4l or about 50 % by weight. Additional auxiliary
, 42, 43, 44, 4-5, 4-6, 47, 48, 49,
agents can be used as minor components by weight to control the wetting by the substrate
(wetting agent), solution foaming or rning, softening agent for substrate hand, and/or
catalyst for binder curing.
{99118} A variety of g techniques known in the art can be applied, such as: dip and
squeeze, solution casting, foam coating, or spraying of the formulated solution onto the substrate
of interest. Substrates include, but are not limited to: woven, knit or nonwoyen fabrics,
continuous filament yarns, spun yarns, spun fibers, wood surfaces, and thermoplastic surfaces.
In some embodiments, upon application of the formulated on to the substrate, the combined
system will be dried to remove the water solvent at which time an even film of P—CDP particles
mixed with polymeric binder will be present During the drying process, the binder material
present as an emulsified polymer will llow together and hecorne a continuous phase. Depending
on the choice of hinder, the P—CDP particles may be held in place through mechanical means or
adhesion to the binder continuous phase only, or additional covalent linkages could be present if
a cure—able binder is selected. Such covalent es could extend the underlying substrate
which would further increase the durability of the P—CDP particle coating.
{99119} As will be readily apparent to a skilled artisan, the resultant PuCDl’ particle filin
conforms to the underlying substrate and is durable to physical on, and g such that
the article can be ed. rmore, if the P—CDP particles have access to the aqueous or
vapor phase within the g, they will demonstrate the same ive and high affinity small
molecule adsorption characteristics as the monolithic particles. Such form factors can be
converted into filter dges, d filters, nonwoven needlepunched filters, hygienic
nonwovens, and apparel.
{M13129} A variety of binders known to a skilled artisan may he used in the context of the present
disclosure, such as any of those disclosed in US Patent Publication No. 20l4/Ol78457 Al, which
is hereby incorporated by reference in its entirety. Suitable hinders include, but are not limited to,
latex binders, isocyanate hinders (eg, blocked isocyanate hinders), acrylic binders (eg,
nonionic acrylic binders), polyurethane binders (eg, aliphatic polyurethane binders and
her based polyurethane binders), epoxy hinders, urea/formaldehyde resins,
inelarnine/fornialdehyde , polyvinylalcohol (PvOH) resins (disclosed in US Patent No.
,496,649, which is hereby incorporated by reference in its entirety) and crosslinked forrns
thereof, poly—ethylenevinylalcohol (EvOH) and crosslinked forms thereof, polym
ethylenevinylacetate (EVA), starch and starch derivatives, cellulose ether derivatives, and
cellulose ester tives, Small molecule, polymeric or inorganic inhing agents could be
used additionally including dehyde, glyoxal, diisocyanates, diepoxides, and/or sodiuni
tetraborate, and ations thereof.
{(39121} ln some embodiments, the P—CDP particles are mechanically bound to a surface, such
as a fibrillating fiber Fibrillating fibers are used to create high surface area, extended ks
which can wrap around and entrap particulate matter. Fibers such as fibrillating polyolefin (such
as Mitsui Fybrel®), fibrillating regenerated cellulose (such as Lenzing TencelTM) or fibrillating
c (such as Sterling Fibers CFFTM) are deployed in wet laid ses to create specialty
papers which ent mechanical properties, good wet strength, and the ability to hold
particulate matter (US Patent No. 4,565,727, which is hereby incorporated by reference in its
entirety), Onxy Specialty Papers, l-lelsa Corporation, and others. in particular, powdered
activated carbon particles with diameters greater than 5 microns have been loaded into specialty
carbon papers that are deployed in liquid and vapor filtration applications such as point of use
water filters or cabin air filters,
{hill 22} ln the paper rnahing s, an aqueous dispersion or slurry blend of short cut fibers
(such as wood pulp, polyester, nylon, or polyolel’in), fibrillating fibers (such as ®,
'llencell‘M, or CFF’E‘M), and particle powder material are mixed (eg, under high shear). This
mixture can then be rapidly passed through a nonwoven mesh or screen to deposit a wet laid
nonwoven web. This web is dried (eg, in hot air oven or on heated rolls) to remove the water
carrier. r bonding may be achieved through cold or hot calendaring either in flat format or
with a patterned roll to produce the bonded specialty paper. The particulate powder used can be
a dispersion of P—CDP particulates of d particle size. Particulate size can be set Via
grinding and milling techniques as defined previously. The particulate loading in the finished
nonwoven can he as high as 60% by weight. The particulate can be used alone or blended with
other particulate such as powdered activated carbon. onal chemical s, such as those
bed herein, may be used to alter or enhance the ties of the paper and will be applied
as one skilled in the art.
{bulls} The resultant powder loaded papers are amenable to a high loading of KGB? adsorbent
particles in a convenient paper filter form factor for water and/or air filtration. The paper can be
used in the flat form, cut into a variety of shapes, or pleated and bonded into a filter media
cartridge.
lilllllZK-ll in some embodiments, the PCB? particles are mechanically entangled in yarn leg,
continuous filament yarn). In some embodiments, the P—CDP particles are mechanically
entangled in continuous filament yarn. As will be readily apparent to a skilled artisan, a l
subset of yarn finishing s the mechanical binding of particulate matter within a continuous
filanient yarn in some circumstances. When a yarn leg, continuous filament) sed of
multiple filaments of a typical tic polymer such as polyethyleneterephthalate (PET) or
polyamide (nylon 6 or nylon 6,6) that bears n'iicrofibrilla‘ting tendencies on each filament
surface, there exists the possibility to incorporate particulate within the yarn bundles. The P—
CDP particles of the present disclosure can be incorporated into the yarn in a variety of ways
One non—limiting example is to apply a dispersion of the P—CDP particles of interest via dip
coating or oil roll application onto a moving yarn bundle during the false twist texturing process.
ln this process, the nts are mechanically separated via twisting, first in one direction
followed by the opposite ion. After the first twisting, the filaments are individualized and
void space is presented within the yarn bundle. The sion solution is applied at this point
within the process after which the bundles are twisted back to the rd orientation and the
yarn heated to dry the solution. This process enables the application of dispersion particles
within the yarn bundles that are held in place by the continuous filaments and microfibrils
emanating from the uous filament surface. Such approaches have been used to apply
various micron sized particles to continuous filament yarns, including microcapsules (US Patent
ation No. 262646 Al which is hereby incorporated by reference in its entirety),
metallic silver inieroparticles (US Patent Publication No. 20l5/036l595 Al which is hereby
incorporated by reference in its entirety), and (US Patent Publication No. 2006/0067965 Al,
which is hereby incorporated, by reference in its entirety) other onal particles to synthetic
fiber yarn bundles. These textured and particle loaded yarns may then be processed through
typical means to create knit and woven fabrics for use in apparel, upholstery, medical, displays,
or other uses.
{99125; In some embodiments, the PSI)? particles are incorporated, into thermally—bonded,
particulate pressed forms. A common form factor for powdered ent material is in
thermally/"bonded pressed forms. Such form factors can contain as high as 95% by weight lb
CDP particles, with the addition of fibrillating fibers (Fybrelfil), 'l'encel"M, or Cll‘FTM), sometimes
inorganic materials such as attapulgite clays, and finally an organic binder material (most
typically cellulose esters and similar derivatives) to create a porous composite structure with
adequate mechanical strength and particulate holding efficiency for medium pressure filtration
applications such as faucet filters and refrigerator filters (US Patent Nos 5,488,02l and
, l 4i both of which are hereby orated by reference in their entireties).
{£39126} P—CDP dry particles or dispersion can be used in place of or blended with other
ent materials to form such a composite adsorbent P—CDP particulate—containing forms as
described above In such embodiments, the solid dry components may be dry d,
optionally ing dry P-CDP particles and organic binder powder with or without nic
clays and/or fibrillating fibers, If an aqueous dispersion of P—CDP particles is used, they may be
diluted with water and added to the mixture. Water is added (egg in 80~l 50 wt%) and the
mixture is blended (eg under high shear) to create a c material. This n'iaterial may be
formed into the d form factor, dried and cured at temperatures ranging from l25 to 250 "C.
This final form factor presents the PCB? adsorbent particles in a form factor common to and
useful for point of use water filters,
{99127} in some embodiments, the P~CDP particles are incorporation into solution processed
polyiner form s. A, variety of means are available to produce filter membrane materials.
For e, via solution cast films or extrude hollow fibers of membrane polymers where
controlled coagulation s a condensed film of controlled pore size. ln some embodiments, a
polymer such as cellulose acetate dissolved in a water miscible organic solvent such as NMP,
DMSQ, or 'l‘llF is used. This solution can be cast as a film into a water bath which causes rapid
ation of the cellulose acetate r and densification of the film. These films may be
processed on roll to roll equipment and many layers are wrapped to create a spiral wound
membrane filter for use in filtration, ultranfiltration, gas filtration, or reverse osmosis
applications. In place of cellulose acetate, common polymers used include polyamides,
polyolefins, lfones, polyetliersulfones, polyvinylidene de, and similar engineered
thernioplastics. It is also possible to extrude hollow fibers into the aqueous solution to create
membrane fibers through the phase inversion process that are ltnown as hollow—fiber membranes
commonly used for dialysis, reverse osmosis, and nation applications.
ionizer in some embodiments, the PnCDP particle matter is incorporated into membrane
material to enhance the performance of the membrane materials. For example, it is possible to
have present in the aqueous ation bath a small ty of P—CDP particle dispersion that
will become incorporated into the dense portions or porous portions of the membrane during the
phase inversion process. A, second manner to incorporate the PCB? les into the membrane
is the incorporation of a small amount of wellvdispersed particles into the organic solution of the
ne polymer that become encapsulated in the membrane following coagulation. Through
each of these methods? the production of P-CDP loaded polymer forms may be enabled. in
various ments, such as micro—filtration, ultra-filtration, and reverse osmosis, the P—CDP
particle incorporation acts to enhance the n'iicropollutant ren'ioval of the membrane system.
{@0129} in some embodiments, the PCB? particles are incorporated into melt extruded
th ermoplastics (cg fibers and molded parts). Having access to small diameter dry powder P~
CDP particle material of low polydispersity enables its incorporation into melt sed
polymer forms including fibers and molded parts. Typical thermoplastics of use include
polyethyleneterephthalate, co—polyesters, efins, and polyamides. Typical extrusion
temperatures are between 250—300 "C and therefore l’uCDP particle stability to those
temperatures either under air (most preferred) or inert atmosphere is required. Single or twin—
screw extrusion is used to blend and mix the powdered material at elevated temperatures under
shear with the thermoplastic in up to five weight percent. Once adequately mixed, the blended
components can be extruded through small round or ise shaped orifices and drawn to
produce fibers g the particulate matter linear ies ranging from l to 20 denier per
filament. A common particle added to most thermoplastic fibers is titanium dioxide added to
whiten and deluster the fiber. The l’nCDP particles will be added in a similar fashion. ln the
most ideal embodiment, the l’nCDP particles will migrate to the surface of the fibers and bloom
due to their higher surface energy such that a portion of the particles are t and accessible
by the vapor or liquid phase. in other embodiments, instead of extruding the polymer melt
through small es, it can be blow molded or otherwise melt processed to produce a plastic
part. This plastic part will also bear the PnCDP particles that bloom to the surface and become
active for the removal of small molecule micropollutants leg. anionic Mill’s) from the vapor and
liquid phase.
{lilililll} The P—CDP of the present sure can be supported or formed into a variety of
shapes (or formmfactors) suitable for various applications. For example, the P—CDP materials of
the present sure can be in the form of s, granules, formed into discs, eg, in a
cellulosic material such as paper or other ven forms, or extruded or pressed into various
shapes suitable for, eg, filtration, water treatment, sample absorption, etc. as described herein,
{@9131} While it is not unknown to provide adsorbents in a. supported form, it is ant that
the methods used to affix the adsorbent to the substrate or support are sufficiently robust so as to
withstand the use conditions. Further, the means of attachment to the substrate should not
interfere with or block the adsorption mechanism of the adsorbent. The adsorbents disclosed
herein can be attached to supports, as described herein, so that the resulting performance
characteristics are only minimally affected by the attachment method. in various embodiments,
the ted polymeric als of the present invention provide performance teristics
which are at least 50% of the same performance characteristic which would be provided by the
same composition of adsorbent prepared without a support material (based on lent
amounts of the ent) when measured under identical conditions. So for example a porous
material grafted to microcrystalline cellulose (eg, a l’uCDP crosslinked with an aryl linker of
formula (l)_Ch/lC substrate complex) may have at least 50% of one or more of a particular
performance characteristic found in unsupported porous material tested under the same
conditions.
{98132} in some embodiments, the performance characteristic can be the amount of uptake
l:adsorption capacity) of a particular pollutant, measured as the milligrams of pollutant adsorbed
per gram P—CDP particle under particular conditions. ln other embodiments, the performance
teristic can be the equilibrium adsorption capacity (tie), defined as discussed herein as:
our,“
qt? m gmax
CQKL+1
wherein qmm (mg ant/g adsorbent) is the maximum adsorption ty of the
t for a particular ant at equilibrium, K1, (mol‘l) is the equilibrium constant and
(:8 (mid) is the pollutant concentration at equilibrium
{99133} ln still other embodiments, the performance characteristic is the rate at which
equilibrium adsorption of a pollutant is reached (rate of equilibrium adsorption for a particular
adsorbent. This rate can be expressed as the time required for a supported or unsupported RC1")?
of the present disclosure to reach brium for a particular adsorbed species (or pollutant),
{99134} ln still other ments, the performance characteristic is the rate at which
competing adsorbents sequester ants. Competing adsorbents may he unsupported P—CDPs
as described herein, or other agents, such as activated carbons (powdered or granular), ion-
ge resins, and specialized resins used for solid—phase extraction (eg, HEB),
{(38135} For any of these performance characteristics disclosed above, the mance of the
supported P—CDP ot‘ the present disclosure is at least about 50%, 60%, 70%, 80%, 90%, WOO/E),
l20%, 140%, least, {80%, 2009/9, 220%, 2a %, zoos/ii, 280%, 300%, 350%, 4a %, 450%,
500% or greater, inclusive of all values, ranges, and subranges therebetween compared to
unsupported P~CDP of the same composition, tested under essentially the same conditions, eg,
with the same pollutant, temperature, pressure, exposure time, etc,
{(38136} The performance characteristics of the present disclosure can be measured, for example
based on bisphenol A or PFASs or another suitable specie as disclosed herein, by a variety of
methods which will be readily nt to a skilled artisan. For example, the contaminant may
be measured at initial concentrations of EPA or another suitable specie g from l ppb (or l
microgram/L or 5 nM) to l ppt (or l g/L or 5 rnM} in any aqueous sample, including but not
limited to drinlring water, wastewater, ground water, aqueous extracts from contaminated soils,
landfill leachates, purified water, or other waters containing salts, or other organic . The
pl-l may be range from 0—l4. For example, the pl-l may be 0, l, 2, 3, 4, 5, t3, 7, 8, 9, l0, ll, l2,
13, or l4, inclusive of all ranges etween. The performance teristics may be
measured substantially as described herein (eg, in Examples l and 2), with routine
modifications (such as temperature and pressure) also being oned.
{@9137} in some embodiments, the present disclosure es an article of manufacture
comprising one or more P—CDl’s or one or more P—CDlLsuhstrate complexes of the present
disclosure.
{98138} ln an embodiment, the article of cture is protective equipment. in an
embodiment, the article of manufacture is clothing. For example, the article of manufacture is
clothing comprising one or more P—CDPs or one or more P—CDl’nsubstrate complexes of the
present disclosure leg, clothing such as a uniform at least partially coated with the porous
polymeric material or. composition). In r example, the article is filtration medium
sing one or more P—CDPs or one or more P—CDl’nsuhstrate complexes of the present
disclosure. The filtration medium can be used as a gas mask . in an embodiment, the article
is a gas mash comprising the filtration medium. In some embodiments, the article is an
extraction device.
{99139} In another embodiment, the article is a solid phase hase (Si’lvfl'i) tion
device comprising one or more PUCDPs or one or more P—CDl’nsubstrate complexes of the
present disclosure, where the P—CDPs or PmCDPeubstrate complexes is the extracting phase the
device
{@9149} ln another embodiment, the article is a device for a solidmphase extraction of polar and
semi,~polar organic molecules. The device comprises one or more P~CDPs or one or more P-
CDP~suhstrate xes of the present disclosure d oflllB media (hydrophilic/lipophilic
balanced). The article with the one or more P—CDPs or one or more P~CDP~suhstrate complexes
outperforms the Hill media.
Willi-ll} ln another embodiment, the article is a device for liquid filtration of polar and semi—
polar organic molecules. The. device comprises one or more RCDPS or one or more Fvlelll
substrate complexes of the iresertt disclosure adhered within a fibrous web (as disclosed in US.
Patent No. 7,655,l l 2., which is hereby incorporated by reference in its entirety). Other
embodiments include the device comprising P-CDP powders fused via thermoplastic hinder
polymer to create porous monolithic filtration media (as sed in US Patent No. 4,753,728,
which is hereby incorporated by reference in its ty).
{98142} The P—CDP als of the present disclosure, in the various forms and form factors
disclosed herein (including supported and unsupported P—CDP materials) can be used in any
application in which it is desirable to separate compounds (eg anionic or cationic MPs) from a
fluid l:gases such as air, liquids such as water, s beverages, biological fluids, etc). The l)—
CDP materials can be used to “trap” or adsorb desired species for further is or
quantification (eg, in analytical testing for environmental pollutants in air or water), to separate
mixtures (eg, in a chromatographic tion), or to isolate desirable or valuable species which
are present as a dilute form in a fluid. in some embodiments, the P—CDP materials of the present
disclosure can be used to purify a fluid (eg, by removing undesirable or noxious impurities), or
can be used to isolate desirable compounds from a mixture or dilute fluid solution.
ltltllclizll ln some embodiments, the present disclosure provides a method of removing one or
more compounds (eg. anionic MPs) from a fluid sample or determining the presence or e
of one or more compounds in a fluid sample comprising: a) contacting the sample with the
porous polymeric material of the t sure or the supported porous polymeric material
of the present disclosure for an incubation period; b) separating the porous polymeric material or
supported porous polymeric material after the incubation period from the ; and c) heating
the porous polymeric material or supported porous polymeric material separated in step b), or
contacting the porous polymeric material or supported porous polymeric material ted in
step b) with a t, thereby releasing at least a portion of the compounds from the porous
polymeric al or supported porous polymeric material; and dl) optionally isolating at. least a
portion of the compounds released in step c), or d2) ining the presence or absence of the
compounds ed in step c), wherein the presence of one or more compounds correlates to the
presence of the one or more compounds in the sample, in some embodiments, the one or more
cyclodextrin moieties are li—cyclodextrin moieties, in some embodiments, said determining is
d out by gas chromatography, liquid chrornatography, supercritical fluid chromatography,
or mass spectrometry. in some embodiments, said contacting is by flowing the aqueous phase
across, over, around, or through the supported porous polymeric al. in some
embodiments, the aqueous sample is contacted with the l’uCDPusubstrate complex under static
conditions for an incubation period and after the incubation period the aqueous sample is
separated from the porous polymeric material. In some embodiments, the sample is a food and
the compounds are volatile c compounds. In some embodiments, the aqueous sample is
drinlring water, wastewater, ground water, aqueous extracts from inated soils, or landfill
leachates. In some embodiments, the sample is a perfume or fragrance and the compounds are
volatile organic compounds. In some embodiments, the compounds are anionic micropollutants,
heavy metals, and/or dyes. In some embodiments, the compounds are c MPs, such as
PFASs (eg. polyfluorinated alhyl compounds and/or perfluorinated allryl compounds). ln some
embodiments, the PEASs are PFOA and/or l’FOS.
339144} In an embodiment, a method of ing an aqueous sample comprising one or more
organic compounds is provided, the method comprising contacting the aqueous sample with the
porous ric material of the present disclosure or the supported porous polymeric material
of the present disclosure such that, for example, at least St‘i‘Z/o to at least 99% of the one or more
pollutants is bound to one or more of the cyclodextrin (cg, ficyclodextrin) moieties of the
porous polymeric material. For example, the aqueous sample is flowed across, around, or
through the porous polymeric material. in another example, the aqueous sample contacted with
the porous polymeric al or the supported porous polymeric material under static conditions
for an incubation period and after the incubation period the aqueous sample is separated (e. g, by
filtration) from the porous polymeric al. The method can be used to purify aqueous
samples such as drinking water, atei', ground water, aqueous extracts from contaminated
soils, and landfill leachates, In some embodiments, the organic compounds are anionic lVlPs,
such as PFASs.
{MIME} In an embodiment, a method of determining the presence or e of nds
(eg, anionic MPs) in a sample comprises: a) ting the sample with the porous polymeric
material of the present disclosure or the supported porous polymeric material of the present
disclosure for an incubation period (eg, l minute or less, 5 s or less, or l0 minutes or
less); b) isolating the complex from a) from the sample; and c) heating the x material
from b) or contacting the complex from b) with a solvent (eg, methanol) such that at least part
of the compounds are then released by the porous material; and d) determining the presence or
e of any compounds, wherein the presence of one or more nds correlates to the
presence of the one or more compounds in the sample, or isolating (e.g by filtration) the
compounds. For example, the determining (eg, analysis) is carried out by gas chromatography
or mass spectrometry. For example, the sample is a food or beverage (eg, mill<, wine, fruitjuice
{e.g., orange juice, appleiuice, and grapeiuice), or an lic beverage (eg, beer and spirits))
and the compounds are volatile organic compounds. The porous polymeric material or supported
porous polymeric material can be the extracting phase in a solid phase microextraction E)
device. In some embodiments, the organic compounds are c lit/3’s, such as PFASs.
{@9146} in an embodiment, a method for removing nds (eg, organic compounds) from
a sample comprises: a) contacting the sample with the porous polymeric material of the present
disclosure or the supported porous ric material of the present disclosure for an incubation
period such that at least some of the compounds are sequestered in the polymer; b) isolating
complex from a) from the sample; c) heating the complex from b) or contacting the x
from b) with a solvent (cg, methanol) such that at least part of the nds are released by
the porous polymeric material; and d) optionally, isolating at least a portion of the compounds.
ln some ments, the compounds are anionic N 3‘s, such as l’FASs.
{99147} Ayariety of nds can be involved (cg, sequestered, detected, and/or isolated) in
the s. The nds can he organic compounds. The compounds can be desirable
compounds such as tlayorants leg, compounds that impact the palatability of foods) or
pharmaceutical compounds (or pharmaceutical ediates), contaminants leg, PCBs, PBAs,
etc), and/or adulterants In some embodiments, the compounds are anionic lit/[P5, such as PPASs.
ln some embodiments, the compounds are c MPs selected from the group consisting of
genifibrozil, oxybenzone, diolotenac, ioxynil, ketoprot‘en, naproxen, sulfamethoxazole, warfarm,
2,4—dichlorophenoxyacetic acid, clol’ibric acid, ibuprofen, 2—methyl—4—chlorophenoxyacetic acid,
mecoprop, yalsartan, perthrorobutanoic acid, perlluorobutane sult‘onic acid, pertluoropentanoic
acid, oropentane sulfonic acid, peril uorohexanoic acid, pertluorohexane sulfonic acid,
peril uoroheptanoic acid, peril uoroheptane sult‘onic acid, pertluorooctanoic acid, peril uorooctane
sull’onic acid, perl'luorononanoic acid, pertluorononane sulfonic acid, perthrorodecanoic acid,
periluorodecane sulfonic acid, oroundecanoic acid, periluorododecanoic acid,
perlluorotridecanoic acid, perl'luorotetradecanoic acid, 2,3,3,3—tetrailuoro—Z—
(heptatluoropropoxy) propanoate, and combinations thereof.
{@8148} The cyclodextrins are chiral. in an embodiment, a chiral compound is sequestered,
detected, and/or isolated. in an embodiment, a chiral column (eg, a preparative—scale or
WO 68104
analytical—scale column is packed with a chiral porous polymeric material or composition
comprising chiral porous polymeric material) is used to separate and detect or isolate (or at least
significantly enrich the sample in one omer} a single enantiomer of a compound.
{B9149} ln the methods, the porous polymeric material or the supported porous ric
material can be regenerated {e.g., for reuse in the s). For, example, the porous polymeric
material is regenerated by heating and/or exposure to solvent (e.g ls such as methanol or
ethanol, and aqueous mixtures thereof).
{@9159} The following es are provided to illustrate the present disclosure, and should not
be construed as limiting thereof.
Example 1: sis ot‘fi—CDETDl polymer
{B9151} Reagents: 841D: Wacker, Cavarnax W7 (Used as~is); ne—2,4_cliisocyanate ('l'Dl):
Sigma Aldrich, 95%, Product # T398533; N,l\l"Dimethylformamide (EMF): Fisher Chemical,
Certified ACS grade, Catalogti Dllguél; Water; Deionized (Dl) water from Milli—Q system
} Procedure: fi—CD (60.0 g, 0.0529 rnol, l erg.) was dissolved in l20 mL EMF in a 500
mL oneuneck round hottorn flask at a magnetic stir rate of 400 rpm and the temperature was set
to 80 “C. An oil bath equipped with thermocouple was used for heating. After completely
dissolving B—CD, 'l'Dl (36.8 g, 0.21l5 mol, 4 eq.) was added subsequently to the flask at 80 0C.
Air bubbles were observed likely due to the presence of water in the reaction medium. After
about 1 min when there was no bubble produced, the flask was capped with a rubber septum.
After 3 h, the reaction was stopped by adding 30 mL of methanol and turning off the heating.
The resulting viscous clear on was precipitated into 1.2 L methanol to obtain white powder
product. After l h stirring, the crude product was filtered under vacuum using a Buchn er funnel.
The filtered polymer powder was transferred back to a 2~L beaker and washed again with 1.5 L
DI water \ 2 times and l2 L methanol X 1 time During each cycle the washing time was l h.
After final filtration, wet solid product was transferred to an evaporating dish, which was placed
into a vacuum oven at 80 °C to yield 726 g dry polymer, lt was ed that starting at a 6
equivalence of Till and above, a hard gel is obtained which is ditficult to work up. In contrast,
TELCD ratios in the range of 2: l—S: 1 provide a powder material upon stopping the reaction with
methanoi (Table 1}. These polymers are aiso soiuhie in a variety soiyents such as DIVE but not in
water. See Fig. 5 for a further comparison of the polymers of Table 1.
Table 1: Synthesis of fi—CD—TDE eis
Materiai h—fggbi Soivent "1“ 9(3) Time Yieid Notes
SL-E—GGtA 1:4 Anhydrous DMF 80 15 h 58% White powder*
ESL-20828 1:fi Anhydrous DMF 80 15 h We Get
SL-O()2C 1:8 Anhydrous DMF 80 ’15 31 111a Gei
02B 1:1(3 Anhydrous DMF 80 16 h We Gei
SL—2-004A 1:2 Anhydrous DMF 80 3 h 36% White powder
04B 1:3 Anhydrous DMF 50 3 h 55% White powder
SL004C 1:4 Anhydrous DMF so 3 h 61% White powder
SL~2~604D 1:5 Anhydrous one so 3 h 72% White powder
SL004E 1:6 Anhydrous DMF 80 3 h We Get
*Washed with methanoix1,water x 2, and methanoix1.
{(38153} fi~CD—TDI thnnizntion s
{@9154} The fi~CD—TDI poiymer was thither optimized by checking the soiubihty of BSD (es~is
and dried) in reguiar and anhydrous DMF, the i'esuits of which are shown in Table 2. As—is B~CD
has a water content in the range of 12— i 4% water.
Table 2: Soivents and iii-CD water coi'itent comparison in the synthesis of B-CD—TDI polymers
Solubility test Register DMF ous EMF
Asais £34312) 0.5 giant. 0.5 giant.
Bried sen 0.25 g/mL 0.22 g/mL
; As shown in Table 2,, the soiuhiiity of B—CD is significantly affected based on its water
content. Consequently, when dried, {LCD is used, the poiyineiizntion can only he d, out
iowei initial concentrations that impact reaction yields. In comparison, the water content of
DIVE? is insignificant and therefore has iess impact on the soluhihtyt ing us to use regular
DIX/ll: in the reaction. A comparison of ButiDuTDl polymers made via small and large scale
hatches is shown below in Tahle 3.
Table 3: A comparison of Jl‘Dl ers rnaole via small and large scale batches
Material n (anhydrous) {Till} (mollL) T (”Cl Time Yield
volume
SL~1~010A 1:47 4 mL 176 80 3 h 7§%
03 1:4? 120 ml. 1.78 80 3 h 82%
Water t of B—CD used: 111%
{99156} lt was previously understood that the use of dried til—CD and anhydrous solvents was
critical for nialong polyurethane~type Cl) polymers; however, as described herein, using c‘wet”
solvents (also referred to as “regular” solvents) such as EMF and/or as~is , the resulting
polymer is structurally different than the polymers bed in the literature and are much more
effective for PFAS sequestration, It was surprisingly discovered that using wet/regular solvents
resulted in partial isocgranate reduction, shown below in Scheme l for TDli
Scheme l: Effects of water on isocyanate groups of "fill
{(38157} The presence of amine groups into the polymerization reaction is believed to result in
the formation of urea linkages in addition to the urethane es which result from the
crosslinlring of {hill} and TDl under anl'iydrous conditions (eg‘ completely anhydrous
conditions). Additionally, the presence offree arnines in the B—CD-TDl polymer are believed to
contribute to PFAS removal. The high amine and urea content provides a polyn'ier that is
urally different from the prior art and which is more advantageous for the rernoval of
anionic niicropollutants (cg. PEAS).
{$19158} Elemental analysis data shows that final CD:TDl ratio is l:8~l :lO when a feed ratio of
lt4 is used, which ts the presence of excess 'l‘Dl units on cyclodextrins. Additionally, 1H
NMR spectroscopy shows the presence of~-—Cl-l3 protons resulting from the arnine functionalized
phenyl unit (Fig. 3}. Amine groups can be quantified using the “(ll-l3 peak at ~l.9 ppm that
originates from a ‘TDl unit with amine groups on it. The ratio of that integration to total
integration of -—-—Cl-l3 pealrs provide the percentage of TDls with amines. Since te ‘T‘Dl
density can be calculated from the elemental analysis data, the concentration (mmol/g) of amine
groups in the polymers can be calculated by correlating Nl‘le and EA data. See Table 4. The 33-
CDnTDl polymer additionally tested positive in the chloranil test, further ming the amine
presence.
Table 4: Determination of amine content of meDnTDl polymers made with regular Eli/ll:
NEVER integration {based on one pnCD unit} Elemental Analysis
CD:TDl TDHED TDEKBD
Sample Cflgttotal) CHglamlne) Amine (0/6; {TDQmmot/‘g {Aminegmmol/g
feed ratio ratio ratio
SL—1-O‘i0A 114.7 0.15
SL—QnOD'IA 1:4 0.17
Sl_.—2u003 1:4.7 0.16
04A 1:2 0.34
SL004B 1:3 0.22
SLmZ-OMC 1.4 3.21
04D 1:5 0.16
{88159} The amine—containing SEE—ml polymers were further tested against a panel of l2
PFASs (fig. l} as well as t the binary mixture ot‘l’EOA and PEOS (Fig. 2). The polymer
made with 4 eq. oi" TDT (:SL— l —0l 0A) showed 70% removal of PFQA and excellent l of
PFOS (96%} in only 30 min and reached nearly 90% PFQA and l00% PFOS removal over 48 h
in the panel study. A similar l performance was also observed when tested for the binary
mixture of PFOA and PFOS.
Example 2: Synthesis and PEAS removal activity of fi—Cflmlsocyanate polymers
litltlltitl} Following the general procedure outlined in example l, fi~£§Duisocyanate polymers
obtained from 4,4’uMDl were synthesized and tested for their ability to remove l’FASs.
} The polymers of Table 5 were tested for their ability to remove PFASs. All experiments
were conducted with l000 ng/L of each of l2 Pli'ASs and l0 mg/L of adsorbent. Control
experiments were performed with no adsorbent. These experiments were conducted in triplicate.
Samples were taken at the following times: 0 h, 0.5 h, 9 h, and 48 h. Fig. l shows the results at
0.5 and 48 h, with polymers made from Dl and ‘Dl being particularly effective at
PFAS sequestration. Although faster removal lrinetics was observed in the 'l‘Dl polymer (SLul _
010A), the MDl polymer (SL_0420~3) also had good removal mance over the course of 48
h. Polyrners obtained from 6 eq. of Hill and MDl did not exhibit good removal of either PFOA
or PFOS, most lilrely due to the formation of hard gel during their synthesis which renders
binding sites inaccessible in the particle.
Table 5: {luCD polymers made with different isocyanates
Polymer Cresslinker cyanate ratio Sleeved from
scrum DA 2,4x-TDl 1:4 230 mesh
SL-l -O1OA 2,4--TD! 1:6 80 mesh
SLnlnMQO-S 4,4'—l\/lDl 1:4 230 mesh
514—04204 4,4’—MD! 1:6 8-3 mesh
Example 3i: Synthesis and PEAS removal ty of e dewmodified fiwCD~TFN
polymer
{Blilfil} In this example, positive charges were added onto CD polymers in order to enhance the
binding ty for anionic PFASs Without being hound hy any particular theory it is believed
that the presence of phenol groups produced in a side reaction during polymerization results in
anionic charge on the polymer and diminishes the PFOA and PFOS uptake of polymers. This
effect was experimentally ohserved in another polymer ation? TFN—CDP, which
demonstrates good removal performance against a hroad range of micropollutants except
negatively charged ones including PFASs. 'l‘FNuCDP can he produced in relatively large scales
using tetrafluoroterephthalonitrile (TFN) as the crosslinker Therefore, it was desired to modify
the adsorption properties for PFASs by incorporation of positive s on the r
backbone. in this example, choline chloride------a quaternary ammonium salt with a yl
group------was chosen as an additive to the polymerization reaction of TEN—(EDP. Choline chloride
can react with TFN just like fi—CD and thus is incorporated into the polymer, which hereafter will
be denoted as TEN—CDPi- (Scheme 2).
Scheme 2: Synthetic overview for choline chloride—modified l3—CD—l‘FN polymers
H:33““‘((‘ H‘s
l l
C“ -.‘- ,v\~
wmnh< yflguluul F‘ )\ F Hi}f\\fl§;§\ LEE
CNS + I \' WW
HO : K2593
‘ F” ”\F
i7 {3N HzO/DWESO
E 60 "C
34:33 TFN
Table 6: Synthetic conditions and, yields for 'l'li‘NnCDP+ rs
\: followln :—' -:.
_ ms. {EPA}.) 2 23 ppm, {Polymerl 1 rng/inL Contact time ‘9 min MO uptake measured under
. Co time '4 ”i h.
Table m/: Porosity comparison for TEN—(I‘D??- rs
Sample Choline Chloride (sq) Surface area (me/g)
NEE-$036 3 574
MB-‘t -037 6 19
Table 8: Elemental analysis for ’l7FN~CDP-t-- polymers
if; ? Cl
Feed equivalents Ratios
Sample
fi—CD TFN CC C:N N:F N5CE PC: (31:! (mmollg) (mmoiig; tmmolig)
M 8-1 —036 7.45 2.23 71.51 3.38 55.98
MEI-M —C-37 71.19 2.73 5.07 1.86 36.44
{W163} Prior to measuring PFAS l, a comparison of EPA (a neutral molecule) and
methyl orange (Mt), a negatively charged dye molecule) uptakes CDP and P-+—
was performed. W'liile EPA uptake was not affected, M0 uptake was significantly improved,
from ~30% for TFN-CDP to >99% for TFN—CDP-lz As expected, TFN~CDP1~ polymers
demonstrated significantly less all’imty towards positively charged molecules such as i'rietliyleiie
blue compared to TFN-CDP (Table 9; Fig. 7). Encouraged by this preliminary data, TFN—CDP—i-
was tested for the removal of PFGA and PFGS at environmentally relevant trations.
Table 9: MI? removal efficiencies of choline chloride modified and unmodified TFN-CDP
Sample BRA Methyl Orange Methylene Blue
pliant—036 74% 99% 34%
M84 ~03? 57% 99% 10%
TFN—CDP 80% 30% 160%
} gh further experiments are needed to fully characterize the adsorption
mechanism, this approach allows one to (l) take advantage of dual g ism
(inclusion complex with B—CD and ionic interactions) at the same time in a single material and/or
{2) enhance the binding affinity of the inclusion complex through the presence of positive
charges in the vicinity of CD cavities. Furthermore, TFN—CDP-r is still synthesized in one step
and the amount of positive charges incorporated can be easily modified by ng the amount
of choline chloride used in the reaction.
{(130165} Experimental: 1}ij (l g, 0.88l mniol), TEN (l .06 g, 5.286 nimol), lizCGs (2.44 g,
l7.62l mniol), e chloride (0.37 g, 2.643 mmol), and 5.4 mL HzO/DMSO (2:3, v/v') were
added to a 20—mL scintillation vial equipped with a magnetic stir bar. The mixture was stirred at
60 °C for 2f: h. Additional solvent (1 mL) was added after the first hour of stirring. After 20 h, 10
mL of water was added and stirred to disperse the polymer for 30 min. After ing, the crude
product was transferred to a centrifuge tube. The sample was washed with hot methanol (”\rllOmL)
three times (3 0 min for each cycle). After decanting ol, Dl water (~30 mL) was added. 1
M HCl was added se while stirring the sample until the pH was stable between 3—4. The
crude product was further washed two more times with hot methanol (~49mL). The final
methanol wash was filtered under vacuum and product was dried at 80 “C overnight.
{anion} Testing PFOA and PFOS removal performance — PFAS adsorption experiments were
performed to measure the removal performance of different TFN—CDP+ polymers. In an effort to
facilitate the screening process for a large number of polymer formulations, adsorption cs
were performed using a mixture of l2 PFASs in nanopure water. The understanding of
adsorption kinetics is essential as it reveals information on ent doses and required contact
times that are relevant for treatment processes. in addition to ing insights into PFOA and
PFOS uptake, this panel study also allowed assessment of performance against other PFASs such
as GenX and short- and long~chain PFASs in order to determine broadspectrum PFAS l
capabilities of these polymers. The results summarized in Fig. l show the removal percentages
for each PFAS at 30 mm and 48 h contact times. These experiments were conducted in triplicate
with ~l pph of each of the 12 PFASS in nanopure water at a polymer loading of l0 mg/L.
Control experiments were also performed with no adsorbent and reported removal percentages
are corrected for any losses observed during the control experiments. All polymers were sieved
with 230 mesh.
{(130167} lmpressively, the two derivatives of TFN—CDP-l- (namely, 1343443363 and MBul ~037
made from 3 and 6, eq. of choline chloride. respectively) demonstrated the best l
performance of all polymers tested, with near te removal of all l’FASs in the panel. Over
min, MB—l—Q37 displayed effective removal of GenX and short~chain l’FASs, in on to
PFOA and PFOS. presumahly due to its higher quaternary ammonium loading (Fig. 2 9
{till 163} After performing initial screening under the panel study, removal assessments were
narrowed to select polymers using a binary mixture of PFOA and PFOS ("l‘ahle 10). ln this
specific task, all adsorption experiments were conducted with 0.5 pph of PFOA and l pph of
PFOS at a polymer loading of lt‘i mg/L. Control experiments were performed with no adsorbent
and all measurements were done in cate. Samples from each solution were taken for
analysis at ermined time : 0, 0.5g 2., 4., 8, and 24 h. Polymers selected for these
measurements were SL—l—Gl 0A, (TDD, 36 C), and hClB—l —03’7 C). All the
polymers tested demonstrated great removal of PFQS over 24 he but SL—l—Ol 0A (Till) and two
PWL derivatives displayed high removal (>90%) in only '30 min. As for removal of
PFOA, even though Mid—01014 (TDT) showed similar performance to the panel study; l‘vle—l —036
and M84 ~03? outperformed the other two polymers in terms of both kinetics and removal
capacity over 24 h.
Table l0: Removal data of selected polymers for PFOA (0.5 pph) and PFOS ( l pph) mixture.
stud-9199. 2,4-TD! 59% 79% 91% 94% 95%
M94 -999 TFN+co 93% 99% 99% 99% 99%
MB—t "99? Tern-cc 99% 99% 99% 99% 99%
set-919A 2,4—TD3 99% 99% 9?% 99% 99%
MB—t "999 Tern-cc 99% 97% 99% 99% 99%
M94 -99? TFN+co 95% 99% 99% 99% 99%
{98169} Micropollutant Adsorption Studies
{(130179} $421) is known to form a stable inclusion complex with rnicropollutants. EPA and MO
were chosen as model compounds to study the uptake of neutral and negatively charged
ollutants, respectively, for understanding the adsorption mechanism in choline chloride—
modified 'l‘lFNuCDP polyniers. Furthermore, fitting the mi lutant adsorption data as a
on of concentration to a Langmuir model (Equations l and 2) enables the determination of
the thermodynamic parameters of the materials tested.
{M13171} 'l'he singleusite Langmuir model that considers homogeneous adsorption surface, is
given as
qmax ., KL ., Ce
0' ...
‘8 1 + KL . Ce
(Equation 1)
where qe (mg/Cg) is the amount of MP adsorbed per gram of adsorbent at equilibrium, qmax
(mg/g) is the m adsorption capacity of ent at saturation, KL (L/mg) is the
equilibrium constant and C3 (mg/L or ppm) is the concentration at equilibrium. The dualusite
Langmuir model that takes the two distinct adsorption sites into account, is given as
gmaXJ ‘ K143 ° Co qmaxz ’ K52 ' Ce
qe +
1 ’l' Km ‘ Ce 1 + Km “ Ce
(Equation 2)
where qe (mg/g) is the amount ofMP adsorbed per gram of adsorbent at equilibrium, :3.”wa and
Qmaxo (mg/g) are maximum adsorption capacities of adsorbent for each site at saturation, K[4,1
and Km (L/rng) are equilibrium constants and are {mg/L or ppm) is the concentration at
equilibrium. By fitting the experimental tion data using nonlinear sion, quad and KL
parameters can he obtained. Single~site Langmuir model was determined to he suitable for fitting
the EPA adsorption data, whereas MO adsorption data were best fitted using the dual~site model.
{(130172} For choline chloride—modified ’lFNmCDl’ rs, urn M0 capacities (9mm) of
46.6 and 78.8 mg/g were found for polymers made with l5 and 3.0 equivalents of choline
chloride, tively, for the first adsorption site (Table l I, Fig. 8). The second adsorption site
(aiming) yed rnaximurn uptalre capacities of 37.3 and 33.0 nig/g, both of which are quite
similar to the maximum capacity of unmodified TFNuCDP (grim 37.6 mg/g). This data, as well
as similarities hetween K1; and K12 values, suggests that the second adsorption site in choline
chlorideuniodilied TEN—CD? polymers is associated with MG tion within the CD cavity.
The comparison between K1.,1 and K112 values also indicates a significantly stronger first
adsorption site which likely originates from the interaction of anionic MO molecules with
quaternary ammonium sites. BPA adsorption data were fitted using a singlemsite Langmuir model
and r K1 values were determined, for all three polymers, indicating the presence of similar
adsorption site for a l molecule. Maximum EPA ties of llZl and, l00.l nig/g were
found for the two choline chlorideunodified 'l‘FN—CDP polymers and a capacity of l06.l mg/g
was determined for the fied NnCDl’ (Table ll; Fig. 9). Notably, these saturation uptake
values are in good agreement with the density of CD sites in these polymers. This observation
also suggests that EPA adsorption occurs within the cavity of CDs.
Table l l: ir fitting parameters for EPA and MO adsorption
ECDl EN‘I Gale. rima for Sale. qnnx for al
Sampie MP qmw Km om: Km a?
(mmmrsl. lmmellgl. [CDllmaisl [Mime/s)+ qmaxlms/al
MB051 (15 en CC) M0 46.6 27.9 37.3 0.37 0.0828 0 48 0.15 157 49 206
[Via-1036 (3 en CC}, MO 78.8 54.4 33.0 0.19 0.9970 0.37 0,63 121 205 327’
., [CD] (talc. qmax for Cale. total
Qmax KL R"
lmmnllsl, {Wilma-'91. .
11W (mo/st
TFN-CDF‘ MO 37.6 0.02 0.9828 0.51 167’ 107
M84051 (1.5 on GO) EPA 112.1 0.10 0.9711 0.48 109 109
M81036 (3 eq (:0) EPA 100.5 0.09 0.9651 0.37 84 84
TFN-CDP BF’A 106.1 0.14 0.9714 0.51 118 116
Example 4: sis and PEAS removal activity of choline chloride—modified fimCD—Tlll
{00173} finCl) (2 g, 1.76 rnmol, l eq.) was dissolved, in 5 mL Elli/ll? in a 20 mL scintillation vial
equipped with a magnetic stir bar at a stir rate of 400 rpm and a temperature of 80 ”C. 4 g
Choline chloride was ved, in 110 mL DMSO at 80 °C to achieve a concentration of 0.4 g/inL.
A variety of stoichiornetric ratios of choline chloride solution ((03075 ntL, 0.1230 g, 0.5 eat),
(0.6l50 nil..., 0.2460 g, l, on), (09225 niL, 0.369 g, 1.5 eq.) or (1.2300 nil..., 0.492 g, 2 eq.)) was
added to the B—Cl) solution at 80 °C, After mixing for 5 min at 80 0C, toluene diisocyanate (2.94—
'lBl, l.84l7 g, l057 mmol, 6 ed.) was added uently. Air bubbling was observed after the
diisocyanate addition, presumably due to the moisture in the on system. After about l min
when huhhling suhsided, the vial was . After 3 h, the reaction was stopped by adding l0
rnL of methanol and g off the heating. White powder product precipitated out after
methanol addition. The mixture was erred to a 50 ml; polypropylene centrifuge tube. After
centrifuging, the solvent was decanted and the crude product was washed with water (4t) mL X 2
times), and methanol (40 ml; X 2 . ln each wash cycle, the mixture was stirred for 30 min
and followed by centrifuge. In the final cycle, the product in methanol was ed under vacuum
and dried at 80 °C overnight. Fig. l0 shows a 1ll NMR spectrum of a choline chloridenmodified
B—CD—TDI polymer made with l:6:l molar equivalents of B—Cl):'l'l)l:choline chloride in 5 mL of
DMF at 80 0C for 3 hours. The ance of urethane and urea groups at 775—96 ppm
indicates successful incorporation of choline chloride into the polymer. The following chemical
shifts are also found in thelH l‘leR spectrum: 6.75—7.75 ppm (protons from the aromatic ring in
TDD; 556 pm (protons from ~OH groups that are attached to C2 and C3 in SSE); 4,8 -5 ppm
(protons that are attached to Cl in 5431)); 4.25—4.75 ppm (protons from ~08 groups that are
attached to err in BmCD); All ppm (protons from —O~CH2— groups in choline chloride); 3.5—4 ppm
(protons that are attached to CZ~C6 in B~CD); 3.3—3.5 ppm (protons from water); 3.18.2 ppm
(protons from €83 groups in choline chloride); 2.5 ppm (DMSO); l.9~2.l ppm (protons from —
CH3 groups in TDl); Peaks noted with star are from residual solvent. Fig. ll shows a
comparison of a choline chloride—modified B-CD—TDE polymer and a B—CD-TDI polymer, with
the key difference being the broad peak centered around 3, l3 ppm. Sharp pealrs at all ppm and
3.l ~32 ppm originates from unreacted choline chloride. Fig. 12 shows a comparison between
three choline cl'iloride-modit‘ied BwCD-TDI polymers with different choline chloride loading
amounts, which supports the position that with increasing amount of e chloride, the pealr
intensity increases at 3. l 3 ppm.
{98174} in accordance with the synthetic procedure outlined above, a y of polymers were
made with varying stoichiometric equivalents as shown below in Table l2. rmore, the
rs were tested for their PFOA uptalre. The s show that by incorporating choline
chloride into a ButiD—E‘Dl polymer, cationic charge can he added to the polymer in a lled
fashion, resulting in PFQA uptake increasing from 70% to 99% when compared to Shul u0l 0A
polymer ('lahle l2). See also Fig. l3.
Tabie 12: Synthesis of ehoiine ehiorideuniedified fimi’CDuTDi polymers
. fi—CDfithc PFDA
Meterinfl Seivent Ti013) Time YBEM. Notes
ratio uptake"
SL—Z-DO4E 1:61) DMF 80 3 h n/a We Get
SL—2-005A 1.6.0.5. ,
a DMF 50 3 h n/a ma
ESL—$0053 1:621 DMF 80 3 h 73% 98%
OfiC 5 DMF 80 3 h 73% 99%
ESL—243050 1:652 DMF 80 3 h 60% 99%
*500 not PFOAHOGG pot PFOS, 10 mg/L poiymer loading at 05 h.
EQUIVALENTS
{WWSE While the present invention has been described in coniunetien with the specific
enibediinents set forth above, niany atives modifications and other variations thereef will
be nt to these of Ordinary skiii in the art. Ail such aiternatives, inedifications and
variations are intended to faii within the spirit and scope 0f the present invention
References
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Claims (1)
1. A porous ric material comprising a plurality of cyclodextrins crosslinked with a plurality of crosslinks comprising formula (I): wherein A is an aryl or heteroaryl moiety; each R1 is independently selected from the group consisting of H, C1-C6 alkyl, C1-C3 kyl, aryl, heteroaryl, -CF3, -SO3H, –CN, -NO2, -NH2, -NCO, -C(O)2R3, -C(O)N(R3)2, and –halogen; each R2 is ndently H, -OH, -O-metal cation, alkyl, aryl, heteroaryl, -SH, –S- metal cation, –S-alkyl, -C(O)2H, or -C(O)NH2; each R3 is independently –H, –C1-C6 alkyl, –C1-C3 haloalkyl, –aryl, (Ra)(Rb), −C(O)Rc, −CO2Rc, −SO2N(Ra)(Rb), or −SORc, and each Ra and Rb is independently H, or C1- C6 alkyl. each W is independently a bond, an alkylene group, an e group, a heteroarylene group, -O-arylene-, -(CH2)a-arylene-, -SO2-arylene-, -NH-arylene-, -S-arylene-, -O- heteroarylene-, -(CH2)a-heteroarylene-, -SO2-heteraoarylene-, -NH-heteroarylene-, -S- heteroarylene-, –(–O–(CH2)a–)x–, –(–NH–(CH2)a–)x–, –(–S–(CH2)a–)x–, , or , wherein a is 0-100 and x is 1-100, and each e or heteroarylene moiety can be substituted or unsubstituted; each Z is a cationic moiety or an anionic moiety; each L is independently a linking moiety selected from the group consisting of –O–, – S–, –N–, C1-C6 substituted or unsubstituted alkylene, C1-C3 haloalkylene, , , , , , , and ; A’ is a covalent bond to A; Z’ is a covalent bond to Z; * is a covalent bond to ; is a point of ment to the plurality of cyclodextrin carbon atoms; x is 0-8; y1 is 1-4; y2 is 1-4; and y3 is 0-4. fix;a? fix? '1‘ - ‘~ :3}:
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