AnaJy&ica Chimica Ada

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THE SYNTHESIS OF SOME NITRATED POLYAMINE RESINS AND THEIR

USE AS ION-EXCHANGERS FOR THE ALKALI AND ALKALINE EARTH
METALS*

CASIMIR A. Ji\NICIiL*+ AND CARL E. bIOOlZE

Dapurtme~tt of CJwnistry, Loyolu Udvevsity. Chicago. III. (U.S..4 .)
(Reccivccl Deccmbcr 28th. 1$23)

The useful ion-exchange resins have a selectivity which permits closely re-
lated ions to be separated by ion-exchange chromatography. However, the use of these
resins is often time-consuming for separations of large amounts of similar ions, though
separations may be improved by the use of complexing agents such as citric acid’, ethy-
lenediaminetetraacetic acid2 and nitrilotriacetic acida.
Attempts have been made to obtain resins of higher selectivity by the prepa-
ration of materials which have a preference for certain counter ions and bind them
to the fixed ionic groups or other components of the matrix. Thus, a cation which
forms strong complexes with, or is precipitated by, a certain reagent should be pre-
ferred by a resin into which this reagent has been incorporated as a structural unit.
SKOGSEID”, wllo was the first to use this approach to ion-exchange resin preparation,
incorporated dipicrylamine into a styrene-type resin. He found that the resin had
considerably greater affinity for potassium than the existing cation-exchange resins.
Dipicrylamine is a well known analytical reagent which precipitates potassium selec-
tively from the lighter alkali metal cations as a red to yellow precipitate of low so-
lubility.
The work of SKOGSEID suggested that other resins based on the dipicrylamine
moiety and similar structures are possible and that more favorable structural cases
may exist. Among these are the nitro-polyamines which are easily synthesized by the
condensation of aromatic diamines and their hydrochlorides, and the subsequent
nitration of the resulting polymer. It was felt that the resin based on m-phenylene-
diamine presented a particularly favorable case for checking this hypothesis and
when compared to the resin prepared by SI~OGSEID would have a greater similarity
to dipicrylamine (Fig. I). Because of this greater similarity it would possess a greater
ability to selectively remove potassium and the heavier alkali metals from large a-
mounts of sodium in systems such as sea water.
Five resins were prepared and studied. They are nitro-poly-m-phenylenediamine,
nitro-poly-$-phenylenediamine, nitro-poly-3,3’-diaminodiphenyl, nitro-poly-4,4’-dia-
minodiphenyl, and nitro-poly-zj7-diaminonaphthalene.

* Presented at the 1966 Anachcm Conference, Wajmc State University, Detroit, Michigan.
** Present address: McNeil Laboratories, l?ort Washington, Pa., 19034.

Axal. CJzim. Ada, 45 (1969) 485-491

 C. A. JANICKI, C. E. MOORE

.~~-ccII-c112-...
I

II

II

./
\ \
N

(b) (c)

Fig. I. (3 Swxwzrn’~ resin; (b) ddxcturc af propascd resin; (c) prqmsccl structure af resin syn-
thcsized (vitro-poly-r,t-phcnylcnediamina).

EXPERIMENTAL

A 3oo-ml Magne-Dash Autoclave (Autoclave Engineer’s, Inc., Erie, Pa.) was

used in the synthesis of the polyamines. A Beckman battery-operated DU Spectro-
phco’tometer *1%-I Yne p3DD $notomti$@ner, Spec’rr& Energy %ecortiqjz anh VIame
Ph&cmnetry Attachments, a Brbwn Recorder, anii &e oxygen-hydrogen Dame were
used for the assay of the metallic cations.

Materials
Practical grades of m-phenylenediamine and p-phenylenediamine were puri-
fie& b_v W$tia$1on unher rehaceh pressure anh p/p’ -b’lan%noti&nen~fi was usea as
obtained. The z,7-diaminonaphthalene was synthesized from z,7-dihydroxynaph-
thalene by the BUCI-IERER reactions. The 3,3’-diaminodiphenyl was synthesized
from m-nitroaniline which was converted to m-iodonitrobenzenefi. The 3,3’-dinitro-
diphenyl was prepaced foam m-imkmihdmxz~n~ by the ULLMANN reaction7, The
diamine was obtained by reduction of 3,3’-dinitrodiphenyls.
The hydrochloride salts of the amines were prepared by passing dry hydrogen
chloride gas through an ether or benzene solution of the amine.
The test solutions used to determine the effect of PH on the exchange were
Clark and Lubs buffers, using only potassium salts. The modified sea water solution
was composed of the acetate salts of sodium (10,600 p.p.m.), potassium (383 p.p.m.),
magnesium (1~~75 pp.m. ) and c&$22 .(+xY p. gun, ). The acetate .sd.ts were arbjtzzd~y
chosen to have a common anion jn &m%n a~2rlias a means ti7 cc&r19 px. The p=
was controlled so that another variable could be kept constant.

Al&al. Chits. Ada, 45 (1969) 485-491

NITRATED POLYAMINE RESINS AS ION-EXCHANGERS 487

Resin jhreparation
The condensation technique. heating an amine with an amine hydrochloride,
was successfully used in synthesizing diphenylamine from aniline and aniline hydro-
chloride as well as tetramethyldiphenylamine from 3,g-dimethylaniline and its hy-
drochloride salto. These reactions served as model reactions for the resin preparations.
Equimolar amounts of the aromatic amine and its corresponding hydrochlo-
ride salt were mixed, transferred to a glass tube, inserted into the autoclave, and heat-
ed under nitrogen. In some instances iron wire, iron(ITI) chloride or aluminum chlo-
ride were used to effect the condensation. The black product obtained was washed
in turn with dilute hydrochloric acid, acetone, water. dilute ammonia, ethanol and
finally acetone. The washing procedure rem&bed starting materials and low-molecular-
weight products.

Nitration of the polyantines

The polyamine was dissolved in oleum at room temperature and the solution
ccoled to 0’. Red fuming nitric acid was added dropwise with vigorous stirring, the
temperature being kept below 10~. The solution was stirred for an additional 3 11.The
solution was poured over ice and the precipitated product collected on a fritted glass
funnel, washed with water, and dried at Go”.

Ion-exchange study) of the resins

A batch method was used to determine t.he exchange capacities and effect of
pH on the exchange. The nitrated polyamines were ground to 270 mesh, conditioned
by several exchange cycles, and the acid form of the resin washed with water and
dried at 60”. The resin (0.2-0.5 g) was transferred to a flask, shaken with 50 ml of the
test solution and equilibrated for 48 11at 25 *I:“. The mixture was filtered through a
fine fritted glass funnel, washed free of test solution, air-dried, and washed with a
known amount of 0.1 M hydrochloric acid. The acid solutions were diluted and
assayed.

Cation detevntinatio?t
The acid solutions were assayed for the various cations by flame photometry.
The standards used were nearly identical in composition to the samples. Preliminary
assays of solutions of mixtures of cations were performed so that standards, containing
approximately the same concentrations of the samples, could be prepared. Calcium
was measured at 554 nm, magnesium at 383 nm, potassium at 767 nm and sodium
at 589.6 nm.

RESULTS AND CONCLUSIONS

The five polyamines that were synthesized are listed in Table I with the syn-
thesis conditions, yields, and nitrogen analyses. The ash found in the last three po-
lymers was entirely due to the particular agent used to effect the condensation. The
polyamines were usually very black and found to be insoluble in most common or-
ganic solvents. The polymer of m-phenylenediamine, one of the more soluble poly-
mers, was soluble in N,N-dimethylformamide (DMF), dimethylsulfoxide, N-methyl-
pyrrolidine, sulfuric acid, and formic acid. The molecular weights of the polymers

Asal. C/aim. Ada, 45 (IgGg) 485-491

 ‘l’IIlc CQNDIT,ONS, YIILLIlS AND NITROGEN ANALYSISS I’OR Tl4lX POLYAMINRS
_---.-_ ---_- ____.____--v-e - .“______
hro. of nrolcs Tcnzp. (“) 7Yme Field N Ad6
of a1wi7rc /I$) fR) fmalysis ((x1)
__-_. _._,....
-.._..__.____._-_.___- ._1.__1_.-
-~-.-----.-.~-. -._.- .____.
..-..___---_--* _.__..
__._____.___~ -_____..._
err-X’hcnyfcllcclinnlinc O,O$ 275 =t; 10 24 g.t-33 Calcd : r5.38
Founti: r4.82
f>-Thcnylcncd iatni nc 0.073 ZGfj f IO 24 8.50 Catcd : 15.3s
Found: 12.82
3,3’-l~i~~n~iliotlipllcl_ryl 0.010 280 f IO 7”“1’ 2.50 Calcd : 8.38
Pau11c1 : B*++ .545
.t,4’-Diaminodipl~~~lyl 0.029 2G5 & IO 57” 5.58 Calcd : 8.38
Pountl : 7.77 3.00
2,7-I~)iaminonapf~ti~~~l~l~~ 0.106 275 & to 2 4 ‘b 2.45 Calccl : 9-W
Found : x0.93 3.25
_. __._._..
___....
-.--_..-.-. _. ... ^_I ..-.-- -......-..._-_--“_*-_.- _-...._
---.-.-_
n iron wire, iron( I II) chloride cx ;~luminu in chloride used.

were very difficult to obtain because of the lack of solubility in a suitable solvent. A
molecular weight of 4200 to 5200 was obtained for poly-m-phenylenediamine. This
was determined on a vapor-pressure osmometer at a temperature of 37” with DMI? as
the solvent.
The nitrated polyamines were soluble in diluted alkali and acetone. Only one
nitro group per monomer unit could be accounted for by analysis for nitrogen. More
vigorous nitrating conditions did not improve the nitrogen values and in many cases
destroyed the polymers. The same method was successfully used to nitrate diphenyl-
amine to obtain dipicrylamine in very high yields, and hexanitrotetramethyldiphenyl-
amine from tetramethyldiphenylamine~.
Since the nitrated polymer of ~~-pll~nylenediall~ine was studied more extcnsi-
vely than the other polymers and it also resembles dipicrylanline more closely than
the other polymers, most of the discussion will relate to it. Any major differences be-
tween nitro-poly-wz-phenylenediamine and the other four nitrated polymers will be
pointed out. The nitrated polymers were tested for their ion-exchange properties as
well as the reversibility of the eschange. A small column of nitro-poly+z-phenylene-
diamine was prepared, washed with dilute hydrochloric acid, and washed with water.

TABLE 11
THE RIXQVERY ANR REVERSIBILITY 0?3 THE BSCIh%NG& FOR NITRO-POLY-ltt-l’tI~NYLENEDIAhtlNE

Potassium 3x.7 31.9

30.2 29.9
28.2 28.7

Potassium 29.6 31.9

30.5 32.G
30.7 3x.8

Calcium 23.6 23.1

Sodium X4.9 X5.5

i19ad. Chh. ilCtc2, 45 (I$-&?) 485-491

 NITRATED I'OLYAMINE RESINS AS ION-EXCHANGERS 4%

A so-ml aliquot of a solution of 164 p.p.m. of potassium (as potassium chloride) was
poured through the column, collected and assayed. The column was washed free of
excess reagent and eiuted with zg ml of I M hydrochloric acid. The acid was collected
and assayed. The cycle was repeated twice (Table II). A second sample from an en-
tirely different batch of nitro-poly-m-phenylencdiamine was used to obtain another set
of results for the potassium exchange. An additional sample was used for the sodium
and calcium exchange (Table II). The results indicate that the resins exhibit cation-
exchange properties and that the exchange was fully reversible.
The effect of PH on the exchange was determined by the batch method using
MacIlvaines buffers of PH 2, 4, 6, and 8. Sodium ion was the only metal ion present.
The results obtained for nitro-poly-nt-phenylenediamine and nitro-poly+phenylene-
diamine are given in Fig. 2. The polymers were found to dissolve slowly above pri 7,
and rapidly above PH IO. From the data the polymers would have to be classified as
weak ion exchangers. The capacities of the five polymers for potassium at PH G arc
given in Table III.

TABLE III
THE CAPACITIIlS TOWARD POTASSIUh! AT pli 6 FOR THE FIVE NITRATED I’OLYAMINES
__._. -..- _.______.... - _...____. - _.__..__._ -.____.__ .____ _____
Nitr’utcd polymer of Meq potusshtt/g
---- - _...- -.---
rtr-l’llenylcncdii~lnillc 1.80
p-Pl~cnyl~nccliaminc I.35
3,3’-Diaminocliphcnyl I.30
4,4’-Diaminocliphcnyl 1.08
2,7-Diaminonaphthalcnc I.09

2.4I-

2.0 -
.c
xf
& 1.6-

j- x2-

Ho,-
B ’
= 0.4-

1 I ,

2 4 6 0
PH
Fig. 2. Titration cm-w for the nitro-poly-m-phenylcnccliaminc (a). and nitro-poly-p-phcnylcne-
&amine ( 0).

The selectivity of the resins is characterized by the ion-exchange isotherm.

When the equivalent ionic fraction of the ion in the resin is plotted against the equi-
valent ionic fraction of the ion in solution, a curve is obtained. The theoretical curve,
if the resin had no selectivity, is represented by a diagonal (Fig. 3). The deviation
from the diagonal is an indication of the selectivity of the resin for a particular ion in
an ion-pair. The data obtained for nitro-poly-m-phenylenediamine are given in Fig. 3.

Anal. CIdm. Acta, 45 (1969) 485~4gr

490 C. A. JANICKI, C. E. MOORE

The general nature of the selectivity of the polymer is of the same order as the com-
mercial exchangers, calcium, magnesium, potassium and sodium being preferred the
least..
In order to compare the nitro-polyamines with SKOGSEID’S resin, the nitro-
polyamines were tested against an artificial sea water solution, The solution (PH 6)
was added to the nitro-polyamine and the batch technique was used. S~ocsErn cal-
culated separation factors which were obtained by dividing the mole fraction of cat-
ion in the ion-exchanger by the mole fraction in solution. His separation factors are

A.Co/K
B.Mg/K
C.K/bla
I 1 I 1 I ,
0.2 0.4 0.6 0.8 1.0
Equivalent ionic fraction in solution
Fig. 3. Ion-cxchan~o isotherm for the nitrated polynwr of ~11-l~henylcncclialninc.

COMPARISON OP THE SEPARATION FACTORSO OF SKOGSEID’S RESIN WIT11 THE NITRATED POLYAMINB
RESINS

RtXi?t Sodirrw iWuptesi~rm Calcium Poluss~itrwr

-
SICOGSEID’S Q.650 I.62 3.04 6.00
Nitrated poly-lvr-photlylcncclinmille 0.632 2.82 7.18 2.27
Nitrated poly-t)-phcnylencdinminc 0.501 3.65 9.20 I.95
Nitrated poly-3,3’-diaminodiphcnyl 0.544 3.43 8.51 I.73
Nitrated poly-4,4’-diaminodiphcnyl 0.527 3.20 9.95 2.32
Nitrated poly-2.7-dinminonaphthalene O-544 3.16 9.15 .?.Go
_- -. -
a Mole fraction in exchanger divided by mole fraction in solution.

presented in Table IV with those calculated for the five nitropolyamines. The sepa-
ration factor for SKOGSEID’S resin for potassium is very large, being 6. For nitro-poly-
m-phenylenediamine, which has a separation factor for sodium of less than SKOG-
SEID’S resin, the sodium occupies 39% of the exchange sites of the polymer. Because
sea water contains comparatively little potassium, an exchanger would have to have a
SKOGSEID separation factor much larger than 6 to be considered for separating potas-
sium from systems such as sea water.
Although nitro-poly-m-phenylenediamine did not have such a good selectivity
towards potassium as that of SKOGSEID’S resin, it is felt that a fully nitrated polyamine

Anal. Chitit. AC&U, 45 (1969) 485-491

NITRATED POLYAMINE RESINS AS ION-EXCHANGERS 491

couId be more selective. The sites are available for nitration, since bromination and
chlorination of poly-tiz-phenylenediamine resulted in products having two halogens
per monomer unit.

SUMMARY

Five polyamines were synthesized by the condensation of an amine with its

corresponding amine hydrochloride salt, and the polyamines were nitrated, averaging
I nitro group per monomer unit. The nitro-polyamines were found to be weak cation-
exchangers. The resins did not have the same selectivity towards potassium as the
exchanger synthesized by SKOGSEID, who incorporated dipicrylamine onto a poIy-
styrene resin.

Cinq polyamines ont pu Gtre synthetisees par condensation d’une amine avec
son chlorhyclrate d’amine correspondant. Ces polyamines sont ensuite nitrees, en
moyenne un groupe nitro par unite monomere. Les polyamines nitrecs constituent
des echangeurs de cations faibles. Les r&sines n’ont pas la n$me selectivite envers le
potassium que les Cchangeurs synthetises par SK~GSEID qui incorporent de la dipi-
crylamine sur une resine polystyrene.

ZUSAhfMENFASSUNG

Es wurden fiinf Polyamine synthetisiert durch Kondensation eines Amins mit

seinem korrespondierenden Aminhydrochloridsalz. Diese Polyamine wurden im
Durchschnitt mit einer Nitrogruppe pro monomerer Einheit nitriert. Die Nitro-
polyamine sind schwache Kationenaustauscher. Die Harze besitzen nicht die gleiche
Selektivitat gegentiber Kalium wie die Austauscher, welche durch Skogseid syn-
thetisiert wurden und welche Dipicrylamin auf ein Polystyrolharz enthalten.

REFERENCES

I F. H. SPEDDING, Discrtssiorrs Faraday Sot., 7 (1949) 214.

2 E. J. WHEELWRIGIIT AND F. H.SPEDDING,J. Am. Chem.Soc.,75 (1953) 2529.
3 J. LORIERS AND D. CARMINATI, Cornfit. Revrd., 237 (1953) 1328.
4 A. SKOGSEID, Dissertatiova, Oslo, 1948.
5 H. T. BUCHERER, J. Pvakt. Chew., Gg (1904) 49.
6 D. A. SHIRLEY. Preparatiovr of Organic Intevmediufes, Wiley, New York, 1943, p. 184.
7 F. ULLMANN AND J. BIELEcKI, Bev., 34 (x901) 2174.
8 A. H. BLATT, Orgavric Synthesis Coil., Vol. II, Wiley, New York, x943, p. 160.
g C. E. MOORE, T. S. MEYER AND J. W. HUDSON, Talavzta, 13 (1966) 171.

Anul. Cl&a. Acfa, 45 (1969) 485-491