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SYNTHESIS AND USE OF POLYDADMAC FOR WATER PURIFICATION

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 SYNTHESIS AND USE OF POLYDADMAC FOR WATER
PURIFICATION

W Johna, CA Buckley b, EP Jacobs c and RD Sandersonc

a. Umgeni Water, 310 Burger Street, Pieternaritzburg, 3201: wilson.john@umgeni.co.za

b. School of Chemic al Engineering, University of Natal, Durban, 4041:buckley@nu.ac.za
c. Institute of Polymer Science, University of Stellenbosch, Matieland,
7602:epj@sun.ac.za and rds@sun.ac.za

ABSTRACT

Polydiallyldimethylammonium Chloride (polyDADMAC) is synthesised by free radical addition

polymerisation of diallyldimethylammonium chloride using a persulfate initiator. In this study,
the exothermic reaction was conducted under controlled conditions of temperature, pressure
and monomer concentration. Poor control of the above parameters results in the formation of
a waxy solid early in the reaction which was unable to be used for the purposes of water
treatment. Under better controlled conditions, polyDADMAC was synthesised and isolated
from aqueous solution by precipitation and characterised by spectroscopic techniques (1H-
NMR, 13C-NMR) and gel permeation chromatography (GPC). The molecular mass
distribution (MMD) was determined and based on a calibration using polyethylene oxide
(PEO) narrow standards.

The effectiveness of the polymer was determined using the standard jar test and bentonite
suspensions at a concentration of 70 mg/L. The optimum dose was determined from the
residual turbidity measurements of the supernatant liquid after a period of 15 minutes of
settling. The results obtained for stability studies of polyDADMAC with water treatment
chemicals such as chlorine, different conditions of pH, temperature and UV radiation are
presented. Changes in the polymer structure was followed by GPC, HPLC and GC-MS and
the results indicate that the product is affected by the above conditions.

Paper presented at the Biennial Conference of the Water Institute of Southern Africa (WISA) 19 – 23 May 2002, Durban, South Africa
www.wisa.co.za ISBN Number: 1-86845-844-X
CD-ROM produced by: Water Research Commission (WRC), www.wrc.org.za Organised by: Conference Planners
INTRODUCTION

PolyDADMAC is a cationic linear polymer used extensively for water purification. It is

synthesised by the free radical initiated addition polymerization of diallyldimethylammonium
chloride [1], according to Scheme 1.

CH2 CH2
CH2 CH CH CH2
R. + CH CH heat
vacuum CH2 CH2
+
CH2 CH2 N
+
N CH3 CH3
n
CH3 CH3

Scheme 1: The synthesis of polyDADMAC by free radical addition polymerization of

DADMAC
13
C NMR spectroscopic studies conducted on the synthesized product, revealed that it
consisted of repeating units of pyrolidine rings [2,3]. The polymer falls in the category of low
to medium molecular mass range and usually exists as a mixture of the cis and trans isomers
[4].

+ +
N N
CH3 CH3 CH3 CH3
cis trans

The objectives of this research were to synthesise polyDADMAC and acquire some insights
into its behavior and properties during a typical water clarification process. Some polymers
are known to be affected adversely by treatment chemicals such as chlorine and ozone and
one of the major concerns is the potential formation of undesirable by-products as a result of
their use.

EXPERIMENTAL

The apparatus used for the synthesis consisted of a 1 L glass reactor attached to a four neck
manifold by an O-ring gasket and clamp system (Figure 1). Two pressure equalizing
dropping funnels were used, one for the addition of the free radical initiator and the other to
replenish water losses. Vacuum was applied through the condenser outlet and controlled by
a bleed valve installed to the main vacuum line using a PVC T-connector. The vacuum was
monitored by the use of a vacuum guage (Wika, Instruments, Durban, SA) fitted on the main
vacuum line. PVC tubing was used for the water inlet, outlet and vacuum lines. Temperature
and stirring of the reaction mixture was achieved with the use of a heater stirrer unit
 vacuum guage needle valve
vent
water funnel
vacuum
catalyst funnel

water outlet

condenser water inlet

thermometer

manifold with O-ring gasket

and clamp

reactor

water bath

heater/stirrer

Figure 1: Schematic diagram of the reactor used for polymer synthesis

Chemicals

All chemicals were of analytical reagent grade. Ammonium persulfate was purchased from
Merck. DADMAC monomer (65%, m/v) was purchased from the Aldrich Chemical Company
(Milwaukee, USA). The polyethylene narrow molecular mass standards were obtained from
Polymer Standards Service (USA). Potassium dihydrogen phosphate, methanol, and EDTA
was purchased from BDH (Poole, UK). All buffers, samples and standards for
chromatography were prepared from Milli Q water (Millipore, MA, USA). Milli Q water refers
to water passed through the Millipore Gradient A10 water purification system which consists
of a series of ion exchange and organic removal resins.
Synthesis

The reactor was charged with sufficient monomer and EDTA as described by Hunter et al [1].
The mixture was purged with nitrogen for 20 min. The reactor was then evacuated and
heated to the recommended temperature after which slow addition of the initiator
commenced. The mixture was stirred gently throughout the exothermic reaction.

INSTRUMENTATION

Jar Tests

A 0.1% (m/v) polymer solution was used as the primary coagulant in flocculation experiments.
The test sample to be clarified was a clay suspension containing bentonite at a concentration
of 70 mg/L. Aliquots of 800 mL test sample was transferred to each of six 1 L beakers and
dosed with increasing amounts (0.21 to 0.77 mg) of polymer. Using a jar stirrer apparatus,
the samples were mixed at 300 rpm for 2 min and 40 rpm for 15 min. The supernatant
turbidity at a depth of 40 mm was measured after 15 min of settling. Conductivity, colour,
TOC and pH were recorded after filtration through Whatman No. 1 filter paper.

Gel Permeation Chromatography

Gel permeation chromatography (GPC) was conducted on 0.5% (m/v) polymer solutions in
water or mobile phase using the Waters Alliance 2690 HPLC system fitted with a Waters 410
refractive index (RI) detector. A Waters Ultrahydrogel 500 column of dimensions 7.8 x 300
mm and 10 µm particle size was used. A 0.25 M phosphate buffer adjusted to pH 2.3 and a
flow rate of 0.5 mL/min was used as the mobile phase. The mobile phase was filtered and
degassed with a 0.45 µm membrane filter supplied by Waters. Column calibration was
achieved using 0.1% (m/v) polyethylene oxide (PEO) narrow molecular mass standards
ranging from 25 300 to 850 000 Daltons. All samples and standards were filtered through 0.45
µm syringe type filters. Data acquisition and analysis was accomplished with the use of
Millenium 32 software having the GPC option, supplied by Waters.

Reversed Phase High Performance Liquid Chromatography

Reversed Phase High Performance Liquid Chromatography (RP HPLC) was conducted on a
Waters Alliance 2690 system fitted with a Waters 996 photodiode array (PDA) UV detector.
A Waters µBondapak C18 column of dimensions 7.8 x 300 mm was used. The mobile phase
was methanol:water (50:50) at a flow rate of 1 mL/min. Samples were filtered through 0.45
µm syringe type filters.
Gas Chromatography

Gas chromatography (GC) was conducted on a Hewlett Packard (HP) 6890 gas
chromatograph fitted with a flame ionization detector (FID). A DB 5 capillary column (J&W
Scientific) of dimension 30 m x 0.25 mm x 0.25 µm was used. Data acquisition and analysis
were conducted using HP Chemstation software. The instrument conditions were as follows:
initial temperature 50oC held for 1 min, ramped at 15 oC/min to 280 oC and held for 5 min. A
splitless injection mode was used with the injector temperature set at 250oC and detector
temperature at 280oC. The gas flow rate was set at 1 mL/min in the constant flow mode.
Sample pretreatment was by solid phase extraction using Waters C 18 Sep-Pak cartridges.

Purge and Trap Gas Chromatography Mass Spectroscopy

An HP 6890 gas chromatograph (GC) interfaced to an HP 5973 mass selective detector

(MSD) was used. Sample introduction for the analysis of volatile organic compounds (VOCs)
was achieved with the use of the CDS 6000 Purge and Trap device having a cryogenic
focusing facility and liquid nitrogen as the coolant. GC MS conditions were similar to that of
the GC FID. The scan range was from m/z 35 to m/z 500 atomic mass units.

CHEMICAL REACTIONS

Chlorination

A stock hypochlorite solution was prepared by diluting aqueous NaOCl (Jik) with Milli Q water
and standardized by iodimetry [6]. This solution was used to treat 0.5% polymer solutions to
give spike concentrations ranging from 0 mg to 22 mg of free chorine. The chlorinated
samples stored in 100 mL volumetric flasks, were sufficiently filled to remove all head space ,
tightly stoppered and sealed with Parafilm to prevent loss of volatile components. After a 24 h
contact period, sodium thiosulfate was added to remove residual free chlorine and the
samples were analysed by GPC and GC MS.

Temperature Experiments

A 0.5% polymer solution was prepared in Milli Q water and subjected to increasing
temperatures (room temperature to 80 oC) and held for 30 min at each temperature. The
solution was stirred gently during heating. A 10 mL aliquot was removed at each temperature
for GPC analysis.

pH Effects

Polymer solutions (0.5%, m/v) were adjusted with phosphoric acid and sodium hydroxide to
range from pH 2 to 12. The samples were allowed to stand for 1 h prior to analysis.

UV Experiments

A 0.5% polymer solution was prepared and exposed to long wavelength UV radiation (365
nm), using a 9 A UV lamp (Spectroline Model EA-160/FE, Spectronix Corporation, USA) for
24 h.
RESULTS AND DISCUSSION

Synthesis

Initial experiments were plagued with problems of poor temperature and pressure control and
resulted in a rapid increase of the reaction temperature well in excess of the recommended
maximum of ca 140oC. This occurred in the early stages of the reaction and resulted in the
formation of a waxy solid material. The product did not dissolve readily in water but dissolved
partially when allowed to stand overnight. About 10 to 15% of the product remained in the
form of a hydrated gel. These findings were consistent with that of Butler and co-workers [5].
The low solubility was attributed to the formation of a highly cross linked product.

In subsequent experiments, good control of the reaction rate and temperature was achieved
by slow addition of the persulfate initiator as well a decrease in the monomer concentration
from 65% to 50% (v/v) with Milli Q water. The reaction proceeded for 3 h without any
precipitation of polymer as noted previously. The polymer was purified through precipitation
from ethanol, filtered through GF/C filter paper and dried in a desicator for ca 3 h. The
product was then characterized by 13C NMR and 1H NMR analysis [2,3].

Gel Permeation Chromatography

The GPC chromatogram (Figure 2), show the typical polymer profile in the form of a broad
peak eluting in the region 11 to 22 min. Small molecular species including residual monomer,
elute as a single peak at 24 min. This region was first established as the useful analytical
range (V 0 to Vt) of the column during calibration.
16.00

14.00

12.00

10.00
MV

8.00

6.00

4.00

2.00

0.00

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00
Minutes

Figure 2: GPC chromatogram of the synthesized product with a refractive index detector and an
Ultrahydrogel 500 column operating at 0.5 mL/min. The mobile phase was 0.25 M potassium
dihydrogen phosphate adjusted with phosphoric acid to pH 2.3
For economic reasons, the molecular mass distribution (MMD) based on a calibration with
polyvinylpyridine standards was not possible. PEO standards were used as a substitute
because of its relatively low cost and it was readily available. The MMD is presented as a
distribution and a cumulative trace in Figure 3. From the peak molecular weight (MP), the
product can be categorised as a low molecular weight polymer.

0.90 100.00

MP=62098
0.85 95.00

0.80 90.00

0.75 85.00

80.00
0.70

75.00
0.65

70.00
0.60

65.00
0.55
60.00
d wt/d(logM)

Mn=32977

Cumulative %
Mw=382940

0.50
55.00
0.45
50.00
0.40
45.00

0.35
40.00

0.30
35.00

0.25
30.00
Mz+1=45367052

0.20 25.00
Mz=14498670

0.15 20.00

0.10 15.00

0.05 10.00

5.00
0.00

0.00
7.50 7.00 6.50 6.00 5.50 5.00 4.50 4.00 3.50 3.00 2.50

Slice Log MW

Figure 3: Molecular mass fractions of the polymer shown as a distribution and a cumulative trace.
Calibration achieved with the use of PEO narrow standards
Performance Assessment

The effectiveness of the product was assessed using the standard jar test on a synthetic
sample with a starting turbidity of 20.1 NTU, pH 7.7, conductivity 0.76 mS/m, colour 6.1 oH and
TOC 1.64 mg/L. Figure 4, is a plot of the supernatant turbidity as a function of polymer dose.

5
Turbidity (NTU)

4
Supernatant

0
0 0.2 0.4 0.6 0.8 1
Polymer Dose (mg)

Figure 4: Plot of supernatant turbidity as a function of polymer dose during the jar test performed on 800
mL sample volumes.

There is a steady decrease in turbidity as a result of particle destabilisation, with each

addition up to 0.49 mg, after which there is an increase. This is consistent with the charge
neutralization model which predicts restabilisation and the formation of positively charged
colloidal particles due to the excess of positively charged polymer adsorbed onto the
particles.

No significant trend occurs with pH (Table 1) and the values remain relatively unaffected with
increasing dose. This pH stability is very important in water treatment in that there is no need
for pH adjustment of the final treated water. The conductivity of the original solution (0.76
mS/m), shows a significant increase with a corresponding increase in the polymer dose. This
may be attributed to the increase in the concentration of ionic species during dosing as well
as the result of the presence of the charged polymer itself. There is a slight drop in the
conductivity leading up to the optimum indicating a removal of ionic components during
coagulation and flocculation. The conductivity increases slightly with particle restabilisation.
Table 1: Filtrate results for jar test experiment
Dose (mg) 0.21 0.35 0.42 0.49 0.63 0.77
pH 7.10 7.45 7.36 7.26 7.20 7.24
Conductivity 1.03 0.86 0.91 0.91 1.00 1.09
(mS/m)
o
Color ( H) <1 <1 <1 <1 <1 <1
TOC (mg/L) 1.96 2.01 2.07 2.00 2.41 2.61
The sample color is reduced from 6.1 to <1oH for all doses of polymer. No trend is observed
due to the low color of the original sample. TOC show a similar trend to conductivity. There
is a slight increase in the TOC of the original sample from 1.64 to 1.96 mg/L after the first 0.21
mg dose and remains relatively constant until the optimum and then increases due to particle
restabilisation. The increase is expected due to the introduction of organic impurities present
in the polymer as well as the possible presence of unadsorbed polymer.

POLYDADMAC REACTIONS WITH WATER TREATMENT CHEMICALS

Some polymers are known to be affected adversely by pH, chlorine, UV radiation and
temperature. The GPC overlay chromatograms of polyDADMAC after treatment with chlorine
(Figure 5), show a significant change in shape and area with increasing doses of chlorine. A
reduction in the amount of the high molecular mass species can be observed in the
distribution. The formation of small molecular species is not observed because of the sharp
drop in the baseline at 22 min. This is caused by the mismatching of the refractive indices of
the sample and the mobile phase.
6.00
Control
5.5 mg Cl2
5.00 11 mg Cl2

22 mg Cl2
MV

4.00

3.00
high molecular weight region

2.00

11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00 21.00 22.00

Minutes

Figure 5: The overlay GPC chromatograms of the control and test sample after exposure to increasing
levels of chlorine for 24 h
Purge and Trap Gas Chromatography

An investigation was conducted to determine what products are formed during chlorination.
Figure 6A is the overlay GC MS scans of a test sample spiked with 11 mg chlorine and a
control (0 mg chlorine) offset by 20%. The appearance of one distinct new peak at 2.9 min is
clearly observed. Based on the mass spectrum of the new peak (Figure 6B), the compound
was identified as chloroform, a well known carcinogen. Screening for semi-volatile
compounds by GC FID and non-volatile compounds by RP HPLC with PDA detection
revealed that no other organic compounds were formed during the chlorination experiment.
Abundance Abundance
New Peak
(2.984 min ) Scan 1081 (2.984 min): CHL11F.D
TIC: CHL0F.D 360000 83
TIC: CHL11F.D (*)
2400000 340000

320000
2200000
300000
2000000 280000

260000
1800000
240000
1600000 220000

200000
1400000
180000
1200000 Test Sample
160000
(10 mg Cl2)
1000000 140000

Control 120000
800000 47
(0 mg Cl2) 100000

600000 80000

60000
400000
40000 35
200000 20000

0 70 118
0 5 35 9 89 100 124132 157
30 40 50 60 70 80 90 1001101 2 01 3 0140150160
2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50
m/z-->

A B

Figure 6A: Purge and Trap GC MS scans of the control and test sample and (B) The mass spectrum of
the new at 2.9 min

Temperature Effects

Figure 7 illustrates that little or no changes in the polymer occurs from room temperature up
to 70oC. At 80oC, however, a significant change is observed and is depicted by a change in
shape of the GPC chromatogram, from an almost symmetrical distribution to one that is
biased towards the low molecular mass region.

The change in the MMD (Table 2) verifies this fact and shows a general decrease in value
and hence would imply a corresponding change in the physical properties of the polymer.
Analysis of C18 extracts of the sample by GC FID and RP HPLC, showed no evidence of the
formation of small molecular species as a result of thermal degradation
 7.00 80 oC for 90 min
Profiles at 80 oC
80 oC for 60 min
80 oC for 30 min
6.00
70 oC for 30 min
60 oC for 30 min
50 oC for 30 min
5.00
40 oC for 30 min
MV

30 oC for 30 min
4.00

3.00

10.00 12.00 14.00 16.00 18.00 20.00 22.00

Minutes

Figure 7: The overlay GPC chromatograms after exposure to increasing temperatures

Table 2: Change in MMD data as a function of temperature.

Temperature (o C) Mn Mw MP Mz Mz + 1 Polydispersity
25 37315 450966 81547 15651673 45405714 12.08
30 39134 460528 76365 15716909 45497405 11.77
40 38282 450141 82811 15500108 45283818 11.76
50 36261 443465 68789 15425754 45316135 12.23
60 36414 439671 86397 15516987 45559208 12.07
70 32219 423423 63859 15148049 45207923 13.14
80 35704 294433 94647 11848584 44921226 8.25
80 34165 302953 80459 12356136 45165263 8.87
80 31846 199101 76006 7932053 44325854 6.25

The pH Effect

The GPC overlay chromatograms of the sample in the pH range 2 to 12 (Figure 8A), indicate
good pH stability up to pH 10. This is consistent with theory which predicts that quaternary
ammonium compounds such as polyDADMAC with no protons to give up, are unaffected by
OH- ions. This is an extremely useful property of polyDADMAC as well as other quaternary
ammonium polymers in that it can be used with a wide range of raw water types without the
need for pH adjustment. At pH 12, however, there is a significant decrease in the polymer
peak area. The peak shape remains largely unchanged. This seems to suggest, that
polymer degradation occurs at high pH extremes. The formation of a quaternary ammonium
hydroxide which subsequently undergoes Hoffman elimination to form water and an alkene, is
proposed. GC FID analysis of C18 extracts, (Figure 8B) show the formation of at least three
new molecular species that elute between 3 and 5 min. A cluster of three peaks appear
between 14 and 15 min that show an increase in peak areas with a corresponding increase in
pH. The identity of the new species remains unknown at this stage.
 new peaks at
pH 12
control
pH 2-10 Cluster of 3 peaks
14.00

12.00 50 50
50

pH 12 45
40
35
45
40

35
45 30 30
10.00 25 25
20 20
MV

4 5 14 15 min
40
8.00
35

6.00
30

4.00 25

2.00 20

11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00 21.00 22.00 23.00 0 5 10 15 20 25 min
Minutes

A B

Figure 8A: The overlay GPC chromatograms of the polymer at different pH values and (B) The GC FID
overlay chromatograms of the samples in the pH range 2 to 12

The Effect of UV Radiation

Figure 9A show a significant difference occurring in the overlay GPC chromatograms of the
test sample (UV exposed) and the control (unexposed sample) especially in the high
molecular mass region. This may be attributed to degradation. The analysis of methanolic
C18 extracts of the sample and control by GC FID (Figure 9B), indicate a number of
components present in the exposed test sample but not in the control. Further
characterization of the degradation products was not completed.

Norm.
Unexposed Control
16.00
28
UV Exposed for 24 hours
14.00
26

12.00
MV

24
10.00

8.00 22

Test Sample
6.00
20

4.00
Control
18
2.00 2 4 6 8 10 12 14 16 18 min
10.00 12.00 14.00 16.00 18.00 20.00 22.00
Minutes

A B

Figure 9A: The GPC overlay chromatograms of the control and UV exposed sample and (B) The GC FID
chromatograms of C18 extracts of the control and test sample
 CONCLUSIONS

PolyDADMAC was successfully synthesized according to the method of Hunter et al [1]. It

was found that experimental parameters such as temperature, pressure, and monomer
concentration required careful control for the successful synthesis of a linear water soluble
polymer. High monomer concentrations produced increased reaction rates and excessively
high temperatures. This resulted in the production of a cross-linked polymer that was
sparingly soluble in water and of no use for water purification. The polymer MMD was
determined and classified as a low molecular mass polymer. The effectiveness of the
polymer was demonstrated using jar tests and supernatant turbidity as the indicator of the
polymer performance. The optimum dose for treating a clay suspension with turbidity of 20.1
NTU, was achieved at a polymer dose of 0.49 mg per 800 mL sample or 0.61 ppm. GPC
data indicates that some degree of change occurs in the product when exposed to high
temperatures, high pH, high chlorine concentrations and to UV radiation. The formation of
chloroform during chlorination was established with purge and trap GC MS. GC FID analysis
produced evidence on new compound formation at high pH and after exposure to long
wavelength UV radiation.

REFERENCES

1. WE Hunter, TP Sieder, US Patent, 4,151,202, 24th April 1979.

2. W John, CA Buckley, EP Jacobs, RD Sanderson, Poster Presentation, UNESCO/IUPAC
Conf., Stellenbosch, March 2002.
3. JE Lancaster, L Baccei, J. Polym. Sci., 14, 549, 1976.
4. SR Johns, RI Willings, S Middelton, AK Ong, J. Macromol. Sci., Chem., A10(5), 149,
1976.
5. GB Butler, RJ Angelo, J. Amer. Chem. Soc., 79,3129, 1957.
6. AD Eaton, LS Clesceri, AE Greenberg, Standard Methods for the examination of Water
and Wastewater, 19th Edition, AWWA, 1995.

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