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Journal of Thermal Analysis, Vol. 33 (1988) 1109-1117 THERMAL ANALYSIS OF MACROMOLECULAR "HALOAMINES" R. Bogoczek and E. Kocio~ek-Balawejder TECHNOLOGICAL INSTITUTEOF CHEMICALAND FOOD INDUSTRY, A, E., IJ1. KOMAN- DORSKA118/I20, 53-345 WROCI-.AW 2. POLAND The TG, DTG and DTA curves of macromolecular macroporous N-halogeno- and N,N-dihalogen- osulfonamides are reported and interpreted. To compare their ti~erma! hehaviour with that of their unfunctionalized matrices,'analogous studies were performed on the porous styrene-divinylben- zene (20%)copolymer and its sulfonamide derivative. Styrene-divinylbenzene (St-DVB) copolymers are widely used in the manufacture of ion-exchangers and specific reactive polymers [1 ]. Starting from a macroporous sulfonic cation-exchange resin, Wofatit KS 10", we have obtained [2] N-monohalogeno- and N,N-dihalogenopoly(St-DVB) sulfonamides containing the following functional groups: @ - SO2NXM and @ -- SO2NX 2 . where Q,) ----- St-DVB matrix, X = C1, Br or I, and M = metal cation. Owing to the presence of halogen atoms with oxidation number +1 covalently bound to the nitrogen atom, these copolymers have bactericidal, disinfectant and oxidative properties. In this respect they resemble the low- molecular chloramines, e.g. Chloramine T or Dichloramine B. Moreover, these copolymers can serve as halogenating reagents and some of them as cation-exchangers. Thus, macromolecular chloramines are interesting from both scientific and technological aspects. Their main advantage (in com- parison to low-molecular halogenosulfonamides) is the possibility of easy separation from treated liquids. The purpose of this study was to establish the thermal behaviour of the halogenosulfonamides obtained. Thermal analysis by means of thermo- gravimetric (TG, DTG) and differential thermal analysis (DTA)methods were performed. In order to obtain comparative data, similar studies were carried out on a non-halogenated copolymeric sulfonamide and on the unfunctionalized St-DVB matrix itself. * Tradename, VEB Chemiek~mbinat Bitterfeld, G.D.R. John Wiley & Sons, Limited, Chtchester Akaddmiai K tad6, Budapest

Thermal analysis of macromolecular “Haloamines”

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Page 1: Thermal analysis of macromolecular “Haloamines”

Journal o f Thermal Analysis, Vol. 33 (1988) 1109-1117

THERMAL ANALYSIS OF MACROMOLECULAR "HALOAMINES"

R. Bogoczek and E. Kocio~ek-Balawejder

TECHNOLOGICAL INSTITUTE OF CHEMICAL AND FOOD INDUSTRY, A, E., IJ1. KOMAN- DORSKA 118/I 20, 53-345 WROCI-.AW 2. POLAND

The TG, DTG and DTA curves of macromolecular macroporous N-halogeno- and N,N-dihalogen- osulfonamides are reported and interpreted. To compare their ti~erma! hehaviour with that of their unfunctionalized matrices,'analogous studies were performed on the porous styrene-divinylben- zene (20%)copolymer and its sulfonamide derivative.

Styrene-divinylbenzene (St-DVB) copolymers are widely used in the manufacture of ion-exchangers and specific reactive polymers [1 ]. Starting from a macroporous sulfonic cation-exchange resin, Wofatit KS 10", we have obtained [2] N-monohalogeno- and N,N-dihalogenopoly(St-DVB) sulfonamides containing the following functional groups:

@ - SO2NXM and @ -- SO2NX 2 .

where Q , ) ----- St-DVB matrix, X = C1, Br or I, and M = metal cation.

Owing to the presence of halogen atoms with oxidation number +1 covalently bound to the nitrogen atom, these copolymers have bactericidal, disinfectant and oxidative properties. In this respect they resemble the low- molecular chloramines, e.g. Chloramine T or Dichloramine B. Moreover, these copolymers can serve as halogenating reagents and some of them as cation-exchangers. Thus, macromolecular chloramines are interesting from both scientific and technological aspects. Their main advantage (in com- parison to low-molecular halogenosulfonamides) is the possibility o f easy separation from treated liquids.

The purpose of this study was to establish the thermal behaviour of the halogenosulfonamides obtained. Thermal analysis by means o f thermo- gravimetric (TG, DTG) and differential thermal analysis ( D T A ) m e t h o d s were performed. In order to obtain comparative data, similar studies were carried out on a non-halogenated copolymeric sulfonamide and on the unfunctionalized St-DVB matrix itself.

* Tradename, VEB Chemiek~mbinat Bitterfeld, G.D.R.

John Wiley & Sons, Limited, Chtchester

Akaddmiai K tad6, Budapest

Page 2: Thermal analysis of macromolecular “Haloamines”

1110 BOGOCZEK, KOCIOEEK-BALAWEJDER: THERMAL ANALYSIS

Experimental

Materials

All the copolymers tested (spherical beads, @ 0 .8 -1 .0 mm) have a common matrix, i.e. S t -DVB copolymer (ca. 20% DVB) with a macro- porous structure. The preparation and the properties of the macromolecular halogenosulfonamides were reported earlier [3, 4]. The unfunctionalized St- DVB copolymer and Wofatit KS-10 were supplied by Chemiekombinat Bit- terfeld, GDR. Samples of the resins were thoroughly powdered and vacuum- dried before each measurement.

Thermal measurements

The TG-DTG-DTA measurements were run with 200 mg samples in air at a heating rate of 10 deg rain -1 in the range 20 -1000 ~ under a constant flow of air (2"104 cm 3 h - l ) , on an OD 102 derivatograph (MOM, Budapest), using ceramic crucibles. A12 03 was applied as reference substance.

Results and discussion

The DTG and DTA peak temperatures and peak widths and the TG plateaus are presented in Table 1. Kinetic parameters for all decomposition steps will be published elsewhere. Typical TG-DTG-DTA curves are given in Figs 1-8 .

Table 1 Thermal behaviour of N-halogeno-poly/St-co-DVB/sulfonamides (Abbreviations: w-----weak,

s = strong, v=very , m = m e d i u m )

Tile kind Plateaus in Peaks in Peak width Peaks in Thermal Peak width in of copolymer TG, ~ DTG, ~ in DTG, ~ DTA, ~ effect DTA, ~

St-DVB upto 140 200 w 140 260 200 endo 30-300 (20%) 480-560 420 vs 260-480 410 endo 300-490

700 w 560-790 530 endo 490--600 720 exo 600-810

residue 0%

~)-SO2NH2 upto 100 140 w 100-160 200 endo 60-340 160-280 375 vs 280-460 380 endo 340-440 above 460 480 exo 460-490

above 500 exo 500-1000

residue 6.9%

J. Thermal Anal. 33, 1988

Page 3: Thermal analysis of macromolecular “Haloamines”

BOGOCZEK, KOCIOEEK-BALAWEJDER: THERMAL ANALYSIS 1111

The kind Plateaus in Peaks in Peak width Peaks in Thermal Peak width in ofcopolymer TG, ~ DTG, ~ in DTG, ~ DTA, ~ effect DTA, ~

~)-SO2NCINa upto 30 120s 30 -200 120 endo 30 -170 200-310 380 s 310-460 260 endo 170-360

760s 620-780 440 exo 360-480 460-620 580 exo 480-620 above 780 700 exo 620-760

residue 14.9%

~)-SO2NCIH upto 50 120m 50-200 125 endo 30 -200 200-300 380 vs 300-460 260 endo 200-330 460-1000 370 endo 330-405

800 exo 405-1000 residue 0%

~)-SO:NCI2 upto 60 120 m 60-160 140 endo 30 -200 220-305 200 m 160-220 170 endo 200-340

370 s 305-480 370 endo 340-390 above 480 720 exo 390-850

residue 7.5%

I~)-SO2NBrK upto 60 120 m 60-180 120 endo 30 -180 180-270 340 s 270-400 250 endo 180-300 400-450 530 w 450-570 400 exo 300-500 570-670 740 w 670-760 530 exo 500-600

700 exo 650-800

residue 12.5%

(~)-SO~NBr 2 upto 80 160 s 80-200 105 endo 30 -180 200-300 340 s 300-400 220 endo ! 80-300 400 450 530 vw 450 600 550 exo 340-1000 over 600

residue 14.5%

~)-SO2 NINa upto 40 140m 40 -230 120 endo 30 -170 230-300 360 s 300-440 270 endo 220-300 440-540 570 w 540-600 420 exo 300-500 600-720 760 m 720-790 570 exo 550-620 above 780 760 exo 640-760

residue 7.5%

The highly porous St-DVB copolymer tested (Fig. 1) is stable up to 140 ~ where a slight weight loss can be noticed. This endothermic process is probably due to the evolution of the residual organic diluent used by the manufacturer to generate the macropores. This is accompanied by an endo-

J. Thermal A hal. 33, 1988

Page 4: Thermal analysis of macromolecular “Haloamines”

1112 BOGOCZEK, KOCIOEEK-BALAWEJDER: THERMAL ANALYSIS

thermic process of pore breakdown. In the range 260-480 ~ the main en- dothermic destruction occurs, which is probably due to depolymerization of the copolymer and elimination of styrene vapour. The solid residue probably melts at 490-600 ~ as indicated by the endothermic effect without weight loss. Above this temperature, the residue burns, showing an exothermic peak as expected, until no matterremains.

DTG

Fig . 1

Exo

&T

I T

Endo

I I 200 400

0

20

40

60

8O

E .,q 100(~ 6OO 8OO IOO0

Temperature ~~

TG, DTG and DT~ curves of St-DVB copolymer Wofatit type

The sulfonamidic derivative o f the St-D VB copolymer (Fig. 2) loses some volatile matter and the pores break down in an endothermic process. In this case, these processes proceed at a somewhat higher temperature than for the parent copolymer. Above 280 ~ the main destruction process takes place, similarly as for the parent copolymer, but in a smaller range of temperature, due to the activating effect of the functional groups. On the other hand, in tl'/e case of the sulfonamidic derivative a notable amount of solid matter

J. Thermal Anal. 33, 1988

Page 5: Thermal analysis of macromolecular “Haloamines”

BOGOCZEK, KOCIOEEK-BALAWEJDER: THERMAL ANALYSIS 1113

remains, which contains sulfur and nitrogen. Afterwards, a short but marked exothermic effect is observed, without weight loss. This is a result of reoxid- ation of sulfur compounds, reduced during the earlier stage of depolymer- ization. Oxidative exothermic destruction then occurs, yielding a coke-like residue of 6.9% in which sulfur is still present.

<~ 100

DTG

E,~o

io 0

2O

4O

6O

2O0 400 600 8O0 IO(X) Temperature ,eC

Fig. 2 TG, DTG and D'rA~ era'yes of poly(Sl-co-I)VB)sulfonamide

The sodium salt of macromolecular "'monochloramine" (Fig. 3) shows a marked endothermic weight loss of 18.4% in the interval 30 ~ to ca. 200 ~ This is connected with the evolution of .water molecules linked with the functional groups. This water loss is followed by an endothermic peak combined with a very small mass decrease, which is due to the low molec- ular matter evolution, and the breakdown of pores. The subsequent exo" thermic process, with a marked weight loss of 20.2%, comprises a com- plicated simultaneous depolymerization and chlorination process, where the chlorine remains in the solid phase. Thus, the mass loss is much smaller than

J. Thermal A nal. 33. 1988

Page 6: Thermal analysis of macromolecular “Haloamines”

1114 BOGOCZEK, KOCIOLEK-BALAWEJDER: THERMAL ANALYSIS

Exo , DTA dT

E n ~

20

40

60

E "=3

200 400 600 80O Ternperoture, ~

E "oJ

Ei~ 1 i' T

!ndo E

C

2C

4C

6C

- �9 8C

Fig. 3 TG, DTG and DTA curves of sodium N-monochloro-poly( St-DVB ) sulfonamide

T

TG

200 400 600 800 1000 Temperuture ,oC

Fig. 4 TG, DTG and DTA curves of hydrogen N-monochloro-poly(St-DVB) sulfonamide

in Figs 1 and 2. An exothermic destruction process follows, separated by non-exothermic isomerization processes. Finally, at 760 ~ "burning-out" takes place and NaC1 remains as residue (14.9%) in the crucible.

Figure 4 gives the thermal curves of the hydrogen form of the functional- ized copolymer presented in Fig. 3. In this case, no solid residue was re- corded at 1000 ~ since no mineral substances were present in the tested sample and the active chlorine helps to oxidize all organic matter. Up to 300 ~ this copolymer behaves similarly to the corresponding sodium form: it loses water linked with the functional groups. Next, the effects are similar to those in Figs 1-3 . However, during the depolymerization step, volatile products arise, and hence there is a mass loss.

The rnacromolecular "dichloramine" (Fig. 5) displays a TG step at ca. 120 ~ like all the other copolymers. Further, a short DTG peak occurs

Z ThermalAnal. 33, 1988

Page 7: Thermal analysis of macromolecular “Haloamines”

BOGOCZEK, KOCIOI:,EK-BALAWEJDER: THERMAL ANALYSIS I 115

Ex~ I i DTA

E <~

Fig. 5

20

/*0 i

60

80

I I I I I 200 t.O0 600 800 1000

Temperature ,~

TG, DTG an~ DTA curves of N,N-6ichloro- -poly(St-DVB) sulfonamide

!T A

0 G

2C

40

< 1000 I I 1 I 200 /-,00 600 800 1000

Temperoture, ~

Fig. 6 TG, DTG and DTA curves of potassium N-monobromo-poly (St-DVB) sulfonamide

without any DTA effect, whereafter the known endothermic effect at 2 0 0 - 3 4 0 ~ with a small weight loss is observed. The endothermic DTA peak at 3 4 0 - 3 9 0 ~ accompanied by a strong mass loss, corresponds to the depoly- merization process. Subsequently, the curves resemble those of Fig. 4.

The thermal behaviour of the salt o f the macromolecular monobromosul- fonamide (Fig. 6) is similar to that of the corresponding chloro- (Fig. 3) and iodo- (Fig. 7) derivatives. Whereas the amount of residual NaCI agrees with the theoretical prediction, the NaBr and NaI residues are much smaller, than predicted. The reason for this is that bromine and iodine undergo intra- molecular halogenation, forming volatile compounds.

The thermoanalytical curves of the dibromosulfonam~de (Fig. 8)resemble those of the dichlorosulfonamide (Fig. 5).

J. Thermal Anal. .33, 1988

Page 8: Thermal analysis of macromolecular “Haloamines”

1116 BOGOCZEK, KOCIOEEK-BALAWEJDER: THERMAL ANALYSIS

6T

0

20

/.,0

60

80 o~ E ,,~ 10(

Fig~ 7

I I I I 200 400 600 800 luO0

Temperature ,~

TG, DTG and DTA curves of sodium N-monoiodo-poly (St-DVB) sulfonamide

DTG

E.o[ I DTA

TG

Fig. 8

200 400 600 800 1000 Temperature ,~

TG. DTG and DTA curves of N,N-dibromo- -poly(St-DVB) sulfonamide

References

1 C. Calmon, Reactive Polymers, 1 (1982) 3. 2 R. Bogoczek and E. Kociol~k-Balawejder,

Polymer Communications, 27 (1986) 286. 3 R. Bogoczek and E. Kociol-ek-Balawejder,

Reactive Polymers, 4 (1986) 311-316.

4 R. Bogoczek and E. Kocio!-ek-Balawejder, Pro- ceedings of 5th Symposium on Ion Exchange, Hungary 28-31 MAY 1986, p. 40-41 .

Zusammenfassung - Die TG-, DTG- und DTA-Kurven makromolekularer makroporOser N-Halogen- und N,N-Dihalogensuifonamide werden beschrieben und gedeutet. Zum Vergleich wurde das thermisehe Verhalten des unsubstituierten por6sen Styren-(20%)Divinylbenzen-Copolymeren und seines Sulfo- namids in gleicher Weise untersucht.

J. Thermal Anal. 33, 19R8

Page 9: Thermal analysis of macromolecular “Haloamines”

B O G O C Z E K , K O C I O I ~ E K - B A L A W E J D E R : T H E R M A L A N A L Y S I S 1 1 1 7

PE3IOME - - FIptmeneH~i ~ o S c y 3 [ ~ e H ~ T F , ~ T F H ~ T A a~ptm~e ~ MaKpoMoJle lcynf lpmdx MaKpo- rIOpHCTbL~ N - r o a o r e H - H N,N-~m'anoKeHcym~dpaMH~OB. C ttem, lo c o n o c T a n z ~ e H ~ x~x TepMHqecicoro rio- Be~eHtm c HX HeaJCTHBH~MH He~aMettteHH~nVlH npoH3BO~[lbn~H, ~I~JIH r/poBe~eEUbl a l E [ S M o ~ e 14ccJl~o

~ o s a m m n o p H c r o r o c o n o y m M e p a CTHpOJm H ~ t m H m t n 6 e H a o n a H e r o c y n t ~ b a M m m o r o n p o K a n o ~ o r o .

J. Thermal Anal. 33, 1988