Synthesis and Characterization of a Poly(amidoamine) wilh

Amidn and Tertiary Amino Groups Regularly Alternating

along (he Macromolecular Chain

L U I SRirsconi,
~ M. Cnsrinri Tonzr, Gobrieiin Gorl~s~helli
Dlparllmenlo dl Chlmlca Indll<lnalc c lngrgncrla Chlmlca dcl Polilecnro.
Plaua Lconardo da Vmcl 32,20133 Mllano, l l r l y

Po010 Ferruli., Luipt An~rohni

lrlilulodi Chlmlra disli lnlrrmadl ddl' Unlvirrld. Vlale Rliorgminlo 4.40136 Uulognn, llaly

(Date or recelnl July 10, 19R21

InIraduction
Linear poly(am#doammc)?in which amtdo and irrllarv amino g r o u ~ sarc rreulrrly arranged
nlang the macromolcrular chain, according ro the rcqucnnc~ rabb or aab , ran he
preparcd hv polyadrllllon or hlrlsec-mmlnc)?,or prlmary monoarnlnc5 co bl~iacrylamldel~".
here polymers show snrere5tlnp proncrtlcr a. far ar their pra~onailonsnd complcr formarloit
~ 8 t heavy
h metal ,on- are conccrncd. m d %rebeing rrlennl~rlvilud8ed # nrhlr rc\srct'" Snmc
of them are a150 bcma rtud~cdr r b#omcd#cal ~ o l y m r r i ,owlns Lo l h c r ablllty lo lorm 7lnblc
ComDlexei u l l h hmrrlne""'.
The aim of lhlr paper Ir lo rcpori a n o v rynrhciic way ro poly(am~doarninc)r,
lcadlng to polymers 10 which amid0 and tertiary amino groop3 regularly alternate.
according l o the sequence: abab
Thls method ha5 been studied with piwrarine as the startme malenal. but in
h t rea\onahl\ appllcd to morc eecondary am~nc,.S l u d ~ c ron (his toi,#c
p l n c l p l e ~ n h ~bc
a'" d ~ t o a l l ?In proglc?\
)(Smthesis
The new synthesis of poly(amidoam~ne)sinvolves the l o l l o v ~ n gsteps:
 \,<" tl r.., ,W?. ,<3?(C C\.<.,S ,r P".,*,$"" ," "I,<, , , I d5 1, ,,,e 1<,,",8, 0" '>f
:.-~
5. , ."','"I . < I..: -., -.,?-.-5llnc.I\
i :>;,:r..r,<. "i.1, , 7.1' .I. cl.i I.,
%. 7,111,'. ."11 112.",.'"11C 'P ?
,>011.. * . - ' I..,,, 4 l , , ..I
Siep~(11 and (4) were pcrformcd ~nclose succession, and m a ryplcal procedure.
intermedialc 5 was nor characrermed. bur after treatment with water and nculrailra-
tion wnh tr#cthylam~ne, both d l o ~ a n cand trtphenylcarbxnai were removed from the
reaction mirtuie, and the aqueou5 ralurion war finally allowed to stand ar room tem-
perature for some days Water war chosen as polymerilalron solvenl because 11 had
been prevkourly found ro be particularly conrcnlenl I" the poiyadd8Ihon o f
birlrecondary arnmels to bis(acrylam~dels'~l.

Polymer 6, ahfamed as above. usually ha?an intrinqic vaco<ityranging between 0.2

and 0.4 dllg l m CHCI, n 30'C)
I t I $ 101uble in water and chloroform. bur lnroluble in most organic tolvenlr IIwas
found by X-ray dlffrsctlon to be highly crycrallinc. Its d~ffracrionpattern shows main
reflection. at 22'. 1R0, and 16.5' and is differen; from that o f the ~somcric
poiy(am~doam#nel 7 with aabb requcnce (see above) deriving from the polyadd8tion
of pipenzine ta I.4-bis(acryioyl)plpeea111e~'~.

DSC anslysid shown an exothermal peak at about 228°C which can besttributed to
thermal drgiadatlon. No tracer o f endolhermic peaks attributable to melting are
pre3enr.
The "C N M R spectrum ii reported m Flg. 1 and shows resonances at 6 = 30.4 and
53.7, attributed lo cham rncrhylene groupr (-CH,CH,CO- and -CH,CII,CO-,
re?pect!vely), and at d = 113.0 artrlbuled to the carbonyl group An lnlerrsling
feature of the spectrum e that fhe i l g n a i ~relatwe to the ring mefhylenr groups are
doubled. In particular, resonances at 6 = 42.1 and 46.0 arc alrrlbuted to rlng
mcthylenes adjacent l o (he amldlc nltrogcn. and resonance%at d = 52.4 and 53.0 l o
tbc mefhylenc~ adjacent ro the aminie nitrogen.
coalcrcence on heaung (ree Fig. 1). A szmiiar beha
m l e n e s bclonghils to !he dlacylated pipcrazlnc ring of poly(am>doam~ne)
l 2 . " 1 and i\ artrthuted l o re\tnctcd rotation around the amidr bond whlch-
ring methylenc groups dlar!ereocon~c.'H and "C NMR studies of the clr-lr.ins
isomerism of plperazine conlaminn polyamider have already been reported"
Fig, 1. "C N V R
~pcclrum(71.5 MHz.
D1O.ref I.&d#oxanel o l
polvmer 6 at room iemp
la1 and at 80'C (b)
,.. I.. .,. Lo .o

"C NMR spectra werr run in D1O with I.4dloxanc as rntcrnal reference on a Bilikcr CxP-
3 M lntlruminl operaunp nr 75.5 LIHL Wbdr angle X-m) oonder dlffracllon 5prdrr were run
on a Phlllor PW lOIOcnunlcr dlflraclometcr, uslnr - Cuh." radlalion.
US' mearuicmcns r e r c carrlcd ou, on a Perkin-Flmcr USC-I rsnnlng calonmctcr $ n air,
wllh a scan rpscd o f 8°C'm8n
l - T r , p h ~ n y i m a h v l p ~ ~ ~(31'
~ ~ Anhydrous
:iii i w r a l l n e (39.3 g, 0.46 moll wnr dlslolvcd=
dr chloroform (2q0 ml). the rolulion war cooled 8n an ~cr-bath.m d lrlphenylmeihyl chlorlde
,F%cTCT{~~~ addell u l l ~ ,tirrmng.
i itlrrtng or Ihc reaction mixere vrs continued a

< a c l l 8n thcrub3equcnl rr 8. .,n i .,. c . .hccllng ~ h ahtcnceofplpcrnllnc

c hyTLC(CHCI,/
2 - p r o p a n o l / c n c f h ~ l a m ~i~v~l ~- ,r r i l o S I 0 31 4 rrr'r)riall~zrd(from I 1 bcnrcnclhiptanel
ramplc had m p. IhR- t i ? * <

C21Hi4N2 (328,4) Cmlc C 84,lI H 7.37 N 8.51

Found C 83,90 H 7.41 N 8.31

I - A ~ r ~ ~ l o y l ~ m p h m v l ~ n e(4): ~ l Frevhly
~ y I p d>rtillrd
~p~~~ scryloyichlondc
~~~~ (2.1 mol. 30.5
d 1 0 m l o l n chloroform(%olulbonA), andNaOH(1.32 g: 13 mmol) war
m m o l l r a ~ d ~ r r o l r c#n
dl?%olv<din 10 ml o l ualer k o l h c n A and B r r r c added by iurn? dronurir a
~olutmnof 3 l l 0 g ) ~n 150 ml nf dr) rhol-~> f<# ~ ~ ~ , 4
cemp ( - i O C by an irc/acc,one bath The renc,,on ",,\,"re .as k i t I I>a, roo,,,,cm,, u l l h
,nan me ~ ~\\,II,~wmi0r
p ursreparatcd, and ~ h~ ~ ~ ,
The cambtned cl,iorofurm exlracir were wsrhed ~ 7 t haq. rrcurnlccl P..lil \ a n i W
ilciul~tratlo 1 : 11 (2 x 30 ml) and wllh aq. ~aturalcdNrC1 12 x 30 ml). Tihcn. lhc\ a e r r drlcd
~~ ~ ~~ ~
ClnHIaN:O 1182.<1 Calc. C 81.64 H 6.58 N 7.32
l ollnd C 81.83 H 6.85 N 1.32

Poiv/l,4-~ipcron,lciliyiIoroinrneth~lend161. 4 13 g l s r d>~mlued ~n 10ml of I.4-dloxanr

hy gc#lllyunrmtn8. md 1 2 n HCI 14.4 ml) urr added Th: urinrc-iolourcd litin^ in^
h.,.icllt r l ~ ,rrllllll.l i i w c for I h. then wa>dl~utedU I I ~4 ,"I ot ila~cr .ini~ ncu~ra~llrd

nrerl~linine>Iullh arrlonr > lrlil 0.6'3 g. (lia'tll

1C,Hl2N2O), (140.2). Calc. C 59.97 H 8,63 N IY.98

Found C 59.12 H 866 N 19.15

Thmkr are duc 80 the Hlwi8/,,iild NMR S l r l x e 01C N R IlSohlnni lor runnlns: thc N\IR
spectra and lo Prof L Liln"::! ,Unl"cni,y of Bologna) for u ~ c f udlscunlon
l

'I F Danu$io. P Fcrrutl. Polymer 11. 88 (1910)

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ll97BI
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Rlolo.
o in
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