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Makromol. Chem., Rapid Commun.

5,27- 31 (1984) 27

Homopolymerization of monoallylammonium salts with


azo-initiators
Susumu Harada*, Sakuro Hasegawa

Research and Development Laboratory of Nitto Boseki Co., Ltd.


Fukuyama, Koriyama, Fukushima-Ken, 963, Japan

(Date of receipt: September 5, 1983)

Introduction
It is well known that monoallyl compounds do not homopolymerize readily by a
conventional free radical mechanism. This has been attributed principally to an
allylic degradative chain transfer I).
The presence of the amino group in the allylic monomer further decreases the
reactivity of the allylic double bond in polymerization reactions, and there is no
method leading to polyallylamine of high molecular weight by radical or ionic poly-
merization.
Kabanov, Masterova et al. in 1976 have prepapred polyallylamine by polymerizing
monoallylamine in a protonic acid such as phosphoric acid by means of irradiation
with a 6oCosource2),and discussed the polymerization mechamism3S4).A recent Ger-
man Laid-Open specification5)discloses the homopolymerization of allylammonium
chloride by 2,2-azoisobutyronitrile(AIBN) in the presence of diethyl phosphite in a
mixture of chlorobenzene and tert-butylalcohol, but all attemps to reproduce it have
been unsuccessful *).
This paper is a preliminary report on the polymerization technique of monoallyl-
amine. The mechanism and the limit and scope of this polymerization method will be
described in a future paper.

Results
We found that a radical initiator containing an azo group and ammonium groups,
such as 2,2-azobis(2-methylpropanediamine)dihydrochloride (1)is capable to poly-
merize some monoallylammonium salts in an aqueous medium quite easily and there-
by poly(ally1ammonium salt)s having a fairly high molecular weight can be obtained
in high yields.
In addition, 2,2-azobis[2-(imidazolinyl)propane]dihydrochloride (2) was also used
as initiator.

*) We repeated the homopolymerization of monoallylammonium chloride described in the


specification and observed that in contrast to the disclosure, only a hygroscopic product was
obtained with a yield pf about 1%.

0173-2803/84/$01 .OO
28 S. Harada, S. Hasegawa

1 2

1 has already been described in 1952@,and thereafter it was used in many polymeri-
zation studies, including the polymerization of diallylammonium chloride'). It is
surprising that no attempts have been made so far to polymerize monoallylammon-
ium salts with this initiator.
Polyvinylamine or polyallylamine, which are typical polymers containing primary
amino groups, are not only of theoretical but also of practical importance, having the
potential of affording a wide variety of soluble functionalized polymers. Various
techniques for the synthesis of polyvinylamine have been However, the
synthesis of polyvinylamine suffers from inherent difficulties in the preparation of the
monomeric precursors and in the unmasking of protected amino groups in the
polymers. Thus, the application of initiators of type 1 provides a very simple method
for the preparation of linear polymers containing only primary amino groups, i. e.
polyallylamine, from the commercially available monomer monoallylamine.
The polymerizations of monoallylammonium chloride (phosphate or sulfate) are
carried out in water, aqueous ZnC1, solution, phosphoric acid, or sulfuric acid in the
presence of 1 or 2. The results of representative polymerizations are summarized in
Tab. 1. In all runs, products were isolated as poly(ally1ammonium chloride).

Experimental part
Monomer: Monoallylamine (from Shell Chemical Co., USA) was dried over solid sodium
hydroxide, rectified through a 50 cm fractionating column under nitrogen, and a fraction
having a boiling point of 52,5 -53 "C was used. Diallylamine in this fraction was less than 0,02
v01.-%, when examined by gas chromatography (Hitachi 663 - 50 FID apparatus). The product
was analytically pure.
Allylammonium chloride (a 70% aqueous solution): A 10 I three-neck flask, equipped with
over-head stirrer, thermometer, and reflux condenser was charged with 4250 ml of 12 N HCI(51
mol). With stirring, 2855 g (50 mol) of monoallylamine precooled to - 5 to 0.C; were added
dropwise keeping the temp. at 5 -10C by cooling. The resulting clear solution was concen-
trated to a volume of about 5,5 1 at 50 - 60 "C under reduced pressure. The concentration of the
hydrochloride in the resulting solution was determined by potentiometric titration and adjusted
to 70 w t . 4 by adding water.
Initiators: 1 and 2 (from Wako pure Chemicals Ind. Ltd.; trade names: V-50 and V-56) were
recrystallized from acetone/water and analytically pure.

Polymerizations
The procedures of run 1 and 3 in Tab. 1 are described below in detail as representative
examples.
Tab. 1. Conditions and results of polymerizations of monoallylamine with azo-initiators 1 and 2 in aqueous mediuma)

Run No. Amount of monomer Medium (g; mol) type Initiator amount Yieldb) Conversion qnh 4 Mnd)
in g (in mol) weight in g in mmol in g in Yo dl.g-1

water 1 8,14 30 418,5 85 0,43 8 500


2 } ~~i!~~rwhloride)e) 2 9,70 30 4333 88 0.35
3 285,5 (5) 85% H,PO, 1 8,14 30 407,8 83 0,85 45 OOO
(1 150; 10)
A0 285,5 (5) 80% H$OA 1 8,14 30 403,8 82 0,36
(613;5 j ~

492 (OS) 60% aq. ZnCl, 2 0,97 3 39,3 80 0,32


(of hydroch1oride)g) (31)

Polymerizations were carried out at 50 f 2 "C for 50 h.


In all runs, polymers were isolated as poly(ally1ammonium chloride) which contained 5% H,O.
Inherent viscosity for 0,5 g of polymer/100 ml of 0,l N NaCl aq. solution at 30C.
Number averagd molecular weight, calculated from membrane osmometry in 1 N NaCl aq. solution.
70% aq. solution.
The procedure similar to that of run No. 3 was used.
70% aq. solution of the hydrochloridewas evaporated to dryness, then it was dried over silica gel in vacuo at 50 to 60"C. The hydrochloride contained
about 5% H,O.

h)
W
30 S. Harada, S. Hasegawa

Run I : Polymerization of allylamine hydrochloride in water with initiator 1: A 2 1 four-neck


flask, equipped with over-head stirrer, thermometer, reflux condenser and nitrogen inlet was
charged with 668 g of a 70% aqueous solution of allylamine hydrochloride ( 5 mol). The solution
was thoroughly deoxygenated and heated to 50C. A solution of 8,14 g of 1 in 35 ml of water
was added. The mixture was stirred for 10 h and the temperature was kept at 48 - 52 "C by mild
cooling. Then, stirring was stopped and the polymerization was continued at 50 k 1 "C for
further 40 h. The polymer was precipitated from the colorless and viscous solution by adding it
slowly to 10 1 of stirred methanol. The precipitate was filtered, washed, and extracted with
methanol in a SoxNet apparatus for 15 h (ca. 60 cycles) to remove unpolymerized monomer,
and dried in vacuo at 50 "C to a white powder of poly(allylammonium chloride). Yield: 418 g.
The elemental analysis indicates that the polymer contains about 5% water, which is in
agreement with the potentiometric titration.

(C&CIN), (93,6), Calc. C 38,51 H 8,62 N 14,97


(C,H,CIN. 1/4H20), (392,3), Calc. C 36,74 H 8,74 N 14,28
Found C 36,71 H 8,80 N 13,78

'H NMR: s. Fig. 1.

Ho 7 C H CH]
~CH~

AH+ CI

Fig. 1. 'H NMR spectrum of


poly(al1ylammonium chloride)
obtained in run 1 (Tab. 1);
determined in D,O at 80 'C;
chemical shift 6 in p. p. m. from
[2H,]-sodium tetramethylsilyl-
--UUI2-1- - propionate (TSP)
3 2 1
6 in ppm

Run 3: Polymerization of allylamine in phosphoric acid with 1: A 3 I four-neck flask,


equipped with overhead stirrer, thermometer, a dry-ice cooled reflux condenser, and dropping
funnel was charged with 1 150 g (10 rnol) of 85% phosphoric acid. With stirring, 285,5 g (5 mol)
of freshly distilled allylamine was added dropwise at 20 - 30 "C. At temperatures lower than
20 "C, phosphate of allylamine crystallized from the solution, which is inconvenient. After the
addition of the monomer, the dropping funnel and the dry-ice condenser were replaced by a
nitrogen inlet and a water cooled condenser, respectively. Then, the mixture was heated to 50 "C
with stirring under a stream of nitrogen, and a solution of 8,14 g of 1 in 40 ml of water was
Homopolymerizationof monoallylammonium salts with azo-initiators 31

added. The mixture was stirred for 15 h at 48-52"C, then stirring was stopped and the
polymerization was continued at 50 f 1 "C for further 40 h. Finally, a very viscous, colorless
solution was obtained. This solution was poured into a large amount of water and the
precipitated pasty polymer (poly(ally1ammonium phosphate)) was washed with water by
repeated decantation. After thorough washing, the wet gummy precipitate was dissolved in 550
ml of 12 N HCI, and the resulting solution was poured into 20 1 of stirred methanol. The
precipitate was filtered and washed with methanol, then redissolved in 300 ml of 10 N HCl and
reprecipitated in methanol. Finally, the precipitate was extracted with methanol in a Soxhlet
apparatus and dried in vacuo at 50C. Yield: 407,s g of poly(ally1ammonium chloride).
Poly(ally1ammonium chloride) is readily soluble in water and aqueous acids but insoluble in
organic solvents.
Polyullylumine: A solution of 30 g of poly(al1ylammonium chloride) in 270 g of water was
passed through a column of Amberlite I R A 4 2 (strongly basic ion exchange resin) and
concentrated in vacuo at room temperature to about 150 ml, then freeze-dried to obtain 16,5 g
of the white polymer. When the above concentrated solution of polyallylaminewas precipitated
by addition to acetone, however, the precipitate was found insoluble after drying at 50 "C in
vacuo.
The IR-spectrumof polyallylamineexhibits absorption bands at 1 320 (symmetrical)and 1 580
cm-' (in plane), which can be attributed to deformation vibration of NH2 groups.
Measurements: The 'H NMR spectrum of the sample of poly(al1ylammonium chloride)
obtained from run 1 was recorded with a JEOL JNM-FX270 instrument using TSP as internal
standard and D,O as solvent at 80 "C (Fig. 1).
A number average molecular weight (M,) of 8 500 was obtained from membrane osmometry
in 1 N NaCl aqueous solution of the sample obtained from run 1 , and from run 3 a considerably
higher M,, of 45 OOO was obtained.

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