JOURNAL OF POLYMER SCIENCE VOL.

5 5 , PAGES 303-309 (1961)

Polymerization of 2,4-Dimethyl-6-vinyl-s-triazine

AKTHONY T. COSCIA, ROBERT L. KUGEL, and JOSEPH PELLO?;,

Chemical Research Department, Central Research
Division, American Cynnnmid Company, Stamford, Conn.

INTRODUCTION
Recent advances in the chemistry of s-triazines by Schaefer and co-
workers' of these laboratories have provided a convenient route to vinyl
dialkyl t.riazines (I). These compounds have not been described in the
CH,=CR'
I

literature, and vinyltriazines with R other than alkyl have also received
little attention. The previously reported work on vinyl-s-triazines is
found in the publications of: Dumont, Reinhardt, and Schiefer,2 who
prepared 2,4-diphenyl-6-vinyl-s-triazine;Overberger, Shapiro, and Miche-
l ~ t t i who
, ~ prepared 2,4-diamino-6-vinyl-s-triazine and 2-amino-4-anilino-
6-vinyl-s-triazine ; and the patcnt of T h u r ~ t o n ,which
~ disclosed the
preparation of methacryloguaiiamine (I, It' = CH3,R = KH,).
In the present work, 2,4-dirnethyl-ti-vinyl-s-triazine (DMVT), R' =
H, R = CH3,was prepared and found to be a highly reactive vinyl mono-
mer. The polymerization behavior of this compound and the properties
of its homopolymer are described. Some preliminary data on the homo-
polymer of isopropenyl-s-triazine R' = CH3, R = H are also reported
here.

EXPERIMENTAL
DMVT was prepared by the pyroIysis of 2-acetoxyethyI-4,6-dimethyl-s-
triazine a t 455' according to the method of Schaefer.' The crude pyrol-
ysate contained approximately 40 mole per cent of the desired monomer.
Distillation through a simple head a t 39-42O and 2 mm. pressure in the
presence of air and hydroquinone separated the greater part of the un-
reacted acetoxy precursor and acetic acid, while treatment of a petroleum
ether solution of the distillate a t ice bath temperature with basic alumina
removed the residual acetic acid. The DMVT was then isolated by
stripping the petroleum ether a t room temperature in vacuo, and was
303
304 A. 'r. COSCIA, R. I,. KUGEL, AND J. PELLON

redistilled through an unpacked column. This fractionation was also

best accomplished in the presence of air and hydroquinone. The center
cut, b.p. 73" a t 19 mm., n?l = 1.5011, was cdlected. Mass spectro-
graphic analysis indicated a purity excceding 98.5%, the impurities being
trimethyl-s-triazine and 2-acetoxyethyl-3,(i-dimethyl-s-tria~ine. Such
highly purified monomer was studied immediately after distillation be-
cause it polymerizes spontaneously. When storage of DhIVT was neces-
sary the compound was kept a t 5" in the dark, in the presence of t o t -
butylcatechol or hydroquiiionc. Batch treatment with basic alumina in
petroleum ether solution was suitable for removal of inhibitor.
Homopolymerization was carried out in heavy-walled tubes. These
were sealed off after the samples had been degasscd by a standard procedure
of repeated freezing and thawing. Thi. DMVT solutions in Iieiieene (5-
20% monomer) were heated at GO" iiI the presence of azobisisobutyro-
nitrile (AIB?;). A typical polymerization of DnlVT with 0.1% AIBS
led to approximately 75y0coilversion in 5 hr. in a 10% benzene solution
of monomer. Polymer was isolated bj diluting the contents of the tube
with 1 vol. of benzene, then adding the resultant solution dropwisc to a
tenfold excess of petroleum ether. The. white amorphous precaipitate was
collected, redissolved, and reprecipital ed, aiid finally freeze-dried from
benzene or water solution. Intrinsic viscosity of polymer employed in this
work, was 1.14 in toluene a t 30". The wight-average molecular weight as
determined by light scattering was 1.22 :< lo6.
Homopolymer of 2,3-dimethyl-6-vinyl-s-triazine (PD1LIVT) softens
a t 105" and flows a t 110-130". A glass tramition temperature of 70"
was recorded during diff ereiitial thermal ai~alysis.~PDMT'T is very
soluble in water and is also soluble in the common organic solvents with
the exception of the aliphatic hydrocarbons. On heating aqueous solu-
tions of PDMVT, the polymer separates from solution a t 73" and redis-
solves upon cooling. The phenomenon is reversible, and presumably
due to hydrate formation.
Aqueous solutions of polymer are iieutral. KOpolyelectrolyte effect
is observed during the determination of intrinsic viscosity. PDMVT
is stable in water solution and in diluie aqueous solutions of alkali. In
acid solution the triazine rings degrade, as evidenced hy ultraviolet
spectroscopy. At a pH of 1 the degradation is rapid and the product
appears to be ail acrylic acid-acrylaniidc. copolymer.
Copolymerizations of DNVT were carried out in a manner similar to
homopolymerization. LIonomer reactivity ratios mere determined with
styrene and methyl mcthacrylate, and the data are presented in Tables
I and I1 (see text).
The synthesis of isopropenyl-s-triazine will be reported elsewhere.
Homopolymer was obtained by spontaneous polymerization a t 5 O and
was purified by dissolving in dimethylformamide aiid twice reprecipitatiiig
from ethanol. Viscosity determination 011 this polymer gave [ 7 7 l 3 O = 0.76
in dimethylformamide. The polymer softens a t 210" and flows a t 220-
 2 , I-DIME’I‘I 1Y L-6-VlNk I~.s-‘IRIA%INI: 305

230°. It is soluble in dimethylformamide aiid chloroform, :uid insoluhle

in water, methanol, ethanol, benzene, acetonitrile, petroleum ether,
I and acetone.

RESULTS AND DISCUSSION

Polymerization Behavior of 2,4-Dimethyl-6-vinyl-s-triazine
DJIT’T polymerizes spontaiieously on standing at room temperature
and can be polymerized readily by the action of such free radical initiators
as bciizoyl peroxide, azohi obutyronitrilr ( h I R S ) , di-tert-hutyl peroxidc,
and x-rays. An idea of the over-all rate of polymerization of DlIVT
is provided by the following experiments.
When 10% solutions of DRIVT in bciizeiie containing O.lc/, A I R S
(weight per cent of monomer) were heated a t G O O , a 37% yield of polymer
[v]g9L= 1.3 was obtained in 1 hr. aiid a 78% yield after 3 hr. With
styrene under the same conditions virtually no polymer was formed i n
1 hr. and in 5 hr. the amount of polymer formed was insufficieiit for Yimple
isolation procedures
A large number of radical-initiated polymerizations n err carried out
and, in several, yields of D?tlVT homopolymer were lower than :mticipated
on the basis of the experiments described above. Variation:, appeared to
be related to monomer purity. Also, gel formation occurred when poly-
merizations were run in bulk, at high nmiomer coiiceiitratioiis, or when
taken to very high coiiversions. Siiice the monomer in these cases coil-
tained up to 0.2 m 0 l e - 7 ~2-methyl-4,G-diviayl-s-triazine ( m a s spectro-
graphic analysis), the formation of gel was attributed to the presence of
this component. The occasional formation of popcorn polymer during
distillation was also related to the presence of the diviiiyl derivative al-
though as little as 0.01 mole-yo may have been present. A more yuaiitita-
tive picture of the reactivity of DAII’T, obtained through copolymeriza-
tion and chain transfer studies, is presented below.

Copolymerization
DiMVT copolymerizes readily with styrene, methyl methacrylate,
acrylonitrile, and acrylamide. Reactivity ratios were calculated for the
styrene and methyl methacrylate systems. The data from the copoly-
merizations arc compiled in Tables I and I1 along with the parameters
described by 1;ineman aiid 130ssGin a rearranged form of the copolymeriza-
tion equation:
F/f(f - 1) = rl(F”f) - r2 (1)
Here f = ml/m2and F = X1/JI2;and m land m2,respectively, represent
the mole fraction of comoiiomers in the polymer and JII and M2the
mole fractions of comonomers in the feed. In Table 111 the calculated
rl,r2 values are compiled along with Q and e ~ a l u e s . ~
 306 A. T. COSCIA, K. L. KUGEL, AND J. PELLON

TABLE I
Reactivity Ratio Data for Styrene (14,) and 2,4-I)imethy1-6-vinyl-s-triazine (14,) at 60"a
~

Mole
Per Mole fraction
cent fraction styrene
Wt. Wt. con- Per cent styrene in
styrene, triazine, ver- N in feed polymer (F/f) X
so. g. g. sion polymerb Ml mi (f - 1) F2/f
1 0.333 0.108 5 15.34 0.8016 0.57 0,9811 12.07
15.37
2 0,250 0.216 17 19.69 0.60 0.43 -0.50 3.0
10.43
3 0.208 0.270 8 21.09 0.50 0.38 -0.64 1.63
21.02
4 0.083 0.432 4 26.74 0.20 0.18 -0.886 0.284
26.65
~~ ~

The weighed monomers and 0.005 g. of AIBN were made up to 10 ml. with benzene
8

and treated as described in the experimental section. Polymrrs from runs 1 and 2 were
isolated after 3 2 / 3 hr. and from runs 3 and 4 after 1 hr.
b Analysis by Schwarzkopf Microanalytical Laboratory.

TABLE I1
Reactivity Ratio Data for Methyl Methacryhte (MI) and 2,4-Dimrt,hyl-6-vinyl-s-
triazine ( M 2 ) a a t 60"
Mole Mole
Per Per fraction fraction
Wt. Wt. cent cent MMA MPYIA in
MMA, triazine, con- N in in feed, polymer, (F/f) x
~~
30. g. g. version polymerh MI 7n1 (f - 1) (F2/f)
1 1.138 0 162 11.4 8.09 0.905 0.7933 7 04 23.64
2 1.523 0.711 1.5 16.11 0.743 0.5595 0.615 6.58
15.93
3 0.918 0.829 6.7 20.29 0 563 0.4160 -0 52 2.84
20.40
4 0.651 1.392 5.5 25.43 0.386 0.2272 -1 .51 1.35
25 63
a The monomers were weighed directly into polymerization tubes and 1.0 ml. of a
benzene solution containing 0.0025 g. of AIBN 'was added to each tube. Tubes were
handled as described in the experimental section. Polymers from run 1 were isolated
after 11/2 hr., from runs 2 and 4 after 4 hr. and from run 3 after '/, hr.
b Analyses by Galbraith Microanalytical Laboratorics.8

TABLE 111
Reactivity Ratios and Q and e Valurs for 2.4-l>imeth~-l-6-vinyl-s-triazine

Reference monomer ( A l l ) rl
~
r2 Q2 e2

Styrene 0.12 0.92 2. la +0.92a

Methyl metharrylate 0.37 1.75 2 .5 i b +1.09b
a Based on Q1 = 1.0 and el = -0.8 for styrene.s
b Based on Q1 = 0.74 and el = f0.40 for methyl methacrylate.8
 2,4-DIMEl'tlYL-6-VINY L-s-'I'J<IAZINE 507

The values of r1 and r2 demonstrate the high reactivity of DMVT

in these systems. The Q and e values for DMVT indicate that the di-
methyl-s-triazine ring is an electronegative substituent with a capacity
for radical stabilization. This is further illustrated in Table IV, in which
are compiled Q and e paramet,ers for a number of monomers with electro-
negative substituents in conjugation with the vinyl group.

TABLE IV
Comparison of Q and e Values for 2,4-Dimethyl-6-vinyl-s-triazine with Other Systems
Reference comonomer8
Styrene Methyl methacrylate
Monomer e Q e Q
DMVT 0.92 2.1 1.09 2.57
p-Cyanostyrene 0 3 1.6 0.7 2.26
p-Nitrostyrene 0.4 1.86
Acrylonitrile 1.2 0.44

Chain Transfer Reactivity of Trimethyl-s-triazine

The effect of a triaxine ring on resonance stabilization of a radical was
also assessed by determining the chain transfer constant of trimethyl-s-
triazine with styrene according to the method of Gregg and Mayo.9 The
data are represented in Table V. The chain transfer constant 4.7 x
obtained for t,rimethyl-s-triazine when compared with toluenes
(1.25 x shows that each of the triazinyl methyl hydrogens (nine in
all) is as susceptible to ab strah o n as each of the three tolyl hydrogens.
This points out the capacity of the triazine ring for radical stabilization.
Also, since the radical obtained by abstraction of a H - from trimethyl-s-
triazine is essentially the same as that derived from DMVT during co-

TABLE V
Determination of the Chain Transfer Constant of Trimethyl-s-triazine
(TMT) with Styrene a t 60"
Intrinsic
(TMT). viscosity
polystyrene
(styrene) i v l b , dl./g. 1/P X lose Chain transfer constant, Cad

0 3.62 10.93
1.021 3.03 13.72
1.075 2.75 15.53 4.68 f 0.50 x
3.037 1.96 23.93
4.758 1.53 32.84
a Mole ratio of TMT to styrene.
Measured in benzene solution at 30.0'.
Calculated from M n = 184,000 [q] see reference 9.
d Determined by the least-squares plot of the data according to the Gregg and Mayo
equationg and giving the 9570 confidence interval.
508 A. '1'. COSClA, I\. I,. RUGI<I,, AND J. I'ELLON

polymerization, further agreement is ohtaiiied for thc c.alculat,ed value

of Q.
Comparison of Polymer Properties
The higher softening point of poly(isopropeny1-s-triazine) (PIT) and
its restricted solubility compared to those of 1'DMVT may be attributed
to great.er attractive forces between chains. These forces are probably
a result of intermolecular hydrogen bonding and are, most likely, absent
in PDMVT. The additional methyl group on the backbone of PIT may
contribute to some extent to the higher softening point, of this polymer by
causing a stiffening of the chains, but it is most probably not responsible
for t,he decreased solubi1it.yrelative to PI>;\IVT.
The authors are indebted to Miss R.Herlmic-k for interpretation of mass spectro-
graphic analysis, t o Mrs. G. McLennari for the light scattering work, and to Mr. I).
Benken for calculation of confidence limits. We also express our thanks to Dr. W. M.
Thomas and Dr. Mary Miller for many helpful discussions.

References
1. Schaefer, F. C., A. T. Coscia, I<.R.Huffmail,and R. I,. Kugel, work to lie reported
elsewhere.
2. Dumont, E., H. Iteinhsrdt, and E. Schiefer? Gerinari Pat. 1,042,230 (1958);
Reinhardt, H., and E. Schiefer, Chena. Ber., 90,2643 (1951).
3. Overberger, C. G., and S. L. Hhapiro, J . Am. Chem. Soc., 76, 1061 (1954); Over-
berger, C. G., and F. W. Michellotti, ihid., 80,988 (1958); F. \V. Michelott,i, Thesis ])is-
sertation, Polytechnic Institiite of I3rooklyn, June, 1957.
4. Thurston, J. T., U. S. Pat. 2,461,943 (1049).
5. Keavnej-, J. J., and E. C. ICberlin, J . .lppl. Polymer Sci., 3,47 (1960).
6 . Fineman, M., and S. I). Ross, J . Po/?pnerSti.,5,250 (1950).
7. Alfrey, T., Jr., and C. C. Price, J . Polynier Sci., 2, 101 (1917).
8. Walling, C., Free Radicals in Solidion, Wiley, S e w York, 195i, p. 143.
9. Gregg, R. A., and F. R. Msyo, Disciissions Faradmy Soc., 1947, S o . 2, 328.
10. Flory, P. J., Principles oj' Polymer Phemislry, Cornell liniv. Press, Ithaca, S e w
York, 1953, p. 391.

Synopsis
2,4-l)imethyl-6-vinyl-s-triazine (A) is readily polymerizetl h,v free radical initiators to
a high molecular weight product. Copolynicrizntion studies with reference mononiers
CHZ=CH
I

(MI), styrene and methyl methacrylate, gave reactivit.y ratios with st,yrene: T~ = 0.12,
r2 = 0.92; with methyl methacrylate: = 0.37, rp = 1.i5. The following &-e values
were calculated: with styrene (3. = 12, er = +0.%2; with methyl methacrylate Q2 =
2.6, e2 = +1.09. These values indicate that the dimethyl triazinyl moiety is a radical
stabilizing and electronegative substituent. Poly(2,.2-dimeth~l-G-viriyl-s-triazine)
(PDMVT) is soluble in water and in all the common org:mic solvents wit,h the exception
of aliphatic hydrocarbons. Poly(isopropcny1-s-triaziric) (PIT) is soluble only in di-
 2,4-DIM E’rI IYTr6-VINY I ~ s - T R I A Z I N E 309

tnethylformaniide and chloroform. The latter also softened at a much higher tempera-
ture than PIIMVT. These differences were considered a result of hydrogen bonding
between chains in PIT.

Resume
La 2,I-dim6thyl-6-vinyl-s-t.ri:~ziric ( A ) polymBrise farilement et fournit des polymilres
de haut poids molkculaire par initiation radicalairc. Ijes 6tudes tle copolymerisation
avec des mononiiws de ri.fPrencc, s t y r i w rt niCthacry1at.e de mdt,hyle (MI) donnkrent
les valeurs de rdactivit,i. suivaiites: aver le PtyrCne: T I = 0.12; r p = 0.92; avec le
mhthacrylate de m6thyle: r1 = 0.37, r p = 1.T5. Les valeurs &-e suivantes furent
calculi.es: pour la copolym4risation avcc le styrime: &? = 2.1, en = +0.92 par rapport
nu mdthacry1at.e de nikthyle: QZ = 2.6, ~2 = + 1.09. Ces valeurs dkmontrent que le
groupe diinethyl-triazi.riyl~, est 4lcctronbg:ttif et, eserce un rBle st,abiliPateur des radicaux.
1,s poly(2,4-dini6thyl-G-vinyl-s-t riazinc) (P1)lIVT) est solublc d:ms l’eau et dans tous
les solvants organiques courants aver exception des hydrorarhures aliphatiques. La.
poly (isoprop6nyl-s-t.riazine) (PIT) (1st uniquemcnt. soluble dans le diiii6thylformamide
et le chloroforme. I1 se raniollit & unc tcmpdrature bien plus 6levi.e que la PDMVT.
On admet que ces diffkrenccs rdsultcnt d’une liaison hydrogkne ent.re les chaines de PIT.

Zusammenfassung
2,4-Dimethyl-6-vinyl-s-triazin ( A ) polymerisiert mit Radikalstartern leicht zu einem
hochmolekularen Produkt. Die Untersuchung der Copolymerisation mit den Bezugs-
monomeren (11,)Styrol und 1Iethylmetharrylat ergaben mit Sytrol folgende Reak-
tivitatsverhaltnisse: T~ = 0,12, r? = 0,92; mit Methylmethacrylat: v1 = 0,37, r2 =
1,75. Die folgenden Q-e-Wcrte wurden bcrechnet: mit Styrol &2 = 2,1, e2 = +0,92;
init Methylmethacrylat Qe = 2,6, er = +l,O9. Ijiese Werte zeigen, dass die Dimethyl-
triazylgruppe ein radikalstaljili~ierender und elektronegativer Substit.uent ist. Poly-
(2,4-dimethyl-6-vinyl-s-triaziri) (I’1)LIVT) ist in TVasser und allen fiblichen organischen
Lijsungsmitteln ausser in aliphatischen Iiolileni~asserstoffenliislich. Poly( isopropenyl-
s-triazin) (PIT) ist nur in I)im(~t.hglformamidund Chloroform liislich. Auch erweichte
PIT erst, bei einer m-esent.lich hiiheren Temperatur als PDMVT. Diese Unterschiede
wcrden auf Wasserstoffbindungen znisrhen den Ketten im PIT zuriiekgefiihrt.

Received March 3,1961