European Polymer Journal, 1973, Vol. 9, pp. 657-667. Pergamon Press. Printed in England.

THE MECHANISMS OF RETARDATION AND INHIBITION

IN RADICAL POLYMERIZATIONS BY QUINONES

A. A. YASSIN a n d A. M. EL-REEDY
Chemistry Department, Faculty of Science, Cairo University, Giza, Egypt

(Received 27 November 1972)

Abstract---The sensitized polymerizations of styrene, vinyl acetate (VA), acrylonitrile (AN), methyl
methacrylate (MMA) and ethyl acrylate (EA) in the presence of benzoquinone (BQ), 2,5-dichloro-
benzoquinone(Dich.BQ), chloranil and duroquinone (DQ) have been studied by isolation and in-
vestigation of the polymers formed during the induction periods. Quinonoid polymeric derivatives
of BQ and Dich.BQ, were obtained for all monomers. In the case of chloranil, quinonoid products
were formed only with MMA and EA. Most of the DQ was recovered intact in all systems; only in
the case of styrene could quinonoid polymers be detected. The results indicate that substitution of the
polymer chains into the quinone nucleus is the predominant mechanism for retardation and inhibition.
The feasibility of substitution is determined by the electron-donating power of the polymeric radical,
the redox potential of the quinone and the presence of hydrogen atoms in its nucleus. The tendency of
the acrylate radicals for disproportionation accounts for the formation of quinonoid products with
chloranil. The suggested mechanisms account for the variety of observations on inhibition reactions.

INTRODUCTION

A RECENT c o n s i d e r a t i o n o f the p r o b l e m o f r e t a r d a t i o n a n d inhibition o f p o l y m e r i z a -

tions reveals that, a l t h o u g h quinones have been the m o s t t h o r o u g h l y investigated
agents, the m e c h a n i s m b y which they function is n o t clear. (1-1°) The p r o b l e m is
c o m p l i c a t e d b y the variety o f factors affecting the m e c h a n i s m o f the r e a c t i o n ; it is
n o w clear that simple theories c a n n o t explain all the facts. O u r t a s k will be to split
the p r o b l e m into its different aspects. The redox p o t e n t i a l o f a q u i n o n e a n d the
presence or absence o f h y d r o g e n a t o m s in its nucleus are considered to be the deter-
m i n i n g factors for the m o d e o f its interaction with free radicals. O f equal i m p o r t a n c e
is the e l e c t r o n - d o n a t i n g or accepting properties o f the m a c r o r a d i c a l s as well as their
t e n d e n c y for c o m b i n a t i o n o r d i s p r o p o r t i o n a t i o n in t e r m i n a t i o n reactions. T h e
d e t e r m i n a t i o n o f the role o f each o f these factors in affecting the m e c h a n i s m o f
inhibition is one o f the objectives o f the present investigation. F o r this p u r p o s e the
p o l y m e r i z a t i o n s o f styrene, VA, A N , M M A and E A in the presence o f BQ, D i c h . B Q ,
chloranil a n d D Q have been studied using a z o i s o b u t y r o n i t r i l e as sensitizer.

EXPERIMENTAL
Materials. Monomers were distilled under reduced pressure of nitrogen; quinones and sensitizer
were recrystallized.
Reactions. The polymerizations were carried out in bulk in a flask provided with a condenser and
a bubbler for a stream of nitrogen, using 6 × 10-SM initiator and 4 x 10-aM quinone per mole
monomer. The flask was kept in a thermostat at 70 ~ 1°. The reactions were stopped at 3-4 per cent
conversion for styrene and VA and at 10-12 per cent for MMA and EA and after 0.5 hr for AN
because the system had solidified. The conversion was determined by distillation under vacuum of a
weighed sample of the reaction mixture. The end of the induction period (complete consumption of
the quinone) was easily determined by checking for unreacted quinone by the Craven test~11) in
657
658 A . A . YASSIN and A. M. EL-REEDY

samples of the reaction mixtures withdrawn at different times; unreacted BQ forms a blue colour
changing immediately to red, whereas partially and fully halogenated benzoquinones produce a stable
violet colour. Quinhydrones of BQ and Dich.Q were detected in the early stages of the reactions with
all monomers other than AN, when samples of the reaction mixtures were evaporated at room temp.
and the residues treated with alcohol. On slow evaporation, deeply coloured deposits were formed
which, on redissolution in alcohol or ether, yielded yellow solutions.
Purification and assay
(a) Polystyrene and P M M A . The residues remaining after distillation of unreacted monomers were
dissolved in benzene and precipitated in ether to isolate fractions of the polymers of high molecular
weight. The filtrates were evaporated and the residues were purified by double precipitation in cold
methanol from benzene solutions. The precipitates of both polymers were pale yellow and were
colourless only in the case of DQ. The alcoholic filtrates of each polymer were combined and evapor-
ated. The residues were deep yellow and viscous in the case of Dich.BQ. For BQ, the precipitates and
residues in the case of styrene were found to produce a positive colour reaction. The precipitates of
polystyrene, although quinonoid (by i.r. spectra), were insensitive to the test. Moreover, the precipi-
tate of P M M A in ether gave a positive colour reaction for both Dich.BQ and BQ. Polystyrenes pre-
pared in the presence of chloranil were found to be insensitive to the test, whereas P M M A precipitated
in ether or in alcohol or remaining after evaporation of the latter produced a very stable blue colour.
(b) PAN. The polymer was washed repeatedly with hot alcohol and filtered until the filtrates con-
tained no unreacted quinones by the Craven test. The purified polymers were insensitive to the
colour reaction. Only polymers prepared in the presence of BQ and Dich.BQ produced a green colour
in conc. ammonia and dilute alkalis and they dissolved in conc. H2SO4 to give brown solutions.
(c) P V A and PEA. Both polymers were difficult to purify by precipitation owing to their solubility
in most solvents. The polymers, however, were found to be completely free from unreacted quinones
as indicated by the Craven test, except in the case of DQ. In any case, both polymers were washed with
boiling petroleum ether 60/80 ° to confirm the complete absence of BQ and Dich.BQ and to isolate
the unreacted DQ. PVA was highly viscous and light brown, whereas PEA was light yellow and semi-
solid in consistency. In the colour reaction, PVA and PEA produced results similar to those for
polystyrene and PMMA, respectively.
The quinonoid products derived from all monomers investigated were easily reduced to colourless
products by Zn dust/acetic acid but they were re-oxidized on exposure to air.

RESULTS AND DISCUSSION

The quinonoid nature of some of the reaction products, although indicated by the
Craven test, was confirmed by the presence of the carbonyl absorption bands in the

700 800 1000 I200 I400 1600 1800 2800 3000 3200 3400 3600

c m -I

Fio. 1. Infra-red spectra (in KBr) of polystyrene prepared in the presence of (a) p-benzo-
quinone (b) 2,5-dichlorobenzoquinone.
 Mechanisms of Retardation in Polymerization 659

1700
o (b

700 800 1000 1200 1400 1600 2800 3000 3200 3400 3600

cm-I

F[o. 2. ln~a-red spectra (in KBr) ofpolystyrene prepared in the presence of(a) duroquinone
(b) chloranil.

(0)

[b)

E
0

o.

t~

<

I000 1200
I I
I'~00
I I I I
1 6 0 017001800 2800
I
3000
I
5200
II
3,q.O0

cm -I

FIG. 3. Infra-red spectra (in chloroform) of polyvinyl acetate prepared in the presence of
(a) p-benzoquinone (b) 2,5-dichlorobenzoquinone (c) chloranil.
660 A . A . YASSIN and A. M. E L - R E E D Y

i.r. spectra of polystyrene (Figs. la, b and 2a), PVA (Figs. 3a and b) and PAN (Figs.
4a and b). The spectra of the quinonoid PMMA and PEA were found to be identical
with the corresponding polymers prepared in the absence of quinones implying that
no shift in the position of the carbonyl group resulted from introduction of the quinone
nuclei in the polymeric chains. The difference in the case of PVA could be detected.

;LS_J
'°' A

m
x~

I f ! J I I I I r
1000 1200 1400 1600 1800 2000 2200 5000 5200 5400 360(

cm-I

FIG. 4. Infra-red spectra (in KBr) of polyacrylonitrile prepared in the presence of (a) p-
benzoquinone (b) 2,5-dichlorobenzoquinone (c) ch/oranil.
The formation of polymeric quinonoid derivatives of BQ and Dich.Q, irrespective
of the nature of the monomer (Figs. l, 3 and 4a and b, respectively) suggests that
substitution in the quinone nucleus is the main mechanism for the retardation and
inhibition. The absence of analogous products when chloranil was used with the same
monomers (Figs. 2b, 3c and 4c) demonstrates the role of the hydrogen atoms in the
quinone nucleus in determining its mode of interaction with polymeric radicals.
Quinones are electron-acceptors and their tendency for reaction with electron-
donating radicals is expected to be much greater than with electron-accepting species.
Two mechanisms are possible: either the radical attacks the ~ C of the quinone,
in which case, the presence of a hydrogen atom in the nucleus will contribute to the
stability of the resulting substituted semiquinone by the keto-enol shift replacing one
of the carbonyl groups of the quinone by an - - O H group thus decreasing its potential:

©
" OH OH
0

RCM); +

0 0 O"

or it may attack the O-atom. Though the gain in stability of the resulting radical is
similarly increased due to aromatization, its redox potential is expected to be higher
due to the absence of the - - O H group. Moreover, the mechanism is favoured by the
formation of the more stable C--C bond instead of the C--O bond in the second
 Mechanisms of Retardation in Polymerization 66l

case. The formation of the latter bond in reactions with quinones is feasible only if
electron-transfer to the O-atom is possible. Accordingly, attack on the C ~ C of the
quinone should be favoured. The feasibility of this process will be determined by the
electron-donating power of the radical, the affinity of the quinone for electrons and
the availability of hydrogen atoms in the quinone nucleus. A quantitative evaluation
of the role of each of these factors becomes possible from comparison of the values of
KJKe, where Kz is the rate constant of the reaction of a polymer radical with an
inhibitor molecule and Kp is the propagation constant. The ratio is 518 ± 25(~2) for
styrene-BQ system but only 5.5 for MMA; (~3) even lower values of 0.94 (~4) and
0.91 (15) are found for the more electron-accepting MA and AN radicals, respectively.
Similarly, while K./Kp is 720 zk 70(~2) for the chloro-BQ-styrene system, it exceeds
10,000 when the monochloroquinone is replaced by the trichloro-BQ of higher
potential. "6) A corresponding decrease in the value of Kz/Kp is also observed in the
polymerization of styrene in the presence of methyl-benzoquinones and reaches its
lowest value for DQ (0.68 a t 90°). (17) The influence of the hydrogen atoms in the
nucleus could be detected by the fact that trichloro-BQ is more than 5 times as
efficient as an inhibitor (for the polymerization of styrene) than chloranil in spite of
the higher potential of the latter. (~6~
The high affinity of the electron-donating polystyrene and PVA radicals for reaction
with quinones accounts for the low tool. wt. of the resulting products. The polymeric
semiquinones formed may readily combine with a propagating chain to form a di-
substituted hydroquinone:

OH H OH

or may attack a quinone molecule:

OH O OH O"

O O OH OH

The latter reaction is largely favoured by virtue of the electron-donating power of the
polymeric semiquinone and the electron affinity of the parent quinone. Studies of
the reactions of model radicals with BQ have shown that polyquinonoid resinous
products are formed only when the radical is electron-rich. Thus while 2,4-dichloro-
benzoyloxy radicals react with BQ to form only crystallizable products, the methoxy-
benzoyloxy radicals formed only traces of the corresponding products; in this case,
the higher the ratio of the quinone relative to the peroxide, the greater is the amount
of resins. (~a)
The reaction of the polymeric semiquinones with unreacted quinone accounts for
the high rate of quinone consumption as well as the fading of the colour of the reaction
662 A . A . YASSIN and A. M. EL-REEDY

mixture." o) Kinetic studies have shown that 16 out of 17 quinone radicals are involved
in one polystyrene chain, c19) The resulting semiquinone, being more electron-deficient
than its precursor, will have a high tendency to combine with a propagating radical
or weakly attack the electron-rich double bond of a styrene molecule rather than to
react with an electron-deficient quinone molecule:
OH O OH OH H

OH OH OH OH
This type of copolymerization accounts for the partial polymerization of styrene
during the induction period. However, the lower reactivity of semiquinones as chain
initiators accounts for the marked suppression of the growth reaction.
On the other hand, the polymeric semiquinones may be oxidized by the unreacted
quinone, the primary or the propagating radicals. In the first case, simple semi-
quinones and quinonoid polymeric products are formed. Although the latter may be
susceptible to further reaction with the polymeric radicals, the affinity for similar
reaction is expected to be low owing to the low redox potential of these quinonoid
products. The simple semiquinones may either disproportionate to form quinones and
hydroquinones (quinhydrones) or occasionally attack an active monomer molecule
to initiate a new chain:
OH OH

O H ~ OH CH2, ~ C~

which may be terminated by coupling with a semiquinone molecule. It follows that

the semiquinones, simple or polymeric, should therefore be the actual inhibitors as
suggested by Price (4) and Kharasch c5) although the mechanisms proposed by them
imply that one quinone molecule is incorporated in the polymeric chain, which is not
so. If the concentration of the semiquinone is decreased, for example, through oxida-
tion by primary radicals, the inhibition period should be shortened and growth reac-
tions should predominate. This accounts for BQ being a very efficient inhibitor for
the thermal polymerization of styrene but only a retarder for the peroxide-catalysed
process.(2o)
The fact that polymeric quinonoid products of styrene formed at higher degrees
of conversion in the presence of Dich.BQ are sensitive to the Craven test and the lack
of this sensitivity for the similar products formed in the case of BQ suggested that the
chlorine atoms in the former quinone remained intact during subsequent stages after
the induction period. In this respect, the attack of the polymeric radical on the carbon
having a hydrogen atom differs from Price's mechanism in which attack occurs
preferentially on the carbon having the chlorine atom. (*)
The requirement of the presence of a hydrogen atom in the quinone nucleus is
demonstrated by the recovei'y of most of the DQ intact from all the polymerizations
 Mechanismsof Retardationin Polymerization 663

investigated. Only for styrene was it possible to isolate a quinonoid product (Fig. 2a).
The presence of a carbonyl absorption band indicates that the quinone has reacted
through the methyl rather than the carbony! group:
O O

R(M)n--CH2--CH ° + CH3 CH3 R(M)n--CH2--CH z + 'CH2~ "/CH3

CH3/'~ "CH 3 CH< ~ "CH3

0 0 0 0 0

0 0 O"

Recombination of the polymeric radical with the first form seems to be the most
probable, both from the steric point of view as well as the stability of the resulting
product. The formation of similar products for VA and MMA, though not excluded,
was difficult to detect, owing to the presence of carbonyl groups in the structural units
of both monomers. The absence of a similar band in the case of AN indicates that the
polymeric radical in this case is incapable of hydrogen abstraction by analogy with
the inability of the 2-cyano-2-propyl radical to abstract hydrogen atoms from tolu-
ene. (21) However, the isolation of most of the DQ intact, even in the styrene poly-
merization, indicates that the quinone is only a weak retarder.
The formation of nonquinonoid products when chloranil was used with styrene
and VA (Figs. 2b and 3c), the band at 1700 cm -1 in Fig. 3c being due to the carbonyl
group of the monomer, re-emphasizes the role of the hydrogen atoms in the quinone
nucleus in determining the mode of its interaction with free radicals. As polystyrene
and PVA radicals are capable of transferring an electron to the carbonyl group of the
quinone and accommodating at the same time the resulting positive charge through
a variety of resonance structures, the activatione nergy should be decreased, so making
the reaction with the carbonyl group energetically favourable: (22)
ct Cl.
R{Mln--CH2--C[[~ + 0 0

i c,c,j

The greater the tendency of the quinone to accept the transferred electron, the higher
c,c
o

will be the rate of its copolymerization with the polymeric radicals. This is indicated
by the fact that chloranil is more than three times as efficient for the inhibition of
styrene polymerization as bromanil. (16) The possibility of acquiring the required
electron from either the polymeric radical or the electron-rich double bond of the
monomer accounts for the high tendency of the oxygen radical to combine with a
propagating radical or initiate a new polymeric chain. ~2a)
The improbability of electron-transfer from the electron-deficient PAN radical to
the carbonyl group of chloranil accounts for the absence of interaction in this case.
If hydrogen atoms are available in the quinone nucleus, the electron deficient radicals
will be directed towards attack on the C ~ C . This mode of interaction has been
experimentally proved by isolation of quinonoid products (Figs. 4a and b) but is
~,P.J. 9/7----o
 664 A. A. YASSIN and A. M. EL-REEDY

expected to proceed slowly because of the higher potential of the resulting semi-
quinones which makes them capable only of recombination with a propagating radical
and not for initiation of a new polymeric chain through attack on the electron-
deficient double bond of the monomer. The resulting substituted hydroquinones if
oxidized will produce quinonoid products incapable of further substitution. This is
indicated by the rapid polymerization of AN in the presence of unreacted quinone as
well as the weak carbonyl absorption bands. The insensitivity of the quinonoid poly-
mers to the Craven test is due to the closeness of the hydroxyl group formed during
the Craven reaction and the nitrile group of the polymeric chain.t2’)
The isolation of quinonoid products derived from chloranil only in the case of
MMA and EA indicates that other factors may operate. The acrylate radicals are
specifically prone to disproportionation which implies that the quinone could be easily
transformed into a semiquinone by abstracting a hydrogen atom from a propagating
radical. This mode of interaction is energetically favourable as it leads to the formation
of a stabilized semiquinone and a stable unsaturated polymeric chain:

a=
CL CL Cl Cl
7H3 - ‘342
+ 0 0 - R (M),---CH2- i! + HO ’ ’ 0’
I3 (Mh-CH2-F’ - -
A -a
CL CL CL Cl
O”b-CH 3 0o ‘O-CH3

Addition to the C==C would lead to the formation of an unstable addition product,
whereas reaction through the carbonyl group is completely improbable owing to the
electron deficiency of both chloranil and the acrylate radical. The resulting semi-
quinone will be able only to combine with a propagating polymeric radical rather
than to attack the electron-deficient double bond of a monomer molecule:

OH
CL

CL-CH,-C’ + R (M)n-cH2-~
or rwnemer

or t?(M) ” -CH -CL%?

2 I
0I’F\O-CH3

cH3

or R(M)n--CH2-CC’ +

c
O’/ ‘O-CH3

The electron-deficiency of both radicals together with the greater stability of the C-C
relative to the C-O bond should favour combination through C* rather than 0.
radicals. Only this mode of combination with subsequent elimination of a Cl* atom
 Mechanisms of Retardation in Polymerization 665

can account for chloranil acting as a chain transfer agent rather than a true inhibitor;
chain initiation by oxygen radicals formed by attack of a polymeric radical on the
carbonyl group of chloranil should be excluded as electron-transfer in this case is very
improbable. The higher the potential of the quinone the greater will be the rate of its
transformation to a semiquinone on reaction with polyacrylate radicals. Accordingly,
chloranil should be expected to be more efficient as an inhibitor than BQ or its par-
tially halogenated derivatives. The kinetic studies have shown the reverse ~13) probably
because of the greater instability of the semiquinone-polymeric radical addition
product for chloranil than for the other quinones. The fact that the ratio K J K p is
more than six times greater for MA than for M M A in the case of chloranil whereas
the reverse is true for BQ or 2,5- and 2,6-dichloro-benzoquinones <13'~4) provides
evidence that the prior formation of chloranil semiquinone by disproportionation with
a polymeric acrylate radical is involved in the inhibition in this case. It seems that
PMA radicals are more susceptible to hydrogen-transfer to chloranil than the P M M A
radicals. If this is so, the semiquinones should be actually the true inhibitors as the
efficiency of inhibition is determined by the possibility of their formation. However,
the higher efficiencies of BQ and its 2,5- and 2,6-dichloroderivatives for the case of
M M A than for MA ~13'14) indicates that either the formation of the semiquinones
in these cases should have been effected by radical attack on the C : C of the quinone
rather than by disproportionation or that both mechanisms were acting. The prefer-
ential attack by P M M A radicals is probably due to their relatively lower electron-
accepting power. As the semiquinones formed in either case will terminate only
through coupling with propagating chains, only one quinone molecule should be
consumed for every polymeric chain. <9) The lower affinity of the acrylate radicals for
reaction with quinones accounts for the high mol. wt. of the quinonoid products formed
as shown by the positive colour reaction for the polymers precipitated in ether.
In conclusion, it may be said that, although the possibility of formation of ethers
of hydroquinone in the inhibition and retardation of polymerization has often been
assumed, real evidence is absent. Moreover, their formation would restrict the posi-
tions of reactivity of quinones to their carbonyl groups which should lead to an
equality in the effects exerted by a particular quinone on different polyrnerizing
monomers irrespective of their natures, as well as to equality in the effect of various
quinones on a particular polymerizing monomer. These and other contradictions can
be eliminated if the specific properties of each of the reacting species are taken into
consideration.

REFERENCES

(1) Encyclopedia of Polymer Science and Technology, 7, 644. Interscience, New York (1967).
(2) F. A. Bovey and I. M. Kolthoff, Chem. Rev. 42, 491-525 (1948); F. A. Bovey, I. M. Kolthoff,
A. I. Medalia and E. J. Meehan, Emulsion Polymerization, pp. 207-236. lnterscience, New York
(1955).
(3) C. C. Price, J. Am. chem. Soc. 65, 2380 (1943).
(4) C. C. Price, J. Polym. Sci. 1, 44 (1946).
(5) M. S. Kharasch, F. Kawahara and W. Nudenberg, J. org. Chem. 19, 1977(1954).
(6) P. D. Bartlett, G. S. Hammond and H. Kwart, Discuss. Faraday Soc. 49, 686 (1953).
(7) P. D. Bartlett and H. Kwart, J. Am. chem. Soc. 72, 1051 (1950).
(8) S. G. Cohen, J. Am. chem. Soc. 69, 1057(1947);J. Polym. Sci. 2, 511 (1947).
666 A . A . YASSIN and A. M. EL-REEDY

(9) J. C. Bevington, N. A. Ghanem and H. W. Melville, Trans. Faraday Soc. 51, 946 (1955).
(10) J. C. Bevington and N. A. Ghanem, J. chem. Soc. 2822 (1955).
(11) R. Craven, J. chem. Soc. 1605 (1931).
(12) F. Tiidos and L. Simandi, Vysokomolek. Soedin. 4,1262 (1962).
(13) J. L. Kice, J. Am. chem. Soc. 76, 6274 (1954).
(14) J. L. Kice, J. Polym. ScL 19, 123 (1956).
(15) Z. A. Sinytina and Kh. S. Bagdassaryn, Zh. Fiz. Khim. 34, 2736 (1960).
(16) F. Tiidos, L. Simandi and M. Azori, Vysokomolek. Soedin. 4, 1431 (1962).
(17) P.J. Flory, Principles of Polymer Chemistry, p. 172. Cornell UniversityPress, New York (1953).
(18) A. A. Yassin and N. A. Rizk (to be published).
(19) F. R. Mayo and R. A. Gregg, J. Am. chem. Soc. 70, 1285 (1948).
(20) H. W. Melville and W. F. Watson, Trans. Faraday Soc. 44, 886 (1948).
(21) F.J. Lopez Aparicico and W. A. Waters, J. chem. Soc. 4666 (1952).
(22) F. R. Mayo and C. Walling, Chem. Rev. 46, 191 (1950).
(23) J. W. Breitenbach and A. J. Renner, Can. J. Res. B28, 507 (1950).

R6sum6----Ona 6tudi6 les polym6risations sensibilis~es du styrene, de l'ac6tate de vinyle (VA) de l'acryl-
onitrile (AN) du m6thacrylate de m6thyle (MMA) et de l'acrylate d'6thyle (EA) en pr6sence de benzo-
quinone (BQ), de dichloro-2,5-benzoquinone (Dich BQ), de chloranile, et de duroquinone (DQ).
On a isol6 et 6tudi6 les polym6res form6s pendant les p6riodes d'induction. On a obtenu des d6riv6s
polym6riques quinoniques de BQ et Dich BQ, pour tousles monom6res. Dans le cas du chloranile,
les produits quinoniques ne se formaient qu'avec MMA et EA. Dans tousles syst6mes on retrouvait
intacte la plus grande part de la DQ; seulement dans le cas du styrene on a d6tect6 des polym6res qui-
noniques. Les r6sultats indiquent que la substitution des chaines de polym6res sur le noyau quinone
est le m6canisme pr6dominant du ralentissement et de l'inhibition. La possibilit6 d'une substitution
est d6termin6e par le pouvoir donneur d'61ectron du radical polym6rique, par le potentiel redox de
la quinone et la pr6sence d'atome d'hydrog6ne dans son noyau. La tendance au disproportionnement
des radicaux acrylate explique la formation de produits quinoniques avec le chloranile. Les m6canis-
rues propos6s rendent compte de la diversit6 des observations sur les r6actions d'inhibition.

Sommario---Le polirnerizzazioni sensitizzate di stirene, vinile acetato (VA), acrilonitrile (AN), metile
metacrilate (MMA) e etile acrilate (EA) nella presenza di benzoquinone (BQ), 2,5-diclorobenzo-
quinone (Dich. BQ), cloranile e duroquinone (DQ) sono state studiate con isolamento e investi-
gazioni sui polimeri durante il periodo di induzione. Derivativi polimerici quinonoidi di BQ e Dich.
BQ furono ottenuti per tutti i monomeri. Nel caso di cloranile prodotti quinonoidi furono formati
solamente con MMA e EA. La maggior parte del DQ fu ricoverata intatta in tutti i sistemi; solamente
nel caso di stirene fu possibile di scoprire polimeri quinonoidi. I risultati indicano chela sostituzione
delle catene polimere nel nucleo quinone 6 il meccanismo predominante per ritardamento e inibizione.
La possibilit/t di sostituzione 6 determinata dalla potenza dando elettroni del polimerico radicale, il
potenziale redox del quinone e la presenza di atomi idrogeni nel suo nucleo. La tendenza dei radicali
acrilati per conti dis proporzionazione per la formazione di prodotti quinonoidi con cloranile, I1 conto
meccanismo suggerito per la varieth di osservazioni su reazioni di inibizione.

Zusammenfassung--Die Polymerisationen von Styrol, Vinylacetat (VA), Acrylnitril (AN), Methyl-

methacrylat (MMA) und ~i,thylacrylat (EA) in Gegenwart von Benzochinon (BQ), 2,5-Dichlor-
benzochinon (Dich.BQ), Chloranil und Durochinon (DQ) wurde untersucht durch Isolierung und
Charakterisierung der w/ihrend der Induktionsperiode gebildeten Polymeren. Mit alien Monomeren
bilden BQ und Dich.BQ Polymere mit chinoiden Strukturelementen; Chloranil bildet nur mit MMA
und EA solche Polymere. Mit Ausnahme yon Styrol wurde DQ bei der Umsetzung mit den anderen
Monomeren unver/indert zuriickgewonnen. Diese Ergebnisse zeigen, dab der Einbau der Chinone
 Mechanisms of Retardation in Polymerization 667

in die Polymerkette der vorherrschende Mechanismus fiir die Verztigerung und die Inhibierung der
Polymerisation ist. Die M6glichkeit zum Einbau h~ngt ab yon der Elektron-Donor-St~irke der
Polymerradikale, dem Redox-Potential der Chinone and der Anwesenheit von Wasserstoff in deren
Ring. Die Neigung des Acrylat-Radikals zur Disproportionierung fiihrt zur Bildung yon chinoiden
strukturen mit Chloranil. Der vorgeschlagene Mechanismus tr~igt den verschiedenen Beobachtungen
fiber Inhibierungsreaktionen Rechnung.