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D e p a m n t of Inorganic and phvscal Chemistry, Indian Institute of Science, Bangelore 560 0 12, India
t 1. Ethylene Polymerization
initiation 02 + C2H4 - kd
2r0' (1) TABLE I. Polymerization of Polar Monomem by
Organometallic Compoundr-Oxygen(OMC-02) Initiator
Svrtamr
propagation +
ro* C2H4 -rl*
k,
(2) 102 x polymer
molar ratio time, temp, yield,
retardation rn*+ oz k,
-+ monomer' initiator 02-OMC h "C % ref
deactivated products or hydroperoxides (3) VAC B(CZHd3 14.3 20 30 40 25
In addition to these, following radical-generating reac- in fact, found this expression to be valid for an Et3B-
tion between a borane and its peroxide derivative, is oxygen initiated MMA polymerization. Further, on the
also known:28>29 basis of the results of Talamini and Viddoto,%a similar
RzBOOR + R3B RzBOR + R2BO' + R' (14) expression was also derived by Reich and Schindler15
+
selectivity in this type of polymerization may arise from pothesis: (i) complex formation between benzoyl per-
differences in the oxygen absorption capacity of the oxide (BP) and R3B has been proposed,* which lends
monomers. Complexation of the monomer with R3B support to the formation of complex of type A and (ii)
was also evoked to explain this monomer-selectivepo- Bu3B and olefinic double bond of a,a-diphenylethylene
lymerization. For example, Bawn et al.% had proposed form4 a complex in ethanol (using the oxygen lone
that a complex is formed between trialkylborane and pair). This then suggests that &B and vinyl monomers
MMA, although no evidence was provided for the same. can form a complex of type B in the presence of oxygen.
On the other hand, in the presence of EGB, Fuji et al.39 It is worth mentioning that Daviesa has proposed the
observed splitting of the carbonyl absorption band of formation of a complex between the monomer and bo-
vinyl acetate into 1754 and 1774 cm-I bands, ascribing ron peroxide instead of the trialkylborane.
it to the formation of a complex between EbB and the The picture is clearer in the case of aluminum al-
monomer. Davies40 suggested that the boroperoxide kyl-acyl peroxide initiated polymerizations. A three-
and the monomer may be forming a complex which component complex formation mechanism is valid in
undergoes 0-0 bond homolysis and induces the po- this case,
lymerization. He also mentioned that the situation
differed from that of Bawn et al.38 for polymerization Al2(c2H5),+ 2M -!% 2A1(C2H5)3M (18)
of MMA in that no molecule of R3B is involved in the
complexation with the monomer.
In the background of the controversial reports men-
Al(C2H&M + BP
[M-A1( C,H,),-BP]
-
-
slow
[M-Al(C,H,),-BP] (19)
tioned above, a more revealing study has been recently
conducted by Dodonov et al.41 to analyze the role of C2H5 + CsH&OOAl(C2H5)2 + C6H5COOM (20)
monomer in Me3SiOOR-R3B-initiated polymerization It may be noted that BP by itself does not initiate
of vinyl monomers. Similar to R3B-02 system, here too, polymerization by its dissociation due to the low reac-
the selectivity in polymerizing certain monomers was tion temperatures involved. Furthermore, Et3A1and
observed; styrene, MMA, and vinyl chloride could be BP form a 2 1 complex in the absence of monomers, but
polymerized, but not acrylonitrile. Based on a detailed not in their presence. Diethylaluminum benzoate and
spin-trapping study of the polymerization reaction, gaseous compounds derived from various reactions of
Dodonov et proposed the following initiation step, ethyl radicals have been detected,%thus supporting the
which is actually a concerted process involving mono- above scheme. Also, the following rate expression
mer participation. commensurate with the above mechanism was found
R3B + Me3SiOOR + [R3B.Me3SiOOR] valid in MMA, acrylonitrile, and vinyl acetate polym-
-
A + monomer (M) [R3B.Me3SiOOR-M]
A erizations:
R, = /z[M][AI(C,H~)~]~/~[BP]~/~
(n >1) (21)
B - RM
B
+ Me3SiO + ROBR2
The formation of complex A and the radicals was
In the case of styrene and vinyl chloride, which cannot
coordinate with aluminum alkyl, the polymerization
could be initiated in the presence of complexing agents
confiied by ESR. It is evident from the above scheme possessing ester or ether groups or a ~ e t o n i t r i l e . ~ ~
that formation of the complex (A) between the borane The chain transfer to trialkylboranes has been re-
and peroxide takes place first, followed by the formation cently discovered by Ivanchev et They found that
of ternary complex (B), by the addition of monomer to if poly(viny1 acetate), prepared at 20 C with R3B-
the complex A. The kinetics study41bsupports this oxygen as initiator, is heated to 55 C a high molecular
mechanism. Thus, according to Dodonov et a1.,4l only weight polymer is obtained. In addition, saponification
those monomers which can form a complex of type B studies showed that the degree of branching for the
could undergo polymerization under the specified con- polymer prepared at 55 OC is significantly larger than
ditions. It was observed41that although monomers like for the polymer prepared at 20 C. They proposed that
styrene or acrylates can easily generate the radicals as the propagating radicals (P,) react with the oxygen
depicted above, esters of aliphatic carboxylic acids fail
to do so. In addition, olefinic hydrocarbons like butene
were not found to generate radicals by the above path
for some unexplained reason. It was concluded41that P,Oz
P, + 0
+ R3B -
2 -
dissolved in the monomer to form a peroxide radical.
P,OZ
P,OOBRZ + R
(22)
(23)
compounds containing functional groups attached to
a-position of the double bond only could generate the This radical reacts with trialkylborane to form organic
radicals. Acrylonitrile could not be polymerized since boroperoxide, which is stable only at low temperatures.
it formed a stable complex with the borane itself. A The boroperoxide breaks apart at high temperature
similar three-component intermediate complex also to initiate further polymerization, yielding a high mo-
forms in the case of R3MOOCMe3-R3B (M = Si, Sn, lecular weight polymer. Since the polymer so obtained
Sb) catalyzed MMA p~lymerization.~~ at high temperature would contain -CH&H(Ac)-
In light of the above study of Dodonov et al.,41we OCH,CH(Ac)- type linkages (where Ac = acetyl group),
believe that a three-component complex is involved in they would yield, upon saponification, two molecules.
the initiation step of R3B-02-catalyzedreactions. The This explains the observed increase in the degree of
rate of reaction of R3B with its peroxide derivative is branching of the polymer obtained at 55 OC. Since h B
too fast to allow the detection of any intermediate is proposed to react with the P,02 radical, the corre-
complex between them. Under circumstances, following sponding reaction of its peroxide may also be possible.
indirect evidence provides support for the above hy- It may be worth studying the efficiency of boron per-
104 Chemical Revlews, 1991, Vol. 91, No. 2 Bhanu and Kishore
oxides as chain-transfer agents in this reaction, since SCHEME I. Mechanism of Phenolic Coupling Reaction
their organic counterparts are known4 to possess sig- la) Formation 01 C - 0 coupling product
nificant chain-transfer activity in radical polymeriza-
tion. Razuvaev et al.47have also reported the chain-
transfer activity of R3B during MMA polymerization.
The telechelic polymers bearing the boroperoxide end
groups can be used for block copolymerization just as
the hydroperoxide-terminated polystyrene (see section I
tost 1-2FVo.
II.A,5), though no such study has been reported yet. - 2ArO
3. Oxidative Coupling of Phenols
Various ortho-substituted phenols are known to un-
dergo oxidative addition reactions to yield poly(phe-
nylene oxide)s [PPO] in the presence of oxygen, Cu+
salts, and some amines. The reaction is given as ArO -
I b ) Formation ot C - C coupling product
PPO
.R1
(24)
\
R2 0 nH20
HO,
*2AIDH
T
Ci
-2%0
OH / ,Cb
DW
This reaction was first discovered by Hay et al.,48in
1959. It has been established that, when the substitu-
ents are small, the preferential pathway is the PPO
diphencqunone
formation. If one of the substituents is very large, such
as a tert-butyl group, or if both are as large as isopropyl,
then the formation of DPQ is favored. If the R s are
electron-withdrawing substituents, it is very difficult
ArOH 6 CH3
i Py : Pyridine
amine, catalyzes the C-0 coupling reaction. More re- The rate expression for oxidative polymerization of
cently, Tsuruya et aLS1discovered that a catalyst system phenols using this scheme was givenS6as
CuCl,-KOH is active for the oxidative coupling of the
phenols even in the absence of organic amines like
rate = kz[Cu1+],[X0H]/(k, + [XOH]) (26)
pyridine. The activity and selectivity of this catalyst where [XOH] and [C U + ~represent]~ the concentrations
with respect to the C-C and C-0 coupling modes has of phenol and copper catalyst, respectively. Also, k,
not yet been ~ptimized.~,Hence it is difficult to com- = (k1 + k 2 ) / k 1 . Although this scheme in principle, is
pare the efficacy of this catalyst with that discovered well founded for oxidative coupling of phenols, MobleY7
by Hay et al.48 Other salts like Ago, PbO,, etc. are also found that 26 is valid only for one cycle of the catalyst
knownS3to catalyze this reaction. Another important operation, because it gets deactivated during subse-
characteristic of this reaction is that the molecular quent recycling. MobleY7 also realized that during this
weight-conversion plot corresponds neither to chain stepwise polymerization reaction of phenols, the re-
growth nor to step growth propagation mechanisms. It activity of the monomer is significantly different than
is considered to exemplify the rare case of reactive in- the oligomers, unlike for typical polycondensation re-
termediate condensation reactions. Scheme I depicts actions. This is consistent with the reactive interme-
the simplest representation of the C-0 and C-C cou- diate condensation character proposed for this polym-
Role of Oxygen in Polymerization Reactions Chemical Reviews, 1991, Vol. 91, No. 2 105
SCHEME 11. Heterogeneously Catalyzed Phenolic However, recent studies49have proved that the homo-
Coupling Reaction geneous phenolic coupling reaction catalyzed by the
kl Cu'+-amine-oxygen system is a very complicated redox
nCu(1) e [cu(x)], process involving four electron-transfer steps. The re-
k2 action catalyst itself is polymeric in nature, and it
contains oxygen in each repeat unit. Further, Davies
et al.59showed that metamorphosis of the initial Cul+
salt into the polymeric catalyst via dimeric and tet-
rameric species can be detected by the controlled ad-
dition of amine. Since the stoichiometry of this mul-
tistep metamorphosis is difficult to study, any kinetic
study, particularly with respect to the rate of con-
sumption of oxygen, may not givem meaningful infor-
mation regarding the structure of the polymeric catalyst
containing oxygen. It is mqre difficult to comprehend
the case of heterogeneously catalyzed reaction since
. oxygen is considered to play an additional role in the
2-6"
L
dissolution of the heterogeneous catalyst.
b. Analytical Studies on Catalyst Structure. One
++ PPQ of the early attempts to understand the structure of
active catalyst of the phenolic coupling reaction was
CH3
made by Coudurier et a1.61 They found that the stoi-
chiometry of the active catalyst Cu-pyridine-O2 is
erization." He, therefore, modified the earlier scheme 1:1:0.5,indicating that oxygen is an integral part of the
of Tsuchida et a1.% as follows: active catalyst. Cu-0-Cu bridges (absorption peak at
575 cm-') were inferred from the IR study and were
[k,,(l - p) + ~,,][CU'+],~-~~~[XOH] thought to be active during polymerization.
rate = (27) Although the exact nature of the Cu-0 interaction
1 / k 1 + [XOH]
was not very clear from this study, Kramer et
where kP1 and k2, represent the rate constants for the speculated it to be peroxidic linkages although they
monomer and oligomer formation, respectively, k3 is the were aware that peroxides of low-valent Cu were not
rate constant for catalyst deactivation, n stands for the known at that time. Khlebnikov et al.63also supported
degree of polymerization, and p is the extent of reaction this view and, while reporting the stoichiometry of the
at time t. [O,] is not directly considered in this reaction catalyst Cu1+-Cu2+-02as 3:2:1, they proposed the fol-
but it can be indirectly expressed since its stoichio- lowing structure:
metric relation with [XOH] is known (as given in eq 24).
Experimental results obtained over several cycles of (cu+-c1--cu2+c1--o~--cu+cl--cu+c1-) (Py),
catalyzed reaction showed that both the above as- In the subsequent studies, Bodek and DaviesMfound
sumptions are valid, and good agreement between the that the catalyst could be obtained by the following
model and experimental data was ~bserved.~' stoichiometric reaction:
The rate expression 28 has been proposed by Tsuruya
et al.51for the heterogeneously catalyzed phenolic cou-
pling reaction of 2,6-dimethylphenol using CuC12-KOH
catalyst (also see Scheme 11). Under the condition k4 (29)
kk3kl1lm[O,][ C U ~ + ] ~ / ~ [ X O H ] A was found to be a simple Cu(I1) complex, green in
rate = (28)
k4 + kk11/m[C~2+]n/m color and catalytically inactive. However, B was found
to yield a brown solution in pyridine and contained
>> kkl1lm[Cu2+Inlm, the rate will be first order in the Cu-py in varied ratios ranging from 1:0.5 to 1:4, de-
concentration of XOH and oxygen while it can have a pending upon the pyridine concentration. The B com-
fractional order with respect to Cu(I1) (if m > n). Ex- ponent was catalytically active and could be separated
perimentally, at low concentration of CuC12, the rate from component A by passing the mixture over a GPC
was found to vary with 0.5 order with respect to CuClP column. Bodek and DaviesMthus discovered that the
At higher concentrations of CuCl,, k4 may be neglected active catalyst (B) is polymeric in nature. The activity
and then, according to eq 28 the rate would be inde- of B however, was observed only in solution. Attempts
pendent of CuC1, concentration, concurrent with the to isolate the polymeric catalyst in the form of a stable
observation. solid either by evaporating the solvent or by complexing
It is clear from the foregoing discussion that kinetic with ligands, like 2,9-dimethyl-l,lO-phenanthroline,
studies of the homogeneously catalyzed reaction support were unsuccessful.M This polymeric catalyst undergoes
the overall stoichiometry of the reaction (eq 24). Apart further polymerization upon heating which explains the
from explaining the role of Cu as a catalyst, these observed induction period during oxidative polymeri-
studies also account for the differences in the reactivity zation experiments at higher temperaturesSM Each
of the various oligomeric species. However, these ki- repeat unit of the polymeric catalyst contains more of
netic studiessss are insufficient to describe the role of pyridine molecules than Cu. This may be the reason
oxygen in C-0 coupling reaction in that oxygen is as- for high ratios of amine-Cu favoring C-0 coupling re-
sumed to be used only in the reoxidation of Cu(1). action.
106 Chemical Reviews, 1991, Vol. 91, No. 2 Bhanu and Klshore
-
kl
reaction initiation initiator + monomer 7 R"' (38)
AH' + S202- A + SO-: + SO4'-+ H+ (31) k
Other redox r e a ~ t i o n s ~involving
l-~~ autooxidizable activation monomer + R'" 2 R"M' (39)
reactants like hydrazine hydrate'l or sulfite ion72also
exhibit similar behavior. propagation R"M' + nM - k,
P,' (40)
(ii) Oxygen can reoxidize the reduced oxidant which
can be recycled for the additional production of radicals. termination 2P; -kt
P (41)
For example, Menon and K a p ~ observed r ~ ~ that redox
reaction between CuS04 and hydrazine generates pri-
mary radicals besides the Cu'+ species. This Cu'+
species can be reoxidized to Cu2+by oxygen, which then
cage recombination 2R' - k5
S(42)
Assuming a steady state, the rate of polymerization
recycles in the redox reaction. is given by
(iii) Oxygen can itself participate in a redox reaction
to generate the initiating radicals. For example, Reddy kika[initiator][MI2
et al. r e p ~ r t e d ' ~the
- ~ polymerization
~ of various vinyl
monomers in the presence of oxygen, ascorbic acid and
transition metal salts (M"+). The initiation is proposed Since experimentally R, was found to depend on [MI2,
to involve the formation of a complex intermediate as it was concluded81 that cage recombination of primary
shown below: radicals was very significant in this case, implying
K k
AH2 + O2 + Mn+e complex -E (32) R, 0: [ 02]1/2[S]1/2[reducing
agent]1/2[M]2
The redox reaction between AH2 and Mn+can take which was observed in certain concentration ranges of
place even in the absence of oxygen. However, the rate each of these species. Although no polymerization took
of polymerization of such reaction is many fold lower place in the complete absence of oxygen, a significant
than in the presence of oxygen. The kinetic data77in induction period was noticed at higher oxygen concen-
the case of Cu2+indicated that the rate of polymeriza- trations.
tion increased with [O,]up to 6.5 X lo-" M and there- Tanakas2 has reported an interesting redox system
after remained constant. The order with respect to [O,] based on TiC13and oxygen, confirmiing the absence of
was 0.5 at low [Cu2+]. A t high [Cu2+],the order was polymerization of MMA in oxygen-free atmosphere.
higher (0.7). The kinetic model proposed to account Most of the above studies give only a qualitative
for these observations is consistent with the view that picture of various roles of oxygen in redox polymeri-
oxygen participates in the initiation reaction. However, zation. The supporting kinetic evidence has not been
no independent evidence for the structure of oxygen acquired in many cases and even crucial information,
containing complex has been presented so far; the like the structure of complex formed between AH2,
complex formation is propounded only on the basis of oxygen and Mn+is lacking.
108 Chemical Reviews, 1991, VoI. 91, NO. 2 Bhanu and Kishore
TABLE 11. Oxidation Product8 of Poly(rtyryl)lithiuma dition of the living polymer to an oxygen-saturated
method of coupling, PS02PS, solution (inverse addition) yielded only 9 % dimer. Also,
estimation* M. solvent % % the corresponding hydroperoxide functionality was
1 18OOO benzene 21 - obtained in 91% yield under!these conditions. A similar
2 18 3 result, i.e., efficient formation of the hydroperoxide, was
3 19 2
1 18000 benzene-THF (75/25) 36 obtained during a solid state oxidation reaction.
2 21 15 Quirk et al.86988carried out a detailed investigation of
3 22 14 the oxidation of polystyryllithium in polar and nonpolar
1 4 200 benzene 28 solvents and have proposed the following scheme for
2 20 8
3
1
2
3
4200 benzene-TMEDA (500/1)
18
36
19
18
10
17
18
PS'
-
the oxidation reaction of polystyryllithium:
PSLi + O2 PS' + Li+O;
+ - PS02'
(45)
-
0 2 (46)
Reference 76. bNumbers represent the following: 1, amount of di-
PS02' + PSLi PS02Li + PS'
a
meric product determined by GPC; 2,amount of PSOzPS estimated by
-
(47)
reduction with lithium aluminum hydride; 3, amount of PSOIPS esti-
mated by degrading it by heating a t reflux in toluene and finding out
the reduction in dimer content bv GPC.
2PS' - 2PS' (PS), (dimer)
(PS)CH=CHPh + (PS)CHZCHzPh
PS' + PSOZ' -
(48)
(49)
-
5. Effect of Oxygen on Anionically Terminated PSO2PS
Polymers
Even in the early days of anionic polymerization
2PS02'
+
[PSO,PS]
(PS)CH&(O)Ph
-+ (PS)CH&H(OH)Ph (51)
(50)
+ -
'02
chemistry, oxygen was known to increase the viscosity
of solution containing living polymers.83 However, no RH PS' PSH + R' (52)
serious attention was paid to study the reaction of such (solvent)
an "adventitious" impurity because the characteristic The overall reaction is given as
"living nature" of the process was a more hotly pursued
topic. The main work on the effect of oxygen on anionic
chain ends has been carried out only in past few years.
PSLi - PSH + (PS), + PSOzPS + PS02H +
(1) 0 2
(2) HzO
(PS)CH&(O)Ph + (PS)CH=CHPh +
Fetters and Fireru observed that the use of polar (PS)CH&H(OH)Ph (53)
additives or solvents resulted in the formation of a
greater fraction (up to 40%) of the coupled material on The formation of all these products is not yet con-
aerial termination, compared to aerial termination in clusively proved; Catala et al.87have found some evi-
hydrocarbon media. Soon after this report, Mansson& dence for the hydroperoxide formation and a macro-
tried to identify the products of the reaction of poly- peroxide (PS02PS)has been reported by Quirk and
styryllithium with molecular oxygen. Though alcohol Chen.@ They also found that PS02PS accounts for
and ketone chain end functionalized products were approximately 50% of the dimer product in the pres-
detected, they are believedB to have formed during the ence of Lewis bases like TMEDA (N,NJV',N'-tetra-
work-up procedures employed. The first quantitative methylethylenediamine) and THF (Table 11). Further,
study on the reaction of polystyryllithium and molec- it was observed that though the Lewis acids lead to a
ular oxygen has been reported by Catala et al.87 They decrease in PS02H content, almost 95% PSOpHcould
studied the influence of a variety of reaction conditions be obtained by solid-state oxidation of polystyryllithium
on the course of oxidation of polystyryllithium and by freeze drying the benzene solution of the polymer
found that a coupling product (a dimer formed from (Table 111). This result comports the earlier report of
two original living polymer chains) and a hydroper- Catala et aLE7
oxide-terminated polystyrene (PS02H)are the resultant The only drawback in this study is the lack of in-
products of this reaction. Furthermore, the ratio of formation regarding the structure of nonperoxidic
these two products varies depending upon the reaction products (POH), which is the major product of this
conditions. For instance, in the oxidation carried out oxidation reaction in liquid state (Table 111). Never-
PSLi + O2 - inverse
dimer ( 9 % ) + PS02H (91%)
(44)
theless, the importance of synthesizing such a peroxide
end group possessing oligomers lies in their potential
applications in block copolymerization,86and they can
also be used perhaps for the "multicomponent
in THF at -65 "C,20% dimer was formed while ad- polymerization", proposed by E a s t m ~ n d . ~ In~ this
TABLE 111. Oxidation Products of Polystyryllithiuma
oxidation molecular yield, wt %
condition weight solvent (PSh PSO*-PSb PS02Hc P-OHd
liquid state 18000 benzene 19 3 9 69
benzene-THF (75/25) 22 15 5 58
4 200 benzene 19 9 5 67
benzene-THF (75/25) 19 18 2 61
benzene-TMEDA' 18 14 3 67
solid state 4 200 - 4 1 95 -
a Reference 76. From LiAlH, reduction and thermal decomposition. e From iodometric titration. POH represents the amount of
nonperoxidic, nondimerized products. e PSLi and TMEDA taken in 1:l molar ratio.
Role of Oxygen In Polymerization Reactions Chemical Reviews, 1991, Vol. 91, No. 2 109
context, therefore, similar studies on the anionic po- amount of oxidizing agent, the displacement polymer-
lymerization of other vinyl monomers could be re- ization requires only a catalytic amount of an oxidizing
warding. agent as an initiator. Shaffer and Percec? have recently
reported the displacement polymerization of 4-bromo-
B. Assorted Studies 2,6-dimethylphenol under phase-transfer condition
wherein aerial oxygen plays the role of an oxidizer.
UeharagOreported a systematic kinetics study of Kovacic and co-workersw have studied the Friedel-
MMA polymerization, using p-toluenesulfinic acid Crafts polymerization of several aromatic compounds
(TSA) in the presence of oxygen and some oxygen ac- to corresponding polyarylenes. Particularly in the
ceptor like N,N-dimethylaniline (DMA), based on an system A1C13-CuC12 and benzene, they have found
earlier report by Hagger.gl Uehara observed that TSA convincing evidence for a cationic, stair-step propaga-
as such fails to initiate the polymerization of MMA. tion mechanism. In one of their reports,1ooit was found
The kineticsg0of the reaction suggests that polyphenylene is also formed during polymeriza-
R, = lz[02][TSA]1/2[DMA]1/2[MMA]1/2 (54) tion of benzene catalyzed by AlC13 alone. This reaction
appears to be interesting because it does not yield a
Formation of a salt between TSA and DMA is spec- polymer under inert conditions, like conventional
ulated to take place, followed by its reaction with oxy- Friedel-Crafts polymerizations. On the other hand,
gen to generate the initiating radicals. polymerization takes place in dry air, and also in the
Wang et aLg2have studied the effect of combining oxygen atmosphere. Although the mechanism of this
photosensitized polymerization with the well-known reaction is not yet confirmed, and it is speculated that
peroxide-amine-based initiation. For MMA polymer- traces of moisture may act as the cocatalyst. The role
ization, they used the system benzophenone-triethyl- of oxygen in this reaction may prove to be interesting,
amine-oxygen. The combination of benzophenone and because usually the cationic intermediates are stable
light produces peroxy radicals in the presence of oxygen only in an inert atmosphere.
which can be efficiently decomposed by the amine,
producing the primary radicals. The rate of oxygena- I I I . Role of Oxygen In Inhlbtilon of
tion was first order for benzophenone concentration and Polymerlzatlon
0.8 order for triethylamine concentration. Carboxylic
acidg3lg4additives were found to promote this polym- A. Study of Polyperoxides
erization. Further, Wang et al.95reported that the low
experimental value of [k,/(kt)1/2] agrees with the ter- Compared to ionic and other types of polymerization
mination by a primary radical (kp and k, are the prop- reactions, more is known about the inhibitory action of
agation and termination rate constants, respectively). oxygen in radical polymerization reactions. Notwith-
Vila et al.95observed that when MMA is polymerized standing early controversies regarding the role of oxygen
under the varying oxygen pressure (in the range 10-60 in radical polymerization (which have been reviewed by
cm), the following linear equation holds: Bovey and KolthofP6),it is now well established6lo1that
log (R,/Rt) = (3.7 f 0.6) - [(9200f 800)/4.6T] oxygen forms an alternate copolymer with a vinyl mo-
nomer (called polymeric peroxide or polyperoxide) in
(55) a reaction which competes with the usual propagation
where Rt is the rate of termination. reaction to bring about the inhibition of polymerization.
The determination of reactivity ratios of comonomers Understandably, because of the presence of thermally
is one of the important aspects of the study of co- labile peroxidic linkages, these polyperoxides decom-
polymerization. It is interesting to know whether ox- pose at higher temperatures ( u s d y about 1 W 1 5 0 "C)
ygen can influence the reactivity ratios since this may to produce free radicals capable of initiating polymer-
bring about changes in the chemical composition of the ization? This has been strongly supported by the recent
copolymer formed and can certainly influence the co- quantitative studies reported from this laboratory,lmJW
polymer properties. Zabotin et al.% found that the which prove that breakage of the peroxidic linkage is
composition of the copolymer of butyl acrylate and the primary step in the thermal degradation of poly-
acrylonitrile (containing about 50% acrylonitrile) was peroxides. The inhibitory action of oxygen is thus
not affected by the atmospheric oxygen. On the other unique in the sense that even during the induction
hand Ivanchev e t al.97 reported an interesting period a polymerization reaction takes place to yield a
observation-during the emulsion copolymerization of thermally unstable polyperoxide. The inhibitory action
vinyl acetate (M,) and butyl acrylate (M2),the reactivity of oxygen in radical polymerization is, therefore, not
ratios were r1 = 0.67 and r2 = 0.91 in deaerated water permanent and strongly depends upon the tempera-
while in aerated water they changed to rl = 0.074 and ture.
r2 = 4.89. Thus the acrylate content of the copolymer Mayo et al.lO4showed that whereas the autooxidation
increased substantially in the presence of aerial oxygen. of hydrocarbons containing relatively unreactive double
Although the exact reasons for such significant changes bonds yield alkyl hydroperoxides, hydrocarbons con-
are unknown, it was suggested that oxygen has perhaps taining reactive double bonds (e.g. vinyl monomers)
attached itself to emulsified monomer particles in simultaneously form polyperoxides under these con-
amounts which differed for the two monomers. ditions. The product ratio (hydroperoxide-polyper-
Poly(pheny1ene oxides) can also be synthesized by oxide) in the overall yield varies with oxygen pressure
displacement of halogen from a 4-halo-2,6-disubstituted although they are formed through a common interme-
phenol in the presence of a base (e.g. NaOH) and a diate. Subsequent studies by Mayo et al.las proved that
catalytic amount of initiator. Unlike oxidative polym- the autooxidation of vinyl monomers at oxygen partial
erization of phenols which requires a stoichiometric pressure of about 1atm and above can be quantitatively
110 Chemical Reviews, 1991, Vol. 91, No. 2 Bhanu and Kishore
I
Termination
ROi t ROi kt (58)
ROj t R, kll Non -radical where f represents the initiator efficiency. Garton and
k
.R, t Rfl com&atlon~ polymeric producls George further assumed that a reasonably high molec-
k,o ular weight peroxide was formed during a significant
Rd + Rn disproportionation+ induction period, which allows the following equality
for the steady-state polyperoxidation:
interpreted by simply assuming that only the co-
polymerization reaction between a monomer and oxy- k4[R'] [ 0 2 1 = k6[R02'1 [MI (59)
gen takes place during the oxidation (Scheme 111). Substituting [R'] = (k6[M]/k4[o2])[Ro2']into eq 58,
These s t ~ d i e s ' ~also
J ~ indicated
~ that the reactivity we get
ratio of vinyl monomers in this copolymerization reac-
tion is very low implying that a typical vinyl
monomer reacts many thousands time faster with ox-
ygen than with itself at equal concentration of the two
reactants. Further, the peroxide radical so formed re-
acts very slowly and hence in radical polymerization
[ROZ'] [ROZ'] + k7[RO2'I2 (60)
reactions carried out in the presence of even traces of where k' = kg + klo.
oxygen, an induction period ( 7 ) is always observed. To Rearranging the above equation one obtains
derive quantitative results on the effect of dissolved
oxygen during polymerizations, Decker and Jenkins" r
studied the photopolymerization of multi-acrylate
systems in air. As expected, they found that homo-
polymerization does not begin until all the dissolved
oxygen forms the peroxide (because k4[02]>> k5[M], see
Scheme 111). Further, they found that the dissolved The rate of consumption of oxygen is given by
oxygen concentration has to decrease by a factor of
about 250 for the homopolymerization to begin. The -d[02] /dt = k,[R'][02] = k6[RO2*][MI (62)
lower limit of oxygen concentration will be dictated, of Substitution of the value of [ROz'] from eq 61 into eq
course, by the polymerization rate and diffusion of ox- 62 yields
ygen.
Many investigatorslW-ll1have tried to correlate 7 with -d[021
-- -
experimental variables like the concentrations of the dt
monomer, oxygen, and the initiator, assuming that r 1112
polyperoxide is the only product of the oxygen-con-
sumption reaction. They have used the peroxide
scheme (Scheme 111) to obtain the quantitative ex-
pressions. The general expression correlating with the
experimental variables, obtained from such studies is Garton and Georgelogwere able to obtain the expo-
= K[02]"[M]b[A]c
T (56) nents a, b, and c of eq 56 using modified form of the
above general eq 63 for the liquid-phase polymerization
The values of the exponents a, b, and c signify whether of vinyl chloride at 55 "C. Thus,if the cross termination
R' terminates by combination or disproportionation reaction between the radicals ROz' and R' is assumed
(Scheme 111) in a particular polymerization reaction to be predominant, eq 63 simplifies to
under consideration. A general approach to arrive at
a specific form of eq 56 is discussed below. -d[O,]/dt = (fklk4k6[M]/k,)'/2[A]'/2[02]1/2 (64)
Role of Oxygen in Polymerization Reactions Chemical Reviews, 1991, Vol. 91, No. 2 111
Substituting for d[02]/dt from eq 64 into eq 57, one SCHEME IV. Important Stepe in the Kinetica of PSP
obtains Initiafion
F" 7"
T =
lo21
AlBN b. CHI
- N2 -7' A CH3-C-o-o'
I
(fk1k&[MI /ka)1/2[A11/2[021
1/2 CN CN
or
7 = k'~02]'/2[M]-'/2[A]-'/2 (65)
where k" = Cflz1k4k6/k8)-1/2. Propagation
The values of a = 1 / 2 and c = -1/2 so obtained in
eq 65 are consistent with those observed experimentally. - CH,-CH-O-O
I
- CH,-CH-O-O-CH,-CH
I I
o -cH~--CH I
- C6H5
O-O-CH2-CH-O-00'
I
C6H5
-
CsHS '6h
the model involving unimolecular termination reaction:
R02' inactive product. They also felt that this was Termination
an incomprehensible result, requiring further atten-
tion.l1
Mayo et al.lo5observed that results of Shulz et al.lo7
and Henrici-Olive et a1.lWregarding the correlation of
T with various concentration terms during the auto-
oxidation of styrene and MMA could not be explained
on the basis of their copolymerization reaction model. the polymerization. Furthermore, this approach would
This is because polyperoxide was assumed to be the eliminate the temperature dependency of the inhibitory
only reaction product during the induction period effect of oxygen in vinyl polymerization.
preceding the polymerization. MayolOS further sug- A suitable example of such a reaction was affordedlls
gested that this disagreement may also arise because on the basis of a recent report by Okamoto and Oka116
the rate constant of either the propagation or the ter- regarding the aerial oxidation of styrene like substrates.
mination step is not a suitable measure of the poly- Okamoto and Oka116found that the Co2+-BH4- redox
peroxidation reaction. Interestingly, theoretical calcu- system catalyzes the oxidation of various olefins to
lations using a S c h ~ l z ' ~or
' Henrici-01ivelo8 scheme corresponding alcohols using aerial oxygen by a radical
match well with the experimental results in more com- mechanism involving a peroxide intermediate (Scheme
plex situation where extra inhibitor is present in ad- IV). They showed that a redox reaction is responsible
dition to oxygen, leading to synergistic inhibition.'12J13 for the generation of radicals from the olefinic substrate.
All the above studies assumed a strictly alternating The aerial oxygen then reacts with this radical to form
structure of the peroxide copolymer, and the reaction a peroxide which subsequently yields the alcohol. In
sequence depicted in Scheme 111. However, the detailed the specific-case of styrene, we observed115 that the
NMR spectral analysis of polystyrene peroxide by Cais CH3(C6H5)CHradical intermediate (Scheme V) can
and Bovey114shows that polyperoxidation is actually initiate polymerization of excess styrene in the absence
a complicated process. They found that during a of oxygen. In the presence of aerial oxygen, the same
AIBN-initiated polyperoxidation of styrene (i) the in- radical yields 1-phenylethanol via a peroxide radical
itiating radicals are not the usual primary radicals ob- intermediate. The inhibitory action of oxygen can thus
tained from AIBN decomposition, and (ii) the termi- be attributed to the formation of 1-phenylethanol. And
nation by bimolecular combination of the growing since the 1-phenylethanol is a thermally stable product,
chains is not the major route. Instead, benzaldehyde, the inhibitory action of oxygen in the present case is
which is formed simultaneously with the peroxide, is permanent.
considered to preferentially terminate the growing Many interesting facets of the polyperoxide chemistry
chains. The polymerization reaction proposed by Cais have been reported in recent years. Cais and Bovey114
and Bovey114is summarized in Scheme IV. This al- studied the microstructure and molecular dynamics of
ternate route for polyperoxidation has been proposed poly(styrene peroxide) using 13C NMR. Autopyrolyz-
on the basis of the end-group analysis and the study of ability of poly(styrene peroxide) has been recently
monomer sequence distribution using 13C NMR. discovered by Kishore and Mukundan.ll8 Amines are
In light of the above discussion we conclude that the known1@'to decompose polyperoxides. This observation
peroxide scheme provides a reasonable qualitative ex- has been successfully exploitedllg to use poly(styrene
planation for the inhibitory action of oxygen in radical peroxide) in combination with various amines as a redox
polymerization. The quantitative correlations are initiator for room-temperature radical polymerization
however lacking in many cases; further studies on ter- of vinyl monomers. Optically active poly(styrene per-
mination reactions during the autooxidation of vinyl oxide) has been synthesized in the presence of optically
monomers will be more revealing. active cobalt complex catalysts.120
An interesting question that emerges from the fore-
going discussion is whether oxygen can permanently B. Other Examples of Oxygen-Inhibited
inhibit a radical polymerization reaction. In this lab- Polymerization Reactions
oratory, we have realized115that if the R02' is diverted
to yield a thermally stable product instead of the con- In the previous section we have discussed about the
ventional polyperoxide, oxygen can permanently inhibit effect of intrusive oxygen on the kinetics of radical
112 Chemical Reviews, 1991, Vol. 91, No. 2 Bhanu and Klshore
SCHEME V. Mechanirm of Okamoto-Oke Reaction Ozols and Parts1%studied the kinetics of polymeri-
Step I C3Ln
eH, HICoLnl
zation of acrylonitrile initiated by Fe3+-H202 redox
system at 26 C in nitrogen atmosphere vitiated by
y 3
Step II H[CoLn] + CH?=CH C @!-CdJLn different amounts of oxygen. Supplemental oxygen
I introduced into the system decreased the rate as well
as the molecular weight of the resultant polymer.
However, no difference in either the rate or molecular
weight of the polymer was noticed when the amount of
U
oxygen in nitrogen was reduced from 13.5 ppm to less
A A than 1 ppm. An anomalous first-order dependence on
&r,
H
2L (YH3
0 c-0-0
H
irradiation intensity during radiation-induced polym-
erization of styrene, MMA, and acrylonitrile as well as
the graft copolymerization onto natural rubber latex,
was explained by Tsurugi et a1.lZ6on the basis of par-
ticipation of oxygen in the termination step. The in-
hibitory effect of oxygen was found to decrease as the
concentration of Fez+additive was increased during the
acrylic acid homop~lymerization.~~ The rate constant
for the reaction of a peroxy radical with Fe2+was found
@p0 H
+
to be 400 times the propagation rate constant. During
the preparation of hydroxy-terminated PMMA, oxygen
was found to retard both the overall rate andd the
conversion,lB but molecular weight showed an increase.
There are several other reports on the effect of oxygen
on c o p ~ l y m e r i z a t i o reactions,
n ~ ~ ~ ~ ~but
~ they provide
only qualitative information.
polymerization reactions. The retarding action of ox- Acrylamide is one of the extensively studied examples
ygen in such cases arises because of the facile formation of solid-state p01ymerization.l~~~ it is normally ob-
of less reactive peroxidic radicals in preference to the served that if the polymerization takes place at the
usual propagating radicals. Apart from these mainly crystal surface, oxygen can retard the polymerization
mechanistic studies, several miscellaneous reports are rate as well as reduce the degree of polymerization. On
available in the literature regarding the manifestation the other hand, if the propagation occurs well inside the
of the inhibitory effect of oxygen under various reaction crystal surface, oxygen cannot penetrate the surface and
conditions, which are discussed below. hence the polymerization proceeds without any inter-
Sluggish reactivity of the peroxidic radicals during ference by oxygen.
propagation step was considered to account for the in- We have studied the melt polymerization of acryl-
hibitory action of oxygen during polymerization of the amide by differential scanning calorimetry.38J39 It was
oligo ester acrylates by Mogilevich et a1.l2l found from these studies that the thermal polymeriza-
Louie et a1.*22explored the possibility of using the tion reaction follows radical mechanism,138and since
peroxide formation reaction in tackling the runaway oxygen can easily diffuse into the melt, a retarding
problem in the batch production of emulsion polym- effect of oxygen is observed in this polymerization.
erization of MMA. Though the above approach seems Quantitative studies139showed that the peak tempera-
to be encouraging owing to a very high rate of the re- ture of the polymerization exotherm shifts ahead by 8
action of oxygen with the normal propagating radical, OC in the presence of oxygen compared to the polym-
unfortunately an instantaneous termination also occurs erization carried out in an inert atmosphere. Also, the
in the presence of oxygen. This causes a substantial overall heat released during the polymerization con-
decrease in the molecular weight of the polymer, which, ducted in oxygen atmosphere is about 6 times less than
however, can be avoided by injecting very small quan- the corresponding heat released in nitrogen atmosphere.
tities of oxygen in short pulses. Thus, even the in-
hibitory action of oxygen can be beneficial if properly I V . Effect of Oxygen on Polymerlraflon
employed! Catatysfs
Lazaryants and K o r c h u n o ~ reported
~ ~ ~ the kinetics
of polymerization of (diethy1amino)ethyl methacrylate A. Metathesis Catalysts
in the presence of oxygen. They observed that the
polymerization rate constant had a normal value (8.5 Metathesis reaction of olefins is a useful method of
X L mol- s-9, albeit a low efficiency of initiation. preparing hydrocarbon polymers, The peculiarity of
This was explained on the basis of monomer-induced this method of polymerization involves the use of very
accelerated decomposition of the polyperoxide which different cocatalysts for the same metal complex cata-
initiated the polymerization. Lavrov et al.% found that lysts, e.g., the typical Lewis acid AlC13 as well as the
in the persulfate-ascorbic acid induced polymerization strong reducing agent n-butyllithium can be used with
of 2-hydroxyethyl methacrylate, the atmospheric oxy- the catalyst WC&.140 Banks and Kukues14 reported a
gen led to a decreased rate of polymerization. Also, the decline in the catalytic activity in the presence of oxy-
presence of oxygen caused increased reaction orders in gen for certain catalysts and an enhanced activity for
the catalyst components, an increased activation energy others. Thoi et al.142have reported deactivation of the
and a reduction in the molecular weights of the re- catalyst during polymerization of phenylacetylene. On
sulting polymers. the other hand, oxygen added in small quantities to
Role of Oxygen in Polymerization Reactions Chemical Reviews, 1991, Vol. 91, NO. 2 113
SCHEME VI. Role of Oxygen in Metathesis Masuda and Takami," on the basis of earlier re-
Polymerization ports151J52 on the sensitivity of Z-N catalysts to oxygen,
[Rul + Oz~Pul-02 studied the system Et&lC1-TiC13 in detail. They found
that the different polymerization effects are observed
if the sequence of mixing of the metallic components
is changed for two experiments conducted in the
presence of oxygen. In the first case, TiC1, was added
to an Et2A1C1-containingsolution exposed to oxygen
and in the second, EhAlCl was added to a heptane
solution of TiC13 exposed to oxygen. It was found that
the catalyst prepared by the first method showed a
marked improvement in catalytic activity without a
decrease in the stereoregularity of the polymer up to
an 0,-A1 ratio of 0.6. The activity decreases signifi-
cantly at higher 02-A1 ratio (>1.2),owing to the for-
mation of an EtAl(0Et)Cltype of the oxidation product
which is usually obtained from the oxidation of EWC1.
In the second case, a lower activity was observed, which
may be due to the formation of catalytically inactive
I NBE_ Polymerization
Ti species.
Dubinkova et al.153published the first report on the
catalytic systems-both h o m o g e n e o u ~ ' ~ ~and -'~~ effect of oxygen on the supported Ziegler type catalyst.
heterogeneo~s'~~-isfound to have a beneficial effect They studied the system, VC14/perlite-Al(i-Bu)3. Here
on catalyst activity. However, little is known about the also, two different experiments were performed to de-
exact chemistry of these reactions in the presence of termine the reaction product of oxygen with each metal
oxygen. For example, in the case of W(CO),(PPh,)(I) center and the resulting consequence on the catalyst
catalyzed methathesis polymerization, oxygen was activity. When the vanadium compound was added
found to enhance the activity of the system I-A1(Et)C12, after exposing the aluminum component to oxygen, the
but not that of I-AICls. It was suggested'47 that oxygen catalytic activity decreased at an 02-Al ratio of about
reacts with AI(Et)C12to form a peroxide derivative. The 0.2. It was found that Al(i-Bu), was oxidized to (i-
peroxide being more acidic than A1(Et)Cl2,facilitates Bu)zAl(i-BuO)which was proved to be responsible for
the metal center to let off one of the carbonyl ligands the reduced activity in a separate experiment carried
in favor of the incoming monomer thus enhancing the out in the liquid phase (using hexane as a solvent). In
polymerization. the other experiment, when the vanadium component
In a particularly important paper, Ivin et al.,'& during was first exposed to oxygen, the catalytic activity was
the R~Cl~(PPh~)~-catalyzed metathesis polymerization enhanced. This was attributed to the oxidation of va-
of norbornene (NBE), demonstrated that oxygen is nadium to a higher valent state, for example VOCl,,
probably involved in the formation of a key interme- which exhibits increased activity in olefin polymeriza-
diate that subsequently initiates the polymerization; the tion.15, When oxygen interacted with the catalyst ob-
rate of reaction was increased by as much as 100 times tained after mixing of the two components, complete
in the presence of oxygen! Based on the isolation and inhibition was observed.
identification of a novel epoxide side product as well Boor and Y ~ u n g m a n studied
'~~ the effect of oxygen
as a ketone, a plausible mechanism involving formation on the preparation of syndiotactic polypropylene em-
of oxometallacyclobutane and its subsequent rupture ploying the Z-N catalyst, Al(i-Bu),-VC14. The effect
to form an initiating metallacarbene was proposed of additives on the syndiotacticity was compared on the
(Scheme VI). This scheme supposes that oxygen is basis of the index ratio A11,53/0.5(A2.32+ A2.35) where
incorporated into the polymer chain as a terminal All.% represents the absorbance at the 11.53 hm band
carbonyl group; however, no evidence was reported for in the IR spectrum of the polymer, AZBs2 and A2.%being
this hypothesis. Amass and M c G ~ u r t e y ,on
' ~ ~the other the absorbance values at the subscripted wavelengths.
hand, detected aldehydic end groups in the IR spectrum A higher value of the index ratio implies a higher syn-
of a polymer obtained from metathesis polymerization diotacticity. For the polymer obtained in the absence
of cyclopentene using WC16 as catalyst. of oxygen, the index ratio was 1.2. With the additions
of 40 and 75 mL of oxygen to VC14 followed by mixing
B. Zlegler-Natta Catalysts with Al(i-Bu), yielded polymers with the index ratios
Ziegler-Natta (Z-N) catalysts have a unique place in of 1.4 and 1.8,respectively. Furthermore, the sequence
the synthesis of stereoregular polymers. Generally, their of additions of oxygen and the catalyst components
syntheses are carried out in an inert atmosphere to were reported to be important. Mixing of 100 mL of
avoid the poisoning of the catalysts. However, it has oxygen and Al(i-Bu), prior to the addition of VC14
also been shown15 that additives such as water and yielded syndiotacticity index of 1.8 only.
oxygen among others have significant influence on the It can thus be safely concluded that the effect of
activity of the catalyst and hence on the polymer oxygen on Z-N catalysts, bimetallic in particular, de-
properties. The bimetallic catalysts are more drastically pends upon which of the bimetallic components is ex-
influenced by oxygen than the monometallic catalysts posed to oxygen prior to mixing with the other com-
as far as tacticity changes are concerned. This is cor- ponent. Further, this effect may be entirely different
roborated in the following discussion. from the effect of oxygen on the "preformed" catalyst.
114 Chemical Reviews, 1991, Vol. 91, No. 2 Bhanu and Kishore
The topic, though interesting, has not received sufficient erization of butadiene to a predominantly 1,2-p0ly-
attention in spite of the fact that hundreds of combi- butadiene with small amounts of trans-1,Cpoly-
nations of bimetallic Z-N catalysts have been known butadiene. On the other hand, in the presence of added
for quite some time. It appears that involvement of oxygen, the main product was of the latter type. When
oxygen in the Z-N polymerization is promising for de- more and more crotyl groups were substituted by
veloping cheaper methods of synthesizing tailor-made chlorine in the parent chromium complex, the per-
stereoregular polymers. centage of cis-1,4-polybutadienewas found to increase.
This result needs to be verified in the light of results
C. Miscellaneous Reports obtained by Wallace and H a r r ~ d . ~ ~ ~
Oxygen-initiated ethylene polymerization yields a
Report by Matsumoto et al.'= that oxygen, peroxides, polymer having properties like density, short chain
and iodine introduce stereospecificity in crotylnickel branching etc., not much different from the polymer
halides initiated butadiene polymerization was dis- obtained under nitrogen atmosphere.166 In fact some
proved by Wallace and Harrod.'% Although the exact patents report that improved polymer properties, like
reaction in the presence of oxygen was not known, it high melt index,167better optical properties,168good
was suspected that oxygen reacts with the nickel com- stress-cracking re~istance,'~~ high drawability, and ad-
plex to form an inactive species. This reaction was hesion,17*were obtained only in case of processes in-
found to be very slow and the catalyst pretreated with volving the presence of oxygen. However, a disadvan-
oxygen, surprisingly, gave a high molecular weight tage of polyethylene prepared under oxygen atmosphere
polymer. The microstructure of this polymer was not was that the long chain branching was higher than for
different from that obtained by using an unpoisoned the polymer obtained under nitrogen atmosphere and
catalyst. On the other hand, in the case where additives consequently, the molecular weight distribution (MWD)
were introduced during polymerization, a slight increase was broader for the polymer prepared in 0 ~ y g e n . l ~ ~
in the cis content of the resulting polymer was found. An extreme case of broadening of MWD of polymer
This was explained by assuming that the above deac- prepared in the presence of oxygen has been reported172
tivation reaction proceeds through the formation of for bulk photopolymerization of MMA induced by
some unidentified radicals, which promote the forma- acetophenone-based initiator. The dead polymer
tion of cis-polybutadiene. molecule bearing the terminal benzoyl peroxide type
The transition metal chelates are well-known initia- end group was postulated to undergo a photocleavage,
tors of free-radical vinyl polymerization. Oxygen has bringing about the formation of additional high mo-
been reported157to inhibit the polymerization initiated lecular weight species, and hence a bimodal MWD
by such complexes. A very interesting phenomenon of curve. Broadening of MWD in MMA polymerization
catalytic chain transfer using a cobalt(I1) porphyrin was also found to result because of the presence of
complex was reported by Yenikolopyan et al.158 The peroxide macroradicals generated in the presence of
distinction of this agent from a conventional chain 0 ~ y g e n . lOn
~ ~the other hand, McGinnis et al.174
during
transfer agent lies in its characteristic ability to bring the bulk photopolymerization of MMA observed that
about the transfer reaction hundreds of times, thus the polymer prepared under oxygen atmosphere pos-
reducing the molecular weight significantly. Pliss et sesses a narrower distribution than the one prepared
reported that the peroxy radical generated in the in nitrogen. On the basis of the experiments carried out
presence of oxygen reacts with the above complex to in inert atmosphere, they found that polydispersity
form Co(II1) and hampers the catalytic chain transfer. index was less than 2, indicating that usual biradical
The cation radical induced polymerization of olefins by termination is absent and primary radical termination
the catalyst EtA1C12was found to be inhibited by oxy- or chain transfer or photoinitiator radical or photo-
gen." The free-radical polymerization of MMA cata- product is predominant. In the presence of oxygen, a
lyzed by silica and metal oxides like alumina was also faster additional reaction competes with the photo-
reported to be inhibited by oxygen.161 Finally, Ryabo- chemically generated radicals or the photoproducts:
suggested that the emulsion polymerization of
styrene catalyzed by K?S208suffered a long induction
period since oxygen inhibited the decomposition of the
R' - ROz' or R' + RO' - inactive products
catalyst. This was considered to be the reason for comparatively
narrower MWD observed in the presence of oxygen.
V. Iniluence of Oxygen on fhe Propertles of PVC is one of the most widely used thermoplastics.
Polymers However, the commercially manufactured material is
very often found to be thermally and photochemically
Oxygen can either improve or deteriorate various unstable. It was suspected for a long time that oxygen
polymer properties. Changes in the chain configuration containing groups get incorporated in the PVC back-
because of the chemical changes introduced by reaction bone to render it unstable. The detailed studies re-
of oxygen with Z-N catalysts have been discussed ported from various groups confirm that instability of
earlier. Poly(viny1idene fluoride) prepared by conven- PVC arises because of carbonyl containing structure^.'^^
tional radical polymerization initiators contains about On the basis of this background, Braun et al.176carried
10% imperfections." Trialkylboraneoxygen catalyst out polymerization of vinyl chloride in presence of de-
was foundla to yield a polymer with only 3% head- liberately added small quantities of oxygen. Their re-
to-head and 3% tail-to-tail imperfections as against the sults show that vinyl chloride is a very interesting mo-
2.7% imperfection content obtained with the conven- nomer in that the alternate peroxide copolymer which
tional Z-N catalyst. Orshikin et al.165found that the it forms with oxygen starts degrading soon after its
a-crotyl complexes of chromium catalyze the polym- formation, and CO was found to be the main degrada-
Role of Oxygen In Polymerization Reactions Chemical Reviews, 1991, Vol. 91, No. 2 115
tion product. Braun et al.176further suggested that this oxygen in polymerization reactions.
liberated CO neither escapes the system nor adds Judging the overall information available so far on
straightaway to vinyl chloride to form an inchain co- the role of oxygen in polymer chemistry, we believe that
polymer. Instead, the radical formed after the addition some attractive topics worth pursuing appear to be (a)
of CO to vinyl chloride radical end undergoes rear- isolation and characterization of the catalysts for phe-
rangement to introduce chlorocarbonyl pendant groups nolic coupling reactions, (b) detailed study of the ki-
as suggested by Ratti et al.177 netics of autooxidation of trialkylboranes and the ki-
Wescot,t et al.178have recently confirmed the structure netics of corresponding polymerization reactions, (c)
in eq 66 of the vinyl chloride-carbon monoxide co- fundamental studies for unravelling the chemistry be-
polymer on basis of the NMR studies of the appropriate hind the beneficial effects of oxygen on various polymer
model compounds. They also concluded that, when properties like molecular weight and MWD, (d) analysis
-CH,-CHCl+ CO - -CH,CHCl-CO
-CH,-CH-COCl-
rearrangement
vinyl chloride
b
of the oxidation products of metathesis, Friedel-Crafts,
and Ziegler-Natta type catalysts (desirable from point
of view of organometallic chemistry as well), and, fi-
nally, (e) specific studies on the effects of these oxidized
-CH,-CH(COC1)-CH,-CHCl- (66) species on the course of polymerization and the resul-
copolymerization of vinyl chloride is carried out with tant polymer properties.
CO at 50 C and above CO pressure of 6.5 atm, mech- Acknowledgments. The authors thank one of the
anism of Ratti et al.177holds good for the free-radical referees (C.K.) for the valuable comments which have
copolymerization of vinyl chloride and CO. been very useful in the preparation of the revised
Conducting polymers have assumed a lot of signifi- manuscript. The private communication with Prof. G.
cance in last few years because of their possible ap- Davies, Northeastern University, Boston; Prof. S.
plications in power transmission and other areas. Po- Tsuruya, Kobe University, Japan; Prof. M. Santappa,
lyacetylene is the single most thoroughly studied Madras, India, and Dr. D. P. Mobley has greatly helped
polymer of this class. This and most of the film-forming to make this article more authoritative. Finally, the
conducting polymers suffer from the disadvantage of authors thank Prof. D. N. Sathyanarayana, Dr. T.
inherent air instability. In fact the detailed studies179 Mukundan, and Dr. V. Krishna Mohan for many useful
on polyacetylene have proved that initial doping re- suggestions regarding the presentation of this review.
action responsible for the initial increased conductivity
Registry No. 02, 7782-44-7.
is soon overtaken by degradation, which leads to the
formation of carbonyl and hydroperoxide groups and References
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