Chapter 2

Mechanisms of Antioxidant Action of

Phosphite and Phosphonite Esters
KLAUS SCHWETLICK
Dresden University of Technology, Dresden, GDR

ABSTRACT

Phosphite and phosphonite esters are used on a large scale for the
stabilisation of polymers against degradation during processing and
long-term applications. They function as antioxidants by various
mechanisms depending on their structure, the nature of the substrate to
be stabilised and the reaction conditions.
All phosphites and phosphonites are hydroperoxide-decomposing
secondary antioxidants. Their reactivity in hydroperoxide reduction
decreases with increasing electron-acceptor ability and bulk of the
groups bound to phosphorus in the order phosphonites > alkyl
phosphites > aryl phosphites > hindered aryl phosphites.
Five-membered cyclic phosphites are capable of decomposing hydro-
peroxides catalytically due to the formation of acidic hydrogen phos-
phates by hydrolysis and peroxidolysis in the course of reaction. The
o-hydroxyphenyl phosphates formed in this way from o-phenylene
phosphites are excellent chain breaking antioxidants.
Aryl phosphites, particularly these derived from sterically hindered
phenols, can act as chain-breaking primary antioxidants by reduction of
peroxyl radicals to alkoxyl radicals. The latter react further with the
23

G. Scott (ed.), Mechanisms of Polymer Degradation and Stabilisation

© Elsevier Science Publishers Ltd 1990
24 KLAUS SCHWETLICK

phosphites by substitution, releasing aroxyl radicals which terminate the

radical chain oxidation. The chain-breaking antioxidant activity of aryl
phosphites is lower than that of hindered phenols, because the rate
constants of their reaction with peroxyl radicals and their stoichiometric
inhibition factors are lower than those of phenols. The stoichiometric
inhibition factors decrease from one to zero with decreasing concentra-
tion of the phosphite and increasing oxidisability of the substrate.
Therefore, phosphites themselves are active chain-breakers only at
rather high concentrations, predominantly in substrates of low oxidisa-
bility at lower temperatures.
In oxidising media at higher temperatures, however, hydrolysis of
phosphites and phosphonites takes place in addition to oxidation. The
phenols so formed synergised by the parent phosphorus compounds and
their hydrolysis products, are responsible for the high antioxidative
activity of aryl phosphites and phosphonites, especially the hindered
compounds, in oxidations at higher temperatures.

1 INTRODUCTION

Esters of phosphorous and phosphonic acids are used on a large scale

as non-disco louring antioxidants for the stabilisation of organic mate-
rials against degradation during fabrication, processing and long-term
applications. In the stabilisation of polymers, such as rubber, poly-
olefins, ABS and PVC, they represent a class of compounds whose
importance is increasing and is now comparable with that of the
sterically hindered phenols. In Scheme 1 are listed the main phos-
phites, I-VII, and a phosphonite VIII industrially used today as well
as some cyclic derivatives, IX-XI, which have been studied repeatedly
in the literature.
Generally, phosphorus antioxidants are used in combination with
hindered phenols and other stabilisers, but the sterically hindered aryl
phosphites and phosphonites which have become available in recent
times are, under some conditions, active by themselves and replace
phenols especially in the processing stabilisation of polyolefins. The
share of phosphorus compounds in the total consumption of anti-
oxidants has increased in the last few years, whereas that of phenols
has stagnated.
In spite of their great practical importance, the detailed mechanisms
of antioxidant action of organic phosphorus compounds and, in
P(OPhh i-C JO H21 0P(OPhh (i-ClOH210)2POPh
I II III

P(~H19)3 p(a-pt),
IV
V
o 0 o 0 ~
Vl

C1s H370-P P-OC 1sH37 ~O-lX\p-~. :z:

""
\0 '~ b d )::=d' ~
IX'd
VI VII ~
~
(4
q-o)'p-Q-O-p(a-p+), ~
VIII
~
tTl
@
:;o:l
Vl

a
r{O
I o"P_o ~\
(X r,- ),-OR
~ d ~. ff -Q-!~R
IX
x
Scheme 1 XI ~
26 KLAUS SCHWETLICK

particular, the relationships between chemical structure and anti-

oxidant activity, have been studied far less intensively than those of
phenols. The influence of diverse reaction conditions and the nature
and role of transformation products of these inhibitors in the stabilisa-
tion process have begun to be elucidated only in recent times. These
investigations started in the USSR, where Kirpichnikov's and Levin's
groups, followed by Mukmeneva and Pobedimskii, pioneered work in
this field; this was later extended by Rysavy & Shima, by Humphris &
Scott, by us and by others.
The efficiency and mechanisms of action of organophosphorus
stabilisers have been reviewed by the Soviet authors 1,2 and by
ourselves. 3 ,4
Phosphites and phosphonites can function as antioxidants by several
mechanisms depending on their structure, the nature of the substrate
to be stabilised, and the reaction conditions.
All phosphites and phosphonites are preventive antioxidants de-
composing hydroperoxides in a non-radical way and so suppressing the
chain-branching step (3) in the familiar radical chain mechanism of
autoxidation depicted in a simplified version in Scheme 2.

(RH)~R' (i)
R'+02~ROO' (1)
ROO' + RH~ ROOH + R' (2)
ROOH + RH~ RO' + H 20 + R' (3)
RO' + RH~ ROH + R' (4)
2ROO' ~ inactive products (5)
Scheme 2

Aryl phosphites, particularly those based on sterically hindered

phenols, are able to act primarily as chain-breaking antioxidants under
certain conditions competing with steps (2) and (4) by trapping ROi
and RO' radicals and so terminating the oxidation chain reaction,
Strong chain-breaking action, furthermore, can result from reaction
products (phenols) formed by hydrolysis and peroxidolysis of aryl
phosphites and phosphonites in the course of oxidation under special
conditions, Additionally, phosphites and phosphonites act as metal-
complex forming agents, blocking metal ions which cause chain
initiation and branching by reaction with ROOH and RH.
 PHOSPHITE AND PHOSPHONITE ESTERS 27

Because of these various action mechanisms the antioxidant activity

of phosphorus compounds is not a fixed unchangeable property but
depends strongly on the oxidation conditions and the nature of the
oxidisable material.

2 HYDROPEROXIDE-DECOMPOSING ANTIOXIDANT
ACTION OF PHOSPHITES AND PHOSPHONITES

2.1 The Stoichiometric Reaction of Phosphites and

Phosphonites with Hydroperoxides
It is well known that organic phosphites readily reduce hydroperoxides
to give alcohols and the corresponding phosphate esters. 5 ,6 The
reaction proceeds with a 1: 1 stoichiometry by a non-radical mechan-
ism, probably a SN2 mechanism at the 0-0 bond with P as the
nucleophile,
, +
ROOH + P(OR'h ~ RO- + HO-P(OR'h ~ ROH + O=P(OR'h
(6)
obeying a second-order rate law, first-order with respect to both
reactants. Rate constants have been determined for the reactions of
various phosphites with l,l-diphenylethyl hydroperoxide,1 tert-butyl
hydroperoxide,s-lo cyclohexenyl hydroperoxide ll and cumyl
hydroperoxide ll- 19 in solution.
Some selected values and activation parameters taken from our own
work, under identical conditions and with systematic variation of
phosphite structure, are presented in Table 1. The rate constants cover
a range of three orders of magnitude. The reactivity of the phosphites
towards hydroperoxides is governed mainly by polar and steric effects
of the groups bound to phosphorus, decreasing with increasing
electron-acceptor ability and bulk of substituent groups in the order
Alkyl phosphites > aryl phosphites > hindered aryl phosphites
Thus, the simple saturated alkyl and cycloalkyl phosphites are most
reactive, whereas the fully hindered aryl and cyclic arylene phosphites
react most slowly. Altogether, the rate constants are rather high, so
that, especially at somewhat higher temperatures, the decomposition
of hydroperoxides by phosphites is a very fast reaction.
This also holds for the decomposition of polymer hydroperoxides.
The reaction of hindered aromatic phosphites with solid polyethylene
28 KLAUS SCHWETLICK

Table 1
Stoichiometric reaction of phosphites with cumyl hydroperoxide in
chlorobenzene ([Plo = [ROOHlo = 0.2 M)17,18

Phosphite 103 x k (30°C) AH* AS* (25°C)

(M- 1 5- 1 ) (kJmor 1 ) (J K- 1 mor 1 )

P(OEt)3 a 350
P(OiPrb 8 760
P(OtBub 220
P(OPhb 31 87 +12

(PhO)'P-~ 6·5

p(a-pt), 4·9

C O
\ .
/-OIPr 330
0
[0\/-OPh 65
0
0=0,I P-OiPr 190
~ 0

0=0
I \p-OPh 99
~
0 /

ao\p-{>-
~ 01 -
3·8 69 -62

,£O~;p-OiPr 120
0
 PHOSPHITE AND PHOSPHONlTE ESTERS 29

Table 1-contd_

Phosphite 103 X k (30°C) aH' as' (25°C)

(M- 1 S-1) (kJ mor 1) (J K- 1 mor 1)

50

37 52 -105

0
""
1
P-OiPr 8-3

4-6 75 -42

-<}\{i
;={/
P- ~ j 0-83 102 +35

~O
Ph-P(OPhb C 600 (continued)
30 KLAUS SCHWETLICK

Table 1-contd.

Phosphite 103 X k (30°C) fiHt fiSt (25°C)

(M- 1 S- 1 ) (kJ mor 1 ) (J K- 1 mor 1 )

1500

/0
Ph-P 13
\

a [Plo = [ROOHlo = 0·1 M.

b [ROOHlo = 0·4 M.
C [Plo = [ROOHlo = 0·05 M.

hydroperoxide at 50-80°C has been shown to proceed initially with

rate constants of the same order of magnitude as with the low-
molecular-weight hydroperoxides in the liquid phase. 20 At higher
conversions, however, a drastic decrease of rate was observed, most
pronounced at low phosphite and high hydroperoxide
concentrations. 20 ,21
Phosphonites react with hydroperoxides in an analogous way to
phosphites giving the corresponding phosphonates,
Ar
ROOH + Ar-P(OR'h~ ROH + )P(OR'h
o::::?'
but their hydroperoxide-decomposing reactivity is very much higher
than that of phosphites (Table 1).18.22

2.2 The Catalytic Decomposition of Hydroperoxides by

Phosphites and Phosphonites
In addition to and following the stoichiometric reaction, five-
membered cyclic phosphites (1,3,2-dioxaphosphole derivatives) are
 PHOSPHITE ANDPHOSPHONITE ESTERS 31

0.2

0.1

o 20
t / min
Fig. 1. Products of reaction of 2,6-di-tert-butyl-4-methylphenyl 0-
phenylene phosphite with cumyl hydroperoxide in chlorobenzene at
50°C. 1S

capable of reacting with alkyl hydroperoxides catalytically, so that

more than a stoichiometric amount of hydroperoxide is decomposed
by these phosphites. 13 This catalytic mode of reaction has especially
been studied with cumyl hydroperoxide, where it leads to decomposi-
tion products, phenol and acetone, which are easily detectable
indicators for the catalytic pathway.1O,13,17,19,23,24
The catalytic decomposition is preceded by a fast reaction stage in
which the catalytically active species is formed from the phosphite and
hydroperoxide. We have observed by HPLC and 31p_NMR spectros-
copy two phosphates during the course of reaction of 2,6-di-tert-butyl-
4-methylphenyl o-phenylene phosphite (IX) with cumyl hydroperoxide
(Fig. 1).15 The first (XII), going through a maximum of concentration,
is the one formed by stoichiometric oxidation of IX with hydropero-
xide. It is transformed into the second phosphate (XIV) in two ways,
rapidly by reaction with water (from the dehydration of cumyl alcohol
and from moisture) and more slowly with the hydroperoxide giving a
peroxyphosphate (XIII) which is unstable and decomposes to XIV
and phenol and acetone (Scheme 3). The proportion of these two
 32 KLAUS SCHWETLICK

0~/ 0

o
\p_OAr + Ph-~~OOH
I
Me
--+ 0=
~
I
0\

0
~O
/p ~
OAr
¥e
+ Ph-C--UI
r!te
IX XII

¥e ~CH2
Ph-C-OH --+ Ph-C"" + H 20
I Me
Me

OH
Me
I
+ Ph-C-OOH
I
--+ , O-~-O-O-t-Ph
0- -
/ 0

I
Me

I
Me OAr Me
XIII
+HzO 1- PhOH-MezCO

OH

0=6
~
I
0
\p
~o

~OAr
+ H 20 --+ r<
\J-O-~-OH
I
OAr
XIV

Me Me
Ph-t-OOH XIV~ Ph-OH + ~C=O
I M/
Me e

Scheme 3
 PHOSPHITE AND PHOSPHONlTE ESTERS 33

routes depends on the water/hydroperoxide ratio. The open-chained

hydrogen phosphate XIV is the acidic catalyst in the presence of which
cumyl hydroperoxide is decomposed to phenol and acetone. 15
XIV is also formed in the reaction of the o-phenylene phosphite IX
with other hydroperoxides, e.g. tert-butyl and tetralyl hydroperoxide. 15
It is, as a substituted phenol, a very efficient chain-breaking anti-
oxidant and responsible for the inhibiting activity of IX in the later
stages of the oxidation of hydrocarbons (cf. Section 3).
Cyclic o-phenylene phosphonites react with hydroperoxides simi-
larly to phosphites, giving initially the corresponding o-phenylene
phosphonates which decompose hydroperoxides catalytically. 22
Unlike the o-phenylene phosphites of type IX which catalytically
decompose cumyl hydroperoxide even at -20°C, ethylene phosphites,
e.g. XV, are not able to react with the peroxide in a molar ratio
[ROOH]/[P] > 1 at temperatures below 50°C and in the absence of
water. 17 A catalytic decomposition, however, is observed at 75°C. The
analogous reaction products to those with IX (Scheme 3) are formed,
but the open-chained hydroxyethyl phosphates XVII are unstable
under the reaction conditions and condense to give polyphosphate
esters. 17

o o
C\p~
0 HO 0
Cd \p-OPh +ROOH , H 20/ROOH,
HO "'P~
~O/ ~OPh
o I " OPh
xv XVI XVII

--+ polyphosphate esters

The catalytic decomposition of hydroperoxides by cyclic ethylene
and phenylene phosphites proceeds more slowly than the stoichio-
metric reaction at the same phosphite concentrations. This is evident
by comparing Table 1 with Table 2, which contains some second-order
rate constants for the catalytic stage of the decomposition of cumyl
hydroperoxide. With respect to phosphite structure, the following
order holds for the reactivity in the catalytic hydroperoxide
decomposition:
Non-sterically hindered aromatic phosphites > aliphatic phosphites
> hindered aromatic phosphites
which is significantly different from that in the stoichiometric reaction.
34 KLAUS SCHWETLICK

Table 2
Catalytic decomposition of cumyl hydroperoxide by cyclic phosphites in
ch lorobenzene 17.18

Phosphite T [Pl o [ROOHl o 103 x k

(OC) (M) (M) (M s-')

C 0

0
:P-OiPr 75 0·05 0·25 0·42

CO,P-OPh
75 0·05 0·2 0·84
0
EtOCO
X O

o
'P-O
I
~
If
-
~ 75 0·05 0·25 0·22

ceo\
EtOCO

30 0·01 0·2 1·5

I P-OiPr
~ 01 75 0·01 0·25 39

( C IO ,P-OPh 75 0·01 0·15 120

ceo\°
"'" 0/

~
I P-O
7 ~
-
75 0·05 0·25 10

In contrast to some claims,13,24 six- and higher-membered cyclic

phosphites are not capable of decomposing hydroperoxides in a
catalytic manner. 17 ,19 This parallels the well-known circumstances in
the hydrolysis of cyclic phosphate esters, where only the five-
membered derivatives exhibit an extraordinary reactivity. 25--27
Certain phosphite derivatives, such as arylamidophosphites,28
thiophosphites/8 ,19 phosphorus acid esters of thiobisphenols,29 and
some diaryl hydrogen phosphites,30 are capable of decomposing
hydroperoxides catalytically.
 PHOSPHITE AND PHOSPHONITE ESTERS 35

2.3 Radical Side Reactions

The heterolytic mechanism of hydroperoxide decomposition by
phosphites is accompanied by a homolytic reaction in a minor
proportion. The reacting phosphite-hydroperoxide system exhibits
chemiluminescence31 and 31p_CIDNp32-34 and initiates radical oxida-
tion and polymerisation reactions?3,24 Intermediate radicals can be
detected by ESR spectroscopy35 and can be trapped by NO and stable
nitroxyl radicals. 12 ,36 In the case of cumyl hydroperoxide, the forma-
tion of acetophenone as by-product can be considered a good indicator
for the radical side reaction. 17 ,24 From the trapping experiments and
the acetophenone yield, the extent of the homolytic pathway has been
estimated to be below 1% for alkyl phosphites and up to 5% for aryl
phosphites at 20°C. 12 ,36 A mechanism for this radical side reaction
starting with an electron transfer from the hydroperoxide to the
phosphite, has been postulated (Scheme 4).8
. - + .
ROOH + P(OR'h~ ROOH + 'P(OR'h~ RO' + HOP(OR'h
HOP(OR'h~ HPO(OR')z + R'O'
RO' ~ PhCOMe + Me'
Scheme 4

This mechanism explains the formation of aryloxyl radicals (if

R' = Ar)35 and acetophenone as by-product in the decomposition of
cumyl hydroperoxide by aryl phosphites. 17 ,24 The formation of
phosphonates, observed by 31p-CIDNP, obviously also results from the
intermediate phosphoranyl radicals with participation of the solvent. 34

3 CHAIN-BREAKING ANTIOXIDANT ACTION OF

PHOSPHITES AND PHOSPHONITES

It is now generally accepted that certain phosphites, particularly the

sterically hindered aryl phosphites, are also capable of acting as
chain-terminating antioxidants l --4 in addition to their hydroperoxide-
decomposing action, although in the past some workers denied the
direct reaction of those phosphites with peroxyl radicals and related
their observed activity to their ability to release phenols in the course
of autoxidation. 15 ,37
In order to act as a chain-breaking antioxidant, a stabiliser must
36 KLAUS SCHWETLICK

fulfil two basic requirements: it must be able to compete effectively

with the substrate RH for the chain-propagating ROi radicals and it
must form an efficient chain-terminating agent in this reaction with
ROi radicals. Hindered aryl phosphites always meet the second
requirement. They react with alkylperoxyl radicals to give hindered
aryloxyl radicals which are capable of terminating the autoxidation
chain reaction:

ROO' + P(OArh~ ROOP(OArh~ RO' + O=P(OArh (7)

RO' + P(OArh~ ROP(OArh~ ROP(OAr)z + 'OAr (8)
ROO' + ArO' ~ inactive products (9)

On the other hand, alkyl phosphites react with ROi radicals to form
the corresponding alkyl radicals R' which do not terminate but
propagate the oxidation:

ROO' + P(OR'h~ ROOP(OR'h~ RO' + O=P(OR'h (7)

RO' + P(OR'h~ ROP(OR')3~ R' + O=P(OR')3 (10)
R'+02~ROO'

In both cases the phosphite is oxidised by ROi radicals in a first

reaction step giving the phosphate and RO' radicals. Crucial for the
antioxidative efficiency of phosphites, therefore, is the second step,
their reaction with the alkoxyl radicals formed in the first step. Only
those phosphites which react with alkoxyl radicals by substitution to
give isomeric phosphite-releasing chain-terminating aryloxyl radicals
can act as primary antioxidants. In this case the intermediate
alkoxyphosphoranyl radicals undergo a-scission, whereas {J-scission
leads to oxidation of the phosphite and chain-propagating alkyl
radicals:

--
/'
I. . ~ RO-P~ + ArO'
RO'+ ~P-OAr
/
RO-f-OAr ~ o Substitution
'./
/p"" + R'
OAr
. Oxidation
The diverse reactions of phosphoranyl radicals which depend on
their structure are understood rather well and have been reviewed in a
more comprehensive context. 38,39
 PHOSPHITE AND PHOSPHONITE ESTERS 37

3.1 The Inhibition of Autoxidation by Phosphites and

Phosphonites
The chain-breaking antioxidant efficiency of phosphites can best be
studied in the inhibition of hydrocarbon oxidation by phosphites at low
temperatures «100°C), where the homolytic decomposition of
hydroperoxides formed does not yet occur and, therefore, inhibition is
also not caused by the hydroperoxide-decomposing action of the
phosphites. From the kinetics of such inhibited oxidations the two
quantities characterising the effectiveness of a chain-breaking anti-
oxidant can be evaluated; namely, the rate constant, k7' of its reaction
with peroxyl radicals and the stoichiometric inhibition factor f, the
number of peroxyl radicals trapped by one molecule of the anti-
oxidant. The constant k7 determines the rate of the inhibited oxidation
and the effective antioxidant concentration; f determines the length of
the inhibition period.
The inhibition of the oxidation of hydrocarbons by organic phos-
phites at low temperatures has been studied by several authors, with
partially contradictory results and interpretations. 15,23,40,41
In Fig. 2 is depicted the fate of the phosphorus species studied by
31p_NMR spectroscopy in the course of cumene oxidation inhibited by
the sterically hindered 2,6-di-tert-butyl-4-methylphenyl neopentylene
phosphite at 65°C. 41 The phosphite is consumed at a rate slightly
higher than the rate of initiation (r; = 2·4 X 10- 6 M S-I), giving the

0.1

0.06
-
L
°

0.02

o
t/min

Fig. 2. Transformation of 2,6-di-tert-butyl-4-methylphenyl neopentylene

phosphite in the AIBN-initiated oxidation of cumene in chlorobenzene at
65°C ([Pl o = 0·1 M, [RHl = 1·71 M, [AIBNl o = 0·1 M).41
38 KLAUS SCHWETLICK

corresponding phosphate and the substituted alkyl phosphite which is

further oxidised to the substituted alkyl phosphate. The ratio of
oxidation to substitution products of the parent phosphite,

[><Arll([>OR] [><R]) +
is larger than 1, as might be expected according to the mechanism,
reactions (7)-(9), indicating, as does the higher consumption rate of
the phosphite, that additional processes must be involved in the
oxidation of the parent phosphite. The reaction of the phosphite with
hydroperoxides formed in the course of oxidation [reaction (6)] is the
main process involved.
In the oxidation of tetralin inhibited by 2,6-tert-butyl-4-
methylphenyl o-phenylene phosphite (IX), the situation is similar
(Fig. 3),41 but the hydroxylphenyl phosphate XIV appears addition-
ally, due to ring opening of the intermediate phosphate XII by
peroxidolysis and hydrolysis according to Scheme 3.

0.2
(lCD,
'" I O/P-OAr (IX)

0.16
•

~o"l •

0,,1
0

u
, ~O
/P'OAr 0

~P-OR

0 120 240 360

tlmin
Fig. 3. Transformation of 2,6-di-tert-butyl-4-methylphenyl o-phenylene
phosphite in the AIBN-initiated oxidation of tetralin in chlorobenzene at
65°C {[P]o = 0·2 M, [RH] = '·75 M, [AIBN]o = 0·' M).41
 PHOSPHITE AND PHOSPHONITE ESTERS 39

BOO

H09:

a 2 00
t/min
400

Fig. 4. Oxidation of tetralin in the presence of phosphites in chloroben-

zene at 60°C ([Pl o = 5 x 10- 4 M, [AIBNl = 5 x 10- 3 M, [RHl = 3·73 M).68

The oxygen uptake of tetralin at 60°C in the presence of 5 x 10- 4 M

antioxidant is shown in Fig. 4.41 At this low concentration, none of
the phosphites used retarded the oxidation, whereas the hindered
phenols, 2,6-di-tert-butyl-4-methylphenol (BHT) and the hydroxy-
phenyl phosphate XIV, caused a pronounced induction period. The
behaviour of the o-phenylene phosphite IX is exceptional in that it
acted antioxidatively in the later stages of the reaction. As mentioned
above, this is because this cyclic phosphite is transformed into the
hydroxyphenyl phosphate XIV in the course of oxidation.lo,l?
At higher concentrations, phosphites with open-chain sterically
hindered aryl groups inhibit the autoxidation of tetralin and cumene
(Fig. 5). The non-hindered aryl phosphites are inactive initially, but
become active in the later stages of oxidation. Sterically hindered
eight-membered cyclic arylene phosphites are also inefficient. Al-
together, the anti oxidative efficiency of all phosphites is less than that
of the hindered phenol, BHT.
It is remarkable that phenylphosphonites including the hindered
aryl ones, do not initially inhibit the oxidation of cumene and tetralin
at 65°C. 18,42 In the further course of oxidation, however, inhibition
becomes evident as in the case of phenyl phosphites referred to above.
40 KLAUS SCHWETLICK

E
--
>

t /min
Fig. 5. Oxidation of cumene in the presence of phosphites in chloroben-
zene at 65°C ([Pl o = 0·05 M, [AIBNl = 0·1 M, [RHl = 1·71 M).41

Table 3 reveals that, at equal phosphite concentrations, the induc-

tion periods are longer and the rates of inhibited oxidation are lower
in cumene than in tetralin, i.e. the antioxidative efficiency of phos-
phites depends on the nature of the hydrocarbon substrate; it is
higher, the less oxidisable the substrate. 41 Stoichiometric inhibition
factors, f, and rate constants of the reaction of phosphites with
peroxyl radicals, k7' evaluated from the inhibited oxidations of these
two hydrocarbons are also listed in Table 3. For the sterically
hindered aryl phosphites k7 is in the order of 2 X 102 to 1 X
103 1mol-I S-I at 65°C, which is 102 to 103 times smaller than some
other values reported in the literature,40 but in good agreement with
the values determined from the inhibition of alkyl phosphite oxida-
tions by these phosphites48 and with a value extrapolated directly from
ESR-measurements of the rate of tert-butyl peroxyl radicals with
phosphites at lower temperatures. 43 These values of k7 are about 50
times smaller than the corresponding values for hindered phenols,
reflecting the smaller retarding effects of phosphites on the rates of
inhibited oxidations in comparison with phenols.
 PHOSPHITE AND PHOSPHONITE ESTERS 41

The induction periods and stoichiometric inhibition factors for

phosphites are also smaller if < 1) than those of phenols (BHT: f = 2).
The dependencies of the induction periods and stoichiometric
factors on the concentration of the phosphites are striking. The length
of induction period is not directly proportional to the phosphite
concentration but decreases at a greater rate than the antioxidant
concentration. Its dependence on [P]o is approximately linear but
below some apparent critical antioxidant concentration no induction
period can be observed (Fig. 6).41 This is also reflected in the
dependence of the stoichiometric factor, f, on the antioxidant con-
centration: f is not a constant, as in the case of phenols, but decreases
with decreasing phosphite concentration from 1 at very high con-
centrations to zero at very low concentrations (Fig. 7). These
observations may be rationalised kinetically by taking into account the
destruction of the phosphite according to eqn. (6) in the course of
oxidation,41 which leads to the following expressions: for the induction
period,

. =! {[P]
tmd'j 0
_ k2[RH] 1
2k7 n
(1 + k2k[RH]
2
[P]o)}
7
(11)

for the stoichiometric inhibition factor,

f = 1 - k2[RH] In(1 + 2k7 [P]o) (12)

2k7 [P]o k2[RH]
and for the critical antioxidant concentration,

[P] = k 2 [RH] (13)

cr 2k7

The destruction of the phosphite by hydroperoxide is more pro-

nounced the more hydroperoxide is formed in the reaction, e.g. the
lower the phosphite concentration, the more easily is the hydrocarbon
oxidised. That means that the chain-breaking antioxidant efficiency of
phosphites depends not only on their intrinsic antioxidative properties
(k7) but also on the nature of the substrate to be stabilised. The higher
the oxidisability of the substrate (k 2 ), the shorter the induction period,
the lower the stoichiometric factors of inhibition and the higher the
effective antioxidant concentration of the phosphite needed for inhibi-
tion. Therefore, in the easily oxidisable aralkyl hydrocarbons, the
required minimum phosphite concentrations are rather high. The same
should be true for the analogous polymers (polystyrene, polydienes,
 tl

Table 3
AIBN-initiated oxidation of cumene and tetralin inhibited by phosphites and BHT, respectively, in
chlorobenzene at 65°C ([P]o] = 0·05 M, [AIBN] = 0·1 M, [cumene] = 1·71 M, [tetralin] = 1·75 M)41

Antioxidant Cumene Tetralin

t ind f 106 x ro k7 t ind f 106 x ro k7

(min) (M 5- 1 ) (M- 1 5- 1 ) (min) (M 5- 1 ) (M- 1 5- 1 )

None 0 0 10·5 0 0 19·8 ~

c::
P(OPhb 0 0 9·3 0 0 12·8 '"
~
:t:
300 0·72 3·33 300 95 0·26 5·46 640
p(y), ~~
310 0·75 3·04 500 200 0·55 4·26 1420
>C;~ >-
~O'P_~ 3·16 400 5·03 810
LVL-OI ~.
 PHOSPHITE AND PHOSPHONITE ESTERS 43

b...
x
o
M

C?
N

It)
N
0
M
...
v
0

...
N
~

N M
<.9 It) o:t
M N
"
M
0
0 N
It)
o:t

Il..
~

0
J
/~O o
* 0
I
/Il.."",
0
:I:
0

~x
44 KLAUS SCHWETLICK

800

-
.S
E
c:
..:..-

o 0.04 0.08
[P]/M

Fig. 6. Induction periods in the AIBN-initiated oxidation of cumene and

tetralin inhibited by 2,6-di-tert-butyl-4-methylphenyl neopentylene
phosphite and BHT, respectively (conditions as in Fig. 5).41

2 0!--
0 0 BHT

1.0

.....

0.5

[P] 1M

Fig. 7. Stoichiometric inhibition factors of 2,6-di-tert-butyl-4-methyl-

phenyl neopentylene phosphite and BHT, respectively, in the AIBN-
initiated oxidation of cumene and tetralin. Curves best fitted with eqn
(12) giving k7 =370M- 1 S-1 for cumene and 1 x 103 M- 1 S-1 for tetralin
(conditions as in Fig. 5)41
 PHOSPHITE AND PHOSPHONITE ESTERS 45

polyacrylonitrile, polyethers and their copolymers), whereas in satur-

ated aliphatic hydrocarbons and polyolefins these minimum concentra-
tions should be lower.
Unfortunately, there are few kinetic studies of phosphite-inhibited
oxidations of polymers at low temperatures to prove these suggestions;
only the oxidation of solid isotactic polypropylene at 85°C has been
reperted. Here, the hindered tris(2-tert-butyl-4-methylphenyl)
phosphite as well as the non-hindered triphenyl phosphite are effective
as inhibitors40 above some 'critical' antioxidant concentration, but
these concentrations are of the same order (and not lower) as in the
case of the higher oxidisable liquid aralkanes. 44 This may reflect the
lower rate constants, k7' of the reaction of the phosphites with
polymer peroxyl radicals in the solid state due to restricted diffusion
compared with the liquid phase. Therefore, the antioxidant activity of
phosphites in the solid polymer is lower than in liquid hydrocarbons. 40

3.2 Reactions of Phosphites and Phosphonites with

Alkylperoxyl Radicals
The structural features determining the chain-breaking antioxidant
ability of organophosphorus compounds have been elucidated in detail
by studying their reactions with alkylperoxyl radicals and alkoxyl
radicals. These investigations confirm and expand the results obtained
in the inhibition experiments mentioned so far.
Peroxyl radicals, generated by thermal decomposition of azo-
compounds in the presence of oxygen,
R-N N-R ~ 2R' + N2
R'+02~ROO'

were reacted with phosphites and phosphonites. 45-5o.

Trialkyl phosphites react with O 2 in the presence of azo-bis-
isobutyronitrile (AIBN) in a rapid radical chain reaction to give the
corresponding phosphates45 ,47-49
P(OR'h + !02 ~ O=P(OR'h
according to eqns (7) and (10). Dialkyl arylphosphonites behave
analogously giving the corresponding phosphonates: 5o

o
II
PhP(OR')z + !02 ~ PhP(OR')2
46 KLAUS SCHWETLICK

Therefore alkyl phosphites and phosphonites cannot act as chain-

breaking antioxidants.
From the rates of oxidation, the rate constants k7 for the reactions
of trialkyl phosphites with 2-cyanopropyl-2-peroxyl radicals have been
calculated (Table 4).49 They are in the order of 103 1mol- 1 S-1 at 65°C,

Table 4
Products and kinetic parameters of reactions of phosphites and phosphon-
ites with oxygen/AIBN in chlorobenzene at 65°C ([Pl o = 0·2 M, [AIBNl =
0·1 M, rj = 2·4 x 10- 6 M S-1)42.49

~P-OR' ""p ~p
/ / ~OR'
(mole fraction)
(mole fraction)

P(OEt)3 1 o 1500 a 1840

P(OiPrb 1 o 1080 a 1330
P(OtBU)3 1 o 580 a 730
P(OPhb 0·96 0·04 12

p(y), 0·7 0·3 1·8

(;PrOl'P~ 0·7 0·3 1·7

0·8 4

0·5 0·5 1·2

o 790 970

o 55 660
 PHOSPHITE AND PHOSPHONITE ESTERS 47
Table 4--contd.

~ ,j/0
~P-OR' P
/ / ~OR'
(mole fraction)

0·6 0·4 1·4

0\
P-OiPr o 8 100

o
/

0\
P-OPh 0 6 80

I
Ph-P(OiPrb 1 0 22 120
Ph-P(OPh)2 1 0 28 150

p~(V)' 0·95 0·05 4·8

/0
Ph-P 0 5·1 27

~
a [AIBN] = 1·0 X 10- 3 M, 'j = 2·4 X 10- 8 M s-l,
b Ring-opening products.
48 KLAUS SCHWETLICK

similar to that expected by extrapolating the rate constants determined

directly by kinetic ESR spectroscopy43 at lower temperatures. The rate
constant k7 decreases with increasing bulk of R' .
Non-sterically hindered aryl and arylene phosphites and aryl-
phosphonites exhibit the same behaviour in the AIBN-initiated
oxidation as the alkyl esters. They are oxidised to give the
corresponding phosphates46 ,48,49 and phosphonates,4z respectively (see
Table 4).
In the reaction of triphenyl phosphite a small amount (4 mol %) of
the substitution product, ROP(OPhh, is found besides the oxidation
product, OP(OPhh. 49 In this case the intermediate phosphoranyl
radical, ROP(OPhh, undergoes a-scission in addition to {J-splitting.
Because phenoxyl radicals are formed in the a-scission, triphenyl
phosphite should act as chain-terminating antioxidant to a certain
degree.
Phosphites with exocyclic sterically hindered aryl groups, e.g. V,
VII , IX, react with oxygen/AIBN only very slowly. Chain propaga-
tion is almost completely suppressed (rlr; = 1).1,49 In addition to the
oxidation product of the phosphite, the substitution product and its
phosphate are also formed (Table 4):49

2 ""
/P-OAr + RN=NR + 20 z --- "" P ~O
/ ""OAr

',,--
+ /P-OR + O=ArOOR + Nz

pP
""
P-OR + '20z
I
--- ~;/'
P
/ / ~OR
That confirms that alkylperoxyl radicals react with these phosphites
according to eqns (7) and (8) by a-scission of the intermediate
alkoxyphosphoranyl radicals releasing sterically hindered aryloxyl
radicals which effectively trap peroxyl radicals [eqn (9)]. Therefore,
sterically hindered aryl phosphites can act as chain-terminating
antioxidants.
In the reaction of mixtures of alkyl and sterically hindered aryl
phosphites with oxygenl AIBN, the chain oxidation of the alkyl
phosphite is inhibited by the aryl phosphite. From the rates of
 PHOSPHITE AND PHOSPHONITE ESTERS 49

consumption of the phosphites, the rate constants, k 7 , of the reactions

of hindered aryl phosphites with 2-cyanopropyl-2-peroxyl radicals are
accessible. 49 Again, they are in the order of (1-3) x 102 Imol- 1s- 1 at
65°C and somewhat lower than those of alkyl phosphites.
Unlike the open-chained derivatives, sterically hindered cyclic
arylene phosphites, e.g. dibenzo[d,g]-1,3,2-dioxaphosphocins derived
from methylenbisphenol '2246', with non-hindered exocyclic aryl
groups are completely oxidised in the reaction with oxygen/ AIBN
(Table 4). Substitution products by ring opening are not formed.
Remarkably, hindered aryl phenylphosphonites also react with
AIBN/0 2 mainly by oxidation; cyanoisopropyl phenylphosphonites
formed by displacement of a hindered aryloxyl radical are observed
only in minor proportions (Table 4).42
Because of this predominant oxidation, sterically hindered aryl
phosphonites and cyclic arylene phosphites are less effective chain-
breaking antixoidants in low-temperature oxidations than the acyclic
hindered aryl phosphites (see Section 3.1).

3.3 Reactions of Phosphites and Phosphonites with Alkoxyl

Radicals
The reactions of alkoxyl radicals with organic phosphites and phos-
phonites have been extensively studied5,46,51-58 and reviewed,38,39
emphasising the structure and reaction modes of the intermediate
alkoxyphosphoranyl radicals. With respect to the mechanism of
antioxidant action of phosphorus compounds, product studies with
tert-butyloxyl radicals generated from di-tert-butyl peroxide and di-
tert-butyl peroxalate (DTBPO) are most relevant. 46 ,54,58
With tert-butyloxyl radicals from DTBPO,

tBuO-OCOCOO-OtBu~ 2tBuO' + 2C0 2

aliphatic phosphites react to form the corresponding phosphates
according to eqn (10) (Table 5), in accordance with previous results
and confirming that these phosphites are not suitable as chain-breaking
antioxidants.
Aryl phosphites including the non-sterically hindered ones, react
with tert-butoxyl radicals at low temperatures (50°C) exclusively by
substitution according to eqn (8) to give aroxyl radicals and tert-butyl
phosphites which are easily oxidised to tert-butyl phosphates. Phos-
phites with several aroxyl groups react until all aroxyls are displaced,
50 KLAUS SCHWETLICK

Table 5
Products of reaction of phosphites with di-tert-butyl peroxalate in
chlorobenzene at 50°C ([Plo = 0.2 M, [DTBPOl o= 0·25 M)58

-1'0 ~
~P-OR' ~P P-OtBu Phosphonates
/'
/ ~OR' /
(mole fraction)

P(OEtb 1·0 0
P(OiPrb 0·84 0
P(OPhb 0 1·0

ply), 0 0·3 0·6

(iPrOl,P-a-p- 0 0·5 0·5

(PhOI'P~ 0 0·5 0·45

[0\ P-OiPr B 0·44 0

01

CO~P_OPhb 0·2 0·8

0

0 =I0 \P-OiPr 0·8 0·2

~ 0/

0=0
~
I ~P-OPh
0
0 0·9
 PHOSPHITE AND PHOSPHONlTE ESTERS 51

Table fr-contd.

~/O ~
~P-OR' P /P-OtBu PhosPhonates
/
/ ~OR'
(mole fraction)

0=0' a-Q-
"""
I
01
p-
~
'f.
j
O 0·65 0·35

>CO"P-OiPr 0·88 0
0/

x:)-{>- 0 0·8 0·2

\ P-OiPr + + +
I

1·0 o o

8 [DTBPO]o = 0·2 M, 55°C.

b [DTBPO]o = 0·1 M, 55°C.
52 KLAUS SCHWETLICK

after which the tert-butyl phosphite is oxidised:

+tBuO' +tBuO'
P(OPhh
-PhO
. ) tBuOP(OPhh
-PhO
. ) (tBuOhPO Ph

+tBuO' +tBuO'
--.~) (tBuOhP . ) (tBuOhP=O
-~o -ffiu

At higher temperatures (>50°C) the tert-butyl esters formed are

unstable and decompose to hydrogen phosphites by elimination of
isobutylene: 46 ,57

tBuOP(OPhh ~ H2C=CMe2 + O=PH(OPhh (14)

Furthermore, it seems that p-scission of the intermediate phos-
phoranyl radicals also takes place, so that aryl phosphates are
observed as well as hydrogen phosphites. 57
In the reaction of 4-methylaryl phosphites with tert-butoxyl radicals,
phospho nates are always observed as by-products, often in high
yields,58 e.g.

(PhO) 2 p-o-p-~ CH
-
3 +tBuO;
-tBu H~~CH -~(OPh)
-
2 2

The same phospho nates are formed in the reaction of mixtures of

aryl phosphates and 4-methylphenols, for instance BHT, with
DTBPO: 58

Additional phosphonates result from radical reactions of these

hydroxyarylphosphonates at the phenolic moiety.
In contrast to acyclic aryl phosphites, cyclic aromatic phosphites
including sterically hindered ones, react with tert-butoxyls pre-
dominantly by oxidation and not substitution, as is typical for aliphatic
phosphites. The intermediate arylene phosphoranyl radicals mainly
undergo 13- and not a-scission by ring opening. 58
 PHOSPHITE AND PHOSPHONITE ESTERS 53

°""P-OR' +tBuO~
/

-q-
~
-
0
\.
\../
-tBu·1
OtBu / .
P

-Q-o / "OR' \
0'

/OtBu
O-P~
OR'

Likewise, hindered aryl phenylphosphonites react with tert-butoxyl

radicals mainly by oxidation (P-scission of the intermediate phenyl-
phosphoranyl radicals) giving the corresponding phenylphosphonates 18 ,54
(Table 5). This special behaviour of hindered aryl phosphonites and of
hindered cyclic arylene phosphites towards alkoxy radicals accounts
for their poor inhibiting ability in the low-temperature oxidation
of hydrocarbons mentioned in Section 3.1.
Returning to the reactions of the acyclic aryl phosphites, it is
remarkable that phenyl and other non-hindered aryl phosphites react
with tert-butyloxyl radicals in a different manner from cumyloxyl,
tetralyloxyl and cyanoisopropyloxyl radicals mentioned before. With
the latter group, oxidation to the corresponding phenyl phosphates
occurs by p-scission of the intermediate phosphoranyl radicals [eqn
(10)], whereas with the former group, tert-butyl phosphites are built
up by a-scission and substitution of a phenoxyl radical [eqn (8)]:
54 KLAUS SCHWETLICK

Me Me
I ~ I I
Me-C-O· + P-OPh ~ Me-C-O-P·-OPh
I / I I
Me Me
Me
I /
~ Me-C-O-P ~ + ·OPh
I
Me
Me Me
I ~ I I
Ph-C-O· + P-OPh ~ Ph-C-O-P·-OPh
I / I I
Me Me
Me
I
~ Ph-C/ +O=P-OPh
~
Me
I

Obviously, this is because the PhCMe2-0 and NCCMe2-0 bonds are

weaker than the Me3C-O bond and C-O scission successfully com-
petes with P-O scission in the phosphoranyl radical.
Thus the chain-breaking efficiency of non-hindered aryl phosphites
should depend on the substrate to be stabilised. They should exhibit
some chain-breaking antioxidant activity only in saturated aliphatic
hydrocarbons and polyolefins, whereas in compounds and polymers
bearing radical-stabilising substituents, such as polystyrenes, poly-
dienes, polyacrylonitrile, polyethers, etc., their chain-breaking
efficiency should be low.

4 ANTIOXIDANT ACTION OF PHOSPHITES AT HIGHER

TEMPERATURES

Polymers can be exposed to temperatures up to 200-300°C during

manufacture, processing and special end-uses.
In autoxidations at higher temperatures, homolytic decomposition
of the hydroperoxides formed takes place [reaction (3)] giving rise to
reactive radicals which cause auto-initiation and chain branching of the
oxidation reaction. Under such conditions, the hydroperoxide-
decomposing ability of phosphites and phosphonites becomes effective
in suppressing chain branching and so inhibiting oxidation. For
aliphatic phosphites this is the only way of acting anti oxidatively . This
 PHOSPHITE AND PHOSPHONITE ESTERS 55

is responsible for the relatively low efficiency of these phosphites when

used alone, on the one hand, and for their synergistic action in
combinations with phenols, on the other.
Aromatic phosphites may act by chain breaking, in addition to
hydroperoxide decomposition, at higher temperatures, by reaction
with peroxyl and alkoxyl radicals, thus releasing aryloxyl radicals. The
two modes of antioxidant action have different susceptibilities to
changes of temperature: the ratio of direct radical trapping to
hydroperoxide decomposition should decrease with increasing tem-
perature, because the rate of the reaction of alkylperoxyl with the
substrate [reaction (2)] increases very much faster with rising tempera-
ture than the rate of reaction of peroxyl radicals with the phosphite
[reaction (7)] a process of low activation energy.43 But according to
eqn (12), low k7/ k2 ratios give rise to low f factors and, therefore,
to low chain-breaking antioxidant activity. Additionally, the ratio
of £1'- to ,s-splitting in the intermediate alkoxyphosphoranyl radical
RO-P'-OAr should decrease with increasing temperature,54 i.e. sub-
stitution of the phosphite, which leads to termination, is less likely
at higher temperatures than oxidation. Thus, the chain-breaking
efficiency of phosphites, which is already lower than that of hindered
phenols at low temperatures, should decrease further with increasing
temperature.
In practice it has been observed, however, that in the oxidation of
polyethylene64-66 and in the oxidation of polypropylene at 160-200°C,
alkylated aryl and arylene phosphites, the hindered phenyl phosphites
in particular, exhibit a rather high antioxidant activity resembling or
even surpassing that of the parent hindered phenols. 9,15,23,59-63,67,68
This also holds for the hindered eight-membered cyclic phosphites
(dibenzo-dioxaphosphocins) and for the hindered aryl phosphonites 18
which were only poor radical-trapping agents in the initial stages of
low-temperature oxidations (ct. Section 3.1). Some other chain-
terminating action connected with the hindered phenolic moiety of the
molecule, therefore, must be responsible for powerful antioxidant
activity at higher temperatures.
It has repeatedly been suggested, but not unequivocally proved, that
phenols formed by hydrolysis of the parent phosphites are the species
responsible for the antioxidant activity of phosphites in high-
temperature oxidations. 15 ,37,69,7o Other authors have considered the
hydrolysis of phosphates formed from the parent phosphites to be the
source of phenols. 19
56 KLAUS SCHWETLICK

Water, always present in autoxidations, is also present in those

inhibited by phosphorus compounds, resulting from dehydration of
alcohols formed in reaction (6) at somewhat higher temperatures, and
from thermal decomposition of hydroperoxides [reaction (3)]. It is well
known, too, that alkyl and non-hindered aryl phosphites and phospho-
nites easily hydrolyse even at ambient temperatures. Hydrolysis of
hindered aryl phosphites is more restrained, and it does not occur
under the conditions of autoxidation at low temperatures but at higher
temperatures it may become relevant.
The formation of phenols and phosphorous acid has been reported
to take place in phosphite-inhibited thermal oxidations. 69-71 31p_NMR
and HPLC studies of the fate of aryl phosphites and phosphonites in
the autoxidation of cumene and tetralin at 150°C clearly revealed
oxidation to phosphates and hydrolysis to hydrogen phosphites and
phosphonites respectively, did take place from the beginning of the
o
o-~(y),

reaction; the hydrogen phosphites and phosphonites were further

hydrolysed to phosphorous and phosphonic acids, respectively, whe-
reas the phosphates and phospho nates were surprisingly stable under
the reaction conditions (Fig. 8).42 Therefore the phenols released in
the hydrolysis are the essential inhibiting species in these oxidations,
the activity of which may be synergistically enhanced by the hydrogen
phosphites and phosphonites and by the phosphorous acid simul-
taneously formed. Diaryl hydrogen phosphites are themselves anti-
oxidatively active and, as does H3 P0 3 , give synergistic mixtures with
hindered phenols in higher-temperature oxidations. 65 ,7o,71
In the autoxidation of less oxidisable hydrocarbons, for example
polyolefins, hydrolysis and some direct radical trapping by aryl
phosphites may take place simultaneously. The substituted phosphites
formed according to reaction (8) should eliminate olefins at higher
temperatures as mentioned in Section 3.3, eqn (14), so giving rise to
the same hydrogen phosphites as in hydrolysis.
 PHOSPHITE AND PHOSPHONlTE ESTERS 57

0.1

:L
-. P(OAr )3
u

0.06
•

0.02

o 200 400 600

t/min

Fig. 8. Transformation of tris-(2-tert-butyl-4-methylphenyl) phosphite in

the thermal oxidation of tetralin at 150°C.42

The five-membered o-phenylene phosphites of type IX seem to

represent a special case also in high-temperature inhibition. Here,
hydrolysis and peroxidolysis of the intermediate phosphates XII by
ring opening to hydroxyphenyl phosphates XIV (Scheme 3) is so fast
that it takes place even at ambient temperatures. The same processes
occurring at higher temperatures would account for the extraordinary
antioxidant activity of these cyclic phosphites23 ,59,61,62 and also that of
the corresponding phosphates23 in polypropylene oxidation. Acyclic
aryl phosphates do not exhibit this behaviour, they are not hydrolysed
in the oxidising media and are inactive as antioxidants. 42

5 CONCLUSIONS

The basic mechanisms by which organic phosphites and phosphonites

operate as antioxidants now appear to be quite clear. They are
hydroperoxide decomposition (stoichiometric and catalytic) and radi-
cal trapping by themselves and by phenols formed in their hydrolysis.
The efficiency of these different modes of operation and their
contribution to the total antioxidant action are also well understood,
depending on the structure of the phosphorus compound, on the
oxidisability of the substrate and on the reaction conditions. These
mechanisms have predominantly been elucidated in the oxidations of
low-molecular-weight hydrocarbons and very little is yet known about
58 KLAUS SCHWETLICK

these relations in polymers of different structure and under different

reaction conditions. In this field, further experimental studies are
needed to verify forecasts extrapolated from the behaviour of low-
molecular-weight compounds in order to provide a better understand-
ing of the action of this important class of antioxidants in polymer
manufacture, processing and end-use.

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