Fundamental Studies of Grafting Reactions in Free Radical

Copolymerization. IV. Grafting of Styrene, Acrylate, and

Methacrylate Monomers onto vinyl-Polybutadiene
Using Benzoyl Peroxide and AIBN Initiators
in Solution Polymerization

NAI-JEN HUANC and DONALD C. SUNDBERG*

Polymer Research Group, Department of Chemical Engineering, University of New Hampshire,

Durham, New Hampshire 03824

SYNOPSIS

Vinyl-1,P polybutadiene (vinyl-PBD) was used as the backbone polymer for the grafting
of styrene, methacrylate, and acrylate monomers using both benzoyl peroxide and AIBN
initiators. Radical attack on the backbone can occur through the pendant vinyl group or
at the tertiary, allylic hydrogen site. Effective graft sites are formed via double bond addition
of either primary (initiator) or polymer radicals. The production of tertiary allylic radicals
on the backbone chain also occurs and results in moderate to dramatic reaction rate re-
tardation in every monomer system. The type of initiator is only important when the
polymer radicals are not very reactive, as in the case of styrene, and to a lesser extent for
methacrylate monomer. Graft efficiencies are generally higher when using vinyl-PBD than
when using cis-PBD. 0 1995 John Wiley & Sons, Inc.
Keywords: grafting vinyl-polybutadiene styrene acrylate methacrylate

INTRODUCTION resulting allylic PBD radical then needs to

In previous grafting studies's' we used cis-polybu-
tadiene (cis-PBD) as the backbone polymer, and
showed that when the grafting monomer is styrene
or a methacrylate, the graft sites are most likely
generated by the chain transfer to backbone mech-
anism. The graft efficiency was found depend on the
following competing reactions:
1. Competition between monomer and back-
bone for the initiator radicals. When the
benzoyl peroxide (BPO) initiator radical at-
tacks the cis-PBD directly, it results in the
formation of an allylic PBD radical capable
of initiating graft copolymerization.
2. Competition between monomer and back-
bone for the growing polymer radicals. The
* To whom all correspondence should be addressed.
Journal of Polymer Science: Part A Polymer Chemistry, Vol. 33,2587-2603 (1995)
0 1995 John Wiley & Sons, Inc. CCC 0887-624X/95/152587-17
compete with polymer radicals for the mono-
mer in order to form graft copolymer.
3. Competition between the various termination
processes for the free polymer radicals.
The efficiency of the grafting process will be ef-
fected by the mode of termination. Similar conclu-
sions have also been drawn by other^.^,^ However,
in the acrylate system, the grafting site is most likely
formed by the double bond addition mechanism. The
allylic PBD radicals generated by either initiator
radicals or polymer radicals are too stable to compete
with the poly(benzy1 acrylate) radical for the acrylic
monomer to form graft copolymer, thus allylic PBD
radicals in the acrylate system are not effective graft
sites. In regard to graft site formation, the role of
initiator, especially BPO is not nearly as important
as in the styrene and methacrylate systems.
Some ~ t u d i e s have
~ - ~ shown that when the vinyl
content of the polybutadiene increases, the grafting

2587
2588 HUANG AND SUNDBERG

Table 11. Evaluation of kbrm3Values for the

-2 1.817etO5-
Stylvinyl-PBDjAIBN System

3 kiprrn1 k,,,
u 1.433&05-
5
.- (L/mol/s) (L/mol/s) 9 (76)
$ 1.05&05-
r 0.0 0.01 0.476
6.667&04- 0.0 0.10 4.668
0.0 0.15 6.424
5 2.833&04 - 0.0 1.00 31.080

_I.-.

650 960 In0 1580 18N 2200

Retention Time (sec)
Figure 1. GPC UV chromatogram of GBDS-33 a t 0,
10, 18, 27,32,37, and 44% monomer conversions.
in ABS polymers increases, and the double bond
addition reaction was thought to become more im-
portant for grafting. Therefore, in this work we
switched the backbone polymer from the cis-PBD
we had used earlier to PBD with a higher content
of vinyl-PBD. The aim of this work was to under-
stand how the structure of backbone polymer will
affect the grafting mechanism and the subsequent
graft efficiency.
EXPERIMENTAL METHODS
AND MATERIALS
In this article, three types of monomer (styrene, ac-
rylate, and methacrylate) were studied in solution
graft copolymerization. A GPC analytical method
(described in a previous article') was used to de-
termine the graft efficiency. To apply this GPC
method it is necessary to have a monomer that ab-
sorbs some UV radiations, and thus benzyl acrylate
and benzyl methacrylate were chosen to represent
the grafting behaviors of acrylate and methacrylate
monomer. Vinyl-1,2 polybutadiene (vinyl-PBD ) was
used as backbone polymer. The initiators were ben-
Table I. Grafting Results for Experiment GBDS-33
zoyl peroxide (BPO) and AIBN. To avoid phase
separation, the graft copolymerization was con-
ducted in dilute solution environment. In addition,
benzene was chosen as the solvent to avoid chain
transfer to solvent as much as possible. Reaction
temperature was kept constant at 60°C.
Except for the use of vinyl-PBD, all materials,
methods of purifications and solution preparations,
and details of the polymerization reaction process,
and sampling were exactly as those reported ear-
lier.'s2 The vinyl-PBD was purchased from Scientific
Polymer Products, Inc. (cat. no. 688). The com-
position of the PBD was 88%vinyl, 9% cis, and 3%
trans, as determined from the supplier. The molec-
ular weights measured by us via GPC are an
= 34,000, M w = 96,800, Mz = 327,800, &lW/Mn
= 2.85. These values are based upon calibration with
narrow molecular weight polystyrene standards ac-
cording to the details described earlier?
REACTION MECHANISM
A general scheme for free radical grafting in solution
polymerization is described below. It was described
more fully in a previous a r t i ~ l ebut
, ~ listed here for
ease of later discussion. Not included in the mech-
anistic relationships shown below are those related
to the specific use of chain transfer agents, and con-
sideration of chain transfer to initiator or monomer.

Monomer Graft Efficiency (%), Q, Table 111. Evaluation of k,,,, Values for the
Conversion Sty/vinyl-PBD/AIBN System
(%I Total c~s-PBD vinyl-PBD

9.48 6.05 0.41 5.64

18.31 5.80 0.44 5.36
27.12 6.25 0.49 5.76 100.0 0.0 15.450
31.92 6.42 0.52 5.90 50.0 0.0 7.251
37.34 6.70 0.58 6.12 5.0 0.0 0.874
44.34 8.66 0.68 7.98 0.5 0.0 0.106
 FUNDAMENTAL STUDIES OF GRAFTING REACTIONS. IV 2589

50 -
41304-
-5
h

R
40-
IP
a
Ig 3e+04-
.-
6

-
30-
:: 4
B 2e+04-

':
8 20-
Q v v v OMWQ
.................................
10- let04-
.......I""""' &"--"""'"d - = M,
"0 24 48 72
Reaction Time (hrs)
96 120 0i " 10 " 20 30
"

Conversion (%)
"40 "50

Figure 2. Conversion (%) versus reaction time (h) for
GBBA-33: (-) predicted, (0)experimental.
Initiator Dissociation and Polymer Chain
Initiation
1 'Zf2R'
R'+ MB % R - (MB);
Figure 3. Number- and weight-average molecular
weights (time-average value) versus % conversion for
GBBA-33: (-) predicted; (A)and (B) experimental
and M, , respectively.
for M,,
merization with a rate coefficient comparable with
kil. But the occurrence of the transfer reaction
(1) strongly effects the molecular weight of the polymers
(2)
obtained; more details will be discussed later.

PA' + MB 2 PA (MB); - (3) 2 (MB); + PA '* PA' + PBi

S+ M B s -~ (MB); (4) C PA - (MB); + PA PA' + P A - PBi

Polymer chains can be initiated by primary radicals c (MB);+s%s+PB~ (9)

R', backbone polymer radicals PA', or solvent rad- C P A - (MB); + S %! s' + PA - PBi
*
(10)
icals s' reacting with monomer MB. Reaction (3)
2 (MB); + PBj PB; (branched) + PBi
*
gives rise to a grafted chain, while the others initiate (11)
free polymer. C PA - (MB); + PBj
Graft Site Initiation
PB; (branched) + P A - PBi (12)

R' PA
+
-
b m l
PA'SR-H
C (MB); + P A 'FPA' + PBi
(5)
(6)
Chain Propagation Reactions
Both free and grafted chains are in the same envi-
ronment and are presumed t o grow at equivalent
C P A - (MB); + P A '2' PA' + P A - PBi (7) rates a s described by:

s'+ PA 'y4
PA' +S-H (8) 0.01 1
T h e rate coefficients for the attack of free [C
(MB);] and grafted [ C PA - (MB);] polymeric rad-
icals are considered to be equal since they involved
the same polymer radical end group. T h e relative
values of the rate coefficients in reactions (2)-(8)
may vary significantly because of the greatly differ-
ent species involved.

Chain Transfer Reactions 07

If transfer reactions occur, the rate of polymerization Figure 4. The molecular weight distribution at 27%
is not changed markedly, provided the radicals conversion for GBBA-33: (-) predicted, (- - -) exper-
formed upon transfer are able to reinitiate poly- imental.
2590 H U A N G A N D SUNDBERG

Od " 10 " 20 30
"

Conversion (%)
" 40 ' I
50 -0 10 20 30 40 50
Conversion (%)
Figure 5. Vinyl component graft efficiency (%) versus Figure 7. Vinyl component graft frequency versus con-
conversion (%) for GBBA-33: (-) predicted, (0)ex- version (%) for GBBA-33.
perimental values of @.

Termination reactions involving R',CTA', s', and I'

where (Mi); = C (MB); + C PA - (MB);.
Chain Termination Reactions
A termination reaction always involves two radicals,
reacting either by recombination or by dispropor-
tionation, both kinetically identical. Because of this
we only present the mechanistic expression for the
recombination mode, noting that the only difference
will be the molecular weight characteristics of the
dead polymer.
have been neglected given that their individual con-
centrations will be several orders of magnitude lower
than the polymeric radical species. For the same
reason, termination reactions involving PA' will be
neglected in the discussion given in the following.
In a previous articleg we have also derived, in de-
tail, equations for instantaneous graft efficiency.
Here, we will only briefly describe those equations.
When the grafted monomer is terminated by dis-
proportionation and/or transfer, the general equa-
tion for instantaneous graft efficiency 4 is:

2 (MB); + 2 (MB)J -% PBj, (14) In this termination mode, if the primary radical at-
2 PA - (MB); + 2 (MB)J 2 PA - PB,, (15)
tack dominates the grafting site formation, then @
can be simplified to:
2 PA - (MB); + PA - (MB); 2
PA - PBj+j - PA (16)

.:n.
0.125-

1
. .
3
.2 0.1 - 4

6
.- 9.2e+04
;r 0.075- Lt
% 5.8e+04-
0.05 -
....-*...*
*....- @ @
a
>
3 2.4e+04-
0.025 - -
...*-.
...*"@
...a'"-
&'
-le+044 I I I I I , , ,
O'O" 10
' ' 20
' ' 30
' ' 40
' ' 50 650 960 1no 1580 1890 2 Do
Conversion (%) Retention Time (sec)

Figure 6. Vinyl component graft ratio versus conver- Figure 8. GPC UV chromatogram of GBDS-32 a t 0,
sion (%) for GBBA-33: (-) predicted, (0)experimental. 11, 18,24, 32, and 41% monomer conversions.
 FUNDAMENTAL STUDIES OF GRAFTING REACTIONS. IV 2591

Table IV. Grafting Results of Experiment GBDS-32

Monomer Graft Efficiency (%), & 4et04-

Conversion a
(%) Total c~s-PBD vinyl-PBD ,g 3e+04-
bh
10.57 27.36 12.08 15.28 2e+04-
18.36
24.03
27.34
28.82
12.56
13.03
14.78
15.79 : .. .......... v
...-
B v v a , v
i= le+04 ................* a
32.03 28.41 13.76 14.65 ~

A fin
40.75 30.02 14.57 15.45
"0 10 20 30 40 50
Conversion ( Z )

If polymeric radical attack dominates, then: Figure 10. Number- and weight-average molecular
weights (time-average value) versus % conversion for
GBDS-32: (-) predicted; (A)and (B) experimental
for M,,
and Mu, respectively.

The data generated from a grafting experiment

When the grafted monomer is terminated by re-
combination, the general equation for instantaneous
graft efficiency 4 is:
In this termination mode, if the primary radical at-
tack dominates the grafting site formation, then 4
can be simplified to:
yields values of the time-average grafting efficiency,
8. The kinetic analysis leading to an expression for
8 is more involved than that for 4, as shown above,
and numerical integration methods are required.
These are detailed in our earlier article devoted to
kinetic rn~delling,~ and will not be repeated here.
However the relationships for 4 are very useful in
quickly analyzing grafting data obtained very early
in the reaction, preferably data extrapolated to zero
conversion.

DISCUSSION
cis-PBD and vinyl-PBD have different chemical
If polymeric radical attack dominates, then: structures as shown:

H H
I I
-c-c"....-. "....-.c-c=c-c"....-.
I
c=c
vinyl-PBD cis-PBD

In cis-PBD, the residual double bonds lie in-line with

50 - the main chain, while in vinyl-PBD, the double
bonds are pendant to the main chain. The weakest
bond in cis-PBD is the allylic hydrogen bond, while
in vinyl-PBD, it is the hydrogen bond located on
the carbon just above the pendant double bond.
Since this bond is located in both the allylic and
tertiary position, its bond energy should be weaker
than that of the allylic hydrogen bond in cis-PBD.
The radical of vinyl-PBD (formed by hydrogen ab-
straction) should be more stable than the allylic cis-
PBD radical. With these thoughts in mind, one
Figure 9. Conversion (%) versus reaction time (h) for should expect that the chain transfer to backbone
GBDS-32: (-) predicted, (0)experimental. reaction will be much more likely to occur when vi-
2592 HUANGAND SUNDBERG

U '
0 20 40 60
Conversion (%)

Figure 11. The molecular weight distribution at 18% Figure 13. Vinyl component graft ratio versus conver-
conversion for GBDS-32: (-) predicted, (- - -) exper- sion (%) for GBDS-32: (-) predicted, (0)experimental.
imental.

formed by hydrogen abstraction will become a

nyl-PBD is used as compared to when cis-PBD is
grafting site. When we conducted experiment
used. Furthermore, the radicals formed by chain
GBDS-32 (described in detail in the following sub-
transfer to vinyl-PBD will be more stable than the
section), which was a BPO/styrene/vinyl-PBD
allylic PBD radicals generated from cis-PBD. This
system, we found that the graft efficiency was much
chain transfer reaction process will almost certainly
less than that for the BPOlstyrenelcis-PBD system
lead to a decrease in the molecular weights of free
reported earlier.2 If radicals formed by chain transfer
and grafted polymer chains. The double bond in vi-
(in vinyl-PBD) can become graft sites, the grafting
nyl-PBD is in the pendant position, thus its reac-
efficiency of BPO/styrene/vinyl-PBD should be
tivity should be higher than that of the double bond
much higher than BPO/styrene/cis-PBD because
in cis-PBD, but much lower than that of a vinyl
the chain transfer reaction is much easier to occur
monomer. Thus, when either a primary or polymer
for vinyl-PBD than for cis-PBD. Additionally, we
radical attacks vinyl-PBD, it should be easier to add
observed a significant retardation in the reaction
through this double bond than to add to the double
rate for both styrene and methacrylate systems (this
bond in cis-PBD. Therefore, when vinyl-PBD is the
phenomena was not observed when cis-PBD was
backbone of interest, both hydrogen abstraction
used as backbone). Therefore, for the vinyl-PBD
(chain transfer) and double addition should be
backbone system, it appears that the radicals formed
easier to occur as compared to that when cis-PBD
by chain transfer do not become effective graft sites
is used.
(even for styrene) because they are apparently too
For vinyl-PBD, the radical formed by double ad-
stable to compete with polymer radicals for mono-
dition is always active enough to become a grafting
mer. Only the radicals formed via double addition
site. The question at this point is whether the radical
will become graft sites.

("I
60

I
10 20 30 40 50
Conversion (%)

Figure 12. Vinyl component graft efficiency (%) versus

conversion (76) for GBDS-32: (-) predicted, (0)ex- Figure 14. Vinyl component graft frequency versus
perimental values of +. conversion (%) for GBDS-23.
 FUNDAMENTAL STUDIES OF GRAFTING REACTIONS. IV 2593

Table V. Grafting Results of Experiment GBBA-22

5: 4.46et04- Monomer Graft Efficiency (%), @

a
v Conversion
.+
6 3.22e+04 -
.d
(%) Total cis-PBD vinyl-PBD
2
1.98et04-
9.50 59.66 5.95 53.71
a 23.95 62.59 6.02 56.57
> 36.25 62.64 6.10 56.54
5 7400-
45.40 59.97 6.17 53.80
56.52 60.44 6.27 54.17
Y l - -

650 960 127p 1580 1890 2200

Retention Time (sec)
Figure 15. GPC UV chromatogram of GBBA-22 a t 0,
10,24,36,45,57, and 64% monomer conversions.
Although reaction ( 2 4 ) will not generate graft sites,
it will consume both R' and [PA]. For polymer rad-
icals, we also separate the reaction between [MilT
and [PA] into following two reactions:
Since chain transfer and double bond addition
occur simultaneously and only double bond addition H
I
leads to grafting, we separate the reaction between %
.A
.. C' -c-c*
I I
R' and P A into following two reactions: c=o
I
0 +*c-c-
H
I
I
-k,m
-c-c
I
C'
I

0 L c=c c=o

I *c-c*
H
I
0I

e"..] 0

0,-0-c
I
C'
I
-
*c-c*
I
I
H

H
0
- [ M : l r + PA
C'
I
c=o
kvm3

H
PA' (double bond addition) (25)
[4,-

c=c I
-c-c* I I
I
C=N
vinyl-PBD
I 0 +-c-c* I k,_
AlBN
c C'
I I (3-L
\--I
c=c
c-c-c *C-H
I
( I

-
C=N
c=o
I
kprm 0 +*c-c*
R' + PA R-PA' (double bond addition) (23)
(y I
c=c
[M:],+ PA -
kma
inert radical + [M,],-H (chain transfer) (26)
BPO
C
I
1 + *C-C* I
I
H

c=c
-knp Here, only reaction (25) will generate a grafting site,
but this reaction won't affect molecular weight of
vlnyl-PBD
C=N
AlBN Table VI. Evaluation of kiprm3Values for the
Acrylate/vinyl-PBD/AIBN System

C
+ *c-c
I
I
C-C-H
c=c 15.0 5.0 100.0 93.97
I 15.0 5.0 50.0 84.56

-
C=N
15.0 5.0 20.0 62.07
R' + PA
km
inert radical + R-H (chain transfer) (24) 15.0 5.0 10.0 42.12
2594 HUANG AND SUNDBERG

80 -

h
70 -
60-
.# 50-
p 40-
d
8 30-
a-
10-

uLi 4 8 12 16 -07
Reaction Time (hrs)

Figure 16. Conversion (%) versus reaction time (h)for Figure 18. The molecular weight distribution at 24%
GBBA-22: (-) predicted, (0)experimental. conversion for GBBA-22: (-) predicted, (- - -) exper-
imental.

the free chains. Reaction ( 2 6 ) will not generate any where (ratioADD) is the fraction of free chains that
graft sites, but it will consume both [ M;]T and [PA], will be grafted onto cis-PBD by double bond addi-
and thus this reaction will directly affect reaction tion, and is equal to:
rate and molecular weight, and indirectly affect the
graft efficiency. When we performed the computa-
tional analysis, we used the same values of and
kitpfor the same initiator in different monomer sys-
tems. Since no reported ki value can be found for
different monomer systems, we assumed the same
kil value for different monomer systems,2 i.e., kil Similarly (ratiocomb)is fraction of free chains that
= 558 ( L / m o l / s ) .
will be grafted onto cis-PBD by recombination ter-
mination, and is equal to:
The instantaneous graft efficiency was calculated
as

If there is no recombination termination, then (ra-

tiocomb)will obviously be equal to zero. These rela-
tionships are complex and do not yield simple al-
gebraic expressions when the pseudo-steady-state

IU I
- 60 -
0 0 0 0 s g
3.$
d
- .05

40-
*
g
w 30-
t:
E3 let04 e
0
20-
A M, A d A
10-
uO 20 60
Conversion (ijO 3
Figure 17. Number- and weight-average molecular
weights (time-average value) versus % conversion for Figure 19. Vinyl component graft efficiency (%) versus
GBBA-22: 1-( predicted; (A)and (8) experimental conversion (%) for GBBA-22: (-) predicted, (0)ex-
and %w, respectively.
for M,, perimental values of @.
 FUNDAMENTAL STUDIES OF GRAFTING REACTIONS. IV 2595

1.5 1 u

1.25

.E:
i
1
2
t; 0.75
e
c 0.5

I I
20 40 60 650 960 1270 1580 1890 2'200
Conversion (x) ReLention Time ( s r r )
Figure 20. Vinyl component graft ratio versus conver- Figure 22. GPC UV chromatogram of GBBA-21 at 0,
sion (%) for GBBA-22; (-) predicted, (0)experimental. 14, 23, 37, and 43% monomer conversions.

radical concentrations are solved for. Thus our As the PBD backbone does not have a UV response
computations were done with the full kinetic model a t the 254 nm wavelength a t which the data of Figure
incorporating equations (27)-(29). The details of the 1 were obtained, the peaks between 900 and 1300 s
modelling have been described e l ~ e w h e r e . ~ of retention time represent the polystyrene grafted
onto the PBD. The major peaks between 1300 and
Grafting of Styrene 1800 s are due only to the ungrafted polystyrene.
Since the backbone polymer contains 9% cis, 3%
AIBN as Initiator trans, and 88%vinyl, we have to account separately
Figure 1shows the UV detector response for a series for the grafting due to the cis and trans. Here we
of samples withdrawn from experiment GBDS-33 assume cis and trans will have same grafting be-
(formulation shown below) in which not very much havior, and we used the kinetic model developed in
grafting is achieved, but more than that achieved in a previous article' to calculate the grafting associated
the cis-PBD system' where was 3-4%. with the cis and trans portion of the backbone. The
grafting results for experiment GBDS-33 are shown
[Backbone] = [vinyl-PBD] in Table I.
In order to determine the approximate values of
= 0.41 X 88%
kip,' and kiprm3,the following analysis is helpful. The
= 0.36 mol/L data from the above table show that the grafting
efficiency due to vinyl-PBD was between 5 and 6%
[Monomer] = [styrene] = 0.41 mol/L
a t early conversions. Using Tables I1 and I11 we list
[Initiator] = [AIBN] = 2.7 X mol/L the computed values of 6 (at zero conversion) de-
rived from the kinetic model under two sets of as-
[Solvent] = [benzene] = 10.52 mol/L
sumptions. The first is that the value of kiprmlis so
low that only polymer radicals initiate graft sites
(i.e., we set kiprml= 0). Then we compute 6 for a
variety of different values of kiprm3to find which one
yields 6 in approximate agreement with the data.

Table VII. Graft Efficiency in Experiment GBBA-21

Monomer Graft Efficiency (%),

Conversion
(%) Total c~s-PBD vinyl-PBD

14.75 60.70 7.92 52.78

23.33 60.59 8.95 51.64
36.95 61.04 9.01 52.03
Figure 2 1. Vinyl component graft frequency versus
40.17 61.20 9.04 52.16
conversion (%) for GBBA-22.
2596 HUANGAND SUNDBERG

u.uw

- 0.005-
.-
z 0.004-
E :. .
::.:..
*

3 0.003-

-..:....
6.-n
10.m-
c 0.001. ... ...
. - -...*-.-
a .

....-
6 12 18 24 07
Reaction Time (hrs)
Figure 23. Conversion (%) versus reaction time (h) for Figure 25. The molecular weight distribution a t 14%
GBBA-21: (-) predicted, (0)experimental. conversion for GBBA-21: (-) predicted, (- - -) exper-
imental.

In this case kiprm3 0.10-0.15 (L/mol/s). If we now

reverse the procedure and assume that only primary
radicals initiate graft sites (i.e., kiprm3= O), the value
of kiprmlthat leads to 5-6% grafting efficiency is just
under 50 (L/mol/s).
In a previous study,' we have shown that in the
AIBNlcis-PBDlstyrene system, kiprml= 0.1-1.0 (L/
mol/s) and kiprm3= 0.1 (L/mol/s). Since the reac-
tivity of the pendant double bond in vinyl-PBD is
higher than the double bond in cis-PBD, the values
of kiprml,and kiprm3should be higher than those in
the cis-PBD system, although not too much higher.
With this in mind and the values shown in Tables
I1 and 111, we determined that kiprml= 5.0 (L/mol/
s) and kiprm3= 0.10 (L/mol/s) were good values at
which to begin the search for the values of ki, and
ktrpn,as in reactions (24) and (261, respectively. This
search utilized our knowledge of the rate coefficients
for allylic hydrogen abstraction (via the AIBN and
polystyryl radicals) in cis-PBDY1both adjusted up-
ward to reflect the easier transfer reactions with the
vinyl group. With these starting points and the in-
dependent data sets of reaction rate, graft efficiency
and free polymer molecular weight, the search was
accomplished fairly quickly (we kept kiprml = 5.0 (L/
mol/s) and kiPrm3= 0.15 (L/mol/s) throughout the
search) resulting in:
kiprml = 5.0 (L/mol/s)
kitP= 15.0 (L/mol/s)
Kiprm3 = 0.15 (L/moI/s)
k,, = 0.70 (L/mol/s)
These rate coefficients all have the proper (approx-
imate) absolute and relative values, given that rad-
icals will more easily abstract the allylic hydrogen
than add through the double bond of the vinyl group
and both reactions are more easily accomplished
with the vinyl isomer than with the cis isomer. By
using these rate coefficients and initial reactant

2:
k 201
10
uO 10 20 30 40 50
Conversion (%) D
Figure 24. Number- and weight-average molecular
weights (time-average value) versus % conversion for Figure 26. Vinyl component graft efficiency (%) versus
GBBA-21: (-) predicted; (A)and (8) experimental conversion (%) for GBBA-21: (-) predicted, (0)ex-
for M,,
and M,,respectively. perimental values of @.
 FUNDAMENTAL STUDIES OF GRAFTING REACTIONS. IV 2597

1.25- 5: 7.8et04 -
3
.El 1- i

2 0.75- 6
.- 5.6e+04-
8
E 9 3.4e+04-
c5 0.5- c2
0.25 -
5 1.2e+04-

OF' 10
' ' 20
' ' 30
'
Conversion (%)
' 40
' ' '
50 650 960 1270 1580
Retention Time (sec)
1890 2200

Figure 27. Vinyl component graft ratio versus conver- Figure 29. GPC UV chromatogram of GBMA-10 a t 0,
sion (%) for GBBA-21: (-) predicted, (0)experimental. 5, 22, 51, and 64% monomer conversions.

concentrations of GBDS-33 in the computer pro-

gram, one can get the computational results for re-
action rate, grafting efficiency, grafting ratio, graft-
ing frequency and molecular weight.
The predicted and experimental reaction rate
profile are shown in Figure 2. The "normal rate"
curve was computed with the assumption that the
tertiary, allylic radial on the backbone [due to chain
transfer via reactions (24) and (26)] was as active
as that obtained via double bond addition [reactions
(23) and (25)]. The "retarded rate" curve calcula-
tions were made under the assumption that the ter-
tiary, allylic radicals were effectively inert relative
to the others. This retardation is real, and as shown
later in this article, it can be dramatic when using
the acrylic monomer. The average molecular weights
of the free polystyrene are shown in Figure 3 where
two points are evident. The first is that while ex-
cellent agreement between theory and experiment
is obtained for Mn, somewhat poor agreement is for
Mw.This difference was not experienced in our work
with cis-PBD backbone polymer. The second point
is that the molecular weight increases with conver-
I
sion. This is due to the long reaction times involved
and the corresponding large decrease in initiator
concentration, consistent with that seen with cis-
PBD backbone. A sample a t 27% conversion was
analyzed for molecular weight distribution and the
results are displayed in Figure 4.
The graft efficiency results (vinyl portion only)
are displayed in Figure 5 where the predicted results
quite adequately fit the data. Conceptually, 6 should
not be dependent upon conversion because graft site
initiation takes place predominantly by polymer
radical addition to the pendant vinyl group. But
again the significant lowering of the initiator level
with long reaction times leads to an increasing value
of 6.The data and computed values of display
this trend. The graft ratio is displayed in Figure 6
where the agreement is adequate. Predicted graft
frequency (graft and free chains assumed of equal
length), as shown in Figure 7, is low and suggests
that many backbone chains remain ungrafted. In all
of the above calculations, chain transfer to benzene
is not important when using styrene as shown ear-
lier.'
Table VIII. Graft Efficiency in Experiment
GBMA-10

Monomer Graft Efficiency (%), @

Conversion
(%) Total ck-PBD vinyl-PBD

4.93 15.14 1.19 13.95

O F ' 10
' ' 20
' ' 30
'
Conversion (%)
' 40
' ' '
50
22.40
38.14
15.58
19.21
1.21
1.23
14.37
17.98
51.45 19.54 1.26 18.28
Figure 28. Vinyl component graft frequency versus
64.26 20.46 1.29 19.17
conversion ( W ) for GBBA-21.
2598 HUANGAND SUNDBERG

4~04-
IS
a
& 3et04-

U '
0 3 6 9
Reaction Time (hrs)
12 15
U '
0 M *.
Conversion (%)
60 ' ti0

Figure 30. Conversion (%) versus reaction time (h) for
GBMA-10: (-) predicted, (0)experimental.
BPO as Initiator
Figure 8 shows the UV detector response for a series
of samples withdrawn from experiment GBDS-32
(formulation shown below) in which a significant
amount grafting is achieved
[Backbone] = [vinyl-PBD]
= 0.40 X 88%
= 0.35 mol/L
[Monomer] = [styrene] = 0.40 mol/L
[Initiator] = [BPO] = 2.7 X mol/L
[Solvent] = [benzene] = 10.51 mol/L
The grafting is obviously higher than that in the
AIBN system, but is lower than that in the cis-PBD/
BPO system.2 As before, we take out the grafting
due to the cis and trans components of the backbone.
We assumed there was no difference between graft-
ing on the cis and trans, and we used the kinetic
model developed previously2for the cis-PBD/BPO/
Styrene system to estimate the grafting from these
two components. The grafting results of experiment
Figure 31. Number- and weight-average molecular
weights (time-average value) versus % conversion for
GBMA-10: (-) predicted; (A) and (8) experimental
for Bnand M,,respectively.
described for the AIBN system, the following rate
coefficients provide the best fit:
kiprml= 50.0 (L/mol/s)
Kitp = 90.0 (L/mol/s)
kiprm3= 0.15 (L/mol/s)
K,, = 0.70 (L/mol/s)
By using these rate coefficients and initial reactant
concentrations of experiment GBDS-32 in the ki-
netic model, one can make predictions of all of the
important parameters.
The monomer conversion profiles are shown in
Figure 9 where the model is shown to do an excellent
job of predicting the reaction rate when the tertiary,
allylic radical is assumed to be relatively inert. The
molecular weight averages and distribution (at 18%
conversion) are shown in Figures 10 and 11,respec-
0.0175-
h

GBDS-32 are shown in Table IV. It is of interest to .-45 0.015-

point out that nearly half of the total grafting is due 2 0.0125-
LI

+
to the (cis trans) impurity of the backbone. With- 0.01
5g 0.0075-
.-
-

out the removal of this grafted material from our

consideration, greatly erroneous conclusions would v

g 0.005
be drawn about grafting onto the vinyl component.
The kiprmaand k,,, values found in the previous 0.0025 4 . .i \ ..
am..... L
AIBN system are used here because the polymer
radical is the same. Now we need some estimated
values of ki, and kiprmlfor BPO to fit the graft ef-
ficiency, reaction rate, and molecular weight of ex-
periment GBDS-32. In a manner analogous to that
 FUNDAMENTAL STUDIES OF GRAFTING REACTIONS. IV 2599

“0 20 40. 60 80
Conversion (%)

Figure 33. Vinyl component graft efficiency (%) versus Figure 35. Vinyl component graft frequency versus
conversion (%) for GBMA-10: (-) predicted, (0)ex- conversion (%) for GBMA-10.
perimental values of %.

tively. Note that in comparison to the AIBN system (formulation shown below) in which a high level of
as shown in Figure 3, the molecular weight averages grafting is achieved.
in the BPO system do not increase so greatly with
conversion. This is due to the longer half life of BPO [Backbone] = [vinyl PBD]
as compared to AIBN. = 0.18 x 88%
Turning to the graft properties (discounting those
+
due to the (cis trans) portion), Figure 1 2 shows = 0.16 (mol/L)
the graft efficiency and its slight variation with con- [Monomer] = [Benzyl acrylate] = 0.23 (mol/L)
version. The predicted values of @ agree quite well
with the data, as do the graft ratio predictions shown [Initiator] = [AIBN] = 2.7 X lop3(mol/L)
in Figure 13. The graft frequency is higher (Fig. 14) [Solvent] = [Benzene] = 10.58 (mol/L)
than that for the AIBN system (Fig. 7), and together
with the grafting due to the BPO attack on the (cis Considering the relatively low activity of the AIBN
+ trans) portion of the backbone, it accounts for the radical, these results suggest that polymer radical
great difference in graft levels achieved when using attack on the backbone must dominate graft initi-
the two different initiators. ation. Since this backbone contains 9%cis, 3% trans
and 88%vinyl, we have to substract the grafting due
Grafting of Benzyl Acrylate to the cis and trans components prior to analysis.
AIBN as Initiator Treating the cis and trans components as equiva-
lents, we used the kinetic model developed in a pre-
Figure 15 shows the UV detector response for a series vious paper’ for the cis-PBDIAIBNIBenzyl acrylate
of samples withdrawn from experiment GBBA-22 system to estimate the grafting from cis-PBD. There,
0.5

0.4
0 7 7e+04-
5 0.3
.c
v
1,
4

v..
d 6
.* 5et04-
g 0.2 3
3e+04-
E
>
3 le+04-

650 960 In0 1580 1890 i H)

Figure 34. Vinyl component graft ratio versus conver- Retention Time (sec)
sion (%) for GBMA-10: (-) predicted, (0)experimen- Figure 36. GPC UV chromatogram of GBMA-9 a t 0,
tal. 15, 27, 40, and 65% monomer conversions.
2600 HUANGANDSUNDBERG

Table IX. Graft Efficiency in Experiment GBMA-9

Monomer
Conversion
Graft Efficiency ( W ) , 9
5et04

,$ 4et04
a
4 V
(76) Total c~s-PBD vinyl-PBD ,g 3et04 0

15.32 37.03 9.14 27.89

b h l v v I
26.86 39.75 9.88 29.87
38.16 43.69 10.49 33.20 A

I
u
63.01 43.90 12.56 31.34 h
fi“ A &
68.21 44.66 13.40 31.26 I
I
20 40. 60 80
Conversion (%)
double bond addition was the dominant grafting re- Figure 38. Number- and weight-average molecular
action and it was necessary to consider chain trans- weights (time-average value) versus % conversion for
fer to solvent. The grafting results of experiment GBMA-9: (-1 predicted; (A) and (V)experimental
GBBA-22 are shown in Table V. Since we have for B,,
and M,,,,
respectively.
found the kiprmland kitp values for AIBN from the
previous styrene system, we used the same values
weight and graft efficiency data to search for an ap-
for this acrylate system:
propriate values of ktrpaand kiprm3,the best choices
for this system turn out to be:
kiprml= 5.0 (L/mol/s)
ki, = 15.0 (L/mol/s) kiprm3= 21.0 (L/mol/s)

Now, the polymer radical is different in this system,
so we needed to find kiprm3and ktrP,,values for this
acrylate system. To determine the approximate
value of kiprm3,the following analysis was used. The
data from the above table show that the graft effi-
ciency due to vinyl-PBD was between 50 and 53%
at early conversions. Using Table VI we list the
computed values of 4 (at zero conversion) derived
from the kinetic model with kiprml = 5.0 (L/mol/s),
kitP = 15.0 (L/mol/s) and, as a first approximation,
k,,, = 0.0 (L/mol/s). Values of 4 were computed for
a variety of different values of kiprm3to find which
one yields 4 in approximate agreement with the data.
Thus, the initial value of kiprm3is between 10 and 20
(L/mol/s). By using the reaction rate, molecular
ktrpa= 30.0 (L/mol/s)
By using these rate coefficients and initial reactant
concentrations of GBBA-22 in the computer pro-
gram, one can generate predictions to compare with
experimental data.
This system reacts very much more quickly than
styrene, and the acrylate reaction rate is shown in
Figure 16. When all radicals are assumed to have
equal reactivity, the “normal rate” predictions are
far in advance of the experimental data. When we
consider the double bond addition mechanism, and
assume the tertiary allylic radical to be inactive, the
calculated results fit the experimental data very well.

JVI

80 -
I

-s 0.007 -

.- 0.006-
70 - 4

I
2 0.005-
I

07

Reaction Time (hrs)

Figure 39. The molecular weight distribution at 64%
Figure 37. Conversion (%) versus reaction time (h) for conversion for GBMA-9: (-) predicted, (- - -) exper-
GBMA-9: (-) predicted, (0)experimental. imental.
 FUNDAMENTAL STUDIES OF GRAFTING REACTIONS. IV 2601

BPO as Initiator
60 4 I Figure 22 shows the UV detector response for a series
of samples withdrawn from experiment GBBA-21
(formulation shown below) which also displays high
graft levels:

2ol
t: [Backbone] = [vinyl-PBD]

10
= 0.18 X 88%

U '
= 0.16 mol/L
0 20 40. 60 80
Conversion (%) [Monomer] = [Benzyl Acrylate] = 0.23 mol/L
Figure 40. Vinyl component graft efficiency (%) versus
[Initiator] = [BPO] = 2.6 X mol/L
conversion (%) for GBMA-9: (-) predicted, (0) ex-
perimental values of @. [Solvent] = [benzene] = 10.57 mol/L

Although the monomer consumption due to grafting Treating these data in the manner described earlier
on the cis and trans components of the backbone is (i.e. substracting out the grafting on the cis and trans
only about 10% of that due to grafting on the vinyl components), the experimental cumulative graft ef-
component, the model calculations took the former ficiency for the vinyl component in experiment
into account. For that component we treat both the GBBA-21 are shown in Table VII.
allylic PBD radical and that resulting from double The rate coefficients have all been determined from
bond addition to the cis backbone to be equivalent cases described earlier in this article, and they are:
to the reactivity of the radical produced via double
bond addition through the pendant vinyl group. kiprml= 50.0 L/mol/s
Thus, of the four possible PA' radicals, we considered
only those resulting from hydrogen abstraction from ki, = 90.0 L/mol/s
the vinyl component [i.e., reactions (24) and (26)]
to be inert and thus leading to reaction rate retar-
kiprm3= 21.0 L/mol/s
dation. The molecular weight characteristics of the ktrpa = 30.0 L/mol/s
free poly(benzy1 acrylate) are shown in Figure 17
and 18. As in the styrene system, the M,,, is not pre- By using these rate coefficients and initial reactant
dicted very well indicating a broader distribution in concentrations of experiment GBBA-21 in the ki-
the data then anticipated by the model. netic model, we have made predictions for the graft
The graft polymer characteristics are displayed reaction characteristics described below. The first
in Figures 19-21 where the data represent the graft- of these is the speed of reaction as shown in Figure
ing on only the vinyl component of the PBD back- 23 where the retardation effect is quite dramatic.
bone. Although we could have adjusted kiprm3down- Because BPO produces a more active radical than
ward to obtain better agreement with the data, we
chose not to do so as its value needs to be the same
when BPO is used as the initiator. This is described
in the next section. The graft ratio data are pretty
well correlated by the model and the graft frequency
is projected to be very high at about 20 graft chains
per backbone chain.
This acrylate/AIBN/vinyl PBD system is per-
haps the best example of the influence of highly re-
active polymer radicals on graft copolymer forma-
tion. Obviously the AIBN initiator plays little or no
role in graft site formation, and if it were not for
chain transfer to solvent and the loss of active poly-
mer radicals in the creation of inactive tertiary allylic
backbone radicals, the grafting would have been even Figure 41. Vinyl component graft ratio versus conver-
more extensive. sion (%) for GBMA-9 (-) predicted, (0)experimental.
2602 HUANG AND SUNDBERG
does AIBN, the production of inactive tertiary allylic
radicals by the BPO and poly(benzy1 acrylate) rad-
icals is more evident in this system than in the pre-
vious one with AIBN. A comparison of the data and
rate curve in Figure 23 (for BPO) and 16 (for AIBN)
clearly demonstrates the sluggishness caused by this
enhanced production of rather inert radicals. The mo-
lecular weight characteristics of the free acrylate poly-
mer are shown in Figure 24 and 25, again indicating
a poor fit to the Mwdata. At this moment we have no
explanation for this unexpected lack of agreement.
Consistent with the dominant grafting mecha-
nism being the addition of the polymer radical
through the pendant vinyl group, the data and pre-
dictions for graft efficiency (vinyl component only)
are shown in Figure 26. As expected is invariant
with conversion level. The agreement between the
model and the data must be judged by taking into
account the results shown for the use of AIBN, as
in Figure 19. On balance, the predictions are judged
by us to be adequate. Graft ratio data are correlated
pretty well as shown in Figure 27. The graft fre-
quency (Fig. 28) is predicted to be slightly lower
when using BPO than for AIBN (Fig. 21), while the
graft ratios are nearly equivalent. This is accounted
for by the higher molecular weight produced with
the BPO initiator.
It should be kept in mind that the rate coefficients
used in this vinyl-PBD/BPO/benzyl acrylate system
were all determined from previous systems. The kitp
and kiprmlwere determined from the vinyl-PBD/
BPO/styrene system, while ktrpaand hiprm3were de-
termined from the vinyl-PBD/AIBN/Benzyl acry-
late system. Therefore, we contend that these rate
coefficients must be reasonable values in order to
lead to the excellent fit of the experimental data in
this vinyl-PBD/BPO/benzyl acrylate system.
Grafting of Benzyl Methacrylate
Consistent with our previous reports on the grafting
characteristics of several monomers onto C~S-PBD,'.~
we included here the results for benzyl methacrylate.
As expected, due to the intermediate nature of the
activity of the methacrylate polymer radical, the
grafting results with the vinyl backbone were be-
tween those obtained with styrene and benzyl ac-
rylate monomers when using either BPO or AIBN.
The nature of the results and our analysis for this
system are much like those for the other two mono-
mers, so we have tried to keep our discussion brief.
AIBN as Initiator
Figure 29 indicates the quantitative nature of the
overall grafting for experiment GBMA-10:
[Backbone] = [vinyl-PBD]
= 0.27 X 88%
= 0.24 mol/L
[Monomer] = [benzyl methacrylate] = 0.23 mol/L
[Initiator] = [AIBN] = 6.4 X mol/L
[Solvent] = [benzene] = 10.46 mol/L
In a manner consistent with our previous data anal-
ysis, the Table VIII describes the graft efficiency
related to the vinyl component alone.
The values for kiprmland ki, are the same as those
used earlier for AIBN attack on the vinyl PBD
backbone, i.e., 5.0 and 15.0 (L/mol/s), respectively.
Recognizing that the poly(benzy1 methacrylate)
radical is more active than the styryl radical, but
less reactive than the poly(benzy1 acrylate) radical,
the starting point in finding appropriate values of
kiprm3and ktrpowas straightforward. By using the in-
dependent sets of data for reaction rate, graft effi-
ciency and free polymer molecular weight to fit the
model to, we arrived at the following values for the
rate coefficients a t 60°C:
kiPrm3= 2.0 (L/mol/s)
k,,, = 5.8 (L/mol/s)
These compare appropriately with the correspond-
ing values for styrene and benzyl acrylate described
earlier.
The foregoing rate coefficients were used in the
kinetic model along with the above reactant con-
centrations of GBMA-10 to make predictions. As
seen in Figure 30, the retardation of the reaction
rate is much less than seen for the acrylate system
and very similar to the styrene case. Molecular
weight predictions (Figs. 31 and 32) are rather poor
in describing the width of the distributions (MW/M,,
z 3), consistent with the difficulties encountered
with styrene and benzyl acrylate. On the other hand,
the graft efficiency (Fig. 33) and graft ratio (Fig. 34)
predictions are in excellent agreement with the data.
The frequency of grafting shown in Figure 35 indi-
cates that above 50% conversion there are likely to
be few, if any, ungrafted backbone chains.
BPO as lnifiator
The impact of switching from AIBN to BPO is
clearly seen for experiment GBMA-9 (formulation
shown later) comparing Figures 36 and 29; grafting
efficiency was nearly twice as high when BPO was
 FUNDAMENTAL STUDIES OF GRAFTING REACTIONS. IV
used. By using the kinetic model developed
previously2 to remove the grafting on the (cis
+ trans) portion of the PBD, the modified data
shown in Table IX were obtained.
The values of all of the necessary rate coefficients
were obtained from other independent analyses re-
ported earlier in this paper. These are:
kiprml= 50.0 (L/mol/s)
ki, = 90.0 (L/mol/s)
kiprma= 2.0 (L/mol/s)
k,,, = 5.8 (L/mol/s)
To compare predictions with experiment we used
these values along with the following reactant con-
centrations of experiment GBMA-9;
[Backbone] = [vinyl-PBD]
= 0.27 X 88%
= 0.24 mol/L
[Monomer] = [benzyl methacrylate] = 0.23 mol/L
[Initiator] = [BPO] = 6.4 X mol/L
[Solvent] = [benzene] = 10.46 mol/L
Consistent with previous results, the retardation
of the polymerization reaction is more evident in the
vinyl system when using BPO than when using AIBN
(Fig. 37 compared to Fig. 30). The cumulative mo-
lecular weight averages decrease with conversion as
shown in Figure 38, but the molecular weight distri-
bution is significantly broader than predicted. Figure
39 shows how our predicted distribution is shifted to
the low molecular weight side of the data. The graft
efficiency is reasonably well predicted by the model
(Fig. 40),as is the graft ratio shown in Figure 41. We
consider all of these predictions (except A?,) to be
quite good considering none of the data for this sys-
tem were used to evaluate the rate coefficients.
CONCLUDING REMARKS
Vinyl-PBD has turned out to be a very interesting
backbone polymer to study. Because it could not
obtained it in a pure form, the grafting levels
achieved were due to a mixture of the isomeric forms.
Having previously studied the nearly pure cis-PBD
with all three monomers and two initiators, we were
able to separate out from the mixed data the con-
2603
tributions of each isomer (taking cis and trans to
be equivalent relative to grafting). The resulting
analysis of the grafting characteristics of the vinyl
component yielded the following conclusions;
Moderate to dramatic retardation in the re-
action rates for styrene, acrylate, and meth-
acrylate monomers are due to the production
of relatively nonreactive, tertiary allylic rad-
icals generated by chain transfer to backbone
polymer reactions.
Graft sites are predominantly formed via
double bond addition of free radicals, even in
the styrene system.
As in the case of cis-PBD, the type of initiator
( AIBN or BPO) is only important in deter-
mining the graft level when the polymer rad-
icals are not very active (styrene and to a
lesser degree, methacrylate) -little effect is
observed when active acrylate radicals are
involved, and
The rate coefficients for initiator and polymer
radical attack on the PBD backbone (through
the double bond and via hydrogen abstrac-
tion) have higher values for vinyl PBD than
for cis-PBD.
The authors are grateful for the financial support provided
by a consortium of industrial sponsors including Monsanto
Chemical Company, BF Goodrich, Inc., Imperial Chemical
Industries, Ltd. (now Zeneca, Ltd.) ,Rohm and Hass Com-
pany, S. C. Johnson, Inc., and Dow Chemical Company.
REFERENCES AND NOTES
1. N.-J. Huang and D. C. Sundberg, J. Polym. Sci. Part
A : Polym. Chem., 33, 2551 (1995).
2. N.-J. Huang and D. C. Sundberg, J . Polym. Sci. Part
A : Polym. Chem., 33,2571 (1995).
3. R. G. Bauer, R. M. Pierson, W. C. Mast, N. C. Beltso,
and L. Shepherd, Adu. Chem. Ser., 99, 251 (1971).
4. E. Farber and K. Marvin, Polym. Eng. Sci., 8,11(1968).
5. G. Riess and J. L. Locatelli, Adu. Chem. Ser., 142,
251 (1975).
6. J. P. Fischer, Angew. Macromol. Chem., 33,35 (1973).
7. D. J. Stein, G. Fahrbach, H. J. Adler, Angew. Macro-
mol. Chem., 38, 67 (1974).
8. N.-J. Huang and D. C. Sundberg, Polymer, 35,5693
(1994).
9. N.-J. Huang and D. C. Sundberg, J . Polym. Sci. Part
A : Polym. Chem., 33, 2533 ( 1995).
Received J u n e 23, 1994
Accepted March 16, 1995