Block Polymer Preparation via Both Anionic and

Free Radical Polymerization

L. H. TUNG, G. Y. S. LO, and J. A. GRIGGS, Central Research Plastics

Laboratory, 1702 Building, The Dow Chemical Company, Midland,
Michigan .48640

Synopsis
A new method of block polymer preparation using combined anionic and free radical poly-
merization was investigated. In the method the first monomer was polymerized anionically.
The resulting polymeric anions were then reacted with a n episulfide to form a polymer with
mercaptan end-groups. This mercaptepolymer was mixed with a second monomer(s) in a n
inert solvent for the free radical polymerization. Conventional free radical initiation methods
were used to initiate the polymerization of the second monomer but because of the high chain
transfer constant of the mercaptan groups, a large number of the free radical chains would
grow from the first polymer to form a block polymer. Block polymers difficult or impossible
to make by direct anionic polymerization can thus be prepared. Several block polymers, in-
cluding the new thermoplastic elastomers, poly[(styrene-co-acrylonitrile)-b-butadiene-b-(sty-
rene-co-acrylonitrile)] and poly(bromostyrene-b-butadiene-b-bromostyrene)were prepared by
this method.

INTRODUCTION
Anionic polymerization is a convenient method for the preparation of
block polymers of well defined structure but unfortunately not all polymer
blocks of interest can be so prepared. For example anions of less basic nature
cannot initiate monomers that generate more basic anions.' Random co-
polymers therefore can never be prepared by anionic polymerization from
monomers which generate anions of different basicity such as styrene and
acrylonitrile. Anionic polymerization of halogen containing monomers can
only be done with great difficulties.' Block polymers of polybutadiene and
random copolymer of styrene and acrylonitrile @AN) which may have im-
portant use as reinforcing agents in ABS plastics will require preparation
methods of combined anionic and free-radical polymerization. Similarly a
diene block polymer containing a polybromostyrene (BrS)block which could
be an interesting thermoplastic elastomer will also require a combined
polymerization preparation.
Several methods of combined anionic and free-radical polymerization
have been proposed.24 In all of the methods, a polymeric free radical ini-
tiator is prepared by anionic polymerization. The polymeric initiator is then
used to initiate the free radical polymerization to form the block polymer.
Nonideal initiation efficiency, undesirable chain transfer reaction and un-
controllable self initiation of free radical monomers all contribute to the
presence of large amounts of homopolymers in these methods.
In this work we explored the feasibility of using a polymeric chain transfer
agent in place of polymeric initiators as the intermediate. Because block

Journal of Polymer Science: Polymer Chemistry Edition, Vol. 23, 1551-1568 (1985)
0 1985 John Wiley 8z Sons, Inc. CCC 0360-6376/85/051551-18$04.00
1552 TUNG, LO,AND GRIGGS

polymers of polybutadiene (PBD) are useful as thermoplastic elastomers

and as reinforcing agents for thermoplastics, polybutadienes with a mer-
captan group at one or both ends of the chains (mercapto-PBD or di-
mercapto-PBD) were selected as the chain transfer agents. They were
prepared by anionic polymerization and were then used in the subsequent
free-radical polymerization. The primary chains in the free radical poly-
merization were initiated by conventional free radical initiators. Some
homopolymer is expected to be produced but the high chain transfer con-
stants of the mercaptan group should allow a high yield of block polymers.

RESULTS AND DISCUSSION

Preparation of Mercapto-Polybutadiene
Two methods have been reported for making mercaptan-terminated poly-
mers: (1)by reacting the polymeric anions with elemental sulfur: and (2)
by reacting the same with an episulfide.1° The reaction of anions with sulfur
was studied by Brossas and his cO-workers"J2 who showed that the reaction
was complex and yields of over 60% would be difficult to achieve. We thus
chose the second method despite the fact that it had not been well studied.
The reaction of polymeric anions with the episulfides presumably proceeds
in accordance with

The conditions for the reactions, however, were not disclosed in the original
reference. Small amounts of polar solvents such as diethylether, tetrahy-
drofuran (THF) or triethylamine are known to have large effects on the
initiation and propagation rates in anionic polymerization. Morton and
Mikesell13 reported that in a 50/50 hydrocarbon-THF mixture, the initia-
tion of ethylene sulfide by the polyisoprenyllithium was very rapid at
-4O"C, whereas further polymerization of the ethylene sulfide monomer
took several more days. It appeared reasonable that the presence of THF
might also induce rapid and uniform capping of the polybutadienyllithium
chains. The effect of THF was therefore investigated with the other con-
ditions of the reaction.
Two sets of mercaptWPBD samples were prepared-one set at about
50,000molecular weight the other at about 110,000 molecular weight. The
anionic polymerization of 1,3-butadiene was conducted in benzene using n-
butyllithium as the initiator. Ethylene sulfide (ES) or propylene sulfide
(PPS) was then used to react with the polybutadienyllithium to produce
the mercapto-PBD. When used, THF was always added after the completion
of butadiene polymerization. The moles of THF used varied from 8 to 27
times the amount of the active anions; episufide used varied from 2 to 12
 BLOCK POLYMER PREPARATION 1553

times the stoichiometric amount. The temperature of the capping reaction

was varied from 7 to 50°C and lengths of reaction time from 10 to 60 mins.
Because there is no known method to analyze quantitatively the amount
of mercaptan end groups on long polybutadiene chains, the efficiency of
the capping reaction was evaluated indirectly by the amount of block poly-
mer produced in a subsequent free-radical styrene polymerization using the
following recipe: PBD or mercapto-PBD, 6.7%; styrene technical grade,
60.0%; chlorobenzene technical grade, 33.3%. Polymerization of styrene
was thermally initiated at 125°C in unagitated glass tubes. The compositions
of the products were analyzed by solvent e~tracti0n.l~ Preliminary results
showed that while unreacted PBD could be quantitatively extracted, the
separation of the homopolymer of styrene from the block and graft polymers
was difficult. The unreacted PBD as a percentage of total PBD in the feed
was therefore used as an indicator for the efficiency of the episulfide capping
reactions. The results of the capping reactions using PBD of molecular
weights near 50,000 are plotted in Figure 1. The upper curve which passes
through the two points for an uncapped PBD shows the extent of the grafting
reaction which occurred during the free-radical polymerization. The results
of the capping reactions using PBD of molecular weights near 110,000are
plotted in Figure 2.For the sake of comparison a pair of polymeric initiators
prepared by reacting the polybutadienyl anions with azobisisobutyronitrile
(AIBN) as in the method used by Vinchon, Reeb, and R i e ~ sNo . ~ distinction
of the runs made with various conditions are shown in Figures 1 and 2
except when THF was used. The analysis of the data showed that the other
conditions varied in the experiments had no systematic effect on the effi-
ciency of the capping reaction.
The above analytical results were supplemented by the visual observation
of the appearances of the polymerization mixture in the glass tubes. After
2 h polymerization at 125°C and upon quenching to room temperature, the

*n 1 \

'OI

"1
40 ! I I I I I I I I I I

0 2 4 6 8 10 12 14 16 18

Percent Conversion
Fig. 1. Unreacted PBD in thermal styrene polymerization: (*)
Blank PBD, (+)AIBN with
THF, (0)ES with THF, (A) PPS without THF, PPS with THF. PBD molecular weight
near 50,000.
1554 TUNG, LO, AND GRIGGS

Percent Conversion
Fig. 2. Unreacted PBD in thermal styrene polymerization:(*) (e)
Blank PBD, ES without
THF, (0)ES with THF, (A) PPS without THF, 0 PPS with THF. PBD molecular weight
near 110,OOO.

appearances of the runs using PBD of molecular weights near 50,000 were
as follows:

PBD Appearance
Blank uncapped Turbid, coalescing into two layers
Ethylene sulfide capped, with THF Bright clear blue
Ethylene sulfide capped, without Hazy dull blue
THF
Propylene sulfide capped, with and Hazy faint blue
without THF

The appearances of the runs using the higher molecular weight PBD were:

PBD Appearance
Blank uncapped Highly turbid
Ethylene sulfide capped, with THF Bright opalescent color
Propylene sulfide capped, with THF Bright opalescent color
Propylene sulfide capped, without Turbid no color
THF
AIBN capped, with THF Turbid no color

As polystyrene concentration increased during polymerization, polystyrene

and polybutadiene no longer could coexist as a single phase. Normally the
phase-separated mixture would be turbid as when uncapped blank PBD
was used. Block and graft copolymers are emulsifiers and when they are
present in sufficient amount, one of the two phases would be finely divided
 BLOCK POLYMER PREPARATION 1555

and suspended in the other. These finely divided phases scattered light and
give the bluish tint in the first table. These two phases can also assume
lamellar structure which diffract light and give the opalescent appearance
in the second table. Pure high-molecular-weight block copolymer prepared
directly by anionic polymerization have been reported to give the same
opalescent color in solution^.'^ The appearances of these reacting mixtures
were therefore indicative of the amounts of block copolymer produced and
they are in essential agreement with the results obtained by solvent ex-
traction.
The polymeric AIBN samples are shown to have a lower efficiency in
producing block polymers. Unfortunately, the polymeric AIBN had a higher
dissociation temperature than AIBN. The polymerization of styrene using
the AIBN capped PBD had to be conducted also at 125°C at which temper-
ature the thermal initiation was extensive. The comparison was therefore
not a true test of the relative merits of the two methods.
The graft reaction during the polymerization should be the same whether
blank or mercaptan-terminated polybutadiene was used. The extra amounts
of copolymer detected when mercapto-PBD was used must then be the block
copolymers during the polymerization. The results showed a beneficial effect
of THF in the mercaptan capping reaction. Variations in capping temper-
atures, amounts of THF, and amounts of episulfide used in excess, however,
were not critical. The reproducibility of PPS capping reactions appeared to
be better than that of ES capping reactions. The best capping results for
PPS and ES were surprisingly similar.

Chain Transfer Constants of the MercaptwPolybutadienes

According to reactions (1) and (21, capping with ES should produce a
primary mercaptan and capping with PPS, a secondary mercaptan. The
chain transfer constant of a primary mercaptan is normally higher and a
higher efficiency for block polymer formation should be expected at the
early stages of free radical polymerization. This, however, was not observed.
A possible explanation is that the PPS capping might not have proceeded
according to reaction (2). Morton and Kammereck16 reported that in pure
THF at dry ice temperature, ethyllithium and PPS reacted to give a primary
mercaptan in accordance with

/ \
S
CH3CH2-Li+ + CH,CH-CH, -78'C H+
--+

CH,CH,SH + CH,CH=CH, (3)

Thus, the PPS capping reaction could have produced primary mercaptan
end groups. Another possible explanation is that the ES capping reaction
itself was not efficient and making the efficiency of block copolymer for-
mation to be similar to that of secondary mercapton. Morton and Mikesell13
claimed that the dienyl anions metallated ES monomer in their attempt
to prepare butadiene-ES block polymers. To avoid the metallation reaction,
they capped the dienyl anions with PPS before the addition of ES monomer.
 TUNG, LO, AND GRIGGS

Sigwalt17 mentioned that reactions using ES were difficult to handle but

he attributed the problem to the difficulty in the purification of ES. It is
thus possible that ES capping might be inefficient.
To decide which of the two was the correct explanation, we measured
the chain transfer constants of the mercapto-PBD prepared from both e p
isulfides. Conventionally the chain transfer constant of a very reactive
molecule is determined from the rates of disappearance of both the transfer
agent and the monomer in a polymerization reaction.18The concentrations
of these species are easily followed by gas chromatographic analyses. When
the chain transfer agent is polymeric as in our case, the analysis is more
difficult. We decided to follow the reaction by measuring the molecular
weights of the polymers produced at two different stages of conversion.
From these molecular weights, the chain transfer constants were calculated
by iteration. The calculation scheme has been given earlier.lg In the scheme,
termination by coupling was ignored and the ratio of the rate of propagation
to the rate of termination was assumed to be constant with respect to
conversion and was modified only by the chain transfer reaction. Justifi-
cation of these two assumptions was demonstrated e~perimentallyl~ and is
in agreement with observations reported by othersaz2 that in thermal poly-
merization of styrene molecular weight is constant with respect to conver-
sion. These assumptions imply that at any moment of the polymerization
the distribution of molecular weight (or the degree of polymerization) fol-
lowed the most probable distribution and that in the absence of any added
chain transfer agents, the ratio of weight to number average molecular
weight was 2.
The three PBD samples used in the experiment were prepared in one
anionic reaction. The same polybutadienyllithium solution, while still ac-
tive, was divided into three portions. One portion was capped with PPS;
another with ES; and the third portion was terminated directly with acetic
acid. The capping conditions are listed in Table I.
The three PBD samples were then used in the thermal polymerization
of styrene in glass tubes at 125°C.Samples were recovered from the poly-
merization mixtures after 1 and 3 h of polymerization at which times 7.5
and 21.0% of the styrene monomer were polymerized. The conversion of
styrene monomer to polymer was determined by the total amount of poly-
mer recovered from the reaction mixture. Within experimental error all
runs gave about the same conversions at these times. The averages were
7.5 and 21.0%, respectively, and they were used in the calculations. The
molecular weights calculated from the chromatograms obtained from the
UV detector of a dual detector GPC were used as the molecular weights of
the polystyrene produced. The PBD segment in the polymer although in-
visible to the uv detector contributed nevertheless to the molecular weights
of the samples. But the contribution was negligible as the molecular weight
of the PBD segments was only about 5000. Table I1 shows the polystyrene
molecular weights and the chain transfer constants calculated from them.
Three of the four molecular weights determined for the blank PBD in
Table I1 agreed within experimental error indicating that the blank PBD
had negligible influence on the kinetics of styrene polymerization. Some
contaminating impurities must have been present in the run that gave
 F
TABLE I
8
w
Conditions for the Capping of Polybutadiene in Chain Transfer Constant Determinations cd
Anion 8
concentration Capping Capping agent Capping 2
Sample (mequiv/L) Molecular weight agent [mequiv/mequiv of anion)] conditions M
A 18.3 5180 PPS 5.9 TC,12 min
a
cd
THF 5.0
B 18.3 5180 ES 5.9 TC,12 min E3
THF 5.0 ?
C 18.3 5180 none - - N
5
8
Z

Y
1558 TUNG, LO, AND GRIGGS

TABLE I1
Chain Transfer Constants of ES and PPS Capped MercapbPBD in Thermal
Polymerization of Styrene at 125”CEthylbenzene (33% by Weight) Was Used as a Diluent

PBD/styrene Styrene
PBD conversion Polystyrene Chain transfer
sample Wt ratio Mol ratio (%) Mu constant
A 0.0103 0.000207 7.5 134,000 3.72
(PPS) 21.0 150,100
A 0.0530 0.00106 7.5 45,200 3.97
(PPS) 21.0 54,900
B 0.00787 0.000158 7.5 117,000 8.01
(ES) 21.0 144,000
B 0.0533 0.00107 7.5 34,300 (5.9)
(ES) 21.0 61,200 (3.0)
C 0.0109 0.000219 7.5 209,200
(blank) 21.0 251,800
C 0.0523 0.00105 7.5 244,800
(blank) 21.0 248,600

209,200 molecular weight. Because of the limited amount of the sample

available the run was not repeated and the 209,200 molecular weight was
not used in the calculation of chain transfer constants. In the calculation
a iterative procedure was used and a single chain transfer constant was
made to fit the molecular weights at the two different conversion levels.
In the first three cases in Table 11, the fit was within 2%. In the fourth
case, a good fit could not be made and a value was calculated from the
molecular weight at each of the two conversion levels. These two numbers
are shown in parentheses.
The average value of the chain transfer constant determined for the PPS
capped mercapto-PBD was 3.85 which is not too different from the literature
value of 3.2 reported for secondary octyl m e r ~ a p t a nThe
. ~ ~8.01 chain trans-
fer constant for ES capped PBD is much smaller than the 13-25 reported
by others23for primary mercaptans. It, however, is in agreement with the
value of 7.5 determined by one of us19 using the same molecular weight
matching method for the chain transfer of n-butyl mercaptan in styrene
polymerization.
Using the chain transfer constants determined above, we calculated the
theoretical percentage of unreacted PBD for the runs in Figure 2. Some of
the results in Figure 2. were replotted in Figure 3 together with the the-
oretical percentage of unreacted PBD. The theoretical curves included the
contribution from the grafting reaction. The experimental results for the
runs using PPS capped mercapto-PBD agreed well with the 3.85 chain
transfer curve. For ES capped mercapto-PBD, the efficiency is lower than
the 8.01 chain transfer curve.
The efficiency of the chain transfer reaction for mercapto-PBD was il-
lustrated also by the GPC chromatograms for runs shown in Table 11. The
chromatograms for two of the samples taken at the end of 3 h of styrene
polymerization are shown in Figure 4. The peak for the PPS capped mer-
capto-PBD disappeared almost completely whereas a sizable amount of the
blank PBD peak was still present.
 BLOCK POLYMER PREPARATION 1559

aES with THF

t P P S wlth THF

Fig. 3. Unreacted PBD in thermal styrene polymerization (comparison with theory): (0)
ES with THF, (*)PPS with THF. PBD molecular weight near 110,OOO.

Fig. 4. Refractive index detector GPC chromatograms of polymers recovered from thermal
polymerization of styrene in the presence of a 5180 molecular weight PBD. Upper curve: in
the presence of PPS capped mercaptc+PBD at 21% conversion of styrene. Lower curve: in the
presence of uncapped blank PBD at the same level of conversion.
1560 TUNG, LO, AND GRIGGS

The above results showed that the capping reaction of PPS proceeded
predominantly according to reaction (2) yielding secondary mercaptans and
the yield was nearly theoretical. The capping reaction for ES, was probably
equally efficient as the chain transfer constant of 8.01 determined when
low concentrations of the mercapto-PBD were used was in agreement with
the chain transfer constant determined by similar method for n-butyl mer-
captan. The lower than expected efficiency of the ES capped mercapto-PBD
in block polymer production thus cannot be attributed to either of the above
postulated explanations. More likely, some side reaction might have con-
verted the primary mercaptan to an inactive or a less active chain transfer
species during the free radical polymerization. The inconsistancy of the
chain transfer constants determined when higher concentrations of the
mercapto-PBD were used indicated that the effect of this side reaction could
be dependent on the mercapto-PBD concentration. The slightly sterically
hindered secondary mercaptans apparently were not affected by this same
side reaction.

Preparation of Triblock Polymers via Telechelic Dimercapto-

Polybutadienes
Table I11 shows the results of calculated polymer compositions from a
styrene polymerization using a feed of 50/50 by weight of styrene monomer
to a PPS capped dimercapto-PBD. The chain transfer constant used was
3.85 and the molecular weight of the PBD was assumed to be 60,000.
According to Morton et al.F4the properties of styrene-butadiene triblock
polymers (SBS) are more adversely affected by the presence of SB diblock
than by the homopolymer of styrene. In Table I11 at 80% conversion of
styrene, polystyrene present is 13.5% and the presence of diblock is down
to a negligible amount. Under such conditions a good thermoplastic elas-
tomer may be prepared directly from the dimercapto-PBD without using
any fractionation method to isolate the triblock polymer.
Experimentally, preparation of dimercapto-PBD required the use of a
difunctional organolithium initiator. For most of the runs described below
the difunctional initiator was the product from the addition reaction of sec-
butyllithium with 1,4-bis(l-phenylethenyl)benzene(I) or with bis[4-(l-phen-
yletheny1)phenyllether (11).

These difunctional initiators when freshly prepared are fine suspensions

in hydrocarbon solvents but will initiate butadiene polymerization if used
 TABLE I11 W
Calculated Polymer Compositions from a Thermal Styrene Polymerization Using a Feed of 50/50 by Weight of Styrene Monomer to a Telechelic P
DimercaptePolybutadienea
Styrene Product composition (%) % Styrene in block
8F4
Conversion Unreacted PBD cd
(%) (%) Triblock Diblock PS PBD Triblock Diblock Average 8
10 44.4 12.9 46.1 0.6 40.4 21.9 12.3 14.4 2
20 17.9 36.5 47.2 1.3 14.9 24.2 13.8 18.3 M
30 6.4 58.5 34.4 2.2 4.9 26.7 15.4 22.5 a
40 2.0 74.6 20.7 3.3 1.4 29.1 17.0 26.5 cd
50 0.5 84.3 10.6 4.8 0.3 31.5 18.7 30.0
60 0.1 88.6 4.5 6.9 0.1 33.5 20.1
70 0 88.8 1.4 9.8 0 35.0 21.2 ::::
80 0 86.2 0.3 13.5 0 35.8 21.8 35.8
90 0 82.3 0 17.6 0 36.1 22.0 36.1 ?I
100 0 78.3 0 21.7 0 36.1 22.0 36.1 8
Z
a Molecular weight of the dimercaptePBD was assumed to be 60,OOO and its chain transfer constant 3.85.
1562 TUNG, LO, AND GRIGGS

i m r n e d i a t e l ~In
. ~ ~some runs the adduct of sec-butyllithium with 1,3-bis(l-
phenyletheny1)benzene (111) was used.

This last difunctional initiator26is soluble in benzene, toluene, and cyclo-

hexane and can be kept at room temperature for days without losing its
activity.
Other conditions for the preparation of the dimercapto-PBD were iden-
tical to those used in the preparation of monofunctional mercapto-PBD
except that a longer time was allowed to complete the capping reaction as
stirring had to be stopped when gelation set in shortly after the addition
of PPS. The gelled mixture dissolved immediately when acetic acid was
used to convert the mercaptide dianions to polymeric mercaptans.
For the sake of obtaining larger samples for the physical property tests,
the free radical styrene polymerization runs were conducted in larger stain-
less steel tubes instead of the glass tubes used earlier. These stainless steel
tubes were heated in a heating block. Agitation again was not used. The
real temperatures and length of heating were not as precisely controlled
as were in earlier runs. The results are listed in Table IV.
Table IV shows that a rupture strength over 1500 psi and an elongation
over 700% were attainable for SBS triblock polymer prepared from PPS
capped dimercaptWPBD. Today, SBS prepared directly by anionic poly-
merization has rupture strength more than twice this amount. However,
when compared with the 1560 psi and 660% elongation for the early SBS
disclosed in the patent of Holden and Milko~ich:~these properties appeared
reasonable. Conversions and feed compositions as shown in Table IV had
a strong influence on the properties of the final product. The conversions
for these runs were not as reproducible as those for the glass-tube runs
reflecting the lack of control of in temperature and heating times in the
unstirred stainless tube reactors.
To evaluate whether the method was practical for the preparation of
novel block polymers, we prepared three other triblock polymers. They were
poly(methy1 methacrylate-b-butadiene-b-methyl methacrylate) or MMA-B-
MMA, poly[(styrene-co-acrylonitrile)-b-butadiene-b-(styrene-co-acryloni-
trile)] or SAN-MAN, and polyCbromostyrene-b-butadiene-b-bromostyrene)
or BrS-B-BrS. The first triblock, MMA-B-MMA, was chosen because prep-
aration by direct anionic polymerization was complicated and required sub-
zero temperatures for the end block polymerization.28The last two triblocks
were interesting as they cannot be prepared by direct anionic polymeriza-
tion. Because the chain transfer constants of the mercapto-PBD for these
systems are different from those in free radical styrene polymerization it
was necessary to adjust the feed compositions and other conditions. We had
not made a systematic study of the conditions required and the properties
 TABLE Iv
SBS Prepared Via Telechelic Dimercapto-Polybutadiene
Feed (wt %) Styrene polymerization
PBD Temp. Time Conversion Rupture Elongation
Solventa mol wt Styrene PBD Solvent (“0 (h) (%) (psi) (%)
~

BZ 72,000 15 15 70 130 24 49.3 238 775

BZ 82,000 15 15 70 130 24 56.3 182 613
BZ 72,000 15 15 70 130 40.3 85.1 781 563
BZ 82,000 15 15 70 130 40.3 76.8 851 533
BZ 60,000 20 20 60 125 24 gelled
EB 72,000 15 15 70 130 24 77.0 398 475
EB 82,000 15 15 70 130 24 61.9 419 613
EB 82,000 15 15 70 130 40.3 79.4 983 725
EB 54,000 15 15 70 130 41 72.5 629 362
EB 54,000 21 14 65 130 41 84.3 1507 700
EB 54,000 21 14 65 130 40 90.7 1340 700
~

a Bz = benzene, EB = ethylbenzene.

Y
1564 TUNG, LO, AND GRIGGS

of the polymers (all prepared in stainless steel tubes) shown in Table V

were evidently not at their optimum.
For SAN-MAN, thermal polymerization of the SAN block was not sat-
isfactory. Above 125°Cthe reaction mixture gelled easily. At 120°Cthe rate
of polymerization was too low. The runs reported in Table V were poly-
merized at 60-70°C using AIBN as the initiator. The rupture strength at-
tained was similar to SBS but the elongation was less.
Only a few runs were tried for MMA-B-MMA. The properties were all
poorer than SBS.
The easiest triblock to prepare was BrS-B-BrS. The poly(BrS)block could
be prepared thermally and also at lower temperatures using AIBN as the
initiator. The properties were equivalent to those for the SBS triblock pre-
pared from dimercaptePBD.
Several more SAN-MAN runs were made in a 1 L stirred glass flask.
The dimercapto-PBD was prepared in the same flask. After the capping
reaction and protonation, the reaction mixture was left standing overnight
under a nitrogen atmosphere. Styrene, acrylonitrile, and AIBN were added
the next morning and the free radical polymerization was carried out in
the same solvent and in the same flask. The results are tabulated in Table
VI .
In the one-reactor runs shown in Table VI, the relative amounts of the
monomers and dimercapto-PBD used were about the same as those in the
stainless steel tube runs. The overall concentrations were, however, lower
and the properties of the products were also poorer. Of the three solvents
used, toluene was definitely the best and cyclohexane the worst. In one of
the runs, an extra large amount of THF was used in the capping reaction
but the properties of the product did not differ. Capping with ES was shown
to be comparable to capping with PPS. This is in agreement with the earlier
results found in the capping efficiency studies.
The GPC chromatograms of all the polymers prepared in this section
were broad and contained multipeaks. These samples were not carefully
characterized. Some homopolymers were present and some grafting and
crosslinking reactions undoubtedly had taken place during the free radical
polymerization. Despite all these complications interesting new thermo-
plastic elastomers were prepared. A limit to the process appears to be the
hydrogen abstraction ability of the propagating radicals. If the tendency of
hydrogen abstraction is high, then gel will form and good product cannot
be prepared. Thermal SAN polymerization at above 125°C was a case of
such failure.
The molded pieces of all samples prepared in this section had an objec-
tionable sulfur odor. The expected linkage between the blocks should be
the sulfide bond which is expected to be stable during molding. The odor
more likely belonged to some low molecular weight sulfur compounds pres-
ent as impurities in the sample. We have not made any attempt to extract,
remove or identify them.

EXPERIMENTAL METHODS
Anionic polymerization of butadiene was carried out in a three-neck
round-bottomed flask. One of the three necks was connected to a nitrogen
 TABLE V
Triblock Polymers Prepared Via Telechelic DimercapWPBD (Polymerization Solvent Ethylbenzene)
Feed (wt %) Polymerization
PBD Initiator Temp. Time Rupture Elongtion
Triblocke mol wt Monomer PBD Solvent wt/100 g feed (OC) (h) (psi) (%) W
F
SAN-B-
SAN 56.000 15 15 70 AIBN 0.75 70 6 1617 267 8
R
SAN-B-
SAN 56,000 15 15 70 AIBN 0.75 70 4 1488 400
cd
SAN-B- 9
SAN 56,000 8.5 17 74.5 AIBN 0.43 70 6 879 400
SAN-B-
SAN 94,000 15 15 70 AIBN 0.75 70 2 853 333 B
SAN-B- cd
SAN 94,000 8.5 17 74.5 AIBN 0.85 70 4 1018 466 w
SAN-B- $i
SAN 94,000 15 15 70 AIBN 1.50 70 2 916 383
MMA-B-
MMA 85,000 6.7 13.5 79.8 AIBN 1.35 60 18 548 350
MMA-B- E;
MMA 85,000 9.8 13.1 77.1 AIBN 1.31 60 18 1055 300 Z
BrS-B-BrS 80,000 23.7 13.6 62.7 Thermal 115 6.5 330 410
BrS-B-BrS 80,000 31.8 12.1 56.1 Thermal 115 6.5 2714 348
BrS-B-BrS 80,000 31.8 12.1 56.1 AIBN 0.61 70 4 689 379
BrS-B-BrS 80,000 31.8 12.1 56.1 AIBN 0.30 70 6 1620 525
BrS-B-BrS 80,000 31.8 12.1 56.1 AIBN 0.45 70 6 1669 488
“ 3 / 1 (w/w)
styrene to acrylonitrile used in S A N - M A N runs.
 Y

TABLE VI
Preparation of SAN-MAN Via Combined Anionic-Free Radical Polymerization in One Reactor“
Dianion Capping condition Free radical condition Properties
Concn. mol Concn. Temp. Time PBD Monomer AIBN Temp. Time Rupture Elongation
z-8
Solventb (mmol/L) wt Asent (mequiv./L) (“C) (mid (wt %) (wt %) (wt %) (“C) (h) (psi) (%)
450 -z
BZ 1.34 57,000 THF 45.9 20 15 8.05 7.83 0.39 70 4 545
PPS 11.3 *
CYh 1.37 55,000 THF 45.9 25 45 8.80 8.78 0.28 70 6 208 62
PPS 11.3
3
To1 1.31 57,000 THF 45.9 30 20 8.10 8.08 0.33 70 5 1124 462 $2
PPS 11.3
To1 1.32 57,000 THF 229.7 25 60 7.98 7.96 0.33 70 5 1073 475 5
PPS 11.3 $
To1 1.32 56,000 THF 46.0 25 20 7.96 9.60 0.20 70 8 920 338
ES 9.8
8 3/1 (w/w) styrene to acrylonitrile used in all runs.
b Bz = benzene, Cyh = cyclohexane, To1 = toluene.
 BLOCK POLYMER PREPARATION 1567

bubbler through a condenser cooled by dry-ice. The nitrogen for the bubbler
was purified through a washing tower containing a tetraethylene glycol
dimethyl ether solution of sodium-naphthalene complex (0.2N). The center
neck of the flask was equipped with a stirrer through a precision ground
glass sleeve. The third neck was connected to the butadiene supply tank
through two purification columns (an alumina column and a column con-
taining the potassium form of a strong acid ionexchange resin). The round-
bottomed reaction flask had also a side arm. Through a rubber septum on
the side arm, solvents, initiator and capping reagents were introduced. All
glassware was baked at about 150°C for at least 18 h before use.
Rubber grade 1,3-butadiene monomer was purchased from Phillips Pe-
troleum Company. Both n-butyllium and see-butyllium were supplied by
the Foote Mineral Company. They were diluted to approximately 0.5N be-
fore use. Solvents (benzene, toluene, and cyclohexane) were “distilled in
glass” grade purchased from Burdick and Jackson Laboratory. Benzene and
toluene were dried with sodium ribbon. Cyclohexane was dried by passing
through an activated alumina column.
The preparation of the difunctional initiators and the precursor com-
pounds (I), (II), and (111) were described elsewhere.=s
The capping reactions were carried out in the polymerization flask im-
mediately after the completion of butadiene polymerization. The capping
reagents, ES and PPS, were purchased from Aldrich Chemical Company.
They were dried over calcium hydride and vacuum distilled before use. In
the preparation of polymeric initiator, AIBN from Dupont Company was
dissolved first in dry benzene (0.045 g/mL) before use. Distilled THF from
Burdick and Jackson Laboratory was dried by sodium-naphthalene complex
and vacuum distilled before use.
When ES was added to the butadienyllithium solution, a light yellow
color developed. A slight increase of viscosity was also observed (in mono-
functional reactions). When glacial acetic acid was added to protonate the
mercaptide anions, the color persisted and stayed with the polymer even
after it was recovered from the solution by precipitation with methanol and
vacuum dried. When THF was used during the ES capping, there was a
slight fading of the color from light yellow to pale straw. The pale straw
color was also visible in the recovered polymer. When PPS was used, a
similar color change was observed but upon protonation the color disap
peared completely and the recovered polymer was colorless. When AIBN
solution was used, a bright yellow color developed. The color disappeared
also upon protonation and the final polymer was colorless.
Glass tubes of 0.5-in. diam. were used for the thermal polymerization of
styrene. The feed was premixed and about 10 mL was used for each tube.
The tube was then purged with nitrogen and capped with a rubber septum
and then placed in a 125°C silicone oil bath. A 25-gauge hypodermic needle
was inserted through the septum to relieve the pressure during initial
heating. After 10 min in the oil bath, the needle was removed.
The stainless steel tube used for the free-radical polymerization had a
O-ring sealed cap at each end. The high viscosity product of the polymer-
ization could thus be easily pushed out of the tube when the caps were
removed. The capacity of the tube was 75 mL. The tube was filled with the
 TUNG, LO, AND GRIGGS

feed mixture to about three-fourths full and was sealed after purging with
nitrogen. A heating block with holes of the same diameter as the stainless
steel tubes was used for heating.
The monomers used in the free-radical polymerization were all technical
grade. No attempt was made to remove stablizers and other impurities in
them.

We are grateful to Professor G. Riess of h o l e Nationale Suptirieure de Chime de Mulhouse

for valuable discussions relating to this work.

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Received February 8, 1984
Accepted October 18, 1984