Polymer Bulletin 30, 257-264 (1993) Polymer Bulletin

9 Springer-Verlag 1993

Synthesis of block copolymerswith poly(methylmethacrylate):

P(B-b-MMA), P(EB-b-MMA), P(S-b-B-b-MMA)
and P(S-b-EB-b-MMA)
Clemens Auschra* and Reimund Stadler**
Institut fQr Organische Chemie, Johannes Gutenberg-Universit~t, J. J. Becherweg 18-20,
W-6500 Mainz, Germany

Summary
Well-defined diblock copolymers poly(butadiene-b-methyl methacrylate) (= P(B-b-
MMA)) and triblock copolymers poly(styrene-b-butadiene-b-methyl methacrylate) (=
P(S-b-B-b-MMA)) have been prepared by sequential anionic polymerization in THF.
The synthesis of P(B-b-MMA) and P(S-b-B-b-MMA) was most efficient in the pre-
sence of lithium alkoxides. By this method side reactions are suppressed and the
polymerization can be performed at higher temperatures. The resulting triblock co-
polymers have narrow molecular weight distribution. The 1,2-PB midblock was
quantitatively hydrogenated with tosylhydrazide to enhance thermal stability. Alterna-
tively the hydrogenation can be performed at elevated pressure using hydrogen and
Wilkinson-catalyst in butanone. Heterogeneous catalyst systems based on Palladium
did not yield quantitative hydrogenation.

Introduction
Recently, much attention has focused on block copolymers which contain a PMMA
block in the field of block copolymer compatibilizers for polymer blends (1-4). PMMA
is compatibel with several important polymers like PSAN (= Poly(styrene-co-acrylo-
nitrile), PVC (= Polyvinylchloride) or PVF2 (= Polyvinylidenfluoride). In the course of
our work on polymer blends, we investigated in detail the compatibilizing capabilities
of P(S-b-MMA) block copolymers for blends of PSAN and PPE (= Poly-2,6-dimethyl-
1,4-phenylene ether) (5,6). This represents an amorphous blend system of the type
A/C-D/B, in which the blocks of the compatibilizer are chemically different from, but
thermodynamically miscible with the blend components. We extended this work to
systems, in which we use poly(styrene-b-ethylene-co-1 -butene-b-methyl
methacrylate) triblock copolymers (= P(S-b-EB-b-MMA)) as compatibilizers (7). Here
we report the synthesis and characterization of these block copolymers by sequential
anionic polymerization in the presence of lithium alkoxides and the quantitative
hydrogenation under conditions which preserve the narrow molecular weight distri-
bution.

* Present address: R6hm GmbH, Darmstadt, Germany

** Corresponding author
258

Experimental
Anionic Polymerization
Materials: All monomers and 1,1-diphenylethylene were reagent grade materials. Di-
n-butylmagnesium (MgBu2) was used as 0.5M solution in heptane, (AIEt3) as 1M
solution in hexane. THF was technical grade and purified first by distillation under
nitrogen from Call 2 and than refluxing over potassium. Styrene was predried with
Call 2 and condensed from MgBu 2 under high vacuum into teflon stoppered
ampoules. Butadiene was condensed onto MgBu 2, stirred for several hours and than
directly condensed into the reactor. MMA was predried with Call 2, carefully degas-
sed by freeze-thaw cycles in high vacuum, mixed with AIEt3-solution until a yellow
colour persisted and then condensed into ampoules (8). The glass ampoules with
the purified liquid monomers were stored at liquid nitrogen temperature until use. 1,1-
Diphenylethylene was purified by distillation from the deep red initiator solution with
n-BuLl under nitrogen and handled with syringes.
Equipment: The basic equipment consists of a 1,61 stirred glass reactor with a ther-
mostated cooling jacket, steal cappillary connections to introduce gases and sol-
vents and devices to measure temperature and pressure. Solvents were directly
introduced from the distillation apparatus into the reactor. Nitrogen was purified with
Hydrosorb- and Oxysorb-columns (Messer Griesheim). Monomers were introduced
from glass ampoules via a spherical joint. Initiator and capping agents were handled
with syringes.
P(S-b-B-b-MMA): In a typical procedure 20ml n-BuLl (1,4M in hexane) were added to
1200ml purified THF and aged at room temperature over night. On the next day, sty-
rene was introduced and cooled to -80~ The polymerization was initiated with n-
BuLl under vigorous stirring to give the orange solution of living PS. After 30rain
butadiene was condensed into the reactor and the colourless solution warmed up to
-10~ Depending on the molecular weight of the midblock, butadiene was polyme-
rized during 4-6h. Under these conditions most of the butadiene (> 90%) had reac-
ted. After this time an excess of 1,1-diphenylethylene was added to the solution. The
red colour gradually developed within minutes. After cooling down to -60~ MMA
was slowly added. The colourless solution was warmed to -40~ and stirred for l h to
complete the reaction. The triblock copolymer was terminated and isolated by preci-
pitation into MeOH. During the synthesis, aliquots of the PS block and the end-
capped P(S-b-B) intermediate were isolated for analytical purposes. About 80g of
polymer were produced by this technique.
P(B-b-MMA ): The reaction conditions were the same as in the case of P(S-b-B-b-
MMA). Butadiene was condensed to a solution of the initiator n-BuLl in THF with lithi-
um alkoxides at-40~ After the polymerization of butadiene at-10~ the PB block
was capped with 1,1-diphenylethylene. MMA was added at -60~ and polymerized at
-40~ for lh.
Hydro.qenations
Hydro.qenation with DiimLne: Reagent grade tosylhydrazide was used without
purification. Technical grade toluene was purified by distillation from sodium under
nitrogen. In a typical procedure 500ml toluene were first refluxed under a slow stream
 259

of nitrogen to remove traces of oxygen. After complete dissolution of 5g of polymer

and =50mg stabilizing agent (2,6-di-t.butyl-4-methylphenol), a 4-fold excess (relative
to double bonds) of tosylhydrazide was added and kept 4-5h to reflux. The bypro-
duct from the thermal decomposition of tosylhydrazide, p-toluenesulphinic acid pre-
cipitates from the solution. After dilution with 500ml toluene, the sulphinic acid is filte-
red off, the solution concentrated and the hydrogenated polymer isolated by preci-
pitation into excess methanol. Further purification from p-toluenesulphinic acid was
performed by precipitation of THF-solutions of the polymers into methanol.
Hydro,qenation with homoqeneous catalyst: The basic equipment was a 300ml labo-
ratory autoclave with magnetic stirring device, lg block copolymer with 50 mg stabili-
zing agent (2,6-di-t.butyl-4-methylphenol) were dissolved in 100-120ml butanone
(reagent grade). After adding the Wilkinson-catalyst tris(triphenylphosphine)-
rhodium(I)chloride (0.8 Mol% relative to double bonds), the hydrogenation was per-
formed at 90bar H2-pressure at 50~ for at least 24h. The hydrogenation is quantita-
tive without broadening of the molecular weight distribution. No attempts have been
made to determine the minimum amount of catalyst and the minimum time for com-
plete hydrogenation. The hydrogenated block copolymer was isolated by precipita-
tion into methanol. Complete removal of residual catalyst was achieved by filtration of
a 1% w/v THF solution of the block copolymer through a short column (lcm) of basic
AI203.
Analysis
Gel permeation chromatography (GPC) was performed in THF with a set of 10#m
PL-Gel-columns (105, 104, 103 and 102 ~) with refractive index and UV detection at
254nm. Calibration with PS-standards. Membrane osmometry: Hewlett Packard high
speed osmometer 502, the solvents were toluene, CHCl3 or THF. 1H_NMR: 200MHz,
CDCl 3
Results and discussion
Synthesis of P(S-b-B-b-MMA)
It is well-known that defined P(S-b-MMA) diblock copolymers can be prepared by
sequential anionic polymerization of styrene and MMA (9). The reaction is best per-
formed in polar solvents like THF at low temperatures. Under these conditions the
polymerization of MMA is living and essentially free from side reactions. After polyme-
rization of styrene at low temperatures, the living ends have to be capped with a sui-
table capping agent like 1,1-diphenylethylene in order to reduce the nucleophilicity.
Otherwise there will be significant termination by attack to the carbonyl groups of
MMA in the crossover step (10). Therefore the synthesis of P(S-b-B-b-MMA) by
sequential anionic polymerization should also be best performed in THF with capping
of the PB block.
The synthesis of P(B-b-MMA) diblock copolymers with 1,4-PB block is described
in literature (11,12). After the polymerization of the PB block in apolar Solvent like
cyclohexane or benzene, THF was added as cosolvent. In contrast to this, we per-
formed the whole synthesis of P(S-b-B-b-MMA) in THF according to the scheme in
Figure 1. Under these conditions predominantly 1,2-microstructure of the butadiene
block results.
260

~ Bu_~t~BulCH~CH]-CHE-CI-
Li
-80%
P §~"~.
~ ~lx1 [~ 1~176 / HC, / He,
L "~/_1•L CH2Jy.1 CH2

.u CHIC.
1)MMA HC/. ~ ~J I

Figure1: Reaction scheme for the synthesis of P(S-b-B-b-MMA) by sequential anio-

nic polymerization; DPE = 1,1-diphenylethylene
A problem arises due to the low stability of living PB in THF. Under the same reaction
conditions, living PB is much less stable in THF than living PS (13). Nevertheless the
rate of polymerization of butadiene is smaller than of styrene. Such behavior causes
problems with respect to the preparation of block copolymers because longer reac-
tion times favour termination.
In the first efforts to synthesize P(S-b-B-b-MMA) in pure THF, butadiene was
polymerized at low temperatures between -40~ and -75~ In each case significant
amounts of the block copolymers were terminated during or after the polymerization
of butadiene. For the preparation of defined P(S-b-B-b-MMA) without termination of
the P(S-b-B) intermediate, it was therefore necessary to optimize the reaction condi-
tions during the polymerization of butadiene.
Sigwalt et. at found that temperatures below -40~ are necessary for the
preparation of block copolymers with PB in THF (14). Bywater et. al showed that
strong dissociated inorganic salts like lithiumtetraphenylborate enhance the stability
of the carbanionic PB ends (13). In this case the polymerization is living up to higher
temperatures. Recently much attention has focused on the stabilizing effects of salts
like LiCI on the anionic polymerization of methacrylates and acrylates, which can
therefore be polymerized in living fashion at much higher temperatures (15,16).
Similar stabilizing effects on the polymerization of methacrylates, styrenes and conju-
gated dienes are also reported from alkoxides (10,17,18).
On the basis of the beneficial effects of alkoxides, we developed a simple pro-
cedure to synthesize well-defined P(S-b-B-b-MMA) triblock copolymers in the pre-
sence of lithium alkoxides. Organolithium compounds are not stable at room tempe-
rature in THF due to the attack on the ~-CH 2 group. By the pathways outlined in
Figure 2, alkoxides and enolates are formed by the reaction of organolithium com-
pounds with the solvent (19). We used the reaction of n-BuLl with THF at room tem-
perature to introduce lithium alkoxides into the reaction medium. This is simply
accomplished by aging a mixture of THF and n-BuLl at room temperature over night.
The concentration was about 0.025Mol Li + per 11THF.
 261

R-(CH2)4-OeLie
R-Li + 0

_ e~
Li~
Figure 2: Possible reaction pathways of organolithium compounds with THF (19).
Under the reaction conditions we used, the reaction products of n-BuLl with THF
showed no initiating capability for the monomers. Also no reaction with the ester
carbonyl groups of the PMMA block could be detected. Besides the convenience of
this procedure, it has also the advantage that traces of impurities in the reactor and
the solvent are eliminated by reaction with n-BuLl. In comparision to the LiCI-method
it is also not necessary to dry the salt by special procedures.
In the presence of lithium alkoxides, the polymerization rates were strongly redu-
ced. Especially the polymerization of butadiene and MMA took much longer. Due to
the stabilizing effect of lithium aikoxides, butadiene could be polymerized at higher
temperatures between -5~ and -15~ without termination. After capping of the PB
block with 1,1-diphenylethylene, MMA was polymerized at -40~ Under these condi-
tions well-defined P(S-b-B-b-MMA) triblock copolymers were synthesized without
significant amounts of terminated PS-homopolymer or P(S-b-B) intermediate. Under
the same reaction conditions defined P(B-b-MMA) diblock copolymers with 1,2-PB
block were prepared too.
PS PS PS
SB SB
SB
\ S SBM\

2'1 2'3
L, , ,~
25Ve/m127 2'3 2'5Ve/m12~7-2'1 :23 25Ve/m127

Figure 3: GPC analysis of P(S-b-B-b-MMA) triblock copolymers and the correspon-

ding precursors; peaks are normalized to same area.
Figure 3 shows the GPC analysis of different P(S-b-B-b-MMA) triblock copolymers
together with the corresponding PS and P(S-b-B) precursors. Table 1 gives the
analytical results of these block copolymers. The molecular weight of the PS precur-
sor can be accurately determined by GPC and membrane osmometry. Due to the PS
calibration the molecular weight (from GPC) of the P(S-b-B) intermediate and the tri-
block copolymers are too low. The most reliable molecular weights of the triblock
copolymers can be calculated from the molecular weight of the PS block and the
chemical composition determined from 1H_NMR. These calculated molecular weights
262

were in agreement with the results from membrane osmometry. According 1H-NMR
the PB midblock contains 90 Mol% 1,2-units.
Table 1: Analytical results of P(S-b-B-b-MMA) triblock copolymers
PS P(S-b-B) P(S-b-B-b-MMA)
Mn Mw/Mn Mn Mw/Mn Mn Mw/Mn Wps wpB WpMMA
SBM6
GPC: 80 1.04 (93) 1.06 (165) 1.11 0.45 0.06 0.49
Osrnometry: 88 96 225
SBM17
GPC: 100 1.05 (148) 1.06 (205) 1.10 0.48 0.17 0.35
Osmometry: 108 145 238

SBM38
GPC: 57 1.04 (135) 1.07 (189) 1.08 0.24 0.38 0.38
Osmosmetry: 64 175 245

The number after SBM denotes the weight fraction of the elastomeric midblock;
molecular weights in kg/Mol; in brackets: GPC molecular weights of the P(S-b-B)
intermediate and the triblock copolymer are too low due to PS-calibration; Wps, WpB,
WpMMA = weight fraction of the components determined from 1H-NMR
Hydro.qenation of P(S-b-B-b-MMA) with tosylhydrazide
The quantitative hydrogenation of P(S-b-B-b-MMA) was performed according the
method of Lenz at. at with tosylhydrazide in refiuxing toluene (21). The resulting P(S-
b-EB-b-MMA) triblock copolymers preserved the narrow molecular weight distribu-
tion. Fig.4 shows the GPC traces of the hydrogenated triblock copolymers in com-
parison with the unsaturated triblock copolymers.
A SEBM6 ~ SEBM17 SEBM38

-
D-1 11"J/ ll ]tI I ~176
SBM17 sBM3.A IIr 1
D=1.08

22 24 26 22 24 26 22 24 26Ve/ml

Figure 4: GPC analysis of P(S-b-EB-b-MMA) triblock copolymers (= SEBM) in com-

parison with the corresponding P(S-b-B-b-MMA) (= SBM); D = Mw/M n.
Small amounts of p-toluenesulphinic acid are incorporated into the elastomer mid-
block by electrophilic addition to the double bonds. From 1H-NMR, the fraction of
incorporated tosyl groups is estimated to be about 3 Mol% relative to double bonds
in accordance with literature data (21). Figure 5 shows the 1H-NMR spectra of the
P(S-b-EB-b-MMA) triblock copolymer SEBM38 hydrogenated with tosylhydrazide.
 263

According to a quantitative hydrogenation, the absorptions between 4.8 and 5.7 ppm
completely disappeared.
.L b
L ~L CH3Jy 'L ~
| |

~ 9
|

'" b P ~ t ......... g ......... ~ ......... 4 ......... 5 ......... ~......... i ......... 6

Figure 5: 1H-NMR analysis of the P(S-b-EB-b-MMA) triblock copolymer SEBM38

hydrogenated with tosylhydrazide.
CH3
B U4C H~-tOH~[(C H 2)4~H~0H2 - C--~- H
GPC: L ,CH2.JL LtL o J ~ J
OH3 OOH3
BM63
Mn= 84000 EBM63
D = 1.09"",, hydrogenated
/ D = 1.12

;l
22 24 26 28 Ve/ml j ~

' , . . . . , . . . . , . . . . , . . . . , . . . . , . . . . , . . . . , . . . . i . . . . , . . . . , . . . . , . . . . , . . . . L . . . . , . . . . , ,

ppm 6 5 4 3 2 1 0

Figure 6: 1H-NMRanalysb of the P(EB-b-MMA) diblock copolymer EBM63 hydro-

genated with Wilkinson-catalyst. Insert: GPC analysis of the unsaturated
and the hydrogenated diblock eopolymer.
264

Alternatively P(S-b-B-b-MMA) triblock copolymers and P(B-b-MMA) diblock copoly-

mers can also be quantitatively hydrogenated with hydrogen and Wilkinson-catalyst
in butanone (22). Representatively, Figure 6 shows the 1H_NMR and GPC analysis of
the hydrogenation of the P(B-b-MMA) diblock copolymer BM63 (63 wt% of PB).
Under mild reaction conditions (H2-pressure -- 90 bar, 50 ~ C), the hydrogenation is
quantitative without broadening of the narrow molecular weight distribution or other
detectable side reactions.
Attempts to use heterogeneous catalyst systems based on palladium in different
solvents at hydrogen pressures of 90bar gave no quantitative hydrogenation of P(S-
b-B-b-MMA) block copolymers. Best results were obtained with Pd/CaCO 3 and
Pd/1,AI20 3 in THF at 50-70~ (2 Mol% catalyst metal relative to double bonds). In
this case 85 Mol% of the double bonds were hydrogenated without side reactions.

Acknowled.qments
This work has been supported by the BMFT and BASF through joint project number
03M 40414 and by the German Science Foundation through Sonderforschungsbe-
reich SFB 262 - Glaszustand und Glas0bergang nichtmetallischer amorpher Materia-
lien.

References
1 Teyssie Ph., Fayt R., Jerome R. (1988) Makromol.Chem. Macromol.Symp.16:41
2 Brown H.R. (1989) Macromolecules 22:2859
3 0 u h a d i T., Fayt R., Jerome R., Teyssie Ph. (1986) J.AppI.Polym.Sci 32:5647
4 0 u h a d i T., Fayt R., Jerome R., Teyssie Ph. (1986) Polymer Commun. 27:212
5 Auschra C., Stadler R. (1992) Potym.Prepr. 33(2): 262, 264
6 Auschra C., Stadler R. Polymer, in print
7 Auschra C., Stadler R. in preparation
8 Allen R.D., Long T.E., McGrath J.E. (1986) Polym.Bull. 15:127
9 Allen R.D., Smith S.D., Long T.E. (1985) Polym.Prepr. 26(I): 247
10 M011erA.H.E (1989) Compreh.Polym.Sci 3:387
11 Helary G., Ladd B.J., Hogen-Esch T.E. (1987) Polym.Prepr.28(2): 318
12 Fayt R., Theyssie Ph. (1986) Macromolecules 19:2077
13 Garton A. Bywater S. (1975) Macromolecules 8: 694, 8:697
14 Gourdenne A., Sigwalt P. (1967) Europ.Polym.J. 3:481
15 Teyssie Ph., Fayt R., Hautekeer J.P., Jacobs C., Jerome R., Leemans L.,
Varshney S.K. (1990) MakromoI.Chem.MacromoI.Symp. 32:61
16 Varshney S.K., Bayard P., Jacobs C., Jerome R., Fayt R., Teyssie Ph. (1992)
Macromolecules 25:5578
17 Lochmann L., Kolarik J., Doskocilova S., Voska S., Trkoval (1979)
J.Polym.Sci.Polym.Chem.Ed. 17:1727
18 Lochmann L., M011erA.H.E. (1990) Makromol.Chem. 191:1657
19 Rembaum A., Siao S.P., Indictor N. (1962) J.Polym.Sci. 56:S17
21 Mango L.A., Lenz R.W. (1973) Makromol.Chem. 163:13
22 Mohammadi N.A., Rempel G.L. (1987) Macromolecules 20:2362

Accepted January 10, 1993 C