Synthesis of high aspect ratio bisphenols and polycarbonates incorporating bisaryl units

Article abstract of DOI:10.1021/ma048616m

Theoretical arguments linking monomer geometries to polymer fracture strengths and melt flow properties provide the rationale for design of a series of isomeric, high-aspect ratio bisphenols and new polycarbonates. An efficient synthesis of these monomers

Full text of DOI:10.1021/ma048616m

3622
Macromolecules 2005, 38, 3622-3629
Synthesis of High Aspect Ratio Bisphenols and Polycarbonates
Incorporating Bisaryl Units
David A. Boyles,*,† Tsvetanka S. Filipova,†,‡ John T. Bendler,§
Guy Longbrake,†, and Josiah Reams†,|
Department of Chemistry and Chemical Engineering, South Dakota School of Mines and Technology,
Rapid City, South Dakota 57701, and Physics Department, United States Naval Academy,
Annapolis, Maryland 21402
Received July 8, 2004; Revised Manuscript Received September 30, 2004
ABSTRACT: Theoretical arguments linking monomer geometries to polymer fracture strengths and melt
flow properties provide the rationale for design of a series of isomeric, high-aspect ratio bisphenols and
new polycarbonates. An efficient synthesis of these monomers in addition to an optimal triphosgenation-
based method for the synthesis of high molecular weight polycarbonates is presented. Preparation and
polymerization of o-, meta-, and p-tetraaryl bisphenol A are reported, in addition to glass transition
temperatures of the new polycarbonates. In accordance with expectations, the p- and m- isomers form
ductile, amorphous high-heat films, while the o-isomer produces a relatively low-Tg brittle glass.
Introduction
For over 50 years, efforts to understand the molecular
origin of bisphenol A polycarbonate’s solid-state ductility
have continued, although progress to date is limited and
useful structural criteria to guide the design of new high
impact polycarbonates are lacking. The remarkable
success of bisphenol A-polycarbonate (BPA-PC) (Fig-
ure 1) derives from the versatility of its applications
which are a function of its properties, including trans-
parency, heat resistance, and excellent impact tough-
ness. The present work is part of a program designed
to elucidate the role played by overall monomer shape
as a factor influencing ductility.
Ductility necessarily requires that stored elastic
energy can be successfully released by diffuse nonlocal
shear flow before craze formation and breakdown
culminate in brittle failure. All glassy thermoplastics
are ductile in compression and conversely, all glassy
thermoplastics are brittle when the cavitational stress
is sufficiently large relative to the shear stress, implying
that ductility ultimately reflects the relative ease of
shear flow vs the ease of crazing.1,2 As is true in metals,
shear flow in glassy thermoplastics requires solid-state
atomic and molecular motions, and realization of this
fact has spawned a host of studies characterizing local
motions in polycarbonates,3-6 especially the low-tem-
perature dynamic mechanical γ process in BPA-PC and
its homologues, in the expectation that the γ process is
associated with if not responsible for polycarbonate’s
ductility and toughness.
Figure 1. Molecular structure of bisphenol A-polycarbonate
(BPA-PC).
polycarbonate to exhibit ductility;5,7 (b) with modifica-
tions in chemical structure, room-temperature yield
stresses of BPA-based thermoplastics8 vary from a low
of about 45 MN/m2 (for BPA-formal) to a high of nearly
95 MN/m2 (for tetramethyl BPA-PC), or an overall
variation of approximately a factor of 2. In contrast,
critical strains to initiate dry crazes ꢀc in the same group
of thermoplastics vary from a low of 0.5% (in BPA-
formal) to a high of 2.9% (in BPA-arylate-carbonate
copolymers) for an overall variation of nearly a factor
of 6.8 Thus, in this particular group of thermoplastics,
ease of craze initiation shows nearly three times as large
a variation with chemical structure modification as does
the ease of yielding. It is likely, therefore, that the
molecular factors which influence crazing contribute at
least as much to mechanical toughness as does the
dynamic mechanical γ process.
Both theory and experiment indicate that the fracture
strength of glassy polymers is strongly influenced by
monomer geometry and chain flexibility. For example,
Vincent9,10 found from a study of synthetic fibers that
the tensile brittle strengths of thermoplastics could be
correlated with the molecular cross sectional areas
(MCSA) of the polymer chains. In particular, he found
that the smaller the MCSA of the chain, the greater was
the brittle strength of the polymer. Vincent explained
this finding by suggesting that thinner chains could
pack more closely together, so that when a fracture
surface is created in the glassy polymer more chains will
pass through each element of the surface (per unit area)
in the case of a thin chain than will do so for a thick
chain. Since the difficulty of creating a fracture surface
should increase as the number of chain backbones
passing through the surface increases, thinner mono-
mers (with higher backbone densities) should exhibit
higher brittle strengths.
However, systematic studies of both low-temperature
motions and yield stresses σy of a wide variety of
engineering thermoplastics suggest that the connection
between the γ process and ductility is incomplete: (a)
a facile low-temperature γ process is apparently neces-
sary but not a sufficient condition for a particular
* Corresponding author. E-mail: David.Boyles@sdsmt.edu.
† South Dakota School of Mines and Technology.
‡ E-mail: Tsvetanka.Filipova@sdsmt.edu.
§ United States Naval Academy.
E-mail: guylongbrake@yahoo.com.
| E-mail: jreams1@juno.com.
10.1021/ma048616m CCC: $30.25 © 2005 American Chemical Society
Published on Web 03/30/2005

Macromolecules, Vol. 38, No. 9, 2005
Synthesis of High Aspect Ratio Bisphenols 3623
A more recent and possibly more cogent argument for
a relationship between monomer geometries and glassy
polymer fracture strengths is provided by the discovery
that the entanglement molecular weight of a polymer,
Me, is related by a power law to p, the packing length
of the polymer species.11,12 The packing length of a
Figure 2. Molecular structure of tetraaryl bisphenol A-poly-
carbonate (TABPA-PC).
11,13
polymer is defined by
TABPA (bis[4-(4-hydroxyphenyl)phenyl]propane) was
first synthesized from bisphenol A by Bendler et al.17,18
in a process that utilized the Stille19 cross-coupling
reaction. Interfacial and solution polycondensation of
TABPA with BPA and phosgene to prepare copolycar-
bonates (coPCs) was also reported. These copolycarbon-
ates contained approximately 25-75 mol % of TABPA
units and were ductile with glass transition tempera-
tures 30-40 °C higher than that of BPA-PC .
More recently, palladium-catalyzed cross-coupling
reactions have enjoyed favor for the construction of
Caryl-Caryl bonds.20 The Suzuki21 reaction, for example,
uses an organoboronic acid as one reaction partner.
TABPA itself has recently been synthesized by such a
modified Suzuki procedure using a diarylborinic acid
and Fu’s22 catalyst system, resulting in a higher yielding
synthesis for this particular monomer.23 Distinct draw-
backs of this method, however, included the tedious
preparation of a commercially unavailable and unstable
diarylborinic acid, its difficult separation from the
contaminating arylboronic acid and its anhydride byprod-
ucts, and the use of an expensive, liganded Suzuki
procedure requiring strict exclusion of both oxygen and
water.
We report below a facile three-step route for the
synthesis of bis[4′-(4-hydroxyphenyl)phenyl]propane
(TABPA) applicable also to its o- and m-isomers, the key
step being a ligandless Suzuki aryl coupling reaction
which proceeds in aqueous media.24 Polycondensation
results of TABPA with different dihydroxydiaryl com-
pounds using triphosgene to prepare copolycarbonates
by solution and interfacial methods are also reported.
Preliminary results indicate that polymers formed from
the p- and m- isomers are ductile, while those from the
o-isomer are brittle, in accordance with theoretical
expectations.
VC
R2
M
MCSA
lk
p )
)
)
(1)
[ R2 0FNa]
0
where M is the molecular weight of the chain, Na is
Avogadro’s number, R2 is the mean-squared unper-
0
turbed end-to-end distance, F is the density of the
polymer, VC is the chain volume, MCSA is the molecular
cross sectional area of the chain, and lk is the Kuhn
segment length of the polymer. Equation 1 shows that
p is a local quantity independent of molecular weight
and that it is proportional to the molecular cross
sectional area, MCSA. The relationship between p and
Me is given by11
Me ) FNant2p3
(2)
where nt (approximately a constant equal to 21) corre-
sponds to the number of entanglement strands in a cube
having the dimensions of the tube diameter, dt. Though
the packing length-Me relation of eq 2 was established
from melt and solution properties,11,12 it is generally
agreed that a polymer glass inherits its entanglement
structure from the melt, so that eq 2 should also hold
below the glass transition Tg. Equations 1 and 2 imply
a connection between the chain packing length p and
glassy state toughness. Craze strengths are known to
be proportional to entanglement densities.14 Craze
extension ratios decrease and craze fibril diameters
increase as the entanglement molecular weight Me
decreases, and therefore (according to eq 1) crazes
should become tougher as the chains become thinner.14-16
The present article reports the synthesis of high
aspect ratio (and therefore low MCSA and low p)
bisphenols containing one or more bisaryl units and the
polycarbonates made from these materials. The present
research is part of a broader study to explore the
hypothesis that small packing length (or small MCSA)
polycarbonates will display improved ductility and
toughness. Mechanical properties of these new materials
will be reported separately.
Historically, considerable effort has been directed
toward the synthesis of modified polycarbonates with
larger packing lengths and smaller aspect ratios than
BPA-PC, in particular those from bisphenols with
bulky side group substitutions at the isopropylidene
unit.6,7 These common bisphenols have tended toward
sphericity, rather than elongation, giving them rela-
tively lower aspect ratios. Consequently, these bulky
bisphenols have resulted in polycarbonates which were
invariably less ductile than BPA-PC. In contrast, the
relatively high aspect ratio bisphenol “tetraaryl BPA”
(TABPA)sso named by us as it is an analogue of BPA
having four aryl rings rather than the two found in
bisphenol Ashas been synthesized17,18 and appears to
be an attractive prototype of a new class of high aspect
ratio, small packing length p monomers, although the
original synthesis was laborious and difficult to scale
up. The molecular structure of the polycarbonate formed
from TABPA is shown in Figure 2.
Experimental Section
Materials. 2,2′-Diphenylpropane (99%), [bis(trifluoroace-
toxy)iodo]benzene PhI(OCOCF3)2 (97%), iodine (99.5%), pal-
ladium(II)acetate (Pd(OAc)2) (99.9%), potassium carbonate (K2-
CO3) (99+%), 3-methoxyboronic acid (m-CH3OPhB(OH)2) (95%),
2-methoxyboronic acid (o-CH3OPhB(OH)2) (95%), triphosgene
(98%), benzyltriethylammonium chloride (BnNEt3Cl) (99%),
sodium hydroxide (NaOH) (97%), bisphenol A (99+%), and 4,4′-
(hexafluoroisopropylidene)diphenol (HFBP) (97%) were pur-
chased from the Aldrich Chemical Co. and used as received.
4-Methoxyphenylboronic acid (p-CH3OPhB(OH)2) (95%, Op-
tima Chemical Group, LLC), pyridine hydrochloride (Py.HCl)
(97+%, Avocado), and 2,2′-(4-hydroxyphenyl)-1,1-dichloroeth-
ylene (BPC) (98%, Chemical Synthesis & Engineering Labora-
tory GE) were used as received without further purification.
All solvents were dried and purified by standard procedures.
Instrumentation. IR spectra were determined on a BIO-
RAD FT-40 spectrophotometer, using KBr pellets. 1H NMR
and 13C NMR spectra were recorded with a GE-QE300 operat-
ing at 300 or 75 MHz, respectively. 1H and 13C chemical shifts
were reported as δ values (ppm) relative to CDCl3 (7.24) or
DMSO-d6 (2.49). Elemental analyses were obtained from
Midwest Microlab, LLC, Indianapolis, IN. Reactions were
monitored by thin-layer chromatography (TLC) performed on
Kieselgel 60 F254, 0.2 mm plates (Merck) with visualization
under UV light (254 or 366 nm).

3624 Boyles et al.
Macromolecules, Vol. 38, No. 9, 2005
Molecular weights were determined using a Shimadzu
HPLC instrument comprised of an LC-10AD pump, SIL-10AF
autosampler, with an injection volume of 50µL, followed by
two PL gel 5um Mixed-D columns in series maintained at 35
°C in a Shimadzu CTO-10A column oven. All polymer samples
were prepared in HPLC-grade THF at concentrations at or
near 1 mg/mL, and the flow rate was maintained at 1 mL/
min. Degassed HPLC-grade THF served as mobile phase for
polymer characterization. Detection was by a Wyatt miniDawn
light scattering photometer followed in-line by a Wyatt Optilab
DSP differential refractive index detector at 690 nm. Astra
software was used for data collection and calculation of
absolute molecular weights.
Synthesis of 2,2-Bis(4-iodophenyl)propane, I)BPA, 2.
A suspension of 2,2′-diphenylpropane (29.40 g, 149.8 mmol),
iodine (38.10 g, 150.1 mmol), and PhI(OCOCF3)2 (68.80 g, 160.0
mmol) in tetrachloromethane (600 mL) was stirred at 50-55
°C for 1 h. After cooling to room temperature, the suspension
was concentrated under reduced pressure. The cloudy white
residue was recrystallized from ethanol (53.70 g, 80.02%)
giving white needles. 1H NMR (300 MHz, CDCl3): δ 7.56-7-
59 (d, J ) 8.6 Hz, 4H, ArH), 6.92-6.96 (d, J ) 8.6 Hz, 4H,
ArH), 1.61 (s, 6H, CH3). Anal. Calcd for C15H14I2: C, 40.21; H,
3.15; I, 56.64. Found: C, 40.10; H, 3.12; I, 56.53.
3025, 2932, 2834, 1596, 1581, 1514, 1486, 1436, 1397, 1360,
1260, 1234, 1109, 1028, 836, 761. 1H NMR (300 MHz, CDCl3):
δ 7.50-7.53 (d, J ) 8.4 Hz, 4H, ArH), 7.31-7.36 (m, 6H, ArH),
7.16-7.18 (d, J ) 7.7 Hz, 2H, ArH), 7.12 (s, 2H, ArH), 6.86-
6.89 (d, J ) 8.2 Hz, 2H, ArH), 3.85 (s, 3H, OCH3), 1.75 (s, 6H,
CH3). 13C NMR (75 MHz, CDCl3): δ 156.6 (C-OCH3), 149.3
(ArC quat.), 135.8 (ArC quat.), 130.5 (ArC quat.), 131.0 (ArCH),
129.2 (ArCH), 128.5 (ArCH), 126.7 (ArCH), 120.4 (ArCH),
111.2 (ArCH), 55.6 (OCH3), 42.7 (Ar-C(CH3)2-Ar), 30.9 (CH3).
Anal. Calcd for C29H28O2: C, 85.26; H, 6.91. Found: C, 85.01;
H, 6.92.
Synthesis of Bis[4′-(4-hydroxyphenyl)phenyl]propane,
p-TABPA, 6. Bis[4′-(4-methoxyphenyl)phenyl]propane, 3, (8.17
g, 20.0 mmol) and Py.HCl (23.10 g, 199.9 mmol) were added
to a beaker and slowly heated to 220-230 °C with stirring.
Three 5 g portions of Py.HCl were added over the course of
the reaction. The temperature was held at 220-230 °C for 1
h. The resultant viscous, dark, reddish-brown liquid was
poured with stirring into 500 mL of water. The solid was
collected by filtration and recrystallized from aqueous ethanol.
The final product p-TABPA (7.15 g, 94.0%) was fine white
crystals, mp 237-239 °C. IR (KBr, cm-1): 3530, 3300-2600,
3020, 2972, 2964, 1609, 1596, 1524, 1498, 1436, 1390, 1380,
1244, 1227, 1174, 1108, 1080, 823. 1H NMR (300 MHz, DMSO-
d6): δ 9.50 (br.s. 2H, exchangeable with D2O, OH), 7.40-7.46
(m, 8H, ArH), 7.22-7.25 (d, J ) 8.3 Hz, 4H, ArH), 6.77-6.80
(d, J ) 8.3 Hz, 4H, ArH), 1.64 (s, 6H, CH3). 13C NMR (75 MHz,
DMSO-d6): δ 157.4 (C-OH), 148.8 (ArC quat.), 137.9 (ArC
quat.), 131.2 (ArC quat.), 128.1 (ArCH), 127.4 (ArCH), 126.1
(ArCH), 116.2 (ArCH), 42.4 (Ar-C(CH3)2-Ar), 30.8 (CH3).
Anal. Calcd for C27H24O2: C, 85.23; H, 6.36. Found: C, 85.16;
H, 6.35.
Synthesis of Bis[4′-(4-methoxyphenyl)phenyl]propane,
3. I-BPA (31.40 g, 70.08 mmol) and p-CH3OPhB(OH)2 (22.80
g, 150.0 mmol) were dissolved in acetone (100 mL). A solution
of K2CO3 (58.00 g, 419.7 mmol) in water (100 mL) was then
added, and the reaction mixture was stirred 5 min to gentle
reflux. After evacuation and flushing with argon, Pd(OAc)2 (5
mg, 0.02 mmol) was added, and the suspension was heated 6
h under reflux and positive argon pressure. Upon cooling to
room temperature, the crude product was extracted with
methylene chloride (4 × 200 mL) and washed with water (2 ×
100 mL) and brine (1 × 150 mL). The combined organic layers
were dried (Na2SO4) and concentrated under reduced pressure.
The residue was recrystallized from ethanol to afford the title
compound (27.40 g, 95.70%) as white crystals, mp 198-200
°C. IR (KBr, cm-1): 3025, 2972, 2958, 2836, 1606, 1581, 1520,
Solution Polycondensation of Homopolycarbonate PC
p-TABPA, (Table 1, Entry 2). p-TABPA (0.38 g, 1.0 mmol)
was dissolved in 1.5 mL of pyridine and the solution was cooled
to 0 °C. A solution of triphosgene (0.124 g, 0.418 mmol) in
methylene chloride (3 mL) was added dropwise, and the
reaction mixture was vigorously stirred at 0-5 °C for 15 min.
The solution became viscous and saturated with pyridine-
hydrochloride during this time and was subsequently allowed
to warm spontaneously to room temperature. After reaching
room temperature, the suspension was stirred for 4 h. A 5%
aqueous hydrochloric acid solution (10 mL) was used to
neutralize the reaction mixture. The polymer was extracted
with methylene chloride (3 × 20 mL) and washed with water
(3 × 20 mL). The combined organic layers were then dried
(MgSO4) and concentrated. The viscous residue was poured
into methanol, whereupon the polymer precipitated and was
filtered with subsequent washing with methanol. The polymer
was dissolved in methylene chloride and reprecipitated from
methanol. The white pure polymer was dried at 100 °C under
vacuum for 24 h (0.38 g, 93% yield). IR (KBr, cm-1): 3029,
2967, 2871, 1773, 1610, 1595, 1520, 1495, 1394, 1386, 1228,
1
1497, 1385, 1365, 1289, 1248, 1183, 1037, 826. H NMR (300
MHz, CDCl3): δ 7.46-7.53 (m, 8H, ArH), 7.30-7.33 (d, J )
8.6 Hz, 4H, ArH), 6.94-6.97 (d, J ) 8.7 Hz, 4H, ArH), 3.84 (s,
3H, OCH3), 1.74 (s, 6H, CH3). 13C NMR (75 MHz, CDCl3): δ
159.0 (C-OCH3), 149.2 (ArC quat.), 138.1 (ArC quat.), 133.5
(ArC quat.), 128.1 (ArCH), 127.3 (ArCH), 126.4 (ArCH), 114.2
(ArCH), 55.4 (OCH3), 42.6 (Ar-C(CH3)2-Ar), 30.8 (CH3). Anal.
Calcd for C29H28O2: C, 85.26; H, 6.91. Found: C, 85.11; H,
6.90.
Synthesis of Bis[4′-(3-methoxyphenyl)phenyl]propane,
4. A procedure similar to that described for 3 was followed
using I-BPA (0.90 g, 2.0 mmol), m-CH3OPhB(OH)2 (0.67 g,
4.4 mmol), K2CO3 (1.66 g, 12.0 mmol) and Pd(OAc)2 (1.5 mg).
The suspension was heated for 3 h under reflux and positive
argon pressure. After usual workup, the residue was recrystal-
lized from ethanol to afford the title compound (0.55 g, 67%)
as tan crystals, mp 125-6 °C. IR (KBr, cm-1): 3061, 3024,
2970, 2930, 1606, 1581, 1558, 1479, 1433, 1385, 1365, 1268,
1211, 1119, 875, 832, 778, 696. 1H NMR (300 MHz, CDCl3): δ
7.50-7.53 (d, J ) 8.4 Hz, 4H, ArH), 7.31-7.36 (m, 6H, ArH),
7.16-7.18 (d, J ) 7.7 Hz, 2H, ArH), 7.12 (s, 2H, ArH), 6.86-
6.89 (d, J ) 8.2 Hz, 2H, ArH), 3.85 (s, 3H, OCH3), 1.75 (s, 6H,
CH3). 13C NMR (75 MHz, CDCl3): δ 160.0 (C-OCH3), 149.9
(ArC quat.), 142.5 (ArC quat.), 138.5 (ArC quat.), 129.8 (ArCH),
127.3 (ArCH), 126.9 (ArCH), 119.7 (ArCH), 112.8 (ArCH),
112.6 (ArCH), 55.4 (OCH3), 42.8 (Ar-C(CH3)2-Ar), 30.9 (CH3).
Anal. Calcd for C29H28O2: C, 85.26; H, 6.91. Found: C, 84.01;
H, 6.93.
Synthesis of Bis[4′-(2-methoxyphenyl)phenyl]propane,
5. A procedure similar to that described for 3 was followed
using I-BPA (1.00 g, 2.23 mmol), o-CH3OPhB(OH)2 (0.74 g,
4.9 mmol), K2CO3 (1.85 g, 13.4 mmol) and Pd(OAc)2 (2 mg).
The suspension was heated 6 h under reflux and positive argon
pressure. After usual workup, the product was obtained (0.83
g, 91%) as white crystals, which were pure enough to be used
as such in the next step, mp 180-2 °C. IR (KBr, cm-1): 3062,
1
1188, 1162, 1005, 821. H NMR (300 MHz, CDCl3): δ 7.59-
7.63 (m, 4H, ArH), 7.48-7.51 (m, 4H, ArH), 7.33-7.36 (m, 8H,
ArH), 1.75 (s, 6H, CH3).
Solution Polycondensation of coPC (Table 1, Entries
7)12). BPA was used as comonomer. The copolymers PC
p-TABPA-BPA were prepared with triphosgene as described
above. IR (KBr, cm-1): 3036, 2968, 2872, 1775, 1604, 1597,
1496, 1466, 1394, 1364, 1227, 1187, 1162, 1005, 822. 1H NMR
(300 MHz, CDCl3): δ 7.59-7.62 (d, J ) 8.1 Hz, 4H, ArH),
7.48-7.51 (d, J ) 8.1 Hz, 4H, ArH), 7.31-7.35 (m, 8H, ArH),
7.22-7.27 (m, 4H, ArH), 7.17-7.19 (m, 4H, ArH), 1.75 (s, 6H,
CH3), 1.68 (s, 6H, CH3).
Solution Polycondensation of coPC (Table 1, Entries
15)17). HFBP was used as comonomer. The copolymers PC
p-TABPA-HFBP were prepared with triphosgene as described
above. IR (KBr, cm-1): 3032, 2970, 2874, 1779, 1608, 1510,
1
1496, 1395, 1388, 1228, 1190, 1165, 1006, 969, 929, 822. H
NMR (300 MHz, CDCl3): δ 7.61-7.63 (d, J ) 8.4 Hz, 4H, ArH),
7.49-7.51 (m, 4H, ArH), 7.45-7.47 (m, 4H, ArH), 7.32-7.36
(m, 12H, ArH), 1.76 (s, 6H, CH3).
Solution Polycondensation of coPC (Table 1, Entries
19)21). BPC was used as comonomer. The copolymers PC

Macromolecules, Vol. 38, No. 9, 2005
Synthesis of High Aspect Ratio Bisphenols 3625
Table 1. Yields and Properties of Polycarbonates Prepared by Solution Polycondensation of p-TABPA and Various Diols
diol 1,
1 mol
diol 2,
actual mole ratio
triphosgene,
mol
Py,
mL
yield,
%
Mw,
Mn,
Tg,
PC
1 mol
diol 1 to diol 2, %
g/mol
g/mol
PDI
1.5
°C
1
2a
3
BPA
100
100
0.30
0.42
0.34
0.34
0.34
0.34
0.42
0.42
0.42
0.42
0.42
0.42
0.42
0.37
0.42
0.42
0.42
0.47
0.42
0.42
0.42
3.5
1.5
0.75
1
84
93
89
90
83
37
95
89
87
93
93
97
86
57
84
91
95
89
94
91
97
47 430
31 610
150.61
173.97
148.46
151.83
144.21
149.93
171.94
161.14
166.23
161.37
160.51
149.66
157.63
137.87
153.99
153.86
160.18
162.54
138.25
165.95
164.27
p-TABPA
p-TABPA
p-TABPA
p-TABPA
p-TABPA
p-TABPA
p-TABPA
p-TABPA
p-TABPA
p-TABPA
p-TABPA
BPA
BPA
BPA
BPA
BPA
BPA
BPA
BPA
BPA
BPA
HFBP
HFBP
HFBP
HFBP
HFBP
BPC
BPC
BPC
BPC
49.7/50.3
49.1/50.9
51.1/48.9
54.9/45.1
49.7/50.3
50.2/49.8
50.2/49.8
71.0/29.0
25.8/74.2
17.1/82.9
100
47.7/52.3
47.3/52.7
24.9/75.1
14.8/85.2
100
6141
9170
6105
3133
14 500
13 700
14 370
3875
6867
3543
2347
8640
8636
9934
1.6
1.3
1.7
1.3
1.7
1.6
1.4
4
5
1.5
3.5
0.75
1.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
6
7
8
9
10a
11
12
13
14
15
16
17
18
19
20
21
20 710
19 280
40 800
3520
14 690
11 300
27 620
2537
1.4
1.7
1.5
1.4
1.4
1.3
1.6
1.4
1.4
1.5
1.5
p-TABPA
p-TABPA
p-TABPA
p-TABPA
8847
6107
16 170
19 480
48 990
6251
12 140
12 020
34 440
4518
p-TABPA
p-TABPA
p-TABPA
45.6/54.4
31.5/68.5
17.3/82.7
18 520
18 980
12 350
12 560
a Not all dissolved, cloudy solution.
Table 2. Yields and Properties of Polycarbonates Prepared by Interfacial Polycondensation of p-TABPA and Various
Diols
diol 1,
diol 2,
actual mole ratio
triphosgene,
mol
yield,
%
Mw,
Mn,
Tg,
PC
1 mol
1 mol
diol 1 to diol 2, %
g/mol
g/mol
PDI
1.5
°C
22
23
24
25
26
27
28
29
30
31
32
33
34
35
BPA
100
100
0.30
0.40
0.34
0.34
0.34
0.34
0.30
0.42
0.42
0.42
0.42
0.42
0.42
0.42
93
91
96
97
96
97
92
95
87
97
110 900
72 520
152.85
175.77
176.37
169.75
159.12
165.68
134.78
188.23
168.13
156.47
141.07
160.40
166.86
169.73
p-TABPAa
p-TABPA
p-TABPA
p-TABPA
p-TABPA
BPA
38.9/61.1
27.2/72.8
16.4/83.6
10.1/89.9
100
56.4/43.6
26.8 /73.2
23.2/76.7
100
26 910
46 690
134 130
91 040
26 600
30 290
11 910
13 360
17 450
30 140
69 560
56 690
10 440
15 860
4683
1.5
1.5
1.9
1.7
2.2
1.9
2.5
2.1
BPA
BPA
BPA
HFBP
HFBP
HFBP
HFBP
BPC
p-TABPA
p-TABPA
p-TABPA
6357
p-TABPA
p-TABPA
p-TABPA
BPC
51.7/48.3
29.2/70.8
28.7/71.3
94
97
91
29 940
27 530
91 080
14 740
17 250
53 020
2.0
1.6
1.7
BPC
BPC
a Not all dissolved, cloudy solution.
p-TABPA-BPC were prepared with triphosgene as described
above. IR (KBr, cm-1): 3035, 2968, 2872, 1775, 1603, 1592,
1496, 1390, 1367, 1226, 1185, 1161, 1005, 974, 888, 861, 822.
1H NMR (300 MHz, CDCl3): δ 7.60-7.63 (d, J ) 8.0 Hz, 4H,
ArH), 7.48-7.51 (d, J ) 8.0 Hz, 4H, ArH), 7.33-7.35 (m, 12H,
ArH), 7.27-7.30 (m, 4H, ArH), 1.75 (s, 6H, CH3).
Interfacial Polycondensation of Homopolycarbonate
PC p-TABPA (Table 1, Entry 23). A solution of p-TABPA
(0.38 g, 1.00 mmol) and 1 N aqueous NaOH (4 mL) was
prepared and cooled to 0-5 °C. Triphosgene (0.12 g, 0.40
mmol) and BnNEt3Cl (10 mg) were dissolved in methylene
chloride (10 mL), and the solution was added to aqueous 1 N
NaOH immediately. Both phases were then rapidly stirred at
0-5 °C for 15 min and at 10-15 °C for 45 min. The organic
phase was separated, washed with water (4 × 50 mL) and
poured into methanol (200 mL), and the precipitated polymer
was filtered. The polymer was dissolved in methylene chloride,
filtered and reprecipitated from methanol (91% yield). Finally,
the polycarbonate was dried at 100 °C under vacuum for 24
h.
Interfacial Polycondensation of coPC (Table 2, En-
tries 22)27, 29)31, and 33)35). BPA, HFBP and BPC
were used as monomers. The copolymers PC p-TABPA-BPA,
PC p-TABPA-HFBP, and PC p-TABPA-BPC were prepared
with triphosgene as described above.
All homopolycarbonates (Table 2, entries 23, 24, 29, 33) and
coPCs (Table 2, entries 23-28, 30-32, 34-36) obtained by
interfacial polycondensation were found, via comparison, to
be identical with the corresponding PCs obtained from solution
1
polycondensation (IR and H NMR).
Results and Discussion
Synthesis of TABPA Monomers. The synthesis of
the desired TABPA monomers was achieved in three
steps from commercially available 2,2′-diphenylpropane
(Scheme 1).
Facile iodination of 2,2′-diphenylpropane with PhI-
(OCOCF3)2/iodine in carbon tetrachloride solution24 gave
I-BPA, 2, in good yield (80%). Monomers 6-8 were
prepared from commercially available methoxyarylbo-
ronic acids, CH3OArB(OH)2. The method of Wallow25
was used to effect the coupling reaction of I-BPA with
2.2 equiv of p-CH3OArB(OH)2 precursor. Anhydrous K2-
CO3 (2.5 equiv) as base and Pd(OAc)2 were mixed in an
acetone-water solvent system. The reaction proceeded
smoothly under reflux in argon atmosphere for 48 h to
afford the desired Suzuki product 3 in 70% yield. The
coupling product 3 in Scheme 1 was obtained in excel-
lent yield in 6 h using 5 equiv of anhydrous K2CO3 and
2.2 equiv of p-CH3OArB(OH)2. In similar manner the
m- and o-methoxyphenylboronic acids were used to
synthesize the m- and o-isomers 4 and 5 in good yield
and purity.

3626 Boyles et al.
Macromolecules, Vol. 38, No. 9, 2005
Scheme 1. Synthesis of TABPA Monomersa
a Key: (a) I2, PhI(OCOCF3)2, CCl4, 50-55 °C, 1 h; (b) p-MeOPhB(OH)2, Pd(OAc)2, K2CO3, acetone/water, reflux, 6 h for 3;
m-MeOPhB(OH)2, Pd(OAc)2, K2CO3, acetone/water, reflux, 3 h for 4; o-MeOPhB(OH)2, Pd(OAc)2, K2CO3, acetone/water, reflux, 6
h for 5; (c) Py‚HCl, 215-220 °C, 1 h for 6 and 7; 30 min for 8.
Scheme 2. Synthesis of Copolycarbonates by Solution Polycondensation
The reactions were monitored by TLC. The meta
isomer 4 required 3 h reaction time, whereas the ortho
isomer 5 required 6 h for completion, with the latter
reaction giving higher yields. IR and NMR spectroscopy
confirmed the structure of compounds 3-5. The 1H
NMR spectrum exhibited two singlets at 1.75 ppm,
assigned to the protons of the geminal methyl groups,
and a singlet at 3.84 ppm, assigned to the protons of
the methoxy group.
Subsequent demethylation of 3, 4 and 5 to compounds
6, 7 and 8, respectively, was performed using Py‚HCl.26
Thus, the dimethoxy-substituted compounds 3-5 were
treated with Py‚HCl at 230 °C, affording the desired o-,
m-, and p-tetraaryl BPA isomers in excellent yields.
Spectroscopic data were in agreement with the structure
of compounds 6, 7, and 8. The infrared spectra indicated
a broad absorption band at 3500-3200 cm-1 from the
OH stretch. 1H NMR spectra showed a broad singlet at
9.50 ppm for the same group. 13C NMR spectra were
also consistent with the assigned structures, exhibiting
a methyl carbon at 30.8 ppm, the quaternary isopropyl-
idene carbon at 42.5 ppm, four quaternary aromatic
carbons and four secondary aromatic carbons for com-
pound 6 and six secondary aromatic carbons for com-
pounds 7 and 8. We have applied this practical sequence
to the preparation of up to 200 g of monomer 6.
bisphenol solution containing a tertiary amine,28 and
base-catalyzed transesterification of a bisphenol with
a monomeric carbonate such as diphenyl carbonate.29
We employed both solution and interfacial polyconden-
sation methods for the monomers described above.
While BPA-PC is commercially prepared using phos-
gene gas, the literature indicated that relatively high
molecular weight PCs can also be obtained using more
convenient triphosgene on a laboratory scale.30-33 Sun
et al.,30 utilized triphosgene to prepare thermotropic
liquid crystalline polycarbonates although viscosity data
only was reported, making it difficult to ascertain the
molecular weights of the materials. Likewise, Marks,
et al.,31 synthesized randomly branched polycarbonates
utilizing triphosgene obtaining molecular weights Mw
in the range of 16 300 to 75 900 g/mol with polydisper-
sity indices (PDI) ranging from 2.5 to 6.6. Also, Eiffler
et al.,32 disclosed a triphosgene procedure with reported
polycarbonate molecular weights of Mn ) 13 450 g/mol
and Mw ) 45 670 g/mol. Our solution polymerizations
utilized pyridine and methylene chloride as acid scav-
enger and solvent, respectively. The general reaction
route and the structures of polycarbonates are depicted
in Scheme 2.
Solution polycondensation was performed with a 50/
50 molar ratio of p-TABPA and BPA monomers using
various amounts of triphosgene and pyridine to ascer-
tain optimal reaction conditions. Triphosgene was var-
ied from 0.30 to 0.47 mol, and the pyridine was varied
from 0.75 to 3.5 mL. Results are summarized in Table
1.
Polymer Synthesis. Several processes for the prepa-
ration of aromatic PCs have been reported, including
the Schotten-Baumann reaction of phosgene and an
aromatic diol in an amine-catalyzed interfacial conden-
sation reaction,27 direct reaction of phosgene with a

Macromolecules, Vol. 38, No. 9, 2005
Synthesis of High Aspect Ratio Bisphenols 3627
Scheme 3. Synthesis of Copolycarbonates by Interfacial Polycondensation
Extraction of the reaction mixture with methylene
chloride, followed by a water wash, and precipitation
into methanol afforded polymeric materials as white
powders. A second reprecipitation afforded polymers in
37-95% yield with Mw from 3133 to 14 500 g/mol and
PDI from 1.3 to 1.7. During workup, the byproduct
pyridine hydrochloride dissolved in water, and decom-
position of the chloroformate-pyridine complex at both
ends of the polymer chain occurred. The molecular
weight and yield of the polymers show a marked
dependence on the amount of triphosgene and pyridine.
Polycondensation with 0.42 mmol of triphosgene and 1
mmol of diols and pyridine in the range of 0.75-3.5 mL
gave the best results. In the case of entry 9 (Table 1), a
3 cm-1, the region assigned to the stretching vibration
of CdO groups, and 1228, 1186, 1162 cm-1, the regions
assigned to the ether groups. All are characteristic
absorptions of the aromatic polycarbonate system.
1
Quantification of H NMR signal intensities indicated
that monomer incorporation into the polymers was close
to the feed ratio. The 1H NMR spectra revealed that the
incorporation of p-TABPA and BPA, easily detectable
by sharp signals at 1.75 and 1.68 ppm, respectively,
were 71.0% and 29.0% (feed ratio of 75-25), 50.2% and
49.8% (feed ratio of 50-50), 25.8% and 74.3% (feed ratio
1
of 25-75). The H NMR spectra of PC entries 15-17
and PC entries 19-21 also indicated equimolar incor-
poration of the two monomers, which is reasonable for
polycondensation in an organic reaction medium.
copolymer with a moderate molecular weight (Mw
)
14 370 g/mol) was obtained which displayed a narrow
size exclusion chromatography (SEC) curve and a PDI
of 1.4. A series of copolycarbonates was prepared from
p-TABPA with BPA (Table 1, entries 10-12), HFBP
(Table 1, entries 14-17), and BPC (Table 1, entries 19-
21) under the reaction conditions used for synthesis of
the copolymer in entry 9. The molar ratio of diols was
varied from 75/25 to 15/85. Thus, a reaction of 75 mol
% of p-TABPA and 25 mol % of BPA afforded PC entry
10 in 93% yield. The copolymer was slightly soluble after
heating in methylene chloride, chloroform, chloroben-
zene, o-dichlorobenzene, or THF. Levels of p-TABPA
greater than 75 mol % gave essentially insoluble ma-
terials, possibly of high molecular weight polymers since
the homopolymer of p-TABPA was also insoluble. For
this reason further copolymers in this study were
prepared using not more than 50 mol % of p-TABPA
monomer.
The coPCs were soluble in methylene chloride, chlo-
roform, chlorobenzene, or o-dichlorobenzene, and films
could be cast from solvent. Only the homopolymer of
p-TABPA, entry 2, and copolymer entry 10 were poorly
soluble in all common organic solvents, although they
could be dissolved in larger quantities of methylene
chloride, as was necessary during reaction workup. The
chemical structure of the polymers was confirmed by
FTIR and 1H NMR spectroscopy. The IR spectra of the
polymers exhibited strong absorption bands at 1776 (
The weight-average molecular weights of the series
of copolycarbonates PC p-TABPA-BPA (Table 1, entries
9-12), PC p-TABPA-HFBP (Table 1, entries 14-17),
and PC p-TABPA-BPC (Table 1, entries 19-21) were
13 700 to 20 710 with a PDI in the range of 1.4-1.7,
8847 to 19 480 with a PDI of 1.3-1.6, and 6251 to 18 980
with a PDI of 1.4-1.5, respectively, determined by GPC.
As seen from Table 1, increasing percentages of the
comonomers BPA, BPC, and HFBP resulted in a pro-
portional increase in the molecular weight of the
copolymer, although polydispersity remained approxi-
mately constant at 1.3-1.7. The aforementioned in-
crease in average molecular weight Mw associated with
increased comonomer concentration was likely due to
the increase in solubility of the resulting copolymers
with BPA, BPC and HFBP in the polymerization
process.
Liquid-liquid-phase transfer catalysis (PTC) poly-
condensation was used in order to obtain higher mo-
lecular weight polycarbonates. PTC polycondensation
was simpler, required a shorter reaction time, and in
the case of liquid-liquid systems, obviated the use of
anhydrous solvents and reagents. The transport of the
anionic species from aqueous medium into the organic
medium was ensured by catalytic amounts of BnNEt3-
Cl as a lipophilic transfer agent.34
The general reaction route and the structures of
polycarbonates thus obtained by PTC polymerization

3628 Boyles et al.
Macromolecules, Vol. 38, No. 9, 2005
Table 3. Yields and Properties of Polycarbonates Prepared by Interfacial Polycondensation of m- and o-TABPA and
Various Diols
diol 1,
1 mol
diol 2,
1 mol
actual mole ratio
diol 1 to diol 2, %
triphosgene,
mol
yield,
%
Mw,
g/mol
Mn,
g/mol
Tg,
°C
PC
PDI
36
37
38
39
40
41
42
43
44
45
m-TABPAa
m-TABPA
m-TABPA
m-TABPA
m-TABPA
m-TABPA
m-TABPA
o-TABPA
o-TABPA
o-TABPA
100
0.42
0.34
0.34
0.34
0.42
0.42
0.42
0.42
0.34
0.42
90
91
97
98
84
79
89
88
98
83
125.95
183.62
150.32
150.25
158.89
149.62
143.47
100.31
129.61
121.75
BPA
58.1/41.9
41.0/59.0
19.2/80.8
41.3/58.7
22.3/77.7
19.5/80.5
100
154 400
70 840
46 250
182 300
30 880
27 530
8067
64 460
39 600
29 180
96 050
13 700
5588
2.4
1.8
1.6
1.9
2.3
4.9
2.6
1.4
1.3
BPA
BPA
HFBP
HFBP
HFBP
3104
BPA
HFBP
29.6/70.4
33.1/66.9
15 890
12 190
11 730
9362
a Not all dissolved, cloudy solution.
are shown in Scheme 3. TABPA and corresponding
monomers BPA, HFBP, and BPC were dissolved in
aqueous 1 N NaOH. Methylene chloride containing
BnNEt3Cl and triphosgene were added and the two-
phase system was stirred for 1 h. When the polymer
either precipitated from the methylene chloride solution
or when gelation occurred, the organic layer was sepa-
rated from the aqueous layer, and the methylene
chloride solution was poured into cold methanol. Thus,
the p-, m- and o-TABPA monomers were used to prepare
a series of copolycarbonates. Maintaining the reaction
temperature at 0-5 °C for 15 min and subsequently at
10-15 °C for 45 min with an optimal amount of
triphosgene (0.30-0.42 mmol per 1 mmol of diols)
produced 91-97% pure polycarbonates. The results of
the interfacial polycondensation of TABPA isomers with
various diols are summarized in Tables 2 and 3. With
the exception of the p- and m-TABPA homopolymers,
all of the PCs were soluble in chlorinated solvents or
THF. The p- and m-TABPA homopolymers were at best
only slightly soluble in these solvents.
carbonyl signals were sensitive to sequence effects, i.e.,
to diads. All three possible diads were resolved. The
coPC 11 was found to be completely random (according
to the deviation from random statistics given by: c )
P{AB}/P{A}P{B} c ) 1). The coPC 25 had a slight
tendency toward blocking (c ) 0.9).35
The molecular weights of coPCs prepared via inter-
facial polycondensation technique (Table 2) were much
higher than the molecular weights of coPCs prepared
by solution polycondensation. The results in Table 2
demonstrate that different proportions of monomers
generally had an effect on the molecular weight of the
resulting coPCs. The p-TABPA-BPA PCs were obtained
in high yield with molecular weights in the range of
26 910-134 130 g/mol. The weight-average molecular
weight increased as the percent of BPA monomer
increased. The same behavior was observed in the
p-TABPA-BPC PCs.
It was also noted that increased mole percent of
m-TABPA monomer led to increasing molecular weight
of coPCs (Table 3, entries 37-39 and 40-42). Copoly-
mers of BPA and HFBP with m-TABPA showed a
dramatic increase in molecular weight as the mole
percent of m-TABPA monomer was increased. Weight-
average molecular weights ranged from 46 250 to 154 400
g/mol for m-TABPA-BPA coPCs and from 27 530 to
182 300 g/mol for m-TABPA-HFBP coPCs. These re-
sults are in contrast to the results for the para analogue.
Unlike the distal aryl rings in the para analogue which
experience free rotation having no effect on the direc-
tionality of the p-hydroxyl group, free rotation in both
the meta and ortho analogues leads to a rotational
continuum of possibilities for directionality of chain
growth as well as differences in solid-state chain
dynamics of the isomeric polymers.
The fact that the ortho analogue gave lower molecular
weightssranging from 8067 to 15 890 g/molsthan
either the meta and para analogues, may be attributed
to greater steric crowding in the vicinity of the hydroxyl
group leading to hindered chain growth during the
polymerization process. No evidence for cyclic oligomers
in any of the purified polymers was noted by SEC.
Comparison between films cast from isomeric para and
ortho copolymers most similar in molecular weights and
composition (Table 1, entries 11-12 and Table 3, entry
44) showed distinct differences in film quality: the para
formed tough films while the ortho formed relatively
brittle films.
The successful synthesis of PCs was confirmed by IR
and 1H NMR. All homopolycarbonates (Table 2, entries
22, 23, 28, 32) and coPCs (Table 2, entries 22-27, 29-
31, 33-35) obtained by interfacial polycondensation
were identical with the corresponding PCs obtained
1
from solution polycondensation (IR and H NMR). The
IR spectra of the isolated polymers exhibited the ex-
pected bands, specifically, a sharp CO-band at 1777 (
4 cm-1. The 1H NMR spectrum of the m-TABPA homo-
and copolymers displayed a singlet at 1.74 ppm, the
shift assigned to isopropylidene protons of m-TABPA
and a singlet at 1.67 ppm from the methyl protons of
BPA (Table 3, entries 37-39). The protons of the
aromatic rings were shifted to a higher field compared
with the p-isomer and appeared as multiplets at 7.47-
7.51, 7.30-7.35, and 7.16-7.20 ppm.
Interpretation of structure-property relationships
requires knowledge of the copolymer compositions and
sequence distributions for the monomer units. Interfa-
cial polycondensation of two different diols does not
necessarily result in coPCs having either the composi-
tion of the feed ratio or a random sequence, as different
solubilities and acidities of the OH groups may cause
differences in monomer reactivity ratios. 1H NMR
spectra. indicated that the average incorporation of the
monomer units in all the series in Tables 2 and 3
(TABPA-BPA, TABPA-HFBP, TABPA-BPC) was close
to the feed ratio used. The 13C NMR spectra of the two
p-TABPA-BPA coPCs synthesized by solution (Table
1, entry 11) and interfacial (Table 2, entry 25) method
were evaluated. The 13C NMR spectra revealed that the
Conclusions
An efficient synthesis of the high aspect-ratio mono-
mer bis[4′-(4-hydroxyphenyl)phenyl]propane and its

Macromolecules, Vol. 38, No. 9, 2005
Synthesis of High Aspect Ratio Bisphenols 3629
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with high purity and an overall yield of 72-75%.
Solution and interfacial polycondensations with triphos-
gene have been optimized and have proven successful
in giving good incorporation of the new monomers into
high molecular weight polycarbonates having narrow
polydispersities, representing an improvement over
previously reported triphosgenations. The satisfactory
molecular weights obtained from the triphosgene method
afforded clear and tough films which could be cast from
concentrated solutions of the meta and para polymers.
The availability of these new monomers and their
polycarbonates affords a new series of compounds with
which we are now able to further investigate the
theoretical underpinnings prompting their design.
Our findings have implications for the determining
influence of aspect ratios of bisphenol monomers not
only on the ease of their polymerization to high molec-
ular weight polycarbonates, but also on their ability to
significantly influence entanglement molecular weights
and segmental conformational chain motion in the three
isomers studied. Monomer aspect ratio may therefore
be a fundamental factor governing both molecular and
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Acknowledgment. The authors of this paper grate-
fully acknowledge support from the National Science
Foundation (DMR-98-15957) and the Department of
Defense-Army Research Office (DAAD19-01-1-0482). We
thank Dr. Elizabeth Williams of GE for kindly allowing
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Supporting Information Available: Text giving syn-
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polycarbonates and figures showing infrared as well as 1H
NMR spectra. This material is available free of charge via the
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Elizabeth Williams of GE Global Research, Niskayuna, NY,
who kindly gave permission for us to use them.
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