6432 Macromolecules 1996, 29, 6432-6441

Synthesis and Characterization of

Poly(oxy-1,3-phenylenecarbonyl-1,4-phenylene) and Related
Polymers

Mark F. Teasley* and Benjamin S. Hsiao

Central Research and Development, E. I. du Pont de Nemours and Company, Experimental
Station, Wilmington, Delaware 19880-0328
Received April 26, 1996; Revised Manuscript Received July 2, 1996X

ABSTRACT: The title composition, isoPEK, was prepared from 4-fluoro-3′-hydroxybenzophenone in

N-methylcaprolactam at 225 °C. Cyclomer formation interfered with polymerization at lower temperatures
in alternative solvents and dominated in dilute solutions. The 50/50 to 70/30 copolymers of PEK and
isoPEK were prepared using 4-fluoro-4′-hydroxybenzophenone. An analogous composition, poly(oxy-1,3-
phenylenecarbonyl-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene) or isoPEKEK, was prepared
from 4,4′-difluorobenzophenone and 3,4′-dihydroxybenzophenone using similar conditions. Thermal
crystallization of the copolymers was successful, but isoPEK and isoPEKEK were only capable of solvent-
induced crystallization. The semicrystalline materials were studied by thermal analysis and X-ray
diffraction. The copolymers melted at 264-307 °C and possessed random microstructures with isomorphic
crystallization of the PEK and isoPEK repeat units. IsoPEK and isoPEKEK melted, respectively, at the
low temperatures of 180 and 193 °C. IsoPEK crystallized with both Form 1 and Form 2 unit cells, while
isoPEKEK and the copolymers crystallized with the Form 1 unit cell. IsoPEK was also prepared by
ring-opening polymerization of its cyclomers in the melt using cesium fluoride as catalyst. The 3,4′
catenation of the isoPEK repeat unit and the related monomers was used to rationalize the unique
chemistry and properties of these polymers.

Introduction
Poly(arylene ether ketone)s are thermoplastic engi-
neering polymers possessing an excellent balance of
mechanical properties and flexible processing with
thermooxidative and chemical resistance.1 The most
utilized compositions employ p-phenylene units to im-
mer 4-fluoro-4′-hydroxybenzophenone (FHB). These
part semicrystallinity with high melting points. The
semicrystalline polymers require high temperatures to
well-known poly(ether ether ketone), PEEK, retains
maintain solubility in diphenyl sulfone4 or benzophe-
none,5 but more moderate conditions suffice for amor-
phous compositions.6 Alternatively, PEKK is polymer-
ized from mixtures of terephthaloyl and isophthaloyl
chlorides with diphenyl ether by Friedel-Crafts acyla-
tion, although linear polymer requires stoichiometric
aluminum chloride in both stages of a two-stage pro-
cess.7
The solubility and stability of poly(arylene ether
melt processibility because the consecutive ether link- ketone)s in strong acids led to the attempted construc-
ages provide flexibility, while poly(ether ketone), PEK, tion of molecular composites using rigid-rod polymers.
possesses an excessively high melting point. The al- Although phase separation prevented true molecular
ternative poly(ether ketone ketone)s, PEKK, possess dispersions, amorphous matrix resins are hypothesized
lower melting points, despite the rigidity imparted by to prevent such behavior. An amorphous poly(arylene
the consecutive ketone linkages, because m-phenylene ether ketone) reported by Evers and co-workers to show
units are incorporated into their copolymers.2 Both promise for this application is poly(oxy-1,3-phenylen-
PEEK and PEKK are used as matrix resins in high- ecarbonyl-1,4-phenylene).8 Although the trivial name
performance composites. mPEK was used for this composition, it is known as
A principal issue for the preparation of poly(arylene isoPEK in our laboratory because it is the simplest
ether ketone)s is the harshness of the conditions. PEEK
and PEK, as well as many other compositions, are
polymerized by nucleophilic aromatic substitution (SN-
Ar) of fluoro-substituted benzophenones with aromatic
diols in the presence of inorganic bases,3 which proceeds
through the formation of Meisenheimer complexes due
to activation by the carbonyls (Scheme 1). PEEK is
prepared from the AA/BB comonomer system of hydro- isomer of PEK that possesses a well-ordered microstruc-
quinone and 4,4′-difluorobenzophenone (DFB), while ture of alternating m- and p-phenylene rings. A com-
PEK can be prepared from either the AA/BB system of panion composition, poly(oxy-1,3-phenylenecarbonyl-1,4-
4,4′-dihydroxybenzophenone and DFB, or the AB mono- phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene),
reported herein is known as isoPEKEK.
X Abstract published in Advance ACS Abstracts, September 1, IsoPEK was originally prepared from 3-phenoxyben-
1996. zoic acid following the procedure of Ueda and Sato;9
S0024-9297(96)00619-5 CCC: $12.00 © 1996 American Chemical Society
Macromolecules, Vol. 29, No. 20, 1996 IsoPEK and Related Polymers 6433

Scheme 1. Mechanism of SNAr Polymerization

PEK was also prepared by Evers and co-workers from Table 1. NMR Chemical Shifts for Selected Nuclei of
4-phenoxybenzoic acid for comparison. These benzoic p-Fluorobenzophenones
acids are activated for polymerization via Friedel- 1H(CDCl3) 13C(CDCl3) 19F (DMSO-d6)
Crafts acylation in a medium of methanesulfonic acid compd ortho H para C para F
and phosphorus pentoxide. High molecular weights 4,3′FHB 7.85 165.53 -106.47
were only observed for isoPEK, based on solution DFB 7.82 165.27 -106.01
viscosity, although Ueda and Sato reported a higher FHB 7.80 165.24 -107.60
value for isoPEK. Although the 13C nuclear magnetic
resonance (NMR) spectrum of isoPEK10 showed that Monomer Reactivity. The reactivity of fluoro-
para acylation dominated the polymerization, low levels substituted monomers in SNAr polymerizations can be
of ortho acylation below the detection limit are always probed using NMR spectroscopy by correlating their
a possibility with Friedel-Crafts chemistry. chemical shifts with electron density.12 Theoretical
Evers and co-workers induced crystallinity in isoPEK studies verify the correlation of electron density with
by slowly cooling a melt to room temperature. Dif- reactivity and with 13C and 19F NMR chemical shifts.13
ferential scanning calorimetry (DSC) showed a modest Table 1 shows the chemical shifts for the relevant 1H,
melting endotherm (Tm) at 304 °C with an enthalpy of 13C, and 19F nuclei of benzophenone monomers. The
fusion (Hf) of 26.5 J/g. X-ray diffraction confirmed that downfield chemical shifts for the nuclei of 4,3′FHB
isoPEK had the same unit cell as PEK. A solvent- indicate that it should display high reactivity. The 19F
induced endotherm at the glass transition temperature NMR chemical shift for DFB shows that its difluoro
(Tg) of 132 °C was due to a solvent adduct. The nuclei are more electrophilic than that of 4,3′FHB, but
mechanical properties of amorphous samples were the para-carbon and ortho-hydrogen chemical shifts
promising but fell short of the best matrix resins due indicate that this does not translate as effectively to
to the development of microvoids during mold shrink- their nuclei. Since 19F NMR is the most sensitive probe
age. These difficulties might be overcome by crystal- of SNAr reactivity, the initial rates of polymerization
linity or by a polymerization method that gives higher with DFB may be greater than those with 4,3′FHB.
molecular weights and eliminates the possibility for However, polymerizations employing DFB slow with
microstructural defects.
conversion and approach the rates of those using FHB,
The SNAr polymerization of isoPEK was investigated
as para-oxy bond formation in both results in the same
for the potential of higher molecular weights using a
end group.3
monomer that ensures a regular microstructure with
strict alternation of meta and para catenation. This Polymerization of IsoPEK. The SNAr polymeriza-
approach led to the preparation of copolymers with PEK tions of isoPEK from 4,3′FHB in common dipolar aprotic
and that of isoPEKEK as well. Our results are quite solvents are displayed in Table 2. The polymerizations
revealing as to the unique chemistry and properties of were monitored in their early phases by the consump-
these polymers and will be reported herein and in a tion of solid potassium carbonate and the intensity of
subsequent publication. the yellow-orange color for the potassium phenolate end
groups. The completion of polymerization was judged
Results by the increase in solution viscosity, the precipitation
Monomer Synthesis. The SNAr polymerization of of potassium fluoride, and the discharge of color, which
isoPEK requires 4-fluoro-3′-hydroxybenzophenone typically required only a few hours. The polymeriza-
(4,3′FHB), while isoPEKEK can be prepared from DFB tions were initially worked up by coagulating in water
and 3,4′-dihydroxybenzophenone (3,4′DHB). 4,3′FHB and washing with methanol.
was prepared following the method of Irwin for Although high molecular weights were attained, the
3,4′DHB.11 The Friedel-Crafts acylation of fluoroben- polymerizations were plagued by the formation of cy-
zene with m-hydroxybenzoic acid is activated by the clomers. This was first evident by gel permeation
strong acid medium of BF3/HF despite the lower reac- chromatography (GPC), which showed bimodal distribu-
tivity of carboxylic acids. tions with substantial low molecular weight fractions;
the GPC conditions were originally developed for PEEK,14
and the reported molecular weights and integrations are
uncorrected. For example, the polymer from N-meth-
ylpyrrolidone (NMP) and toluene at 200 °C (item 3)
contained 37% low molecular weight fraction, which was
shown by fast atom bombardment mass spectrometry
(FAB MS) to consist of cyclomers from dimer to octamer
6434 Teasley and Hsiao Macromolecules, Vol. 29, No. 20, 1996

Table 2. SNAr Polymerization of IsoPEK in Common Dipolar Solvents

ηinh (dL/g) GPC (cyclomer integral)
item solvent concn (%) temp (°C) yield (%) initial finala Mn Mw Mpeak (%)
1 DMSO/toluene 14 170-190 83.4 0.98 2 260 31 800 52 300 40
2 sulfolane/toluene 14 170-200 70.7 1.07 3 730 22 600 22 600 15
3 NMP/toluene 14 170-200 98.0 2.51 2.80 1 990 84 100 107 000 37
4 NMP 14 200 87.8 1.47 1.85 2 950 51 600 66 500 29
5 NMP 20 190-220 88.4 2.33 8 000 74 900 76 400 9
6 NMP 20 220 80.5b 2.40 12 700 57 100 56 200 0
7 NMP 20 160c 85.2b 2.30 8 150 57 900 55 800 0
a After acetone extraction. b Coagulated in acetone; washed with acetone and water. c 24 h.

Table 3. SNAr Polymerization of IsoPEK in NMC at 225

°C for 4 h
GPC
item concn (%) yield (%) ηinh (dL/g) Mn Mw Mw/Mn
1 20a 1.10 13 300 31 000 2.33
2 20 85.2 1.15 11 400 33 200 2.90
3 25 92.9 1.15 9 710 40 300 4.15
4 30 90.3 1.27 11 600 39 700 3.42
a Immersed in preheated bath.

N-Methylcaprolactam (NMC) is a good solvent for the

SNAr polymerization of poly(arylene ether ketone)s at
moderate temperatures using azeotrope-forming cosol-
vents.15 IsoPEK was successfully polymerized from
4,3′FHB in neat NMC at 225 °C at several concentra-
Figure 1. FAB mass spectrum of residual cyclomers in a tions (Table 3). Although solvent degradation was
sample of isoPEK (Table 2, item 3). The peak at m/z 621.7 avoided with NMC, the completion of polymerization
was due to a matrix-generated ion. was judged solely on solution viscosity because the
yellow color only faded as the solutions were cooled to
(Figure 1). Integration of the high polymer fractions room temperature; 4 h of reaction time was sufficient
showed the same peak molecular weights (Mpeak) as the to reach an apparent viscosity plateau. Good yields of
full chromatographs, and the polydispersities (Mw/Mn) high molecular weight polymers containing no cyclomers
of the former were close to the most probable distribu- were obtained after coagulation in acetone and washing
tion. Simple washing of the isolated polymers with with water. The molecular weight distributions of the
acetone removed some of the cyclomers and increased polymers from NMC were narrower than those from
their inherent viscosities (ηinh). Table 2, and the polydispersities occasionally ap-
Formation of the cyclomers was reduced, but not proached the most probable distribution. The observed
eliminated, by increasing the concentrations of the thermal properties (Table 4) were comparable to those
polymerizations. This was mainly achieved by elimi- previously reported for amorphous isoPEK, but no
nating the toluene used to remove water as an azeo- melting endotherms were induced by slow cooling to
trope. Some aprotic solvents used in SNAr polymeriza- below Tg before the second heating cycles.
tions can displace water at high temperatures without Characterization of IsoPEK Cyclomers. The
the aid of azeotropes, especially when the resulting isoPEK cyclomers were initially assigned by FAB MS
polymer is hydrophobic, and NMP did not require using the polymers from Table 2; Figure 1 shows a
toluene to obtain high molecular weights. Fewer cy- representative example. Samples of the cyclomers were
clomers were observed with NMP at 220 °C (item 5), also isolated from the polymers by extraction with
but coagulation of the polymer preparations in acetone methanol or acetone. The cyclomer mixtures were
reduced the cyclomers to levels undetectable by FAB MS soluble in acetone, but only the cyclic dimer showed
(item 6). Solvent degradation made the completion of limited solubility in methanol. Consequently, the po-
polymerization difficult to judge and the isolated poly- lymerization mixtures were thereafter coagulated in
mers were discolored. Polymerization at 160 °C was acetone to ensure isolation of cyclomer-free polymers.
slower, but the resulting polymer was not discolored, Authentic cyclomer samples were easily prepared in
and it was free of cyclomers after coagulation in acetone. more dilute solutions than those of polymerization. At

Table 4. Thermal Properties of Selected Polymers

DSC [°C (J/g)] TGA (10 wt %) (°C)
polymer source Tg Tm (Hf) Tc (Hf) air N2
isoPEK Table 2, item 6 132 460 430
isoPEK DMAc crystallized 131 180 (26) 490 490
isoPEKEK Table 5, item 1 147
isoPEKEK CH2Cl2 crystallized 145 193 (33) 525 525
50/50 PEK/isoPEK Table 5, item 2a 142 264 (20) 445 460
60/40 PEK/isoPEK Table 5, item 5 146 279 (23) 480 525
65/35 PEK/isoPEK Table 5, item 6 147 296 (20) 225 (19) 525 525
70/30 PEK/isoPEK Table 5, item 7 150 307 (17) 215 (15) 460 495
a Melted and annealed at 210 °C.
Macromolecules, Vol. 29, No. 20, 1996 IsoPEK and Related Polymers 6435

Figure 2. 1H NMR spectrum of the isoPEK cyclomers

prepared in DMSO. The major peaks are assigned to the
structure of the cyclic dimer.
Figure 3. DSC thermogram of the isoPEK cyclomers prepared
a 2% concentration in dimethyl sulfoxide (DMSO) at 170 in DMSO.
°C, a crude yield of 45% was obtained, and the material
was purified by filtering a dichloromethane solution 240-260 °C using 2 mol % cesium fluoride16 as the
through silica gel. FAB MS showed a mixture of cyclic nucleophilic catalyst. Chain growth was indicated by
dimer, trimer, and tetramer with a large majority of the the increase in ηinh from 0.08 to 0.93 dL/g. GPC
dimer. The 1H NMR spectrum also showed a prepon- confirmed that high molecular weight polymer was
derance of cyclic dimer (Figure 2). The upfield reso- obtained with Mw of 22 900, but the low value for Mn of
nance at δ 6.3 supports the structure of cyclic dimer 2080 was affected by the presence of 11% residual
because the assigned hydrogens, which are ortho to both cyclomers. The 1H NMR spectrum showed both polymer
substituents of the m-oxybenzoyl groups, lie in the and cyclic dimer, with the characteristic resonance at
shielding cones of both p-phenylene rings. DSC showed δ 6.3 for the latter, and FAB MS revealed that indeed
a Tg of 84 °C and three Tm at 166, 207, and 235 °C only cyclic dimer remained after polymerization. Judg-
(Figure 3). ing from the GPC and 1H NMR, at least some cyclic
The preparation of cyclomers at a 2% concentration dimer is converted to polymer under these conditions.
in NMP at 150 °C gave a higher yield of 60% after IsoPEKEK Polymerization. IsoPEKEK was pre-
purification. FAB MS showed a mixture of cyclomers pared from 3,4′DHB and DFB in NMC at 225 °C (Table
from dimer up to heptamer. The 1H NMR spectrum 5). The yellow color from the potassium phenolate end
confirmed that it was a more complex mixture than the groups did not discharge until the viscous solution was
product from DMSO, although the relative intensities cooled to room temperature after 7 h. GPC showed high
again indicated a preponderance of cyclic dimer. DSC molecular weight polymer and no evidence of cyclomers.
showed this mixture to be amorphous with a Tg of 101 The Tg was higher than that of isoPEK and slightly
°C. higher than that of PEEK, but the isolated polymer was
Both cyclomer mixtures displayed ηinh less than 0.1 amorphous (Table 4). The 13C NMR spectrum was
dL/g. GPC showed only low molecular weight material, consistent with the structure of isoPEKEK, although it
although these conditions are not calibrated for isoPEK showed apparent doublets for three quaternary carbons
cyclomers. Indeed, both cyclomer samples gave peak whose chemical shifts are consistent with either ether
molecular weights for cyclic dimer that were about one- or ketone substituents.
half of the calculated value of FW 392. Further refine- Crystallization of IsoPEK and IsoPEKEK. The
ments of the synthetic conditions using dilute solutions respective regular and semiregular microstructures of
of DMSO, NMP, and dimethylacetamide (DMAc) gave isoPEK and isoPEKEK were not sufficient to enable
no improvement. their thermal crystallization even after annealing at
Ring-Opening Polymerization of IsoPEK Cy- temperatures below their melting points. However, it
clomers. The ring-opening polymerization of isoPEK was possible to induce crystallization by treatment of
cyclomers was investigated due to the value of such an each with a suitable solvent. IsoPEK showed variable
approach in advanced composite applications. The solubility in DMAc, with good solutions being used to
recent development of this chemistry is well known, but wet spin weak fibers, but the occasional insolubility was
useful examples of poly(arylene ether ketone)s have not found to be due to solvent-induced crystallization of the
been forthcoming for a variety of reasons.16 The syn- polymer. In retrospect, the only apparent uncontrolled
theses of their cyclomers are difficult, except for various variable was the moisture content.
systems with little utility in advanced composites or An insoluble sample of isoPEK was extracted with
those with complex monomer syntheses. Additionally, methanol at reflux to remove DMAc and then with
the ring-opening polymerizations, which are initiated toluene and 2-butanone to extract low molecular weight
using nucleophilic catalysts such as cesium fluoride or materials that interfered with X-ray diffraction analysis.
the potassium salt of 4-hydroxybenzophenone, suffer DSC showed a Tm at the low temperature of 180 °C on
due to the high melting temperatures of either the the first heating cycle (Figure 4), but only a Tg of 131
cyclomers or the resulting polymers. The isoPEK cy- °C on the second cycle (Table 4). The X-ray diffraction
clomer/polymer system could represent a useful com- pattern confirmed that the sample was semicrystalline
promise between polymer properties and ease of pro- and indicated a mixture of the Form 1 and Form 2 unit
cessing via ring-opening polymerization. cells, as is seen for cold-crystallized 50/50 PEKK (Figure
A cyclomer mixture that contained a majority of dimer 5).2 The Form 1 unit cell is seen for PEEK, PEK, and
according to 1H NMR, and up to heptamer according to melt-crystallized PEKK, while Form 2 is seen for PEKK
FAB MS, was successfully polymerized in the melt at crystallized by treatment of amorphous samples with
6436 Teasley and Hsiao Macromolecules, Vol. 29, No. 20, 1996

Table 5. SNAr Polymerization of IsoPEKEK and PEK/IsoPEK Copolymers in NMC at 225 °C

GPC
item copolymer ratio concn (%) time (h) yield (%) ηinh (dL/g) Mn Mw Mw/Mn
1 isoPEKEK 25 7 90.1 2.02 23 600 76 300 3.24
2 50/50a 16 21 99.2 1.72 13 100 40 600 3.11
3 50/50 20 4 93.9 1.45 12 300 39 500 3.21
4 60/40 20 9 94.6 1.03 8 700 30 600 3.51
5 60/40 24 6 91.3 1.29 15 800 43 600 2.76
6 65/35 24 4 93.5 1.09 12 600 31 400 2.50
7 70/30 24 9 93.9 1.24 10 900 29 100 2.67
a 200 °C in NMP.

Figure 4. DSC thermogram of semicrystalline isoPEK. Figure 6. DSC thermogram of semicrystalline isoPEKEK.

Figure 7. X-ray diffraction pattern for semicrystalline iso-

PEKEK.
Figure 5. X-ray diffraction patterns for semicrystalline
isoPEK and cold-crystallized 50/50 PEKK.
same unit cell as PEK, the copolymers of isoPEK and
PEK were expected to show isomorphic crystallization.
dichloromethane. Irreproducible endotherms above 300 The low melting point for isoPEK also suggested the
°C were occasionally observed for isoPEK in our work, potential for an ideal composition possessing a Tg g 150
but the associated samples never gave X-ray diffraction °C and Tm e 300 °C, which would provide a good balance
patterns. of processing and product properties. The PEK/isoPEK
IsoPEK is soluble in chloroform and 1,1,2,2-tetrachlo- copolymers were prepared in NMC at 225 °C (Table 5).
roethane (TCE) and slightly soluble in dichloromethane The conditions were more critical for the copolymers
at reflux, in which solid samples are dispersed into fine with higher PEK contents because of the lower reactiv-
powders. However, the powders showed no crystallinity ity of FHB versus 4,3′FHB, and high molecular weights
by DSC or X-ray diffraction. IsoPEKEK was fully were most easily obtained at concentrations greater
soluble in dichloromethane at reflux, but the solution than 20%.
gelled upon standing at room temperature. The gel was DSC thermal analysis of the copolymers showed
coagulated in methanol to give semicrystalline isoPE- progression in Tg and Tm with increasing PEK content
KEK powder. DSC showed a low Tm of 193 °C on the (Table 4). The values for the 65/35 and 70/30 copoly-
first heating cycle (Figure 6), but only a Tg of 145 °C on mers are from the second heating cycle, and crystal-
the second cycle (Table 4). TGA showed that the lization exotherms (Tc) were observed on their cooling
semicrystalline polymer had good thermal stability cycle and the second heating cycle. The melting endot-
under both air and N2 (Table 4). The X-ray diffraction herms for 60/40 and 50/50 copolymers are from the first
pattern indicated a Form 1 unit cell (Figure 7). heating cycles because they do not show Tc; the Tg are
PEK/IsoPEK Copolymers. Since the X-ray diffrac- from the second cycle. The values for the 50/50 copoly-
tion patterns of isoPEK and isoPEKEK indicated the mer are from an annealed sample because the as-
Macromolecules, Vol. 29, No. 20, 1996 IsoPEK and Related Polymers 6437

Figure 8. Linear dependence of Tg (squares) and Tm (circles)

for isoPEK, PEK, and the PEK/isoPEK copolymers vs their
compositions.

Figure 10. DSC thermograms of semicrystalline 60/40 (top)

and 65/35 (bottom) PEK/isoPEK copolymers annealed at 210
°C.

Multiple melting endotherms were previously observed

for melt-crystallized PEKK with a Form 1 unit cell.2

Discussion

The NMR study of monomer electron densities agrees

with the results of the SNAr polymerizations of isoPEK
and the PEK/isoPEK copolymers in that the 3,4′ catena-
tion of 4,3′FHB renders it more reactive than FHB.
According to electron resonance theory, the para-fluoro
groups of the monomeric anion or polymeric end group
Figure 9. X-ray diffraction patterns for semicrystalline 60/ are activated for ipso substitution by conjugation with
40 (top) and 65/35 (bottom) PEK/isoPEK copolymers annealed
at 210 °C.

isolated copolymers show very broad endotherms. Fig-

ure 8 shows the linear dependence of Tg and Tm versus
the PEK content of the copolymers using the values of
the homopolymers to anchor the lines. This indicates
that the copolymers possess random microstructures the carbonyl group. The electrophilicity of the para-
with isomorphic crystallization. fluoro group in FHB is compromised by the conjugation
The 60/40 and 65/35 copolymers were examined by between the carbonyl group and the para-oxy phenolate
X-ray diffraction using films pressed at 320 °C and
annealed at 210 °C to give thermal-induced crystallinity.
The diffraction patterns showed that both were semi-
crystalline with Form 1 unit cells (Figure 9). DSC
showed that the single melting endotherms of the
original samples had separated into multiple endo-
therms, with the most endothermic peaks of the latter
roughly corresponding to those of the former (Figure 10). anion, or the bond derived during polymerization. The
Also, the average of each set of endotherms appears to para-oxy anion will deactivate the carbonyl more than
qualitatively coalesce to the Tm of 264 °C seen for the the para-oxy bond, due to its higher charge density, so
single endotherm of the annealed 50/50 copolymer. its nucleophilicity will be reduced as well. However, the
6438 Teasley and Hsiao Macromolecules, Vol. 29, No. 20, 1996

Scheme 2. Ring Opening of IsoPEK Cyclic Dimer

meta-oxy groups derived from 4,3′FHB cannot enter unreacted potassium phenolate end groups, supports its
conjugation with the carbonyl group, which will increase role as well. It is also significant that the color faded
the electrophilicity of its para-fluoro group and the upon cooling to room temperature because phenolate
nucleophilicity of its phenolate anion. Such “bridge end groups were not observed in the prior PEK work.
effects” are well known for the SNAr polymerizations of This suggests a recombination of the phenolate end
poly(arylene ether sulfone)s, where the chloro-sulfone groups with the other end group species responsible for
analog of 4,3′FHB demonstrated a rate enhancement transetherification; our results point to the p-fluoroben-
factor of 60 over the same analog of FHB.17,18 zoyl end group. At lower temperatures, the yellow color
The nucleophilicities of the phenolate anion end completely discharges at the completion of polymeriza-
groups derived from 3,4′DHB should be affected by tion, and cyclomers are quite prevalent unless long
conjugation in a similar fashion. The meta-oxy anion reaction times are used, so transetherification is pre-
should be more nucleophilic than the para-oxy anion, sumably much slower under these conditions.
although the latter should be less than the para-oxy The ring-opening polymerization of isoPEK cyclomer
anion end group from FHB. Coupled with the electro- mixtures in the melt confirms the existence of transether-
philicity of DFB, the polymerization of isoPEKEK from ification. The required temperature was not much
3,4′DHB and DFB should show a high initial rate that higher than that for polymerization in NMP or NMC,
slows with conversion as the meta-oxy anion is con- even though the conditions were certainly less polar.
sumed preferentially, and DFB is converted to a less The residue of cyclic dimer suggests that its rate of ring-
reactive para-fluoro end group. Indeed, the polymeri- opening polymerization is slower than those of higher
zation of isoPEKEK gave very high molecular weight, cyclomers. Although this is probably a kinetic steric
although it did take longer than those of isoPEK and effect, one cannot strictly rule out a thermodynamic
the PEK/isoPEK copolymers to reach a viscosity plateau. mixture. The structure of cyclic dimer must retard the
Although 3,4′ catenation imparts high reactivity to rate of the nucleophilic attack by either fluoride catalyst
4,3′FHB and the isoPEK end groups, it also provides or phenolate end groups that leads to the formation of
more degrees of freedom for their conformational iso- the intermediate Meisenheimer complexes (Scheme 2).
mers. Together, they allow cyclization of the linear The steric interaction between the relevant hydrogens
oligomers to compete effectively with chain extension of the m- and p-phenylene rings forces the latter to
for enthalpic reasons. Cyclomer formation plagues the rotate out of conjugation with the ketone functions,
reaction in less than concentrated solutions and domi- which should slow the formation of the Meisenheimer
nates with only simple dilution. However, it can be complexes. Thus the 3,4′ catenation of the isoPEK
overcome by copolymerization with 4,4′-catenated FHB repeat unit favors the formation of cyclomers in dilute
and in the homopolymerization of isoPEKEK from solution yet still permits their ring-opening polymeri-
3,4′DHB and DFB. zation to high molecular weight polymer in the melt.
The polymerizations of isoPEK at higher tempera- Further work will be needed to exploit the potential of
tures, or for a longer time at a milder temperature, gave this chemistry.
lower levels of cyclomers, which shows that they are Although the strict alternation of meta and para
kinetic rather than thermodynamic products. Although catenation in isoPEK is enforced by its AB monomer,
an increase in temperature reduces the rate of cyclomer 4,3′FHB, this does not result in the desired thermal-
formation for entropic reasons, it must also accelerate induced crystallinity. The reasons for its absence and
the equilibration of the linear and cyclic oligomers via for the difference in the previously reported melting
transetherification. The transetherification of PEK is point and that observed here for solvent-induced crys-
catalyzed by potassium carbonate at >250 °C in diphe- tallinity are not clear with the available data. The Form
nyl sulfone,19 but the higher reactivity associated with 1 unit cell implied by Evers and co-workers may have
the isoPEK repeat unit, coupled with the more polar the higher melting point, while the mixed crystallinity
natures of NMP and NMC, may enable transetherifi- of the Form 1 and Form 2 unit cells may lead to the
cation at lower temperatures. In addition, our condi- lower temperature, although the linear dependence in
tions employed a slight excess of potassium carbonate, Tm for the isomorphic PEK/isoPEK system shown in
which could serve as catalyst. Moreover, the ring- Figure 8 supports the lower melting point for isoPEK.
opening polymerization of arylene ether cyclomers, SNAr polymerization ensures a regular microstructure,
which proceeds by transetherification, is catalyzed by while the Friedel-Crafts acylation previously employed
nucleophiles like cesium fluoride or the potassium salt for isoPEK can give structural isomers. The amorphous
of 4-hydroxybenzophenone,16 and our conditions have polymer of Ueda and Sato was of higher molecular
both potassium fluoride and potassium phenolate end weight than that crystallized by Evers and co-workers,
groups to serve this function. but only the former polymer was explicitly shown to
Although transetherification during solution polym- possess a regular microstructure. Since the polymers
erization was not explicitly shown, the persistent yellow prepared here have even higher molecular weights, it
color of the NMC solutions at 225 °C, which is due to is possible that this reduces their rate of crystallization
Macromolecules, Vol. 29, No. 20, 1996 IsoPEK and Related Polymers 6439

to an undetectable level. molecular weight polymer by ring-opening polymeriza-

The analogous AA/BB polymer, isoPEKEK, was pre- tion. This indicates promise for their in situ polymer-
pared to increase the para content in a semiregular way, ization to matrix resin during the fabrication of com-
but thermal-induced crystallinity was still not observed. posite parts.
While this homopolymer might be considered to be a
50/50 copolymer of isoPEK and PEK, isoPEKEK differs Experimental Section
from the 50/50 PEK/isoPEK copolymer because it has General Procedures. All starting materials, anhydrous
strict alternation of the isoPEK and PEK repeat units, solvents, powdered K2CO3 (325 mesh), and N-methylcaprolac-
while the copolymer has a random distribution. How- tam (NMC) were supplied by Aldrich Chemical Co. NMC was
ever, isoPEKEK does not have a regular distribution of purified by vacuum distillation. 4-Fluoro-4′-hydroxybenzophe-
meta and para catenation due to the head-tail isomer- none (FHB) and 4,4′-difluorobenzophenone (DFB) were re-
ism introduced by 3,4′DHB. Although the two pheno- crystallized, respectively, from 2-butanone/cyclohexane and
ethanol/cyclohexane. Pure 3,4′-dihydroxybenzophenone
late end groups from 3,4′DHB are not equivalent in (3,4′DHB) was provided by Irwin.11
reactivity, a preference for head-to-head/tail-to-tail or A Varian Unity 400 spectrometer was operated at 399.952
head-to-tail order was not expected because this re- MHz for 1H NMR and 100.57 MHz for 13C NMR with tetram-
quires a long-range bridge effect through an entire ethylsilane as internal reference and at 376.289 MHz for 19F
repeat unit. Indeed, a small bridge effect is seen in the NMR with CFCl3 as internal reference. Routine 13C NMR used
13C NMR spectrum of isoPEKEK, which showed appar-
acquisition-gated Waltz-16 1H decoupling with adequate delay
ent doublets for three quaternary carbons bearing either times to ensure quantitative spectral integrations, and the
ketone or ether substituents that are due to chemical carbon multiplicities were determined using the APT pulse
shift differences in the head-tail isomers. sequence. A VG ZAB-E double-focusing mass spectrometer
was operated in the FAB MS mode using Xe ionization and
The differences in the microstructures of isoPEKEK m-nitrobenzyl alcohol as matrix; the samples were prepared
and the 50/50 copolymer are readily apparent from their using 1,1,2,2-tetrachloroethane. The ηinh were measured in
thermal properties. While possessing a similar Tg, the methanesulfonic acid at a concentration of 0.5 g/dL at 30 °C.
Tm of isoPEKEK is 70 °C lower than that of the 50/50 DuPont 2100 and 2200 thermal analyzers were used at 10 °C/
copolymer, nor can isoPEKEK be crystallized thermally. min for TGA under air and nitrogen and for DSC under
This is due to the absence of blocks of the PEK repeat nitrogen; the latter results are reported for the second heating
unit, and the disorder introduced by the head-tail cycle unless noted otherwise. X-ray diffraction scans were
isomers. Moreover, the thermal properties of both collected in the symmetrical transmission mode using an
isoPEKEK and isoPEK are unusual compared to those automated Philips diffractometer (curved crystal monochro-
mator, 1° divergence and receiving slits, sample rotating) and
of typical poly(arylene ether ketone)s. For example, Cu KR radiation; the data were collected in a fixed time mode
their value for Tg (K)/Tm (K) of 0.90 is unusually high with a step size of 0.05° 2θ and run from 4 to 65° 2θ. A Waters
compared to typical values of 0.65-0.71. So meta 150C chromatograph was used for GPC following the method
catenation has a more profound effect on the crystal- originally developed for PEEK.14
lization of poly(arylene ether ketone)s when distributed Synthesis of 4-Fluoro-3′-hydroxybenzophenone. Fluo-
in a semiregular fashion along the polymer chain. robenzene (95 mL, 1.0 mol) and 138 g of m-hydroxybenzoic
The linear dependence of Tg and Tm for the PEK/ acid (1.00 mol) were charged to a Hastelloy C autoclave. The
isoPEK copolymers indicates that they have random sealed autoclave was cooled, evacuated, and then charged with
500 g of HF and 136 g of BF3 (2.00 mol). The autoclave was
microstructures. The difference in the reactivities for
shaken at room temperature for 6 h under 30 psig of BF3 with
FHB and 4,3′FHB may affect the rates of polymerization periodic repressurization until uptake had ceased. The BF3
for the copolymers, but their microstructures probably and HF were vented from the autoclave, and the residue was
randomize by transetherification. The 65/35 PEK/ rinsed onto ice with methanol. The acidic slurry was neutral-
isoPEK copolymer has nearly ideal thermal properties ized to pH 7 using 50% aqueous sodium hydroxide. The
for typical applications. product was collected by vacuum filtration, washed with water,
and dried to give 171.1 g of red-brown solid for a 79.2% crude
Conclusion yield. The product was sublimed at 130 °C and 0.5 Torr to
give a light yellow solid, recrystallized from 550 mL of toluene,
The 3,4′ catenation of the isoPEK repeat unit and and dried to give 133.3 g of white solid for a 61.6% yield; mp
related monomers provides high reactivity and unique 99-99.5 °C (lit. 105,20 102 °C21). 1H NMR (TCE-d2): δ 7.115
versatility to this monomer/polymer system. High (1H, ddd, J ) 8.0, 2.8, 1.2 Hz), 7.165 (2H, dddd, J ) 8.8, 2.8,
molecular weight isoPEK that is free of cyclomers can 2.0 Hz, JHF ) 8.4 Hz), 7.274 (1H, ddd, J ) 7.6, 1.2, 1.2 Hz),
be prepared by SNAr polymerization of 4,3′FHB in NMC 7.308 (1H, dd, J ) 2.8, 1.2 Hz), 7.364 (1H, dd, J ) 8.0, 7.6
at 225 °C and coagulation in acetone. Under the same Hz), 7.835 (2H, dddd, J ) 8.8, 2.8, 2.0 Hz, JHF ) 5.2 Hz). 1H
NMR (CDCl3): δ 7.110 (1H, ddd, J ) 8.0, 2.8, 1.2 Hz), 7.148
conditions, isoPEKEK homopolymer and PEK/isoPEK
(2H, dddd, J ) 9.2, 3.2, 2.4 Hz, JHF ) 8.4 Hz), 7.257 (1H, ddd,
copolymers are easily prepared with no evidence of J ) 7.6, 1.6, 1.2 Hz), 7.338 (1H, dd, J ) 8.0, 7.6 Hz), 7.357
cyclomer formation. IsoPEK and isoPEKEK are amor- (1H, dd, J ) 2.8, 1.6 Hz), 7.848 (2H, dddd, J ) 9.2, 2.8, 2.4
phous as isolated from SNAr polymerization and cannot Hz, JHF ) 5.2 Hz). 13C NMR (CDCl3): δ 115.5 (2CH, d, JCF )
be thermally crystallized, but solvent-induced crystal- 21.9 Hz), 116.5 (CH), 120.3 (CH), 122.4 (CH), 129.6 (CH), 132.9
lization shows that these compositions have low melting (2CH, d, JCF ) 9.2 Hz), 133.2 (C), 138.3 (C), 156.2 (C), 165.5
points for poly(arylene ether ketone)s. This makes them (C, d, JCF ) 254.6 Hz), 196.4 (C). 19F NMR (DMSO-d6): δ
suitable for applications that are unusual for poly- -106.5 (tt, JHF ) 8.3 and 5.5 Hz). Anal. Calcd for C13H9FO2:
(arylene ether ketone)s, such as adhesives or films, C, 72.22; H, 4.20. Found: C, 72.33; H, 4.12.
although nucleating agents might be needed to exploit Synthesis of IsoPEK in NMP/Toluene. 4,3′FHB (4.32
g, 20.0 mmol), 1.45 g of potassium carbonate (10.5 mmol), 50
their crystallization behavior. The PEK/isoPEK copoly-
mL of toluene, and 25 mL of NMP were charged to a 100 mL
mers can be thermally crystallized and have a good round-bottom flask equipped with a one-piece Claisen distil-
balance of thermal properties for both processing and lation apparatus and mechanical stirrer. After purging with
typical applications. Mixtures of isoPEK cyclomers are argon, the yellow solution was heated to 170 °C with an oil
easily prepared in moderate yields in dilute solutions, bath, where it evolved gas with the consumption of potassium
and after their purification, can be converted to high carbonate. The toluene/water azeotrope distilled at a head
6440 Teasley and Hsiao Macromolecules, Vol. 29, No. 20, 1996

temperature of 106 °C, which continued for 100 min. The dark Synthesis of 65/35 PEK/IsoPEK Copolymer. FHB (2.81
yellow solution was then heated to 200 °C to drive off residual g, 13.0 mmol), 1.51 g of 4,3′FHB (7.00 mmol), 1.45 g of
toluene. Over the next 4 h, the solution lightened in color with potassium carbonate (10.5 mmol), and 12.5 mL of NMC were
the separation of a white precipitate to ultimately give a charged to a 50 mL round-bottom flask equipped with a three-
viscous brownish-green mixture. The solution was cooled, neck adapter, a mechanical stirrer, a gas inlet, and a gas outlet
acidified with 2 mL of acetic acid, and coagulated in water in connected to a bubbler. The vessel was purged with nitrogen,
a blender to give a fibrous mass. The polymer was collected and then the yellow solution was heated to 225 °C with an oil
by vacuum filtration, washed several times with water, bath under a slow nitrogen purge. The solution became orange
extracted with 150 mL of methanol at reflux for 4 h, collected as it evolved gas, consumed potassium carbonate, and formed
by vacuum filtration, and washed with methanol. The off- a fine white precipitate. After 3.7 h, the solution was very
white polymer was dried in a 50 °C vacuum oven under a viscous and orange-brown. The solution became extremely
nitrogen purge to give 3.84 g for a 98.0% yield. The ηinh was viscous as it cooled to room temperature, and the color
2.51 dL/g. A sample was washed with acetone, and the ηinh discharged to an off-white. The polymer was coagulated in
increased to 2.80 dL/g. FAB MS: m/z 393.3, 589.5, 785.6, 200 mL of acetone with 8 mL of acetic acid in a blender,
981.7, 1178.8, 1375.0, 1572.2; calcd (M + H for cyclic collected by vacuum filtration, and washed with acetone. It
(C13H8O2)n): 393.1 (dimer), 589.2 (trimer), 785.2 (tetramer), was washed with water in the blender to extract the inorganic
982.0 (pentamer), 1178.2 (hexamer), 1374.4 (heptamer), 1570.7 residues, collected by vacuum filtration, and washed with
(octamer). water. The off-white polymer was dried in a 70 °C vacuum
oven under a nitrogen purge to give 3.67 g for a 93.5% yield.
Synthesis of IsoPEK in NMC. 4,3′FHB (4.32 g, 20.0
The ηinh was 1.09 dL/g.
mmol), 1.45 g of potassium carbonate (10.5 mmol), and 9 mL
Synthesis of IsoPEK Cyclomers in DMSO. 4,3′FHB
of NMC were charged to a 50 mL round-bottom flask equipped
(4.32 g, 20.0 mmol), 1.45 g of potassium carbonate (10.5 mmol),
with a Claisen adapter, a mechanical stirrer, and a gas inlet.
and 200 mL of DMSO were charged to a 300 mL round-bottom
After purging with nitrogen, the yellow solution was heated
flask equipped with a large oval magnetic stirring bar, a
to 225 °C with an oil bath. Over a 4 h period, it darkened in
condenser, and a gas inlet. The vessel was purged with argon,
color and evolved gas during the consumption of potassium
and then the yellow solution was heated to 170 °C with an oil
carbonate. Then the color partly faded and the viscosity
bath. The solution darkened with the consumption of potas-
increased slightly with the separation of a white precipitate.
sium carbonate. After several hours, a white precipitate had
The solution increased in viscosity and the color discharged
separated from the dark solution. After 2 days, the mixture
to off-white as it cooled to room temperature. The polymer
was cooled and poured into water to give a suspension. Dark
was coagulated in 250 mL of acetone in a blender, collected
solids were collected by vacuum filtration, and the filtrate was
by vacuum filtration, and washed with acetone. It was washed
extracted with dichloromethane to leave a clear aqueous phase.
with water in the blender to extract the inorganic residues, The organic phase was evaporated to give dark solids. The
collected by vacuum filtration, and washed with water. The solids were combined by dissolving them in acetone, filtering
off-white polymer was dried in a 100 °C vacuum oven under a the solution, and evaporating to give 1.77 g for a 45.1% yield.
nitrogen purge to give 3.54 g for a 90.3% yield. The ηinh was A sample was dissolved in dichloromethane, filtered through
1.27 dL/g. 1H NMR (TCE-d2): δ 7.09 (2H, d, J ) 8.6 Hz), 7.32 silica gel with additional solvent, and evaporated to give an
(1H, d, J ) 7.6 Hz), 7.52 (1H, bs), 7.52 (1H, dd, J ) 7.6, 7.6 off-white solid. The ηinh was 0.06 dL/g. 1H NMR (CDCl3; major
Hz), 7.57 (1H, d, J ) 7.6 Hz), 7.84 (2H, d, J ) 8.6 Hz). 1H peaks for cyclic dimer): δ 6.331 (2H, dd, J ) 2.8, 1.6 Hz), 7.153
NMR (CDCl3): δ 7.059 (2H, AA′XX′, J ) 8.8, 2.8, 2.0 Hz), 7.288 (4H, AA′XX′, J ) 8.8, 2.4, 2.0 Hz), 7.414 (2H, ddd, J ) 8.0,
(1H, ddd, J ) 7.6, 1.8, 1.2 Hz), 7.494 (1H, dd, J ) 8.0, 7.6 Hz), 2.8, 1.0 Hz), 7.541 (4H, AA′XX′, J ) 8.8, 2.4, 2.0 Hz), 7.542
7.504 (1H, dd, J ) 1.6, 0.8), 7.569 (1H, ddd, J ) 7.6, 1.2, 1.2 (2H, dd, J ) 8.0, 7.6 Hz), 7.723 (2H, ddd, J ) 7.6, 1.6, 1.0 Hz).
Hz), 7.829 (2H, AA′XX′, J ) 8.8, 2.8, 2.0 Hz). 13C NMR 1H NMR (TCE-d ; major peaks for cyclic dimer): δ 6.320 (2H,
2
(CDCl3): δ 117.4 (2CH), 120.8 (CH), 123.6 (CH), 125.8 (CH), dd, J ) 2.4, 1.6 Hz), 7.184 (4H, AA′XX′, J ) 8.4, 2.4, 2.0 Hz),
129.9 (CH), 131.8 (C), 132.4 (2CH), 139.8 (C), 155.5 (C), 161.0 7.461 (2H, ddd, J ) 8.0, 2.4, 1.2 Hz), 7.549 (4H, AA′XX′, J )
(C), 194.0 (C).10 8.4, 2.4, 2.0 Hz), 7.584 (2H, dd, J ) 8.0, 7.6 Hz), 7.725 (2H,
Synthesis of IsoPEKEK. 3,4′DHB (2.142 g, 10.0 mmol), ddd, J ) 7.6, 1.6, 1.2 Hz). 13C NMR (TCE-d2; major peaks for
2.182 g of DFB (10.0 mmol), and 12 mL of NMC were charged cyclic dimer): δ 118.3 (2CH), 121.2 (4CH), 122.20 (2CH),
to a 50 mL round-bottom flask equipped with a three-neck 122.24 (2CH), 130.7 (2CH), 131.2 (4CH), 135.1 (C), 138.6 (2C),
adapter, a mechanical stirrer, a gas inlet, and a gas outlet 157.4 (2C), 157.9 (2C), 195.9 (2C). FAB MS: m/z 393.4, 589.5,
connected to a bubbler. The vessel was purged with nitrogen, 785.7; calcd (M + H for cyclic (C13H8O2)n): 393.1 (dimer), 589.2
and then 1.45 g of potassium carbonate (10.5 mmol) was added (trimer), 785.2 (tetramer).
under nitrogen. The flask was heated to 225 °C with an oil Ring-Opening Polymerization of IsoPEK Cyclomers.
bath under a slow nitrogen purge. The clear solution became Cesium fluoride (6 mg, 0.04 mmol) was dispersed in 400 mg
yellow at >200 °C and then orange after 30 min, with the of cyclomer mixture (2.0 mequiv of repeat unit) with 20 mL of
consumption of potassium carbonate and separation of a white methanol in a glass polymer tube. The solvent was evaporated
precipitate. After a total of 7 h, the solution was diminished under vacuum, and then the tube was immersed in a 200 °C
in color to light yellow and was very viscous. The solution metal alloy bath for 2 min before venting to nitrogen. The
became extremely viscous as it cooled to room temperature, heat was increased to 240 °C for 1 h, and then to 260 °C for 1
and the color discharged to off-white. The polymer was h. The initial melt was orange, but it darkened to brown as it
coagulated in 250 mL of acetone with 1 mL of acetic acid in a increased substantially in melt viscosity. The tube was cooled
blender, collected by vacuum filtration, and washed with to room temperature and shattered to isolate the tough
acetone. It was washed with water in the blender to extract polymer with an ηinh of 0.93 dL/g. The 1H NMR (TCE-d2)
the inorganic residues, collected by vacuum filtration, and spectrum showed isoPEK polymer and the resonance for cyclic
washed with water. The white polymer was extracted with dimer at δ 6.3. FAB MS: m/z 393.2; calcd (M + H for cyclic
water, then methanol, at reflux to remove any residues and dimer, (C13H8O2)2): 393.1.
dried in a 70 °C vacuum oven under a nitrogen purge to give
3.53 g for a 90.1% yield. The ηinh was 2.02 dL/g. 1H NMR Acknowledgment. Robert J. Trotman, Joseph P.
(TCE-d2): δ 7.11 (2H, dd, J ) 8.4, 3.6 Hz), 7.17 (4H, m), 7.34 McKeown, Michael J. Halfhill, and Joseph G. Lynch
(1H, d, J ) 7.6 Hz), 7.53 (2H, m), 7.59 (1H, d, J ) 7.6 Hz), provided excellent laboratory assistance. Technical
7.84 (4H, m), 7.88 (2H, d, J ) 7.2 Hz). 13C NMR (TCE-d2): δ assistance was provided by Robert L. Lock.
117.6 (2CH), 118.5 (2CH), 118.7 (2CH), 120.7 (CH), 123.7 (CH),
125.8 (CH), 130.1 (CH), 132.3 (4CH), 132.4 (2C), 132.5 (2CH),
References and Notes
133.1 (0.5C), 133.2 (0.5C), 139.5 (C), 155.6 (C), 159.3 (0.5C),
159.4 (0.5C), 160.0 (C), 160.5 (0.5C), 160.6 (0.5C), 193.9 (C), (1) May, R. Encyclopedia of Polymer Science and Engineering;
194.2 (C). Wiley-Interscience: New York, 1988; Vol. 12, pp 313-320.
Macromolecules, Vol. 29, No. 20, 1996 IsoPEK and Related Polymers 6441

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