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Abstract:
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through the copyediting, typesetting, pagination and proofreading process which may lead to
differences between this version and the Version of Record. Please cite this article as doi:
10.1002/pi.5869
1. Introduction
TR polymers were first recognized as microporous materials useful as membranes for gas
separation by Lee and coworkers.6 The skeletal rearrangement involved in the conversion of the
Whereas, literature alludes to thermal rearrangement of –OH, -SH and –NH2 functional imides, a
significant body of published literature only deals with ortho-hydroxyl imides resulting in poly
(benzoxazole)s. There is only one published reference to poly (benzimidazole)s7 and none to
poly (benzothiozole)s.
In the decade since the TR chemistry was first reported a vast body of literature has accumulated
on a large number of polymers with diverse structures and their gas permeability properties.4,6,7,8
The insolubility of the final products of TR has precluded the ability to understand the precise
polymer structure, thus, limiting reliable structure-property-performance correlations. It is,
therefore, appropriate to review critically the structural information available in the literature of
the products reported so far and understand whether there is some clarity on the structure of
polymers produced by TR chemistry. The ability to precisely control and reproducibly produce
materials with well-defined structure and properties will be a key to large scale manufacture and
industrial applications of such materials. In this review, we focus mainly on polymer structure
and exclude performance and applications of such materials in gas separations. The latter has
3,5
been extensively discussed in other recent reviews on this subject.
This chemistry was further elaborated by Colson et al10 (Scheme 3). They performed the reaction
of o-phenylenediamine with phthalic anhydride in chloroform at 25° C. An amide was isolated
which, when heated to 140-160° C for 30 min in DMAc resulted in the formation of 1 which
upon further heating to 210° C gave 1, 2-benzoylenebenzimidazole (2). 2 was also reported to
form when o-phenylenediamine was reacted with phthalic anhydride in refluxing nitrobenzene
for 90 min. Under these conditions, there was no evidence for the formation of 2-(o-
carboxyphenyl) benzimidazole (4).
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Young also examined the melt phase reaction between o-phenylenediamine and phthalic
anhydride. Approximately 16 % of o-phenylene bibenzimidazole (3), 44 % of 1, 2-
benzoylenebenzimidazole (2) and 22 % 1, 2- phenylenebisphthalimide (5) were formed under
these conditions (Scheme 4). In the absence of vacuum, heating N-(o-aminophenyl) phthalamic
In solution and at room temperature the predominant products are 1 and 4. 1 and 4 upon
dehydrocyclization in melt and under vacuum will result in the formation of compound 2. Under
these conditions there is no conclusive evidence for the formation of benzimidazole by the
decarboxylation of 4.
However, it is not clear how the authors performed the reaction in melt phase at atmospheric
pressure, since N-(o-hydroxyphenyl) phthalimide sublimes at 235° C. Additionally the products
formed in the melt phase reaction can be understood only if some water is present in the reaction
which will cause the partial hydrolysis of N-(o-hydroxyphenyl) phthalimide to phthalic
anhydride and o-aminophenol (Scheme 6).
The above observations were understood based on the relative propensity of inter- or intra-
molecular reaction depending on the extent of conformational mobility extant in the starting
material. The mobility was dependent on the molecular structure as well as the manner of
Based on a careful analysis of all reports on small molecule TR chemistry, we can draw the
following broad conclusions:
(a) The TR chemistry of o-aminophenyl phthalimide is very complex. Even at high temperatures the
formation of benzimidazole has never been demonstrated. The major product of this reaction
appears to be 1, 2-benzoylenebenzimidazole obtained under conditions where water is removed.
(b) Substantial amounts of 1,2-phenyl bisbenzimidazole and 1,2-phenyl bisphthalimide are formed
under these conditions. When extended to polymer analogous reaction, such reactions will lead
to extensive crosslinking.
(c) For o-hydroxyphenyl pthalimides, the course of the reaction depends on whether the reaction is
conducted in vapor phase or in a condensed melt phase. The difference has been attributed to the
degree of molecular mobility which determines whether the reaction will be exclusively inter-
molecular or both inter- and intra-molecular.
(d) Presence of inadvertent moisture can also lead to increased inter-molecular reaction
(e) There is scarcity of model compound studies using more flexible bispthalimides to understand
better the influence of molecular mobility.
(f) Inter-molecular reactions of the type observed in small molecular chemistry have the potential to
cause crosslinking when extended to polymers.
3.1. TR-Polybenzoxazoles
As inferred from the knowledge derived from small molecule chemistry, TR reactions are
complex. All TR products reported so far, irrespective of the monomers used, are insoluble
products, thus, precluding rigorous structural characterization of the product. Characterization
-1
has been restricted to appearance of the IR bands at 1050 -60 cm (corresponding to C-O-C),
-1
1470-1480 cm and 1545-1560 cm -1(corresponding to C=N stretching frequency). These were
taken as evidence for the formation of the benzoxazole rings. There are few papers which
provide solid state NMR evidence for the formation of oxazole ring. Conversions have been
determined by measuring the gas evolved and based on the assumption that the formation of an
oxazole ring involves liberation of two molecules of carbon dioxide.
The efficiency of TR reaction is influenced by many reaction parameters. These are, the nature
of the sample (film or powder), the nature of the environment (nitrogen or air), reaction
temperature and the chemical nature of the monomers used for the synthesis of precursors as
well as the molecular weight of the precursor polymers. Generally, temperatures greater than
450° C are preferred. The air was found to be detrimental to the reaction causing undesirable
degradation products and loss of mechanical properties. This is not surprising since the precursor
polymer contains oxidatively labile phenol group.18 Lee and coworkers showed that a film
The paucity of rigorous proof of polymer structures obtained after TR has led to questions on the
authenticity of the mechanisms implied (Scheme 1) and possible side reactions. Hodgkin and
coworkers questioned the veracity of structures proposed for the products of TR.20 They pointed
out the wide variation in the IR peak positions proposed for the benzoxazole structures in the
literature, the insolubility of the resulting products and the possibility of impurities in the
precursor structures on account of competing reaction of both the amine and the phenolic group
reacting with the dianhydrides. Based on experimental and molecular simulation studies, they
proposed an alternative biphenylene bisimide structure which they felt was consistent with all
experimental evidence. To explain the formation of this compound they invoked the
intermediacy of a reactive benzyne intermediate formed by the elimination of water from the
o-hydroxylphenyl phthalimide. However, it must be recognized that such a mechanism for the
formation of benzyne is unprecedented in the literature. Lee and coworkers contradicted the
conclusions of Hodgkin and coworkers and showed that several experimental parameters such as
the thermal treatment protocol, nature of sample used (powder vs film) as well as the molecular
weight of the precursors employed for TR could have caused the difference in observations.19
The high temperatures used for preparing TR polymers has been a subject of concern and could
severely limit its use in large scale membrane fabrication processes. At the temperatures
typically used 450° C. TR is accompanied by several uncontrollable reactions that could lead to
chain degradation and loss of mechanical properties. Use of more flexible chains in the precursor
polymer structure can result in a reduction of TR temperatures to 350° C; however, this is
accompanied by loss of permeability and selectivity properties in gas transport 8g.
23
Tena et al have reported a novel low temperature chemistry using a Claisen rearrangement
reaction (CR) for the preparation of microporous polymers. The reaction was reported to occur
at temperatures of ~ 300° C. (Scheme 10). The resulting polymers, however, possess a labile
ortho-allyl groups which underwent cross-linking reaction to form a tight network. The CR
polymers showed improvement in mechanical strength which was attributed to the presence of
alkyl groups in the polymer. At 350° C, CR polymers exhibit lower permeabilities and much
higher selectivity. This was attributed to the formation of smaller free-volume elements which
remain stable with increasing temperature unlike the pore structure in TR polymers.
3.2. TR-Polybenzimidazoles
There is only paper which reports a purported TR of N-(o-amino phthalimide).7 It was proposed
that the first formed structure is a poly1,2–benzoylenebenzimidazole (also called polypyrrolone).
This reaction is analogous to what is reported in small molecule TR chemistry (Schemes 2, 3
and 4). Alkaline hydrolysis of poly1,2 –benzoylenebenzimidazole at 100 °C followed by
heating at 450° C was reported to lead to a microprous polybenzimidazole. The structural
evidence provided was weak and limited to broad IR absorption bands at 2500–3500 cm−1
(attributed to free N–H stretching), 1575 cm−1 (attributed to conjugated ring-vibration between
Based on our understanding of small molecule TR chemistry, the only feasible and dominant
product of this reaction is a poly1,2–benzoylenebenzimidazole (path a) accompanied by several
side reactions which will lead to crosslinking of the polymer (path b and c). These are shown in
Scheme 11. Furthermore, it is more appropriate to call the reaction of o-amino phenyl group
with the carbonyl of the phthalimide as a thermal dehydrocyclization reaction. None of the
features commonly attributed to thermal rearrangement, such as, changes in chain conformations
and interchange of spatial locations of atoms, can be expected to occur during thermal
dehydrocyclization reactions. Consequently, the high fractional free volume reported for the
polymers prepared (0.267) should be attributed to some other, as yet unknown, structural
7
features of such polymers.
3.3. TR-Polybenzothiazoles
4. Conclusions
In spite of an explosion of interest that were triggered by the seminal paper by Park et al.,
several issues remain to be better understood concerning this class of polymers 6. Polymers
prepared by TR processes have shown interesting permeability-selectivity relationships in gas
transport. For CO2 / CH4 pair the TR polymers often show transport properties well above the
The answer to this question is ambiguous. The occurrence of unknown side reactions at the high
temperatures used for thermal rearrangement, lead to poorly characterized polymer structures.
There is also little understanding how these side reactions are influenced by reaction conditions.
This will make scaling up of such processes for industrial manufacturing complex and difficult to
ensure reproducibility of properties. This fact also makes it difficult to assess structure-property-
performance relationships, which is a key requirement for a process to be used for large scale
manufacturing. For this to become a reality, TR processes from appropriate precursors must be
designed to occur at lower temperatures and result in soluble polymers which can be adequately
characterized. The large part of the published literature to date deal with only the
poly(benzoxazole) type structures. The generality of TR reaction as often depicted in the
literature (Scheme 1) remains yet to be established.
Processes such as thermal dehydrocyclization and Claisen rearrangement have been proposed for
producing analogous polymers at relatively lower temperatures. In spite of this, the polymers
derived from these reactions are also insoluble. Thermal dehydrocyclization reaction is
mechanistically different from the TR reactions and it is not clear how fractional free volumes
are created in such polymers. There is a paucity of good data on pore sizes and their distribution
in polymers produced by thermal dehydrocyclization. Claisen rearrangement is an interesting
process because it allows the reaction to occur at temperatures as low as 300 ° C. Unfortunately,
the rearranged structure has a labile ortho-allyl group which results in the polymer becoming
insoluble.
In conclusion, we believe that in spite of some attractive and unique gas separation properties of
membranes derived from such polymers, the intractable nature of such materials and poorly
Acknowledgments
AM thanks the Council of Scientific and Industrial Research (CSIR), New Delhi for the grant of
a Research Associateship. SS thanks CSIR for the award of Bhatnagar Fellowship and the
Department of Science and Technology, New Delhi for the award of J.C. Bose Fellowship.
Understanding structure and composition of thermally rearranged polymers based on small molecule chemistry: A
perspective
1 11a 12a - 0.82b - 500 1 1058, 1617 109, 163 100 - - [12]
9 12b - - 301 450 1 1058, 1480 108, 162 100 510,72 0.28 [6,
6 8b]
a
% conversion
b
[ɳ], dL/g
c
TR performed in vacuum
11b 12 b
TR 450 1554, 1057 0.21 780 b 37 b 21 b 21
2
1479
11b 12 b
TCD 350 1554, 1057 0.22 140 b 5.2 b 27 b 21
3
1479
11h 12 b
11h 12 b
11b
Scheme 8: Dianhydrides and diacid chloride used for preparing precursors for TR
11
12