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Understanding structure and composition of thermally rearranged polymers based on

small molecule chemistry: A perspective

A. Murugesan,*1 and Swaminathan Sivaram2


1
SSN College of Engineering (An autonomous institution), Kalavakkam, Kanchipuram, India.
2
Indian Institute of Science Education and Research, Dr. Homi Bhabha Road, Pune, India.

Abstract:

We provide herein a critical perspective of the burgeoning literature on microporous polymers


prepared using Thermal Rearrangement (TR) processes based on the learning derived from
analogous chemistry involving small molecular weight compounds. TR polymers have shown
interesting permeability-selectivity relationship in gas separation and, thus, have generated wide
interest as potential membrane materials for industrial applications. The intractable nature of the
products obtained by TR processes have precluded rigorous structural elucidation of the
polymers. Based on the small molecule chemistry, we conclude that structures are likely more
complex than generally depicted in the published literature. Interestingly, a simpler chemistry,
namely, thermal dehydrocyclization (TCD), leads to products identical to that derived from TR,
but at significantly lower temperatures. However, TCD chemistry does not involve a skeletal
rearrangement of the kind purported in TR during the conversion of the imide to an oxazole ring
resulting in spatially confined heterocyclic ring polymers. Yet, they show similar fractional free-
volume elements as exhibited by TR polymers. This is intriguing and points out to a need for
more careful examination of the factors responsible for microporosity in such materials. TR
chemistry as currently practiced appears limited to only benzoxazole type structures. 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.
Seen from this perspective, the TR processes leaves much to be desired and further
improvements are clearly warranted.

This article has been accepted for publication and undergone full peer review but has not been
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

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Keywords: Microporous polymers; Thermal-rearrangement; Fractional free-volume; Separation
membranes; Polybenzoxazoles; Dehydrocyclization

*Corresponding author: Mobile: +91 9842881227; murugesana@ssn.edu.in

1. Introduction

Microporous polymers, a sub-class of porous polymers have attracted significant attention in


recent years. This is on account of myriad applications of such polymers in areas, such as, gas
separation, gas storage, organic solvent nanofiltration membranes, membranes for selective ion
transport in fuel cells and batteries, and carbon dioxide capture. The preparation, properties and
applications of microporous polymers have been discussed extensively in recent literature, in a
monograph and several reviews.1-4

Among the many methods employed to generate microporosity in polymers, thermal


rearrangement chemistry of ortho-substituted N-arylphthalimides has received unusually large
attention.3-5 Thermal rearrangements (TR) of functionalized polyimides yield rigid microporous
polymers with high free-volume elements which show excellent gas permeability with
reasonable selectivity. Such free-volumes are created by hindered chain mobility and lack of
packing order in gassy polymers and lead to materials possessing pore diameters in the range of
5-10 Å. The fact that TR polymers could have molecular sieving characteristics appear to have
triggered a large number of studies in this area. TR chemistry can be conducted in the solid state
and offers an approach towards fabrication of free-standing membranes from soluble precursors.
In view of these characteristics, such polymers have been considered promising materials for
large scale industrial membrane separation processes, such as, CO2 capture, nitrogen separation
from air, natural gas sweetening etc.

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

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imide to an oxazole ring result in spatially confined heterocyclic ring polymers, and, consequent
changes in the conformation and the topology of the molecule. This was proposed to result in
connected narrow “hour-glass” shaped cavities. Such cavities allow a linear molecule like
carbon dioxide to slide through while inhibiting the passage of a bulkier molecule like methane.
The basic chemistry of thermal rearrangement is shown in Scheme 1.

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.

2. Small molecule TR chemistry

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Understanding TR chemistry in small molecules is useful to predict the course of analogous
reactions in polymers. TR in small molecules typically occurs via a melt phase intramolecular
rearrangement reaction at high temperature and is, generally, accompanied by release of small
molecules such as CO2, H2O, NH3, etc.
The first report of TR of a small organic molecule is due to Dawan and Marvel in 1965. 9 They
examined the melt phase reaction of o-phenylenediamine with phthalic anhydride in a mole ratio
of 1:1 in the temperature range 115 to 300° C (Scheme 2).

At lower temperature, 115° C, 32% yield of N-(o-aminophenyl)phthalimide (1) was obtained by


a loss of one molecule of water. At higher temperature (140° C), the condensation proceeded
with the elimination of two molecules of water resulting in 1, 2-benzoylenebenzimidazole (2). At
250° C, 49% yield of o-phenylene bibenzimidazole (3) was formed. Using a mole ratio of 2:1,
the authors reported three products, namely N-(o-aminophenyl) phthalimide (1.5%), 1, 2-
benzoylenebenzimidazole (5%) and o-phenylene bibenzimidazole (49 %). The authors had
limited access to analytical methods at that time and the conclusions were drawn based only on
dispersive IR and elemental analysis. No attempt was made to elucidate the reaction mechanism.

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).
11
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

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acid resulted in the formation of about 27 % of 2-(o-carboxyphenyl) benzimidazole (4) along
with 2 (14 %) and an imidazole –imide derivative (18%). The same reaction when performed in
solution (DMF, 25 ° C) resulted in the formation of 1, 3 and 4.

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.

TR of N-(o-hydroxyphenyl) phthalimide (6, Scheme 5) to benzoxazoles has also been


examined.8a, 12 The o-hydroxy containing imides do not have the necessary functionality to form
stable heterocyclic ring such as observed in the case of N-(o-aminophenyl) phthalimide. Mathias
and co-workers examined the TR of N-(o-hydroxyphenyl) phthalimide, both in vapor phase and
melt phase. They reported formation of 2-phenylbenzoxazole (7) in 83% yield in the vapor
phase. However, in the melt phase reaction several products were observed.

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).

Mathias and coworkers also attempted the TR reaction of bispthalimide of 3,3’-dihydroxy-4,4’-


diaminobiphenyl (9) at 400 ° C (Scheme 7). The bis benzoxazole product (10) could be obtained
only in 5 % yield, balance being a black insoluble product.12

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

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conducting the TR (vapor phase or melt condensed phase). Low molecular mobility was invoked
in the vapor phase leading to good yield of the desired TR product. In the melt phase, larger
mobility of molecules led to intermolecular reaction leading to products, such as 8. A more rigid
biphenyl structure (9) led to the inefficient TR reaction. When the model reactions were
extended to polymer analogous reaction, it was proposed that the TR in the solid state resemble
vapor phase chemistry of small molecules (low molecular mobility) leading to the formation of
poly(benzoxaxole)s.

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.

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3. Macromolecular TR chemistry

3.1. TR-Polybenzoxazoles

The TR chemistry of ortho-substituted N-arylphthalimides has been extended to the preparation


of the corresponding poly (benzoxazole)s in the solid state. The pthalimides were derived from a
variety of dianhydride (Scheme 8) and aminophenol (Scheme 9) monomers. The monomers that
have been used for the synthesis of the precursors used for TR, the properties of the precursors,
reaction conditions used for TR and some key properties of the products of TR are summarized
in Table 1. This compilation affords at a glance the information that has been reported in the
literature so far and enables us to draw some general conclusions.

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

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sample derived from monomers 11b and 12b leads to improved conversion during TR compared
to a powder sample.19 Higher molecular weight of the precursor polymer was also found
necessary for better results.

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.

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Therefore, new approaches to reduce the temperature at which such reactions are conducted has
been reported. Kushwaha et al21 reported a comparative study of thermal rearrangement (TR) of
poly (o-hydroxy phthalimide) and thermal cyclodehydration (TCD) of poly(hydroxyamide).
Polybenzoxazole membranes were obtained at 350° C which is about 100° C lower than that used
for TR reactions. Similar polymers were also obtained at 375° C by Díez et al using a TCD
process.22 The results of the two studies were similar and the polymers formed were found to be
insoluble. An interesting observation is that both TR and TCD processes produce polymers with
similar FFV. TCD process does not involve any skeletal rearrangement of the kind that has been
proposed for TR; nevertheless, fractional free-volume is created in such polymers,

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

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benzene and the imidazole ring) and few additional broad absorptions between 1441cm−1 and
1411cm−1.

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

There is no example of a polybenzothiazoles prepared by thermal rearrangement reactions in the


literature. It is unlikely that such a reaction will occur since –SH groups are poorly
nucleophilic. Furthermore benzene thiols are known to fragment into radicals at higher
temperatures resulting in the formation of disulfides. On account of these reasons preparation of
polybenothiazoles by TR chemistry may not be possible

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

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2008 upper-bound, making such polymers the among the best materials for natural gas
processing. This apart, they also exhibit resistance to plasticization and high chemical resistance.
An interesting question, is therefore, whether such polymers can be considered for practical
membrane application for gas separation applications.

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

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understood chemistry may make it difficult for them to be widely deployed in commercial
applications.

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.

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The literature on microporous polymers prepared using thermal rearrangement is reviewed based
on analogous chemistry involving organic compounds with the objective of understanding the
complex nature of this reaction
Accepted Article

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Accepted Article Understanding structure and composition of thermally rearranged polymers based on small molecule chemistry: A
perspective

A. Murugesan,*1 and Swaminathan Sivaram2


1
SSN College of Engineering (An autonomous institution), Kalavakkam, Kanchipuram, India.
2
Indian Institute of Science Education and Research, Dr. Homi Bhabha Road, Pune, India.

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Accepted Article Tables

Understanding structure and composition of thermally rearranged polymers based on small molecule chemistry: A
perspective

A. Murugesan,*1 and Swaminathan Sivaram2


1
SSN College of Engineering (An autonomous institution), Kalavakkam, Kanchipuram, India.
2
Indian Institute of Science Education and Research, Dr. Homi Bhabha Road, Pune, India.

Table 1 Synthesis and properties of TR polybenzoxazoles

Properties of TR TR Products Ref.


precursors Conditions
Entr Monomers
Structure Properties
y used for
precursor
No
synthesis Mn ɳinh Tg Temp Time FT-IR Solid % Surfac FFV
(cm-1)
(dL/g) (° C) State Conv e Area
(° C) (h) 13
C- ersion (m2/g)
a
NMR
(ppm)

1 11a 12a - 0.82b - 500 1 1058, 1617 109, 163 100 - - [12]

2 12b - - - 450 1 - - 68 - 0.24 [8c]

3 12bc - - - 450 1 1030, 1470, 63 - - [13]


1547 (ATR)

4 12c 26200 - - 425 2 1059, 1558 - 100 306 0.20 [14]


(ATR)

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Accepted Article 5 11b 12a - - - 350 1 - - 39 - 0.15 [8f]
400 - - - 60 - 0.16
450 - - - 76 - 0.20

6 12a - - 314 450 0.5 - - 78 - - [8g]

7 12a - - - 350 1 - - 45 - 0.14 [15]


- - - 400 1 - - 76 - 0.19
- - - 450 0.5 - - 118 - 0.20

8 12a - - 314 450 1 1050, - 50 - - [8g]


1480, 1560

9 12b - - 301 450 1 1058, 1480 108, 162 100 510,72 0.28 [6,
6 8b]

10 12b - - - 450 1 1059, - 97 500 0.26 [8c]


1474 (ATR)

11 12b - 1.03 251 450 0.5 1050, 1475 - 71 - 0.23 [8j]

12 12b - - 303 450 1 1050, - 75 - - [8g]


1480, 1560

13 12c 21500 - - 425 2 1059, 1558 - 100 466 0.27 [14]


(ATR)

14 12d 28900 - - 420 4 1064, 1555 - 100 417 - [16]

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Accepted Article 15 12e - 1.30b - 400 1 1050, 1480, - 92 - - [17]
1560 (ATR)

16 12f - 1.58 b - 400 1 - - 88 - - [17]

17 12g 21300 0.70 280 400 1 1054, 1475 - 90 - 0.17 [8d]


(ATR)
- - 243 2 - 96 - 0.18
- - 239 3 - 100 - 0.17
- - 242 450 1 - 95 - 0.18
- - 250 2 - 100 - 0.19
- - 311 3 - 100 - 0.207

18 11c 12b - - - 450 1 - - 97 - 0.22 [8c]

19 12b - 0.23 231 450 0.5 - - 71 - 0.18 [8j]

20 12b - - 266 450 1 1050, 1480, - 91 - - [8g]


1560

21 11d 12b - - - 450 1 - - 97 - 0.20 [8c]

22 12b - 0.37 246 450 0.5 - - 71 - 0.18 [8j]

23 12b - - 280 450 1 1050, 1480, - 84 - - [8g]


1560

24 11e 12b - - - 450 1 - - 97 - 0.19 [8c]

25 12b - - 288 450 1 1050, 1480, - 64 - - [8g]


1560

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Accepted Article 26 12c 16100 - - 425 2 1059, 1558 - 100 283 0.22 [14]
(ATR)

27 11f 12d 42400 - - 450 2 1064, 1555 - 100 480 - [16]

28 11g 12b - - 216 450 1 1050, 1480, - 100 - - [8g]


1560

29 12c 24000 - - 425 2 1059, 1558 - 100 4.7 0.17 [14]


(ATR)

30 11b 12h - - - 450 3 1058, 1480 - 100 447 0.27 [6]

a
% conversion
b
[ɳ], dL/g
c
TR performed in vacuum

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Accepted Article Table 2 Comparison of TR route with TCD and CTR

M1 M2 Type Temp IR assignment FFV Pure gas Ideal Ref


Entry
of (° C) permeability select
No
reactio (Barrer) ivity
n C=N C-O-C CO2 CH4 (α)
CO2/
CH4
TR 450 1480 1058 0.28 4201a 151a 28a 8b
1

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

TCD 375 1460-90 1040-90 0.20 206 c 6.62 c 31 22


4

11h 12 b

TR 450 1620 1060 - 109 a 6.8 a 28 a 23


5
12 a
11b
CR 300 1620 1060 0.15 109 a 2.1a 49 a 23
6

11b

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Accepted Article
a
1 bar, 25° C
b
4.1 bar, 35° C, Nitrogen
c
3 bar, 30° C

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Understanding structure and composition of thermally rearranged polymers based on
small molecule chemistry: A perspective

A. Murugesan,*1 and Swaminathan Sivaram2


1
SSN College of Engineering (An autonomous institution), Kalavakkam, Kanchipuram, India.
Accepted Article
2
Indian Institute of Science Education and Research, Dr. Homi Bhabha Road, Pune, India.

Scheme 1: Thermal rearrangement reaction of o-functional polyimides

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Accepted Article

Scheme 2: Melt phase reaction of o-phenylenediamine with phthalic anhydride

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Accepted Article

Scheme 3: Solution and melt phase reaction of o-phenylenediamine with phthalic


anhydride

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Accepted Article

Scheme 4: Solution and melt phase reaction of o-phenylenediamine with phthalic


anhydride under various conditions

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Accepted Article

Scheme 5: Vapor and liquid phase TR of N-(o-hydroxyphenyl) phthalimide (6)

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Accepted Article

Scheme 6: Hydrolytic process occurring during TR Reaction of 6 leading to the formation


of 2,2’-o-phenylenebisbenzoxazole

Scheme 7: TR reaction of bisphthalimide of 3,3’-dihydroxy-4,4’-diaminobiphenyl

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Accepted Article

Scheme 8: Dianhydrides and diacid chloride used for preparing precursors for TR

Scheme 9: Diaminophenols and tetraamines used for preparing precursors for TR

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Accepted Article

Scheme 10: Claisen rearrangement of ortho- allyl ether of 6-FDA-HAB

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Accepted Article

11

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Scheme 11: TR of N- (o-aminophenyl phthalimide)
Accepted Article

12

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