REACTIVE

&
FUNCTIONAL
POLYMERS
ELSEVIER Reactive & Functional Polymers 30 I 1996) 61-69

Polyimides derived from nonaromatic monomers: synthesis,

characterization and potential applications
W. Volksen *. H.J Cha, M.I. Sanchez, D.Y. Yoon
IBM Resenrck Dir’ision, A11mdr11 Research Cenrel; 650 Harv Roud, .Snn Jose, CA 95120-6099, USA

Received 31 October 1995: accepted 14 February 1996

Abstract

,4 number of mixed aromatickycloaliphatic as well as fully nonaromatic polyimides have been prepared. Whereas
all the poly(amic acids) derived from nonaromatic diamines involved salt-formation during the initial stages of the
polymerization, the majority of these eventually formed homogeneous, highly viscous polymer solutions. Only in a few
select cases involving all nonaromatic monomers traditional solution polymerization was unsuccessful. The polyimide
derived from hexafluoroisopropylidene diphthalic anhydride (6FDA) and trans- I ,4-diaminocyclohexane (DACH) yielded
films with tough mechanical properties, a glass transition temperature of -36O”C, good solvent resistance, and a low
dielectric constant of 2.6. Thermal stability of this polyimide as determined by thermal gravimetric analysis in both
air and nitrogen was quite good, exhibiting a weight loss of only 0.07 wt’%/h at 350°C under isothermal conditions in
nitrogen. However, mechanical properties as a function of thermal aging in both air and nitrogen indicated a maximum use
temperature of only 350°C under inert conditions and less than 300°C in the presence of oxygen.

KQWYX&: Polyimide: Cycloaliphatic: Dielectric constant; Thermal stability: Mechanical properties

1. Introduction orientation layers [lo-l 21. Other potential appli-

Although conventional polyimides are gen-
erally derived from aromatic dianhydrides and
aromatic diamines, a number of literature re-
ports have appeared in recent years describing the
preparation of polyimides incorporating nonaro-
matic monomers, such as cycloaliphatic dianhy-
drides and/or nonaromatic diamines [l-9]. Of
course, the use of nonaromatic polymer con-
stituents implies that the ultimate end-use of such
materials is targeted for applications with less
stringent thermal requirements. In this respect, lit-
erature reports point toward potential display ap-
plications. such as color filters and liquid crystal
* Corresponding author. Fax: (408) 927-33 IO.
cations include the use of nonaromatic polyimides
as NLO buffer layers, which are required to pos-
sess low intrinsic optical losses as well as the abil-
ity to be able to prepare variable T, materials in
order to optimize polymer conductivity for effi-
cient poling of the latest, polyimide-based, NLO-
active polymers. Furthermore, nonaromatic poly-
imides may be of interest for use as permselec-
tive membranes, useful for gas separation. Finally,
since nonaromatic polyimides are comprised of a
less polarizable polymer backbone as compared
to aromatic polyimides, they should exhibit lower
dielectric constants, a property which is highly de-
sirable for microelectronic applications.
Unlike aromatic polyimides, which are read-
ily prepared via the two-step synthesis involving

1381-5148/96/$15.00 0 1996 Elsevier Science B.V. All rights reserved

P/IS1381-514R(96)00024-7
62 W Volksen et al. /Reactive & Functional Polymers 30 (1996) 61-69
R2 = -@ -@oe
RZ = G -@he
Scheme 1.
the reaction of an aromatic dianhydride with an
aromatic diamine to produce a soluble poly(amic
acid) in the first step, nonaromatic monomers
can introduce synthetic problems in this phase
of the synthesis. However, since the poly(amic
acid) synthesis represents the essential polymer-
forming reaction, the successful high molecular
weight formation and concomitant realization of
optimum polymer properties originates in this
phase of the polyimide synthesis. Therefore, the
relative reactivity of monomers with respect to
polymer formation and potential side reactions
is of paramount importance. In this context,
it is highly relevant to consider the nature of
the monomeric reagents. First, considering aro-
matic and nonaromatic dianhydrides, their rela-
tive reactivities are expected to be comparable
and interchange of these two monomers should
present little or no effect on the overall poly-
merization behavior, In contrast, the difference
in nucleophilicity and basicity when comparing
aromatic and aliphatic or cycloaliphatic diamines
is quite significant. Thus, aromatic diamines are
etc
--w~)~- etc.
considered to be poor nucleophiles and basic-
ities (expressed as the pK, of the conjugate
acid) range from 4.5-6 in contrast to aliphatic
or cycloaliphatic diamines, which are good nu-
cleophiles, with associated basicities of 9-l 1.
Based on these characteristics, it is possible to
group poly(amic acids) derived from partial or
entirely nonaromatic monomers into two distinct
categories. Hence, category 1 would be com-
prised of poly(amic acids) derived from aromatic
and/or nonaromatic dianhydrides in conjunction
with aromatic diamines. Category 2 would con-
sist of poly(amic acids) based on aromatic and/or
nonaromatic dianhydrides in conjunction with
nonaromatic diamines, as illustrated in Scheme 1.
Whereas category 1 based poly(amic acids) are
expected to present no significant problems in
their preparation, category 2 type monomers have
been argued to preclude high molecular weight
poly(amic acid) formation [ 13,141. Presumably,
such basic diamines form salts during the initial
stages of the polymerization, involving pendant
carboxylic acid groups from the amic acid moi-
 W Volksen et al. /Reactive & Functional Polymers 30 (I 996) 61-69 63

( Step 2 (
-==iiy

Scheme 2

eties along with unreacted amino-functionalities, with respect to the synthesis of such polyimides
as illustrated in Scheme 2, Step 1. This in effect along with the characterization of a new poly-
offsets the initial monomer stoichiometry and in- imide derived from a mixed system of aromatic
terrupts the polymer-forming reaction. However, and cycloaliphatic monomers.
the propensity of highly basic diamines to form
carboxylic acid salts should not necessarily pre- 2. Experimental
vent the attainment of high molecular weight
poly(amic acid). Assuming that such low molec- 2.1. Materials
ular weight, quaternized species exhibit suffi-
cient solubility in the polymerization medium Dianhydrides, such as cyclobutane tetracar-
and exclusion of moisture prevents the hydrol- boxylic dianhydride (CBDA) and hexafluo-
ysis of unreacted anhydride functionalities, an roisopropylidene diphthalic anhydride (GFDA),
equilibrium between quaternized and nonpro- were commercially available materials, which
tonated amino-functionalities should eventually were generally sublimed prior to polymeriza-
permit the polymer-forming reaction to proceed, tion. Cycloaliphatic diamines, such as trans-
see Scheme 2, Step 3. Of course, in the case of 1,4-diaminocyclohexane (DACH) and bis(4-
insoluble quaternized oligomers, only low molec- aminocyclohexyl) methane (PACM), cis/trans =
ular weights would predominate. 80/20, were obtained from DuPont and AirProd-
In light of these expected differences in the ucts, respectively. They were purified by distilla-
preparation of polyimides comprised of nonaro- tion over CaH2. N-methylpyrrolidone (NMP) was
matic monomers, we present our initial results purified by vacuum distillation over PzOs.
64 W Voksen et al. /Reactive & Functional Polymers 30 (1996) 61-69
2.2. Polymerizations
Polymerization reactions were generally con-
ducted analogously to traditional poly(amic acid)
syntheses. The following description is a repre-
sentative example of such preparations. A 20-ml
vial was charged with 2.5 mmoles of the desired
diamine and approximately 14 g of dry, distilled
NMP. Once dissolution of the diamine was com-
plete, 2.5 mmoles of the desired dianhydride was
added in one portion and the vial capped. The
preceding operations were performed in a glove
box under a He atmosphere. The vial was then
removed from the glove box and vigorously ag-
itated with a wrist-action shaker. When the vis-
cosity had increased to the point where shaking
was no longer effective, -15 min, the vial was
transferred to a tumbler and gently agitated for an
additional 48 h, resulting in clear, highly viscous
poly(amic acid) solutions with a solids content of
approximately 10 wt%.
2.3. Film preparation
Samples for evaluation of mechanical prop-
erties and dynamic mechanical properties were
prepared by doctor blading the poly(amic acid)
solution onto 1” by 3” glass slides and heat-
ing the specimens under nitrogen. They were
subsequently heated at S’C/min with final cure
temperatures of 300°C or 350°C ranging from 30
min to several hours. The polymers films were
then lifted off the glass substrate by immersion in
water. 0.25” wide strips were then cut from the
free standing films using a JDC@precision cutter.
2.4. Characterization
Thermogravimetric analyses (TGA) were con-
ducted on a Perkin-Elmer Model TGA-7 using a
heating rate of lO“C/min.
Dynamic mechanical analyses (DMTA) were
obtained on a Polymer Laboratories DMTA in
tension mode and at a heating rate of lO”C/min.
Refractive indexes, measured at a wavelength
of 633 nm, were obtained on a Metricon PC-
2000 prism coupler employing 4.5 f 0.02-mm
thick specimens on quartz substrates.
UV spectra were measured on a Hewlett-
Packard Model 8452A diode array spectropho-
tometer using polyimide coated, l-inch round,
quartz wafers.
Dielectric measurements were carried out
with a Multi-Frequency LCR Meter (HP Model
4275A), utilizing 10.7 f 0.05-mm thick spec-
imens on glass substrates with 1500-angstrom
thick, evaporated Al electrodes.
3. Results and discussion
In the case of nonaromatic polyimides, the
availability of nonaromatic monomers, i.e. cy-
cloaliphatic dianhydrides and diamines, is a cru-
cial consideration in the design of such materi-
als. Although a number of cycloaliphatic dianhy-
drides, many of which are originally targeted as
crosslinking agents in epoxy formulations, are
commercially available, nonaromatic diamines
are pretty much restricted to aliphatic diamines
and a few cycloaliphatic diamines, see Fig. 1. Re-
tention of the best thermal stability along with a
relatively high glass-transition temperature elim-
inates the use of aliphatic diamines and generally
dictates the use of aromatic monomers as one
of the polyimide components. The preparation
of only partial nonaromatic polyimides provides
additional benefits in that it significantly expands
the spectrum of potential polyimide systems. For
these reasons, we considered a number of partial
nonaromatic polyimides in addition to a couple
of fully cycloaliphatic systems.
Upon preparing poly(amic acids) based on
various combinations of aromatic and cy-
cloaliphatic monomers, the following general
synthetic observations were made. In contrast
to category 1 type amic acid polymerizations,
which were generally characterized by gradual
dissolution of the dianhydride in a solution of
the diamine in a polar, aprotic solvent, category
2 type poly(amic acid) preparations were sig-
nificantly more exothermic and involved a more
rapid dissolution of the dianhydride. This initial
dissolution was followed by gelation or salt for-
mation, which in many cases rapidly disappeared
and yielded clear, highly viscous poly(amic acid)
solutions. Aromatic dianhydrides in conjunction
 K? Volksen et al. /Reactive & Functional Polymers 30 (1996) 61-69 65

IXANHYDRIDFS

1,2,3,4-cyclobutane 1,2,3,4-cyclopentane 2,3,4,5tetrahydrofuran

tetracarboxylic dianhydride tetracarboxylic dianhydride tetracarboxylic dianhydride
(CBDA)

Bicyclo[2.2.2]oct-7-ene 5-(2,Sdioxytetrahydro)
2,3,5,6-tetracarboxylic dianhydride 3-methyl-3-cyclohexene
1,2-dicarboxylic anhydride
(84400)

INFS

W(-+ HW(-+b~W
1,4-diaminocyclohexane I,1 -bis(4-aminocyclohexyl) methane
(DACH) (PACM)

I, 1-bis(3-methyWaminocyclohexyl) methane
(ANCAMINE)
Fig. 1. Chemical structure of nonaromatic dianhydrides and diamines.

with aliphatic or cycloaliphatic diamines gener-
ally exhibited this type of behavior.
In the case of category 2 type polymeriza-
tions involving cycloaliphatic dianhydrides and
aliphatic diamines, the polymerization behavior
was considerably more complex. The initial ho-
mogenization of the gelled and/or precipitated
salt occurred significantly slower and in some
select cases never occurred at all. For exam-
ple, CBDA polymerization with either PACM
or truns-DACH resulted in a highly viscous
poly(amic acid) in case of the more flexible
PACM diamine and an insoluble, heterogeneous
mixture in case of trans-DACH. As a matter of
fact, we were unsuccessful in preparing a solu-
ble poly(amic acid) derived from trans-DACH in
conjunction with any cycloaliphatic dianhydride.
Compiled in Table 1 are a series of polyimides
comprised of nonaromatic monomers many of
which have been reported to exhibit acceptable
thermal and mechanical properties. Also included
are a number of polyimides synthesized in our
66 W Volksen et al. /Reactive & Functional Polymers 30 (1996) 61-69
Table 1
Selected properties of polyimides derived from nonaromatic monomers
Polymer
j-~+~~~()t. CBDA/P*CM
jjj+&+$+ Ci3DA/ODAQ
laboratory. Tg can vary from 270°C to >35O“C
and mechanical properties appear to be accept-
able as judged by whether the films are flexible
or brittle. The 6FDA/DACH polyimide exhibited
a particularly nice balance of properties and in
part due to its expectedly good optical properties,
became the main focus of our study.
6FDA-based polyimides are known to ex-
hibit significantly better optical properties, i.e.
increased UV transmittance, when compared to
traditional, nonfluorinated, aromatic polyimides,
such as PMDA/ODA [15]. For this reason, it
was not surprising that the 6FDA/DACH_based
polyimide coatings yielded clear, colorless films.
As shown in Fig. 2, the UV transmittance im-
proves upon decreasing the aromatic character
of the polyimide as reflected by the polyimides
T, (“0 Solubility Other
- no brittle
tough
>350 tough
325 no tough
no brittle
yes tough
derived from 6FDA in conjunction with hexaflu-
oroisopropylidene dianiline (6FDAN) and truns-
1,4-diaminocyclohexane (DACH), respectively.
Only the fully cycloaliphatic polyimide based
on CBDA/PACM displayed significantly better
UV transmittance. However, one noticeable fea-
ture of the fully cycloaliphatic polyimide is the
slow increase of the transmittance from 90% to
greater than 95%, which occurs over a wave-
length range of approximately 80 nm. Similar
increase in the transmittance for the 6FDA-based
polyimides requires a corresponding increase of
only 15 nm. In addition to UV spectroscopy, the
6FDA/DACH polyimide was characterized with
respect to the refractive index, as shown in Ta-
ble 2, along with other well-known polyimides
for comparative purposes. Determination of both
 WI Volksen et al. /Reactive & Functional Polymers 30 (1996) 61-69 61

of fluorinated monomers or complete nonaro-

matic character. In this respect, 6FDA/DACH
polyimide compares quite favorably to the fully
cycloaliphatic CBDA/PACM system in both the
absolute value of the refractive index and its low
associated anisotropy.
Since the refractive index can be related to
the dielectric constant, E, of the material by
Maxwell’s equation, 6 y n* (at optical frequen-
cies), refractive index measurements, which can
200 300 400 500 600 700 be made with relative ease, provide a good first
Wavelength (nm)
approximation of the expected dielectric con-
Fig. 2. Comparative polyimide UV transmittance of .5.0- stant and its associated dielectric anisotropy [ 161.
mm thick films: (a) CBDA/PACM; (b) 6FDA/DACH; (c)
6FDA/6FDAM.
Thus, a refractive index of 1.53, as determined for
6FDALDACH, should roughly translate into a di-
electric constant of -2.6 including an additional
the in-plane and out-of-plane refractive indexes contribution of approximately 10% from the in-
provided additional information with respect to frared absorption [17]. Fig. 3 illustrates the ex-
orientational effects observed in a variety of rigid perimentally determined dielectric constant of dry
polyimides [ 161. It is quite apparent that de- 6FDA/DACH polyimide as a function of tempera-
creasing the aromatic character of the polyimide ture and frequency. It is evident, that the dielectric
primarily eliminates the anisotropy in the refrac- constant is relatively unaffected in the tempera-
tive index as exemplified by the comparison of ture regime of -50 to +2OO”C and at frequencies
BPDA/PDA and 6FDA/DACH. Overall lowering ranging from 10 kHz to 1 MHz. The experimental
of the average refractive index requires the reduc- value of 2.6 is also quite consistent with the value
tion of the polymer polarizability through the use expected from the refractive index data.

Table 2
Comparative refractive index data for various polyimides as experimentally measured at 633 nm

Polymer Refractive index Anisotropy (An)

&n-plane ~our-of-p~ane

0.24

/H+o+/ - CBDA/ODA 1.60 1.59 0.03

jm+ - 6FDAlDACH 1.53 1.52 0.01

1.54 1.53 0.01

68 W Voksen et al./Reactive
Temperature ("C)
Fig. 3. Dielectric behavior of dry 6FDAIDACH polyimide as a
function of temperature and frequency; (x) 10 kHz, (0) 100 kHz,
(+) 1 MHz
20
I... I * 8 ..I. . ..I........
0 100 200 300 400 500
Temperature ("C)
Fig. 4. Thermogravimetric analysis of 6FDA/DACH polyimide:
(a) in N2, (b) in air. Heating rate = 1OWmin.
Thermo-oxidative stability is generally the
weakest feature associated with nonaromatic
polymers. However, since a large fraction of
polyimide processing is performed under rela-
tively inert conditions, we also considered the
thermal stability under nitrogen. Fig. 4 is a
thermogravimetric analysis of the 6FDA/DACH
polyimide in the presence of oxygen and under
nitrogen, respectively. Both curves reveal no sig-
nificant weight loss up to temperatures exceeding
450°C with the air samples actually exceeding
500°C. Of course, weight loss is only one aspect
associated with thermal degradation. Functional
testing as a function of high temperature ag-
ing with respect to key physical properties, i.e.
& Functional Polymers 30 (1996) 61-69
0 IO0 200 300 460 SliO
Time (minutes)
Fig. 5. Degradation of mechanical properties of 6FDA/ODA
polyimide as a function of thermal aging. (-.-) elongation
at break in Nz at 350°C. (- ??-_) elongation at break in air at
300°C (-- . - -) modulus in Nz at 350°C (- - ??- -) modulus in
air at 300°C.
mechanical properties, provides a significantly
better insight into the thermal stability of a poly-
mer. In particular, elongation at break is quite
sensitive to changes in molecular weight, caused
by thermal degradative processes, as shown for
aromatic polyimides [ 181. Fig. 5 illustrates the
observed tensile modulus and strain at break for
6FDA/DACH polyimide samples as a function of
high temperature aging both in air and nitrogen,
respectively. The reason the aging temperature
. in air was chosen to be 300°C was mainly dic-
600
tated by the fact that at 35O“C,degradation in the
properties was so fast that an accurate measure
could not be obtained. Comparison of the ob-
served modulus as a function of high temperature
aging in air and nitrogen, respectively, indicates
an increase in the modulus from 2.9 to 3.2 GPa
in the presence of air and only a slight decrease
of the modulus in the presence of nitrogen. The
increase in the tensile modulus in for samples
annealed in air suggests that the oxidative degra-
dation apparently occurs via crosslinking of the
polymer chains. Thermal aging under nitrogen is
more apt to promote degradation via chain scis-
sion as reflected by the slight decrease in the
modulus, consistent with other literature reports.
The corresponding elongation at break, a prop-
erty found to be very sensitive toward thermal
degradation, reveals similar behavior. Thus, ag-
ing the 6FDA/DACH polyimide under oxidative
conditions can only be tolerated for a maximum
 W Volksen et al./Reactive & Functional Polyners 30 (1996) 61-69 69

of 90 min at 300°C, assuming a minimum accept- Acknowledgements

able elongation of -5%. Under inert conditions
at 350°C it takes 4 h to reach a similar strain The authors express their gratitude for support
at break, which does not appear to change any of this work by the NIST Advanced Technology
further at least for measurements up to 10 h. Program, Contract 70NANB3H136.5.

4. Conclusions References

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