Synthesis of highly refractive and transparent poly(arylene sulfide sulfone) based on 4,6-dichloropyrimidine and 3,6-dichloropyridazine

Article abstract of DOI:10.1016/j.polymer.2012.12.008

A highly refractive and transparent poly(arylene sulfide sulfone) (PASS) containing pyrimidine (or pyridazine) unit has been developed. The polymer was prepared by a polycondensation reaction of 4,4′-dimercaptodiphenyl sulfone (DMDPS) and 4,6-dichloropyri

Full text of DOI:10.1016/j.polymer.2012.12.008

Polymer 54 (2013) 601e606
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Polymer
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Synthesis of highly refractive and transparent poly(arylene sulfide sulfone) based
on 4,6-dichloropyrimidine and 3,6-dichloropyridazine
,
a,c,
*
Gang Zhang a, Hao-hao Ren b, Dong-sheng Li a, Sheng-ru Long a , Jie Yang
**
a Institute of Materials Science & Technology, Analytical & Testing Center, Sichuan University, Chengdu 610064, PR China
b College of Physical Science and Technology of Sichuan University, Chengdu 610065, PR China
c State Key Laboratory of Polymer Materials Engineering (Sichuan University), Chengdu 610065, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A highly refractive and transparent poly(arylene sulfide sulfone) (PASS) containing pyrimidine (or pyr-
idazine) unit has been developed. The polymer was prepared by a polycondensation reaction of 4,40-
dimercaptodiphenyl sulfone (DMDPS) and 4,6-dichloropyrimidine (DCPM) (or 3,6-dichloropyridazine
(DCPD)). They showed good thermal stabilities such as a relatively high glass transition temperature
of 193e202 ꢀC and a 5% weight loss temperature (T5%) of 370e372 ꢀC. The optical transmittance of the
polymer at 450 nm is higher than 81%. The heterocycles unit and plural eSe linkages provides the
polymer with a high refractive index of 1.737e1.743 at 633 nm and a low birefringence of 0.003e0.004.
Ó 2012 Elsevier Ltd. All rights reserved.
Received 12 September 2012
Received in revised form
21 November 2012
Accepted 1 December 2012
Available online 6 December 2012
Keywords:
Synthesis
Optical property
Heterocycle
1. Introduction
Various kinds of high-n polymers containing sulfur elements
were reported, such as epoxies [6], polyurethanes [7], poly-
High refractive index polymeric materials have been rapidly
developed and attract significant interest in recent years. They were
used in lenses, prisms, components for charge-coupled devices
[1] and complementary metal oxide semiconductor image sensors
[2e4] because of their lightweight, impact resistance, process-
ability, and dying ability compared to inorganic glasses. A general
approach for increasing the refractive index of polymers is the
introduction of substituents with a low molar volume and high
molar refraction according to the classic LorentzꢁLorenz equation
(the refractive index (n) of a material is related to the molar volume
methacrylates [8], and polyarylenethioethers [9]. However, the
polymers have relatively low refractive indices in the range of 1.5e1.7
at 633 nm. Recently, aromatic polyamides (PAs) [10,11] and poly-
imides (PIs) [12e18] containing sufur have been developed for
optical applications, with their advantage of thermal, oxidative,
chemical, and mechanical properties. Although they exhibit high
refractive index in the range of 1.7e1.77, their films have large
birefringence and coloration (That is resulted into coloration of
aromatic PIs for its formation charge transfer complexes (CTC)
between the electron-donating diamine and the electron-accepting
carbonyl group), which are the problems of aromatic PAs and PIs.
Poly(aryl thioether)s, such as in poly(phenylene sulfide),
poly(phenylene sulfide ketone) [19], and poly-(phenylene sulfide
sulfone) [20e23] are of well-known high performance engineering
thermoplastics. They all have excellent processability, mechanical,
thermal, and antioxidant properties. Recently, fluorene and sulfone
substituents have been introduced into the poly(aryl thioether)s
mainchain to form soluble and thermal stable optical resins
[9,24,25]. Most of them exhibit excellent optical transparency
and low birefringence. However, the refractive indices of these
polymers are still in the range of 1.6e1.7 at 633 nm. The relatively
low refractive index is mainly attributed to the low sulfur content
(because the refractive indices of sulfur containing polymers
mainly depends on the sulfur content in the repeating unit.) and
sterically bulky substituents such as fluorene groups would endow
(VM), polarizability (a) and the molar refractions of functional
groups and the backbone repeating unit of the polymer (RLL)) [5].
Among these high refractive index substituents (Cl, Br, I, sulfur
atoms and metallic elements), the sulfur element is commonly
selected because of its high polarizability, stability, and facility to
introduce to polymers.
ꢀ
ꢁ
n2 ꢁ 1
n2 þ 1
4
3
X
VM
¼
N
p Aa
¼
ðRLLÞ
i
i
* Corresponding author. Institute of Materials Science & Technology, Analytical &
Testing Center, Sichuan University, Chengdu 610064, PR China. Fax: þ86 28 8541
2866.
** Corresponding author. Fax: þ86 28 8541 2866.
E-mail addresses: lsrhome@163.com (S.-r. Long), ppsf@scu.edu.cn (J. Yang).
0032-3861/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.polymer.2012.12.008

602
G. Zhang et al. / Polymer 54 (2013) 601e606
Table 1
sodium 4-methylbenzenesulfonate (AR, Aladdin Reagent Company)
and other reagents and solvents were commercially obtained.
The molar refraction of common atoms and groups.
Group
Molar
Group
Molar
Refraction (R)
Refraction (R)
2.2. Monomer synthesis
H
C
1.100
2.418
1.733
2.398
2.211
1.643
0.95
Phenyl(C6H5)
Naphthyl(C10H7)
Cl
Br
25.463
43.00
5.967
8.865
13.900
7.69
4,40-dimercaptodiphenylsulfone (DMDPS) (shown in Scheme 1).
We prepared DMDPS following a similar procedure as earlier
reports [27]. We carried out the reaction with sodium sulfide
as reagent. Also we used sodium benzoate and sodium
4-methylbenzenesulfonate to assist the dissolution of the sodium
sulfide [28].
C]C
C^C
C]O
eCeOe
F
I
eSH
eSeSe
CeN]C
8.11
4.10
NeN]C
3.46
Polymer synthesis (DMDPS-DCPM) (shown in Scheme 1).
A typical polymerization was performed as shown in Scheme 1.
In a 250 ml three-necked flask fitted with a mechanical stirrer and
thermometer, DMDPS (14.1 g, 0.05 mol), DCPM (7.45 g, 0.05 mol),
potassium carbonate (10.4 g, 0.075 mol), toluene (30 ml) and NMP
(100 ml) were added. The mixture was stirred at 130e150 ꢀC for 1 h
to remove water; then stirred at 160 ꢀC for 6 h to yield a viscous
pale-yellow solution. Next, the reaction solution was poured into
water to obtain a white fibrous precipitate, which was washed with
water and ethanol; then dried under vacuum. The fibrous precipi-
tate was pulverized to powder, and washed with water and ethanol
again. After drying under vacuum at 100 ꢀC for 12 h, 16.5 g (92.3%)
of DMDPS-DCPM was obtained.
DMDPS-DCPM: elemental analysis (%), Found: C: 53.8 (53.6); H:
2.87 (2.79); N: 7.61 (7.82) (data in brackets are calculated). FT-IR
(casting film, cmꢁ1): 3081 (CeH aromatic ring), 1539, 1499 (C]C
aromatic ring), 1395 (CeN), 1331, 1155 (eSO2e), 1091 (CeSeC), 835
(para-substituent of aromatic ring). 1H NMR (600 MHz, DMSO-d6/
TMS, ppm): 7.259 (s, 1H, H1), 7.819e7.841 (d, 4H, H2), 8.034e8.056
(d, 4H, H3), 8.599 (s, 1H, H4). DMDPS-DCPD was prepared following
a similar procedure as that of DMDPS-DCPM.
DMDPS-DCPD: 16.3 g, Yield: 91%, elemental analysis (%), Found:
C: 54.0 (53.6); H: 2.85 (2.79); N: 7.56 (7.82) (data in brackets are
calculated). FT-IR (casting film, cmꢁ1): 3090 (CeH aromatic ring),
1595, 1482 (C]C aromatic ring), 1379 (CeN), 1323, 1147 (eSO2e),
1075 (CeSeC), 820 (para-substituent of aromatic ring). 1H NMR
(600 MHz, DMSO-d6/TMS, ppm): 7.588 (s, 2H, H1), 7.711e7.748 (d,
4H, H2), 7.983-8.018 (d, 4H, H3).
We also synthesized comparative samples which had no
aromatic herocycles (m-DMB-DCDPS: the polymer of m-DMB and
DCDPS, p-DMB-DCDPS: the polymer of p-DMB and DCDPS) under
190 ꢀC to compare their optical properties with DMDPS-DCPM and
DMDPS-DCPD.
large free volumes among polymer chains, which lowers the
refractive index. Therefore, the breakthrough of the trade-off
between the refractive index and optical transparency, birefrin-
gence becomes an important subject. From Table 1, we can find that
NeN]C and C]NeC bonds possess relatively high molar refrac-
tion (3.46) and (4.10) as compared to C]C bond (1.73) [26]. Thus, in
order to enhance the refractive index and optical transparency,
introduction of aromatic heterocycles such as pyridazine and
pyrimidine units containing eC]Ne bonding would be an effective
method [15]. On the other hand, the sulfonyl (eSO2e) group
endows polymers with low refractive index dispersion and high
transparency. On the basis of these considerations, we designed
a novel polymer that contained sulfur, sulfonyl and aromatic
heterocycles to achieve high refractive index, low birefringence and
high optical transparency. This article reports the synthesis and
properties of the pyridazine and pyrimidine ring containing PASSs
prepared from 4,6-dichloropyrimidine (DCPM) (or 3,6-
dichloropyridazine (DCPD)) and 4,40-dimercaptodiphenylsulfone
(DMDPS). The obtained PASSs exhibited high refractive indices in
the range of 1.737e1.743, a low birefringence of 0.003e0.004, and
high optical transparency over 81% at 450 nm.
2. Experimental
2.1. Materials
Commercially available 4,6-dichloropyrimidine (DCPM) and
3,6-dichloropyridazine (DCPD) (99%, Quzhou, Rainful Chemical
Industry
Company),
4,40-dichlorodiphenylsulfone
(DCDPS)
(AR, Suzhou Yinsheng Chemical Industry Company), 1,3-
dimercaptobenzene (m-DMB) (97%, Alfa Aesar Chemical Company
Ltd.), 1,4-dimercaptobenzene (p-DMB) (98%, Zhe Jiang Shou Er Fu
Chemical Industry Group Company Ltd.), sodium hydroxide (NaOH)
(AR, SiChuan ChengDu ChangLian Chemical Reagent Company),
sodium sulfide (Na2S$xH2O, Na2S% z 60%) (Nafine Chemical
Industry Group Co., Ltd.), N-methyl-2-pyrrolidone (NMP) (JiangSu
NanJing JinLong Chemical Industry Company), sodium benzoate,
2.3. Characterization
Limiting viscosity and molecular weights analysis: the limiting
ꢀ
ꢁ
ꢂ ꢃ
hsp
viscosities
h
¼ lim
of PASSs were obtained by one-point
C
c/0
Scheme 1. Synthesis routes of DMDPS and polymers.

G. Zhang et al. / Polymer 54 (2013) 601e606
603
method at 30 ꢂ 0.1 ꢀC with 0.500 g of polymer dissolved in 100 ml
of NMP, using a Cannon-Ubbelhode viscometer:
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ꢄ
ꢅ
2
hsp ꢁ lnhr
C
½
h
ꢃ ¼
where hr
¼
h
/h0
,
hsp
¼
h
/h0 ꢁ 1.
The number-average molecular weights (Mn) and weight-
average molecular weight (Mw) were obtained via GPC performed
with a Waters 1515 performance liquid chromatography pump,
a Waters 2414 differential refractometer (Waters Co., Milford, MA)
and a combination of Styragel HT-3 and HT-4 columns (Waters Co.,
Milford, MA), the effective molecular weight ranges of which were
500e30,000 and 5000e800,000, respectively. N, N-dimethyl
formamide (DMF) was used as an eluent at a flow rate of 1.0 ml/min
at 35 ꢀC. Polystyrene standards were used for calibration. Elemental
analysis: the samples of monomer and polymers were measured
with an elemental analyzer (EURO EA-3000). Chemical structure
analysis: FT-IR spectroscopic measurements were performed on
a
NEXUS670 FT-IR instrument. Nuclear magnetic resonance
Fig. 1. FT-IR spectra of DMDPS-DCPM and DMDPS-DCPD.
(1H NMR) spectra were determined on a BRUKER-600 NMR spec-
trometer in deuterated chloroform or deuterated dimethyl sulf-
oxide. Thermal analysis: differential scanning calorimetry (DSC)
was performed on a NETZSCH DSC 200 PC thermal analysis
instrument. The heating rate for the DSC measurements was
10 ꢀC/min. Thermogravimetric analysis (TGA) measurements were
performed on a TGA Q500 V6.4 Build 193 thermal analysis instru-
ment with a heating rate of 10 ꢀC/min under nitrogen atmosphere.
Mechanical testing: an Instron Corporation 4302 was used to study
the stress-strain behavior of the films (according to GB 13022-91).
Dynamic Mechanical Analysis (DMA) was performed on TA-Q800
apparatus operating in tensile mode at a frequency of 1 Hz in
the temperature range from 30 to 250 ꢀC, with a heating rate of
3.2. Synthesis and characterization of polymers
The polycondensation reaction was carried out by nucleophilic
substitution polymerization using potassium carbonate as the
catalyst. The reaction temperature was about 160 ꢀC, it is lower as
that of polyethersulfone (PES: 180e200 ꢀC). The most reason is that
the strong electron withdrawing effect of eN]Ne and eC]Ne,
then it is easy for the AreSꢁ to attack the positively charged
carbon atoms which linked to chloride atoms. The molecular
weights of the polymers were measured by limiting viscosity and
GPC. As shown in Table 2, the [h] values of DMDPS-DCPM and
5
ꢀC/min. Optical analysis: the transmittance of the films was
DMDPS-DCPD were 0.82 and 0.64 dL/g, the Mn values were
8.1 ꢄ 104 and 6.3 ꢄ 104, Mw values were 1.47 ꢄ 105 and 1.16 ꢄ 105,
respectively. The polydispersity indices (PDIs) of polymers DMDPS-
DCPM and DMDPS-DCPD were 1.8 and 1.84.
determined by UVeVisible spectroscopy (U-2310Ⅱ). The out-of-
plane (nTM) and in-plane (nTE) refractive indices of the PASSs
films were measured with a SPA-Lite prism coupler (SPA-4000) at
the wavelength of 633, 1310 and 1550 nm. The in-plane (nTE)/out-
The structures of the resultant polymer were characterized by
elemental analysis, FT-IR and 1H NMR spectroscopies. The FT-IR
of-plane (nTM) indices and birefringences (
D
n) were calculated
with the following equation:
D
n ¼ nTE ꢁ nTM. The average
refractive index was calculated according to the following equa-
tion: nAV ¼ [(2 nT2E þ nTM 2)/3]1/2 [29]. Experiment of solubility: The
solubility of polymers in various solvents was tested at room
temperature and the boiling point of the solvent.
3. Results and discussion
3.1. Synthesis of monomers
In this study, the monomer (DMDPS) containing a sulfone group
and sulfur content of 34.06% was prepared with the nucleophilic
substitution reaction in the presence of sodium benzoate and
sodium 4-methylbenzenesulfonate. It is better to control the
temperature of vacuum-drying below 35 ꢀC, or DMPDS may be
oxidized to disulfide compounds. The structure of DMDPS was
characterized by elemental analysis, FT-IR and 1H NMR spectros-
copies (see Supplementary data).
Table 2
Limiting viscosity ([
h]), molecular weights and thermal properties of PASSs.
Polymers
[
h] (dL/g)
Mn (g/mol)
Mw (g/mol)
PDI (Mw/Mn)
DMDPS-DCPM
DMDPS-DCPD
0.82
0.64
8.1 ꢄ 104
1.47 ꢄ 105
1.8
1.84
6.3 ꢄ 104
1.16 ꢄ 105
Fig. 2. 1H NMR spectra of DMDPS-DCPM.

604
G. Zhang et al. / Polymer 54 (2013) 601e606
Fig. 4. TGA curves of polymers at a heating rate of 10 ꢀC/min in N2.
we had not find the endothermic melting peak of polymers. It
suggests the amorphous nature of the resultant polymers. That is
beneficial for the polymers’ transparency. In additionally,
DMA analysis were carried out under nitrogen at a heating rate of
5 ꢀC/min. Fig. 6 illustrates the variations in the storage modulus (E0)
and loss modulus (E00) at different temperatures. It can be seen from
Fig. 6 that the storage modulus remained constant or decreased
slightly on heating over a wide temperature range up to 190 ꢀC.
They were kept above 1.0 GPa at 200 ꢀC. The Tgs determined as the
peak temperatures of the E00 method, are nearly the same as those
obtained by the DSC method. The slight differences are mainly
attributed to the different responses of the polymers to these two
measurements.
Fig. 3. 1H NMR spectra of DMDPS-DCPD.
spectra (Fig. 1) of polymers exhibit the characteristic eCeNe and
thioether stretching at 1323e1331 and 1075e1091 cmꢁ1, respec-
tively. The absorptions near 1320, 1150 cmꢁ1 were attributed to the
sulfone group. Comparing with the spectrum of DMDPS, the char-
acteristic absorption around 2560 cmꢁ1 (eSH) has disappeared.
Fig. 2 shows the 1H NMR spectra of DMDPS-DCPM. The signals of
protons on bezene ring are shifted to low field because of the
deshielding effects of unit of eC]Ne compared to monomer
DMDPS. The signals at 7.259 and 8.599 were assigned to the
pyrimidine units. The ratio of corresponding integral curves was
1:4:4:1. Combined with the FT-IR and elemental analysis results
suggest that the polymerization proceeds as descript in Scheme 1.
The structures of DMDPS-DCPD were also characterized by the 1H
NMR (Fig. 3), FT-IR spectra and elemental analysis.
3.4. Tensile properties
The average tensile strengths of the casting films of the poly-
mers treated at 120e140 ꢀC for 10 h, then at 180 ꢀC for 10 h, are
given in Table 3. As shown in Table 3, the average tensile strengths
and the Young’s modulus values of the films were 88e104 MPa and
2.0e2.5 GPa, respectively. That suggests the polymers had good
mechanical properties. While the elongation at break was more
than 5%, suggesting the films have better toughness than that of
earlier reported by our group [10,11].
3.3. Thermal properties of polymers
The thermal properties of polymers were evaluated by TGA, DSC
and DMA measurements. The results of weight loss temperatures
(T5%) and glass transition temperatures are summarized in Table 3.
As shown in Fig. 4 (TGA), the polymers show good thermal stability,
such as 5% weight loss were 370e372 ꢀC (It attributed to the
thermal decomposition of pyrimidine and pyridazine ring [15]).
They provided about 48% char yield at 800 ꢀC in nitrogen. The glass
transition temperatures (Tgs) of the polymers estimated by DSC
(Fig. 5) and DMA (Fig. 6) exhibit similar values. The resultant
polymers show high Tgs of more than 190 ꢀC. In particular, DMDPS-
DCPD has 10 ꢀC higher Tg than those of DMDPS-DCPM because of
the rigid structure of the pyridazine ring. Also from the DSC curves
3.5. Optical properties
The optical properties of PASSs films and comparative samples
(m-DMB-DCDPS and p-DMB-DCDPS), such as the cutoff wavelength
(
lcutoff), the in-plane (nTE) and out-of-plane (nTM) refractive indices
measured at 633, 1310, 1550 nm, the average refractive indices (nav
and birefringence ( n) are summarized in Table 4. Fig. 7 displays
the optical transmission spectra of PASSs films and comparative
)
D
samples (9e11 mm thick) at the region of 200e800 nm.
Table 3
Tensile properties of PASSs.
Polymers
Tg (ꢀC)
T5% (ꢀC)
Char yield (%)
Tensile strength
(MPa)
Young’s modulus
(GPa)
Elongation
at break (%)
Storage modulus
at 200 ꢀC (GPa)
Glass transition
Temperature (ꢀC)a
DMDPS-DCPM
DMDPS-DCPD
193
202
372
370
48.2
48.8
104
88
2.0
2.5
6.8
5.3
1.3
1.1
196
214
a
Detected by dynamic mechanical analysis (DMA).

G. Zhang et al. / Polymer 54 (2013) 601e606
605
Table 4
Optical properties of PASSs’ films.
Polymers
Sc (%) lcutoff T400 T450 633 nm
(nm) (%) (%)
nTE
nTM
nAV
Dn
DMDPS-DCPM
DMDPS-DCPD
m-DMB-DCDPS 27.06 346
26.82 341
26.82 356
68.6 83.4 1.738 1.735 1.737 0.003
72.4 81.2 1.744 1.740 1.743 0.004
78.8 85.4 1.724 1.721 1.723 0.003
78.0 84.3 1.727 1.724 1.726 0.003
p-DMB-DCDPS
27.06 349
Polymers
1310 nm
1550 nm
nTE
nTM
nAV
D
n
nTE
nTM
nAV
Dn
DMDPS-DCPM 1.706 1.702 1.705 0.004 1.701 1.697 1.700 0.004
DMDPS-DCPD 1.708 1.703 1.706 0.005 1.703 1.698 1.701 0.005
Sc: the content of S; T450: the transmittance of films at 450 nm; ε: dielectric
constant; nTE: the in-plane refractive index; nTM: the out-of-plane refractive index;
Dn: birefringence.
that the heterocycles moiety endows high polarizability and high
refractive index compared to aliphatic chain and phenyl ring. Fig. 8
is the wavelength-dependent refractive indices of polymers at 633,
1310 and 1550 nm, as shown in Fig. 8, the nav at 1310 and 1550 nm
was near 1.7, the dispersion of nav with wavelength is well.
Fig. 5. DSC curves of polymers at a heating rate of 10 ꢀC/min in N2.
The cutoff wavelengths (lcutoff) of DMDPS-DCPM, DMDPS-DCPD,
m-DMB-DCDPS and p-DMB-DCDPS films were 341, 356, 346 and
349 nm, respectively. The transparencies of the films measured at
400 and 450 nm were almost 68.6e78.8% and 81e85%, respectively.
Comparing m-DMB-DCDPS and p-DMB-DCDPS, it suggests that the
introduction of pyrimidine and pyridazine units do not significant
deteriorate the optical transparency of polymers. Also we find the
PASSs have better transparency than aromatic polyimides con-
taining pyrimidine and pyridazine units [15]. As listed in Table 4,
the in-plane (nTE) and out-of-plane (nTM) refractive indices of
DMDPS-DCPM and DMDPS-DCPD at 633 nm were in the range of
1.738e1.744 and 1.735e1.740, respectively. The nTE values are
slightly higher than those of the nTM ones for PASSs films since the
molecular chains are preferentially oriented in the film plane. The
nav values of DMDPS-DCPM, DMDPS-DCPD, m-DMB-DCDPS and p-
DMB-DCDPS measured at 633 nm were 1.737,1.743,1.723 and 1.726,
respectively. The nav depended on several factors, such as sulfur
content, molecular chain flexibility and molar volume. The refrac-
tive index of DMDPS-DCPD is slightly higher than that of DMDPS-
DCPM. In addition, we found that PASSs exhibits higher refractive
index value in spite of having lower sulfur content than m-DMB-
DCDPS, p-DMB-DCDPS and PES [30,31]. This result clearly indicates
Fig. 7. UVeVis spectra of polymers’ (DMDPS-DCPM, DCPD) films.
Fig. 8. The wavelength-dependent refractive indices of polymers at 633, 1310 and
Fig. 6. The storage modulus and loss modulus curves of polymers.
1550 nm.

606
G. Zhang et al. / Polymer 54 (2013) 601e606
Table 5
for advanced optical device applications, such as optical wave
guides for CMOS image sensor.
Solubility behavior of polymers.
Solvents
Polymers
DMDPS-DCPM
DMPDS-DCPD
Acknowledgment
concentrated sulfuric acid
formic acid
NMP
DMF
pyridine
þþ
e
þþ
e
This work was supported by research grants from the Youth
Fund of Sichuan University (Grant No.: 2012SCU11009).
þþ
þþ
þe
e
þþ
þþ
e
acetone
e
Appendix A. Supplementary data
chloroform
DMSO
1, 4-Dioxane
toluene
cyclohexanone
Phenol þ tetrachloroethane
þe
þþ
e
e
þþ
e
Supplementary data related to this article can be found online at
http://dx.doi.org/10.1016/j.polymer.2012.12.008.
e
e
e
e
þ
þe
þþ: soluble at room temperature; þ: soluble at solvents boiling point; þe: swelling
with heating; e: insoluble with heating.
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D
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Through the solubility experiments (Table 5), we found that the
polymers were soluble in NMP, DMF, DMSO and concentrated
sulfuric acid at room temperature. Thus, they can be processed
using following methods, such as electro-spinning and solution
casting. As listed in Table 5, these polymers were not soluble in
toluene, formic acid and acetone and so on. Thus, these polymers
showed good balance between the solubility and corrosion
resistance.
4. Conclusions
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Aromatic dithiol (DMDPS) with a sulfone unit and high sulfur
content was synthesized to develop high-n PASSs. The PASSs were
prepared by the nucleaphilitic polycondensation of DCPM and
DCPD with DMDPS. The resultant PASSs showed good thermal
stabilities, such as Tgs higher than 190 ꢀC, a T5% around 370 ꢀC and
mechanical properties. The PASSs exhibited good optical perfor-
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mance. The transmittance of PASSs films with about 11 mm thick-
ness is around 81% at 450 nm. The polymers exhibited refractive
indices about 1.74 at 633 nm and low birefringence of 0.003e0.004.
It can be concluded that the high refractive indices are caused by
high sulfur contents and heterocyclic units, while keeping the
solubility of polymers in organic solvents, such as NMP, DMF and so
on. Moreover, the synthesis of the DMDPS is more facile and
affordable than the other monomers reported for sulfur containing
polymers. Thus, the PASSs can be good candidates as components
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