New monomers with trifluoromethyl and phenylphosphine oxide substituents for polynaphthylimides and polyperyleneimides

Full text of DOI:10.1134/S0012500811090023

ISSN 0012ꢀ5008, Doklady Chemistry, 2011, Vol. 440, Part 1, pp. 248–252. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © N.M. Belomoina, E.G. Bulycheva, A.L. Rusanov, Jinꢀgang Liu, Shiꢀyong Yang, 2011, published in Doklady Akademii Nauk, 2011, Vol. 440, No. 3,
pp. 346–350.
CHEMISTRY
New Monomers with Trifluoromethyl and Phenylphosphine Oxide
Substituents for Polynaphthylimides and Polyperyleneimides
†
a
N. M. Belomoinaa, E. G. Bulychevaa, A. L. Rusanov , Jinꢀgang Liub, and Shiꢀyong Yangb
Presented by Academician A.R. Khokhlov May 30, 2011
Received June 8, 2011
DOI: 10.1134/S0012500811090023
There is increasing interest in polymers containing poor solubility in organic solvents, which confines
their processing for items manufacture.
fused heterocycles on account of the growing need of
advanced technologies in novel materials showing
improved thermal, heat, chemical, and photochemiꢀ
cal stability, optical transparency, electrographic and
other special properties [1]. The introduction of
perylene [2] and phenylene [3–5] fragments in the
main chains of polymers allows one to impart them
electrochromic and electroluminescent properties.
In this paper, we describe the synthesis of new solꢀ
uble polynaphthylimides (PNIs) and polyperyleneimꢀ
ides containing phenylphosphine oxide and trifluoꢀ
romethyl substituents [6, 7].
The key compounds further used in the synthesis of
monomers are 1,1ꢀbis(4ꢀhydroxyphenyl)ꢀ1ꢀ[3'',5''ꢀ
bis(trifluoromethyl)phenyl]ꢀ2,2,2ꢀtrifluoroethane (
prepared by superelectrophilic activation of carbonyl
I)
However, the majority of polyheteroarylenes have compound [8] (Scheme 1):
2
CF3
C
O
CF3
4'
C
HO
OH
1
CF3SO3H
+
2HO
5''
3''
F3C
CF3
F3C
CF3
I
Scheme 1.
and bis(4ꢀhydroxyphenyl)phenylphosphine oxide (II) [9] prepared according to Scheme 2
:
1. Mg, THF
2. H3O+
O
P
O
+
2H3C O
Br
H3C O
O CH3
Cl P Cl
O
P
HBr, AcOH
HO
OH
II
Scheme 2.
†
Deceased.
aNesmeyanov Institute of Organoelement Compounds,
Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia
bInstitute of Chemistry, Chinese Academy of Sciences, Beijing, P.R. China
248

NEW MONOMERS
249
Certain characteristics of bis(naphthalic anhydride)s of general formula
O
O
C
C
O
R
O
O
O
C
C
O
O
Elemental analysis, found/calculated, %
Compound
–R–
Tm
,
°
C
Yield, %
C
H
F
P
CF3
C
62.77
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
2.27
ꢀꢀꢀꢀꢀꢀꢀ
18.54
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
I
150–152
159–161
46
53
63.08
2.40
19.54
F3C
CF3
O
P
C
70.03
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
3.30
ꢀꢀꢀꢀꢀꢀꢀ
4.17
ꢀꢀꢀꢀꢀꢀꢀ
II
71.79
3.28
4.42
Bis(naphthalic anhydride)s were obtained monaphthalic anhydride under conditions of aroꢀ
by the reaction of bisphenols of appropriate strucꢀ matic nucleophilic substitution similarly to [10],
ture with a twofold molar amount of 4ꢀbroꢀ Scheme 3:
O
Br
+ 2
OH
C
HO
R
O
C
O
O
C
O
O
C
O
1'
8'
4'
O
R
O
K2CO3
C
C
O
O
⎛
⎞
CF3
O
P
2C
⎜
⎟
–R– is
(
III),
(IV)
⎜
⎟
⎟
⎟
⎟
⎟
⎟
⎠
1
⎜
⎜
⎜
⎜
⎜
⎝
3''
5''
CF3
F3C
Scheme 3.
The experiment resulted in previously unknown bis[(1',8'ꢀdicarboxynaphthꢀ4'ꢀyl)phenoxy]ꢀ1ꢀ[3'',5''ꢀ
bis(naphthalic anhydride)s: dianhydride of 1,1ꢀ bis(trifluoromethyl)phenyl]ꢀ2,2,2ꢀtrifluoroethane (III
)
DOKLADY CHEMISTRY Vol. 440
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250
BELOMOINA et al.
and dianhydride of 1,1ꢀbis{[(1',8'ꢀdicarboxynaphthꢀ ing to vibrations of carbonyl groups in the anhydride
ring, a band at 1278 cm–1 typical for the absorption of
ether bond –C–O–C–, and a band at 1595 cm–1
corresponding to the absorption of the naphthalene
ring.
4'ꢀyl)phenoxy]phenylphosphine oxide (IV).
The reaction was carried out in a medium of freshly
distilled DMA with addition of chlorobenzene to
remove resulting azeotrope at 150°C for 10 h in an
argon flow.
The bis(naphthalic anhydride)s were used for the
synthesis of previously unknown polynaphthylimides.
The structure and purity of the dianhydrides were
confirmed by the data of elemental analysis (table) and
IR spectroscopy.
The IR spectra of compounds III and IV show
absorption bands at 1773 and 1736 cm–1 correspondꢀ Scheme 4:
The synthesis of PNIs was carried out by the reacꢀ
tion of the above dianhydrides with binuclear aromatic
diamines containing bridging groups according to
O
C
O
C
O
O
R
O
+ n
n
H2N
R'
NH2
O
C
C
O
O
O
O
C
R
O
C
O
R'
N
N
–2nH2O
C
O
C
O
n
⎛
⎞
⎟
⎟
⎟
⎟
⎟
⎠
CF
C
O
P
3
⎜
–R'– is –O–, –CH –
–R– is
,
;
2
⎜
⎜
⎜
⎜
⎝
F C
3
CF
3
Scheme 4.
The reaction was conducted under conditions of 0.84 dL/g (25
°
C, NMP). According to TGA, degradaꢀ
tion onset temperatures are in the range of 470–
500 C, softening points are within 260–290 C; the
highꢀtemperature catalytic polycyclization in phenol.
A mixture of benzoic acid and benzimidazole was used
as a catalyst, and the synthesis was accomplished
°
°
phosphorusꢀcontaining PNIs have higher softening
points as compared with the fluorineꢀcontaining polyꢀ
mers.
under homogeneous conditions at 80–180
°C for
15 20 h in an argon flow.
⎯
The IR spectra of resulting polymers show absorpꢀ
New polynaphthylimides and polyperyleneimides
were obtained by the reaction of anhydrides of naphꢀ
tion bands at 1670 and 1720 cm–1 typical for the vibraꢀ
tions of sixꢀmembered imide rings, a band at 1250 cm–1
typical of the absorption of –C–O–C– ether bond,
and a band at 1592 cm–1 corresponding to the absorpꢀ
tion of the naphthalene ring.
thaleneꢀ1,4,5,8ꢀtetracarboxylic
and
peryleneꢀ
3,4,9,10ꢀtetracarboxylic acids or dianhydride of 1,3ꢀ
bis(1,8ꢀdicarboxynaphthꢀ4ꢀoyl)benzene with a new
diamine, 1,1ꢀbis[4ꢀ(4'ꢀaminoꢀ2'ꢀtrifluoromethylpheꢀ
noxy)phenyl]ꢀ1ꢀ[3'',5''ꢀbis(trifluoromethyl)phenyl]ꢀ
The obtained PNIs are soluble in such organic solꢀ
vents as NMP, DMF, DMA, DMSO, and phenolic
2,2,2ꢀtrifluoroethane (V), which was obtained in sevꢀ
solvents; their reduced viscosities are within 0.36– eral stages according to Scheme 5.
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NEW MONOMERS
251
O
CF3
C
K2CO3
2
O
+
NO2
+
Cl
F3C
OH
NO2
DMA
F3C
CF3
F3C
CF3
CF3
C
CF3SO3H
O2N
O
O
NO2
F3C
F3C
CF3
CF3
2CF3
1C
c
e
f
4'
Pd/C
NH2NH2 · H2O
H2N
O
O
NH2
g
d
2'
b
F3C
3''
5''
F3C
CF3
a
V
Scheme 5.
The structure of diamine
V
was confirmed by eleꢀ Hd, He, Hf), 7.03 (d, 2H, Hc), 7.55 (s, 2H, Hb), 8.27
mental analysis data and H NMR spectrum. Yield
55–60%. Compound does not melt according to
DSC data.
1
(s, 1H, Ha).
Integrated intensity ratio of the signals agrees well
V
with the presented formula.
For C36H21F15N2O2 anal. calcd. (%): C, 54.15;
H, 2.65; N, 3.51.
Polynaphthylimides were obtained under the above
conditions, while polyperyleneimides were prepared
in a chlorophenol medium at 210
Found (%): C, 54.10; H, 2.67; N, 3.50.
1H NMR (400 MHz, DMSOꢀd6
,
δ
, ppm): 5.53 (s,
°C for 10 h according
4H, –NH2), 6.86 (dd, 2H, Hg), 6.94–6.99 (m, 8H,
to Scheme 6:
O
C
O
C
F3C
CF3
n
O
+ n
O
H2N
O
C
O
NH2
C
C
O
CF3
O
F3C
CF3
O
C
N
O
C
N
F3C
C6H5OH,
C6H5COOH,
benzimidazole
CF3
O
C
O
–2n H2O
C
C
CF3
O
O
n
F3C
CF3
⎛
⎞
⎟
⎟
⎟
⎟
⎟
⎠
O
C
O
C
⎜
⎜
⎜
⎜
⎜
⎝
is
,
,
Scheme 6.
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252
BELOMOINA et al.
The structure of these polymers was also confirmed
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2011