120 Pol. J. Chem. Tech.

,
PolishVol.
Journal
18, No.
of Chemical
1, 2016 Technology, 18, 1, 120—126, 10.1515/pjct-2016-0018

Multifunctional oligoetherols and polyurethane foams with carbazole ring

Renata Lubczak
Rzeszów University of Technology, Department of Organic Chemistry, al. Powstańców Warszawy 6, 35-959 Rzeszów, Poland
Corresponding author: e-mail: rlubczak@prz.rzeszow.pl

A new method of preparation of multifunctional oligoetherols containing carbazole ring is presented. The oli-
goetherols were obtained in the reaction of 9-(2,3-epoxypropyl)carbazole with sorbitol and oxiranes like ethylene
and propylene oxide. The structure of obtained oligoetherols was determined by IR, H-NMR and MALDI-ToF
spectroscopies. Physical properties of the products render them good candidates for preparing polyurethane foams.
The foams were obtained and their properties were examined. It has been found that the foams are rigid at room
temperature and their apparent density was 50–70 kg/m3. The water uptake was low, maximum to 6.5 mass%.
Obtained foams have high thermal resistance. Dynamic thermal analysis of these foams showed that 5% mass
loss was initiated at 250–300oC, while temperature of 50% mass loss was 370–404oC. Concomitantly the increase
of compression strength was observed.
Keywords: carbazole, sorbitol, hydroxyalkylation, oligoetherols, thermal stability of foams.

INTRODUCTION to 200°C resulted in dimension and shape changes of

samples. Probably the reason was too low functionality
The progress in research on synthesis and properties
of used OGE with carbazole ring which were three-
of new polymeric materials containing carbazole ring
-functional. Therefore, described synthesis of derivative
has been observed in recent years. Carbazole and its
of carbazole with more hydroxyl groups was undertaken
derivatives are used in chemistry and technology of
and obtained derivative was further used to obtain PU
polymers, dyes, pesticides, drugs, surfactants, stabilizers
foams with enhanced thermal stability.
and other additives for plastics1–7. Some of derivatives
were demonstrated to have unique physical properties
like photo- and electroluminescence, liquid crystallinity, EXPERIMENTAL SECTION
electric conductivity, and non-linear optics8–14. Polymers
with carbazole ring fall into two categories, namely those Syntheses
with carbazole group in main chain and inside chain. The synthesis of EPC was performed as previously22.
In the latter group, some polymers contain carbazole
attached by nitrogen and others in which the carbazole Opening of epoxide ring with sorbitol
ring is bonded via carbon. The side chain length between 52.48 g (0.235 mol) of EPC and 18.22 g (0.1 mol)
main chain and carbazole is crucial for physicochemical of sorbitol (pure, POCH Poland, sorbitol: EPC 1: 2.35
properties like phase transition temperature, solubility in molar ratio) were placed in three-necked 100 cm3 flask
organic solvents, the ability of formation of charge trans- equipped with reflux condenser, mechanical stirrer and
fer complexes, and non-linear optical properties. Polymers thermometer. The mixture was stirred and heated at
containing carbazole in main chain are usually obtained 95 °C to dissolve reagents followed by addition of 6 cm3
from monomers with two functional groups attached to triethylamine (TEA, pure, Fluka, Buchs, Switzerland).
the ring. These polymers, having the system of conjugated The temperature of mixture was then increased to 140°C
π bonds posses advantageous electrooptical properties15. and maintained for 35 hours under nitrogen atmosphere.
The macrocyclic composed of eight carbazole units in The progress of reaction was monitored by determina-
main chain indicate useful electroluminescence16. The tion of epoxide number. Brown, semi solid resin was
syntheses of multifunctional oligoetherols (OGE) with obtained upon cooling, from which the volatiles were
carbazole ring was not reported till now. High thermal further removed by vacuum drying at 80°C.
resistance of carbazole makes it useful substrate to in- Analytical results of semiproduct I:
crease thermal stability of OGE and polymers obtained
from them, like polyurethanes (PU) and polyesters17–20.
Thus, the linear OGE were obtained from carbazole and
epichlorohydrin leading to 9-(2,3-epoxypropyl)carbazole
(EPC) followed by epoxide ring opening upon reaction
with water or ethylene glycol or on alternative route by
reaction of carbazole with ethylene chloride and further
conversion of semiproduct by dietanolamine to give diol,
which was finally converted to oligoetherol by reaction
with oxirane axcess18, 19. All obtained OGE showed high
thermal resistance. When propylene glycol was replaced
by 3-(9-carbazoil)propane-1,2-diol in synthesis of poly-
ester resin, the obtained polymer indicated remarkable
increase of thermal stability21.
The PU foams obtained till now were thermally stable
up to long storage at 150°C. The exposure of foams
 Pol. J. Chem. Tech., Vol. 18, No. 1, 2016 121

with EA 1108, Carlo-Erba analyzer. The IR spectra of

products were recorded with Specord 71 IR, Carl Zeiss
spectrophotometer in capillary film or in KBr pellet; the
1
H-NMR spectra were recorded at 500 MHz Bruker
UltraShield in DMSO-d6 with hexamethyldisiloxane as
internal standard. MALDI ToF (Matrix-Assisted Laser
Desorption Ionization Time of Flight) of OGE were
obtained on Voyager-Elite Perseptive Biosystems (USA)
mass spectrometer working at linear mode with delayed
ion extraction, equipped with nitrogen laser working at
337 nm. The method of laser desorption from matrix
was used with 2.5-hydroxybenzoic acid in THF at mg/cm3
concentration. The samples with diluted with methanol
to 1 mg/cm3, followed by addition of 10 mg/cm3 NaI
in acetone. Therefore in some cases the molecular ion
masses were increased by the mass of Na+ and CH3OH.
Thermal analyses of foams (DTA, DTG and TG) were
performed in ceramic crucible at 20–1000°C tempera-
ture range, about 200 mg sample, under air atmosphere
with Termowaga TGA/DSC 1 derivatograph, Mettler.
The number-average molecular mass Mn of product of
reaction EPC with sorbitol was determined cryoscopically
in DMSO solvent.

Physical properties of OGE

Refraction index, density, viscosity, and surface ten-
sion of OGE were determined with Abbe refractome-
ter, picnometer, Höppler viscometer (typ BHZ, prod.
Prüfgeratewerk, Germany) and by the detaching ring
method, respectively.
Scheme 1. Structure of semiproduct I
Yield: 83%; elemental analysis – % Calcd. C 70.10; Preparation of polyurethane foams
H 6.31; N 4.66; % Found C 69,64; H 6,41; N 4,76; IR Foaming tests were conducted on laboratory scale in
(KBr) [cm–1]: 3370 (OH), 3048, 3022 (Ar-H), 2927, 2875 500 cm3 paper cups at room temperature. In details
(CH2), 2720 (CH), 1925, 1889, 1772 (aromatic overtones), oligoetherol (10 g) was mixed with 0.2 g of Silicone
1627, 1597, 1576 (C=C in carbazole ring), 1491, 1484, 5340 (pure, Houdry Hülls, USA) as surfactant, TEA as
1460 (OH), 1453 1349 (CH2), 1326 (C-N), 1121, 1090, catalyst (0.4–2.4 wt%) and water (3 wt%) with respect
1063, 1023 (C-O-C and OH), 750, 723 (Ar-H); 1H- to OGE. A calculated portion of polymeric diphenyl-
NMR (DMSO-d6 ) [ppm]: a: 3.80–3.95; b: 3.95–4.20; methane 4.4’-diisocyanate (pMDI, Merck, Darmstadt,
c: 4.20–4.60; d: 4.60–5.0; e: 5.00–5,40; f: 7.00–7.20; g: Germany; containing 30–32% isocyanate groups) was
7.20–7.50; h: 7.50–7.75; i: 8.00–8.20. then added and the mixture was vigorously stirred until
the contents were creamed. Test samples were cut out
Reaction oxiranes with semiproduct I from the foams thus obtained.
14.12 g (0.02 mol) of semiproduct I, 0.25 cm3 (0.001
mol) TEA and 21.1 g (0.48 mol) ethylene oxide (EO, Characterization of foams
pure, Fluka, Buchs, Switzerland) or 0.5 cm3 (0.002 mol) The following properties of foams were studied: appa-
TEA and 20.9 g (0.36 mol) propylene oxide (PO, pure, rent density24, water uptake25, linear shrinkage estimated
Fluka, Buchs, Switzerland) were placed in pressure reak- on the basis of the change of linear dimension of the
tor of 100 cm3 capacity equipped with magnetic stirrer sample heated for 4 hours at 100°C26, thermal stability
and thermometer. The mixture was heated at 50°C for as the weight loss at 150, 175 and 200°C within one
11 hrs (in case of EO) or at 90°C for 26 hrs (in case month and compression strength27.
of PO). The progress of reaction was controlled by de-
termination of epoxide number. The products as brown RESULTS AND DISCUSSION
resins were obtained, which were further heated under
reduced pressure (p = 2132 Pa, T = 80°C) in order to Synthesis and characteristics of OGE
remove the catalyst.
The epoxidation was first step of functionalization of
Analytical methods carbazole on the route to OGE. The reaction was per-
The progress of reactions with oxiranes were monitored formed in acetone at 50–56°C using six molar excess of
by determination of epoxide number using hydrochloric epichlorohydrin and two-molar excess of KOH in relation
in dioxane method23. The product formation was also to carbazole. The reaction mixture was poured into water
controlled by hydroxyl number (HN) and elemental to obtain crude EPC as cream colored solid as described
analysis. Elemental analysis for C, H, N, were done in22. The compound was subjected to ring opening with
sorbitol assuming that both primary hydroxyl groups of
122 Pol. J. Chem. Tech., Vol. 18, No. 1, 2016

sorbitol were able to react with EPC according to the

following scheme:

Scheme 2. Reaction of sorbitol with 9-(2.3-epoxypropyl)carba-

zole
In order to check whether obtained product was and the only decrease of intensity of OH resonance was
suitable reagent for synthesis of OGE, the solubility observed. These spectral observation lead to conclusion
of compound in oxiranes: EO and PO was tested. The that synthesis of oligoetherol requires excess of EPC
crude product was well soluble in oxiranes, while unre- higher than simple 1:2 sorbitol : EPC stoichiometry.
acted sorbitol, which was still present in post-reaction Therefore, considering previous results the synthesis of
mixture was not. The undissolved solid was isolated oligoetherol was then performed at 1:2.35 sorbitol : EPC
and identified as sorbitol by melting point (96°C) 1H- molar ratio. However, in such conditions the excess of
-NMR, IR spectra, and elemental analysis (% exp. C EPC (0.35 mol) reacts with secondary hydroxyl groups
40.85; H 7.85 versus 40,85, H 7,85; ufunkcyjne pol % to give the product, which can be described by formula
calc. C 40.55; H 7.74). Indeed the 1H-NMR spectrum I. The formal stoichiometry can be represented by C41.
of post-reaction mixture (Fig. 1a) contains characteristic 25H44. 55N2. 35O8. 35 formula. Molar mass determined by

resonances of sorbitol within 4.2–4.6 and 3.3–3.7 ppm cryscopic method in DMSO was 702.1 g/mol, while that
regions corresponding to hydroxyl and aliphatic protons. calculated was 706.1 g/mol. Elemental analytical data are
The purification of crude product by dissolving in PO, in good accordance with the formula. In order to obtain
removal of undissolved sorbitol and evaporation of PO the oligoetherol, the obtained product was mixed with
from filtrate, gave pure product which showed still mi- appropriate oxirane and TEA catalyst, heated at 50°C
nor resonances from methylene and methine protons in (EO) or 90°C (PO) to homogenize reaction mixture
the 1H NMR spectrum at 3.3–3.7 ppm (compare Fig. 1 and initiate the reaction which lasted 11 or 26 hours in
a and b), while signal at 3.4 ppm belongs to the over- case of EO and PO, respectively. The obtained products
lapped resonances of aliphatic protons of oligoetherol. were OGE of following stoichiometry: sorbitol : EPC :
The resonances of hydroxyl protons in the product EO = 1 : 2.35 : 24 and sorbitol : EPC : PO = 1 : 2.35
remains unaltered in comparison with that of sorbitol : 18, represented by formula II:

Figure 1. 1H-NMR spectrum of mixture obtained in reaction

of sorbitol with EPC in molar ratio 1:2 (a) and after
removal of sorbitol precipitated in PO (b)
 Pol. J. Chem. Tech., Vol. 18, No. 1, 2016 123

where:

Scheme 3. Structure of oligoetherol

Figure 2. IR spectrum of product obtained in reaction of
Elemental analysis and HN (Table 2) confirmed the sorbitol with EPC in molar ratio 1:2.35
stoichiometry of products obtained from EO: % calc. C
hydroxyl proton resonances are observed at 5.0–5.3 ppm.
60.77; H 7.98; N 1,87; % exp., C 60.65; H 7.92; N 2.05;
Based on integral intensity of resonances one can conc-
and from PO: % calc. C 65.25; H 8.73; N 1.88; % exp.,
lude that sorbitol was totally consumed with EPC. Upon
C 65.32; H 8.43; N 1.42) as well as IR and 1H-NMR
reaction of the semiproduct with EO the spectrum of
spectra. In the IR spectrum of the semiproduct obtained
product simplifies and only aromatic resonance (within
from sorbitol : EPC = 1:2.35 (Fig. 2) the bands of OH
7.0–8.1 ppm) and aliphatic proton resonances within
groups were observed at 3370 cm–1 and 1020–1200 cm–1,
3.0–3.9 ppm are observed (Fig. 4). In the spectrum of
the latter overlapping with C-O-C bands. The bands at
theproduct obtained from PO, the additional resonan-
1626 cm–1 the C=C stretchings were observed, while that
ces from methyl protons at 0.9–1.1 ppm are present as
at 1326 cm–1 belongs to C-N in carbazole aromatic ring,
well as methylene and methine proton resonances at
which suggests the attachment of carbazole to polyhy-
3.4–3.6 ppm. Further on composition of obtained pro-
droxyl alcohol. In the IR spectra of OGE the intensity
ducts was gathered on the basis of their MALDI-ToF
of bands at 3370 cm–1 decreased, while the opposite
spectra. The presence of series of peaks differing of
effect of intensity was found for the bands at 2867cm–1
m/z = 44 or 58 (Table 1, for example entry 4–8,12 or
and at 1084 cm–1 obviously due to increase of number of
10–12, 14, 15, 17–19) indicate clearly of incorporation
alkyl groups and ether bonds, respectively (Fig. 3). The
1 of oxyalkylene subunits into oligomers, originating from
H-NMR spectrum of the semiproduct obtained from
EO or PO substrates, respectively. Thus, the products
sorbitol : EPC 1 : 2.35 molar ratio shows the presence
of variable substitution are formed. Moreover the pe-
of resonances both from carbazole ring (7.0–8.2 ppm)
aks of m/z = 487, 523, 563, 599 and 639 (Table 1 entry
and aliphatic protons of sorbitol (at 3.3–3.7 ppm). The

Table 1. Interpretation of MALDI ToF spectrum of oligoetherol obtained in reaction of product sorbitol : EPC = 1:2.35 with PO
124 Pol. J. Chem. Tech., Vol. 18, No. 1, 2016

Figure 3. IR spectrum of oligoetherol obtained in reaction of Figure 4. 1H-NMR spectrum of oligoetherol obtained in re-
sorbitol with EPC and EO in molar ratio 1:2.35:24 action of sorbitol with EPC and EO in molar ratio
1:2.35:24
4–8) demonstrates presence of product of 1:1 molar of
reaction between sorbitol and EPC; this semiproduct by compression strength. It was found that the best fo-
reacts further with oxiranes. Detailed analysis of peaks ams, considering the rigidity and pore homogeneity was
of m/z >639 suggests that OGE can also be formed by achieved when amount of isocyanate was 100–120 g and
reaction of oxiranes with semiproducts of 1:2 and 1:3 amount of water was 3 g per 100 g of OGE. Isocyanate
sorbitol: EPC (Table 1 entry 9–20), which is consistent index was circa 136 for foamed compositions. Cream
with general formula of oligoetherol II. The following time was very short 12–18 seconds) and rise time was
physical properties of obtained OGE were tested: den- also short (within 8–60 s). Tack free time was variable
sity, viscosity, surface tension and refraction index. All within wide range of time (5 s–5 min). Considering the
these properties change with temperature quite typically amount of catalyst, which had to be higher in case of
(Table 2). It was found that this kind of oxirane had products obtained from PO was 2.0–2.4 g per 100 g of
relevant influence on properties of OGE. It has been oligoetherol and 0.4–0.8 g in compositions obtained from
noticed that the lower viscosity, density, refraction index EO (Table 3). When these conditions were not met,
and surface tension indicate that these are oligotherols the foams were not rigid (catalyst deficit), low blowing
obtained from propylene oxide. These properties are (water deficit) and irregular pores (water excess). Some
caused by the least packed structure of oligoetherol properties of foams like apparent density, water uptake
related to branched oxyalkylene chain caused by the and polymerization shrinkage are the same as for classic,
presence of methyl group. The results obtained here commercial PU foams (Table 4). The obtained foams
suggested that OGE II are suitable for obtaining PU indicated low polymerization shrinkage, usually less than
foams. The criteria of substrates were based on surface 1.4%. Apparent density was within 50–70 kg/m3, water
tension, viscosity and its temperature dependence. uptake was maximum 6.5%. The foams obtained from
OGE synthesized from PO showed less water uptake.
Formation and properties of polyurethane foams Thermal stability of foams was tested by mass loss
The obtained OGE were tested on laboratory scale as measurements of samples heated at 150, 175, and 200oC
substrates for PU foams. The optimization of foaming (Fig. 5) within one month. The samples before heating
was performed changing the concentration of TEA and after being heated were tested for compression
catalyst, amount of MDI and blowing agent (water). strength (Table 4). The foams are thermally stable at
Then the thermal stabililty of foams was determined 150°C; the mass loss at this temperature is less than 8%
by mass loss test and changes of mechanical properties (Fig. 5a). The highest thermal stability has the compo-

Table 2. Some properties of OGE

 Pol. J. Chem. Tech., Vol. 18, No. 1, 2016 125

sition obtained from oligoetherol synthesized from PO are 15 and 30%. Dynamic thermal analysis indicated
(Table 3, comp. No 1), for which the mass loss is 5.5%. (Fig. 6) that the foam of best thermal stability occured
Its compression strength increases twice upon heating for the ample obtained from oligoetherol containing
at 150°C. The compression strength of the sample pre- oxyethylene units; its decomposition started at 300°C,
pared in analogous way but obtained from EO increases while the sample prepared from oligoetherol containing
even three times (Table 4). Generally, thermal exposure oxypropylene units decomposed starting at 240°C. Total
at 175°C causes the mass loss 25%, while exposure of decomposition occur at 560–580°C; no further mass loss
sample to 200°C results in 45% mass loss; in case of was observed.
the sample of the best thermal stability these values
Table 3. The influence of composition of foaming process

Table 4. Some properties of polyurethane foams

a) c)

b)

Figure 5. Thermal stability of PU foams as the weight loss after heating at a) 150, b) 175 and c) 200°C for a month (the composi-
tion number from table 3 is given in inset)
126 Pol. J. Chem. Tech., Vol. 18, No. 1, 2016

12. Tirapattur, S., Belletete, M., Drolet, N., Leclerc, N. &

Durocher, G. (2003). Steady-state and time-resolved studies
of 2,7-carbazole-based conjugated polymers in solution and
as thin films: determination of their solid state fluorescence
quantum efficiencies. Chem. Phys. Lett. 370, 799–804. DOI:
10.1016/S0009-2614(03)00178-7.
13. Zhang, X.J., Tian, Y.P., Li, S.L., Jiang, M., Usman, A.,
Chantrapromma, S. & Fun, H.K. (2003). Zn(II) and Cd(II)
N-carbazolylacetates with strong fluorescence. Polyhedron.
22,397–402. DOI: 10.1016/S0277-5387(02)01360-8.
14. Zhu, W. H., Hu, M., Rao, R. & Tian, H. (2003). A novel
family of twisted molecular luminescent materials containing
carbazole unit for single-layer organic electroluminescent
devices. J. Photoch. Photobio. A 154, 169–177. DOI: 10.1016/
S1010-6030(02)00325-8.
Figure 6. Mass loss of PU foams vs temperature (the composi- 15. Jin, S.H., Sun, Y.K., Sohn, B.H. & Kim, W. (2000).
tion number from table 3 is given in inset) Synthesis and electro-optical properties of electroluminescent
polymers containing carbazole unit. Eur. Polym. J. 36, 957–963.
CONCLUSIONS DOI.org/10.1016%2FS0014-3057%2899%2900138-X.
16. Zhang, Y., Wada, T. & Sasabe, H. (1996). A new synthetic
Hexafunctional OGE with carbazole ring can be ob- approach to macrocyclic molecules and main-chain polymers
tained from carbazole and glycerine epichlorohydrin to containing carbazole moieties. Chem. Comm. 5, 621–622. DOI:
get EPC. Its epoxide ring opening can be performed org/10.1039/CC9960000621.
by reaction with sorbitol; the product can further be 17. Lubczak, R. (2008). Oligoetherols and polyurethanes with
converted to oligoetherols by its reaction with oxiranes carbazole ring in side chain. Polimery 53, 587–590.
EO and PO. 18. Lubczak, R. (2008). Bifunctional Oligoetherols with
Obtained OGE have similar properties to typical po- Carbazole Ring. J. Appl. Polym. Sci. 110, 3501–3507. DOI:
lyols used for PU foam preparation except much higher 10.1002/app.28935.
19. Lubczak, R. (2010). Bifunctional Oligoetherols with
thermal stability. PU foams obtained form polyfunctional
Carbazole Ring. J. Appl. Polym. Sci. 117, 16–23. DOI: 10.1002/
OGE with carbazole ring have remarkable thermal re- app.31088.
sistance demonstrated by long-time exposure to 200oC. 20. Lubczak, R. (2012). Trifuntional Oligoetherols and Po-
lyurethane Foams with Carbazole Ring. Open J. Org. Polym.
LITERATURE CITED Mat. 2, 1–6. DOI: 10.4236/ojopm.2012.21001.
21. Lubczak, R. (2013). Polyester resins with carbazole ring.
1. El-Nagger, A.M., Ahmed, F.S.M., Abd El-Salam, A.M. Polym. Int. 62, 1243–1249. DOI: 10.1002/pi.4415.
& El-Gazzar, M.A. (1982). Synthesis and biological activity of 22. Lubczak, R. (2006). Diols with carbazole ring and their
some new aminoacylcarbazole derivatives. J. Heterocyc. Chem. aza derivatives. Heterocycl. Comm. 12, 201–208. DOI: 10.1016/
19, 1025–1028. DOI: 10.1002/jhet.5570190509. S09253467(02)00-141-6.
2. Nishide, K., Yamanouchi, T. & Kinjo, K. (1974). Photosen- 23. Epoxide resins. Method of testing. Determination of
sitive material for electro-photography. US Patent 3 832 172. the epoxide number and epoxide eqiuvalent, Polish Standards
3. Renfrew, E.E. (1974). Thiazolylazo- or benzothiazolylazo- PN-C-89085-13:1987, Ed. Polish Committee for Standardiza-
carbazole dyes for polyester fibers. US Patent 3787178. -tion, 1987.
4. Shattuck, M.D. & Vahtra, U. (1968). Photoconductive 24. Cellular Plastics and Rubbers. Determination of Apparent
composition sent. UK Patent 1112458. (Bulk) Density, Polish (European) Standards PN-EN ISO 845-
5. Spanggaard, H., Jorgensen, M. & Almdal, K. (2003). 2000, Polish Committee for Standardization, 2000.
Mechanical Strain Sensing in a SIS-Type Elastomer with 25. Cellular Plastics, rigid. Determination of Water Absorp-
Single Site Strain Probes Based on Carbazole. Macromol 36, tion, Polish (European) Standards PN-EN ISO 2896–1986,
1701–1705. DOI: 10.1021/ma0256791. Polish Committee for Standardization, 1987.
6. Yang, W., Davis, P. & Drug, P. (1992). Microbial models 26. Cellular Plastics, rigid. Test of Dimensional Stability,
of mammalian metabolism. Biotransformations of N-methyl- Polish (European) Standards PN-EN ISO 2796–1986, Polish
carbazole using the fungus Cunninghamella echinulata. Metab. Committee for Standardization, 1986.
Dispos. 20, 38–46. 27. Cellular Plastics. Compression Test for Rigid Materials,
7. Kinjo, K., Yamanouchi, T., Kondo, E., Matsuno, H. & Polish (European) Standards PN-EN ISO 844–1978, Polish
Nishide, K. (1971). Electro-photographic liht-sensitive material. Committee for Standardization, 1978.
Germ. Patent 2035679.
8. Gratt, J.A. & Cohen, R.E. (2003). Optical properties of
block copolymers containing pendant carbazole groups and
in situ synthesized CdS nanoclusters. J. Appl. Polym. Sci. 88,
177–182. DOI: 10.1002/app.11620.
9. Ke, X.J., Yan, X.Z., Srisanit, N., Wang, M., Yang, J.W.,
Huang, X.F. & Shong, S.Z. (2003). Holographic storage in
carbazole-azo binary compound doped polymer. Optical Comm.
217, 69–74. DOI: 10.1016/S0030-4018(02)02341-6.
10. Lee, J.H., Woo, H.S., Kim, T.W. & Park, J.W. (2003).
Blue organic light-emitting diodes with carbazole-based small
molecules. Optical Mater. 21, 225–229. DOI: 10.1016/S0925-
3467(02)00141-6.
11. Monttilier, J.P. (1974). Electrophotograpic photoconduc-
tors. Germ. Patent 2360102.