materials

Article
Natural Rubber/Dendrimer Modified Montmorillonite
Nanocomposites: Mechanical and
Flame-Retardant Properties
Chenyang Zhang and Jincheng Wang *
College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science,
Shanghai 201620, China; zcy9372@163.com
* Correspondence: wjc406@sues.edu.cn; Tel.: +86-21-67791219; Fax: +86-21-67791214

Received: 21 October 2017; Accepted: 26 December 2017; Published: 28 December 2017

Abstract: A series of flame-retardant nanocomposites were established based on compounding

of natural rubber (NR) and dendrimer modified flame-retardant organic montmorillonite
(FR-DOMt). The merits of these nanocomposites were focused on their better mechanical and
flame-retardant properties. X-ray diffractometer (XRD) together with scanning electron microscopy
(SEM) and transmission electron microscopy (TEM) analysis revealed that exfoliation, intercalation,
or aggregation status in the NRmatrix can be achieved by addition of different amounts of FR-DOMt.
The sound effects of blend ratio of FR-DOMt on mechanical, thermal stability, and flame-retardant
(FR) properties of NR were studied. The NR/FR-DOMt-20 composite possessed the highest tensile
strength, and this resulted from complicated interactions between layered silicates and elastomers.
In addition, with loading of 20 phr of FR-DOMt, the flammability parameters of NR, such as
heat release rate (HRR), smoke evolution area (SEA), and carbon monoxide (CO) concentration,
were obviously reduced from cone calorimeter analysis.

Keywords: FR-DOMt; natural rubber (NR); nanocomposite; structure; properties

1. Introduction
In order to reduce polymer consumption and production cost, clay minerals including
montmorillonite (Mt), saponite, hectorite, etc., were widely used as fillers in polymeric industry
for many years [1]. In the past decades, nanocomposites based on polymer matrix and organoclay were
designed and produced with high mechanical properties and thermal stability [2–5]. Much attention
was paid to rubber nanocomposites filled with organoclay recently, which included chloroprene
rubber [1], cis-1,4-polybutadiene rubber [6,7], fluoroelastomer [8], ethylene-propylene-diene
terpolymer [9,10], nitrile rubber [11], and isobutylene-isoprenerubber [12].
Compared with synthetic rubbers, natural rubber (NR) possessed unique advantages required
for manufacturing of aerotires, suspension elements, various latex products, etc. However, NR had
the shortcoming of high flammability. This setback may limit its application in mine conveyor belts,
power cables, aircraft tire treads, etc. [13].
The compounding of NR matrix with inorganic flame-retardant additives was an effective and
economical way to improve its flame-retardant behavior [14–16]. Due to small size, high thermal
stability, and intercalation abilities, Mt has been paid special attention in the field of flame-retardancy.
It was hard to prepare intercalated or exfoliated NR/Mt nanocomposites due to no polar groups
in the backbone of NR. Lots of efforts were focused on improving the compatibility between NR
and Mt by using organic modification methods. Khanlari et al. [17] studied the thermal stability,
flame-retardance together with the hardness and mechanical properties with addition of organoclay
in NR nanocomposites. Its aging hardness was decreased more than 55% and the ignition time

Materials 2018, 11, 41; doi:10.3390/ma11010041 www.mdpi.com/journal/materials

Materials 2018, 11, 41 2 of 17

was delayed about 150% by loading 3 wt % of organoclay in NR. In addition, the decreased peak
value of heat release rate was about 54% compared to the pure NR. Liu et al. [18] researched
the nanocomposites of NR and tributyl phosphate modified Mt (TMt) by the mixing intercalation
method. Their flame-retardant property was tested by cone calorimeter analysis. Results showed that
the NR/TMt nanocomposites presented better flame-retardant properties. The heat release rate,
mass loss rate, and smoke producing rate of NR/TMt nanocomposites were obviously reduced.
Efforts have also been made to combine organoclay and other flame-retardant additives [14,19].
In the near future, more attention was focused on dendrimers, a novel type of polymer which
possessed porous networks, reactive end groups, less crystallization ability, and good compatibility
with other macromolecules [20]. In addition, dendrimers owned the special features of step by step
controlled synthesis and together with their synthesis from monomers, which were resulted from
molecular and polymer chemistry-like properties [21,22]. In our previous work, a novel type of
flame-retardant dendrimer modified OMt (FR-DOMt) was prepared and characterized [23]. It was
disclosed that the employment of dendrimers can increase the d001-value and thermal stability of
organoclay. In addition, this dendrimer containing phosphorus and boron elements behaved like a
surfactant for surface modification. As can be deduced, the flame-retardance and smoke inhibition
effects of phosphorus, boron, and silicon elements in FR-DOMt can be used to fabricate a new type of
enhanced clay-polymer nanocomposites (CPN).
In the present work, NR/FR-DOMt nanocomposites were prepared using this novel type of
organoclay. The NR nanocomposite with 20 phr of FR-DOMt exhibited better mechanical properties.
Moreover, this NR nanocomposite also possessed excellent thermal stability and flame-retardance.

2. Experimental Section

2.1. Materials
A type of flame-retardantand dendrimer modified OMt, named as FR-DOMt, was prepared
by us [23]. To compare the physical, mechanical, and flame-retardant properties of different NR
nanocomposites, following formulation, which was presented in Table 1, was used.

Table 1. Formulation of NR vulcanizates.

Component Information phr

3#, industrial grade, provided by Hainan Rubber
NR 100
Company, Hainan, China.
sulfur 2.5
zinc oxide 5.0
chemical pure, provided by Shanghai Guoyao
stearic acid 1.0
Chemical Agent Company, Shanghai, China.
2-bezothiazolethiol 1.2
tetramethyl thiuram disulfide 0.2
chemical pure, provided by Shanghai Lingfeng
diphenyl guanidine 0.3
Chemical Agent Company, Shanghai, China.
chemical pure, provided by Shanghai Gaoqiao
antioxidant D 1.0
Chemical Agent Company, Shanghai, China.
FR-DOMt self-prepared. 0, 5, 10, 15, 20
Materials 2018, 11, 41 3 of 17

2.2. Preparation of FR-DOMt

The water solution of tetra-hydroxymethyl phosphonium chloride (THPC, 8.57 g) was placed in a
three-necked flask. Inorganic Mt (40 g) was added into above mixture, and a cation exchange reaction
was occurred. THPC-OMt was thus obtained. N,N-dihydroxyl-3-aminmethyl propionate (27.54 g) and
toluene-p-sulfonic acid (0.07 g) were gradually added to above THPC-OMt. The resultant dispersion
was vigorously stirred for 10 h. In addition, this reaction was repeated for three times, and the dried
cake was ground to obtain different generations of dendrimer modified OMt, DOMt-1,2,3. Last,
boric acid (71.23 g) was added into above DOMt-3 in a three-necked flask provided with a stirrer.
The mixture was treated at 75~80 ◦ C for about 2 h. The liquid product was distilled, and thus FR-DOMt
was obtained [23].

2.3. Preparation of NR Nanocomposites

On a double roller plasticator (Shanghai Sinan Rubber Machinery Company, Shanghai, China),
NR gums were mixed with different common additives which was illustrated in Table 1. After mixing
for about 15 min, FR-DOMt was added in different amounts to the mixture. Thus, different types of
NR mixtures were prepared. Before adding into NR matrix, FR-DOMt was dried and cured at 150 ◦ C
for about 2 h. Then, the mixtures were placed in a dumbbell mould, and the corresponding curing was
carried out at 150 ◦ C for 10 min. Last, different NR nanocomposites were successfully prepared.

2.4. Characterization of NR Nanocomposites

X-ray diffraction (XRD) was conducted by packing the samples into an aluminum sample holder.
A Rigaku D-Max/400 X-ray diffractometer (Tokyo, Japan) was used. The X-ray beam was nickel-filtered
CuKα (λ = 0.154 nm) radiation which was operated at 50 kV. The scanning range was from 1 to 10◦
and the scanning rate was 2◦ /min. The corresponding d001 spacings may be calculated by Bragg
law. Transmission electron microscopy (TEM) was conducted on a JEM-2010 instrument (JEOL Ltd.,
Tokyo, Japan). Cryo-ultramicrotomy was used to prepare the ultra-thin films at −100 ◦ C with an
acceleration voltage of 80 kV. The thickness of the thin sections was 80–100 nm. Scanning electron
microscopy (SEM) was carried out by a Hitachi S-2150 equipment (Hitachi, Tokyo, Japan). The photos
were obtained by a potential of 25 kV. The specimens were previously coated with a conductive
gold layer.
The curing parameters were measured on an oscillating disk rheometer (MDR-2000, Wuxi, China).
The samples were cured at 150 ◦ C under 15 MPa pressure on an electrically heated press.
The formulation shown in Table 1 was used to prepare the corresponding samples. The tensile
properties were tested using a TCS-2000 universal tensile testing machine (Gotech easting machines
company, Taichung, Taiwan) according to Chinese National Standard GB 528-82. These tests were
carried out at room temperature with a crosshead speed of 500 mm/min. The samples used were
dumbbell and 6 mm wide in cross section. The selected value for each sample was a median value
of five specimens. The wear resistant property was performed on a WML-76 Akron abrasion testing
machine (Jiangsu Zhenwei Machinery Company, Shanghai, China). In each case, the rotating velocities
of the sample and emery wheel were 76 rpm and 33 rpm, respectively, and a pressure of 26.7 N was
used on the samples. Shore hardness test was measured by using a XY-1 rubber hardness instrument
(Shanghai Chemical Machinery Factory, Shanghai, China).
TGA test was carried out on a Linseis PT-1000 apparatus (Linseis, Selb, Germany). During the test,
the atmosphere was nitrogen, and the increasing rate of the temperature was 20 ◦ C/min. The mass
of the samples was 10 mg for each test. They were measured in the temperature ranges from room
temperature to 600 ◦ C. The flame-retardant property was evaluated using horizontal burning test on
a horizontal burning tester (Yang Yi Test Equipment Company, Kunshan, China) according to the
standard ASTM D635. In this test, a size of (125 ± 5 mm) × (13.0 ± 0.5 mm) × (3.0 ± 0.2 mm) was
used and different rubber sheets were prepared. In addition, the flame-retardant parameters were
 Materials 2018, 11, 41 4 of 17

measured using a Stanton Redcroft cone calorimeter (Stanton Redcroft, London, UK). The heat flux was
25 kW/m2 according to ASTM 1356-90. The dimensions of the samples were 10 cm × 10 cm × 2 mm.
The cone data reported here were an average of three replicated measurements.

3. Results and Discussion

3.1. Structure and Properties of FR-DOMt

The preparation process of FR-DOMt was presented in Scheme 1. Firstly, OMt was obtained
Materials
by a2018, 11, 41
cation exchange reaction between Mt and tetra-hydroxymethyl phosphonium chloride (THPC).4 of 17
Then, three dendrimer modified OMt, DOMt-1, 2, and 3, were prepared from repeated reactions using
fromthe
anmomomer,
esterification reaction between hydroxylpropionate.
N,N-dihydroxyl-3-aminomethyl and acid groups [23]. Results
Lastly, FR-DOMt wasexhibited
fabricated that
fromthis
an FR-
DOMt possessedreaction
esterification good thermal
between stability
hydroxyl (Figure
and acid1a). It showed
groups improved
[23]. Results exhibitedthermal behavior
that this FR-DOMt in the
possessedrange
temperature good thermal
from 100 stability
to 300(Figure 1a). It showed
°C. Notably, improved thermal
an increased layeredbehavior
spacinginwas the temperature
formed and an
range from 100 to 300 ◦
exfoliated structure was C. Notably, an
obtained fromincreased
the losslayered spacing
of bands was formed
from 6.1° and and an exfoliated
7.2° structure
(Figure 1b). The new
was obtained from the loss of bands from 6.1 ◦ and 7.2 ◦ (Figure 1b). The new stretching vibrations
stretching vibrations at 1650 and 1250 cm appeared in FTIR spectrum of FR-DOMt (Figure 1c), and
−1
−1 appeared in FTIR spectrum of FR-DOMt (Figure 1c), and these were ascribed
theseatwere
1650 ascribed
and 1250 cm to B–O bonds. In addition, the peaks at 3150–3550 cm−1 and 1300–1450 cm−1 were
to B–O bonds. In addition, the peaks at 3150–3550 cm−1 and 1300–1450 cm−1 were attributed to
attributed to N–H groups resulting from the monomer by the dendrimer technology. This analysis
N–H groups resulting from the monomer by the dendrimer technology. This analysis together with
together with morphology observation by SEM (Figure 1d1,d2) demonstrated that FR-DOMt
morphology observation by SEM (Figure 1d1,d2) demonstrated that FR-DOMt possessed a novel
possessed a novel
structure structure and
and composition, andcomposition, and wasfor
was a new candidate a new candidateinfor
its application its application in polymers.
polymers.
For For
a better and easier understanding of synthetic process,
a better and easier understanding of synthetic process, the formation of the the formation of the dendrimer
dendrimer
molecules, FR-DTHPC,
molecules, FR-DTHPC, was wasgiven
givenininScheme
Scheme 2. 2. In this process,
In this process,first,
first,THPC
THPC was was used
used as core
as the the core
material, andand
material, thethe
monomer,
monomer, N,N-dihydroxyl-3-aminmethyl
N,N-dihydroxyl-3-aminmethyl propionate, propionate, wasasused
was used as the branched
the branched unit.
unit.Then,
Then,three
three generations
generations of dendrimer
of dendrimer werewere synthesized
synthesized by transesterification.
by transesterification. Last,
Last, boric acidboric
was acid
was used
usedtotoreact
reactwith
withthethe
end groups
end groupsof G-3, and thus
of G-3, and FR-DTHPC
thus FR-DTHPC was obtained [24].
was obtained [24].

OH O CH3
NH2
NH 2
H 2N H2 N H2 N NH 2
N H2
HN
NH2 HN H2 N
NH O
NH N NH
H 2N N HH 2
HN O NH2
NH2 O O O
H 2
N H N
O O O
NH N H H N
N H2
N H N
H N O
O N O O NH
O N
H N HN
2 O
H2 N N H N N N H2
N
O
NH
O N H N H N N
N H NH2
HN O O NH
O
H N O O HN
H2 N NH
O O
NH NH O NH
N 2
HN O
N
N
O N O
H2 N N O
NH
N O NHH 2
O O
HN HN N H N
HN O NH
N H O
H HN N H2
H O
H O
N N
H2 N N O N O
N O N
O N N NH
H2 N O O N H
N O
N O O N NH
HH HN 2
O NH N
N H N
H N HN O O
H O
O O
H2 N H H NH O

HOH2C CH2OH
N O N NH 2
O H N N N
N
H2 N N

P+
N N O N N H
N N O N H
H N O N
H H O
NH
O
N NH N H O
O N H2
O
O
H2 N
O
O
C

O
H2 N O O NH 2
O O
HN O

N
HN
O H N N
H N O
N O O H H
N N N N

O
N H H
O N
N N
H2 N N NH 2
O N N H
HN H N O N O
H N
O O O N H2
O O H
NH NH NH 2
N HN NH N N H2
H 2
N N
O O N H O H2 N H2 N NH
H O N HH H N 2
2

Cl
HN N NH 2
N N O O N H2 HN
O N N
N O O N H2 HN H2 N
O H N N H2 NH O HN
O N H N N H NH2
H2 N N N 2 NH
O H N O O N H2
NH HNH N H2 O O
N H H N H2 N HN
O O HN O O O
HN H N NH N HH NH HN

P+
H2 N O O N H NH 2
N O NH N O
O HN O N
N O O N H
N O N H2 O N
O O N H2 N H N
N O NH
H2 N N H H2 N NH N N 2
N
O HN N
NH H N NH O
HN O O N H2
H N O O O O N HN HN N
H 2N NH NH N H2
O O HN O O O NH
N H N NH H N
NH N H N O O O HN
O H N H N N H
2 O O
N NH NH O N H2
NH 2 N
NH N H N H N O
N NH 2 N
O N
HN O O N NH2 O N O
O H2 N N O
H 2N O N O N H NH2
N N O NHHN
N H HN H N O O
HN H N NH
O HN H N O NH
N H2 O O N H NH O
O O O N H2 H H N N H2
O N H2 H
H2 N HN NH O H O
N H N H2 N N
N H2 O H N HN H N N O N O
N H 2 N O N
N H2 O N NH
NH N
H2 N H 2N O O N H
N O
H2 N NH 2 N O O NH2
N H2 N H2 H HN N
H O NH N
H2 N N HN
H2 N HN H N O O
H O
O O
H2 N H H NH O
N O N N H2
O N N N
H N
H 2
N N
N N O N N H
N N N H
H N O O N
H H O
O NH
N O
NH NH O NH
2
O
NH2 H N O
2 O
NH2 O
H2 N H2 N
H N NH2 C
2
NH 2 HN
O
N H2 H N O O N H2
H N NH O H 2N 2 O
H2 N NH N NH2 H N O O
NHH H N
HN O O NH2
NH2 H2 N O O O H N N
HN O O O H N
NH NH HN N O O O H H
H N H N
NH N NH2 N N N
H N O N O N O N N
O O O NH H N N NH2
N 2 N
H2
N O H N O H N H N N N H O
H2 N N NH2 O N
N H N O H O NH
N O O 2
O O H
N

OH
NH H N N H NH
O N HN HN N H2 N N NH N
HN N H N H2 O
O O O NH O O NH H H
H N O H O N
H N O NH H N N
2 O O HN O
N H N H O N H2 N N N N O NH2
N O N O O
H N O N
N N O H NH 2
N O O N N N
H2 N O H 2N
N O NH2 NH O H
N O NHHN HN H
O O N H O O HN
HN N NH NH
HN O NH H N H N O HN N H N H
NH O HN 2 N O
H H NH2 O O
O O
N N H N N N H2
H2 N NH O N O O N O
N O N O
O N N NH N
H2 N O N H 2
N NH
N O H O N
O NH HN HN
H N O O N NH2 HN O
H O NH N O NH 2
N HN H2 N HN O O O
O NH

P
HN HN O
H O O O N H
H2 N O O H NH N H N
NHN N H O NH N H NH N O

P+
O N O 2 O HN
H N N N N
H2 N N NH2
N N O N N H
N N O N H NH N N H N NH2
H H N O N O
H O H N O N N H2
O NH O
N O O
NH N H O NH H2 N O N O NH
2 N
O O NH H N HN
H2 N O O H N
O NH O O NH
C 2 O O O NH 2
HN O N H NH 2

+
H 2
N
O NH O HN NH 2
H2 N O O NH 2 NH 2 HN
O O NH
HN O NH 2
HN NH
O HN N H2 N
H N
N O O H H H2 N N H2
N H N N N H N NH 2 NH 2
O N
N N N H 2
N
H2 N N NH2 H 2N
O H N H N N N H O
O N
O HO O NH2
O H O
O NH N H
N HN NH N
H2 N N
O O NH O HH
H O N
H N N
N N O O N H2
N N
O N O O
O H N NH
O N 2
H2 N N N
NH O H
NH HN HNH
O O H N
HN HN NH
H2 N O O NH
N O
O
N N NH2
O N O
O
H 2
N NH N
N
O H N
NH HN
HN O O NH2
H N HN O O O
2 NH
N O H N O N H
NH NH N O
O HN
N
N H2
NH N N H N NH2
O
HN O N N H2
O O
H2 N O N O NH
N
NH HN HN
O H N
O
N H2 O O NH N H2
O O O NH2
H2 N HN NH
N H NH 2
N H2 O HN H N
N H N H2
NH
H2 N
H2 N N H2
NH2 NH
2
H2 N
H2 N

HOH2C CH2OH P+ monomer H 2N

H2 N
NH2

H N

N H
H
2
N

O
N H2

O
HN

NH
H 2
N

N
NH
N H2

HN

N
O
H2 N

O
NH

N
HN
NH

O
2
H2 N

O
N H
H N

N
NH 2

H N

O
2

O
N HH

N
N
NH 2

O
H2 N

N H
HN

O
N H2

O N H
N H2

H N
N H2

NH
2

P+
N

P+
O
N H
O N HN HN N
N H N H2
H N O O NH
O
H N O O
H2 N NH HN
O O
NH O N H2
NH N
H N
N O
N
O N O
H 2N N O
O NH2
O N N HHN
O NH
H N HN O
HN NH
N H O
H HN NH
H O 2
H O
N N
H2 N N O N O
N O N
O N NH
N
H2 N O O N H
N
O
H N HN O O N NH 2
H O N
N HN NH
H N HN O O
H O
H N O O H NH
2 N N H O NH
O N O 2
H N N N
H2 N N N
N N O N H
N N O N H
H N O N
H H O
NH
O
N NH NH O
O N H2
NH 2
O NH
H2 N O 2
O H2 N H2 N
O H N N H2
2
C N H2
H N
NH
H2 N O NH 2 HN N H H 2N
O O 2 NH O N NH
O H2 N N HH 2
HN O HN
H N N H2 O O O O NH 2
O HNO N H N H N
H N 2 O O O
N O O H N H HN
O H N H
N H N N N H N NH N NH 2
O N O
N N HN O N
H2 N N NH 2 O O O NH
O N N
HN H N N N H O H 2N HN
H O N O NH
O O N H2 H2 N NH N N 2
O O
O N H H NH N
N H N O
H 2N N N H N N H
O N HN N
O O NH H H O HN
H O N HN N H O O NH NH 2
N O
H N O H N O
N N N O NH 2 O NH HN
O N H 2N O O
N O O
O H N NH N H N H O NH 2
O N 2 N H N
H2 N N N O
O H N N
NH H
NH H N O N O
O O HN H2 N N O
H N H N NH O N H2
H2 N O O N H N H O N NHH
N O O
O HN HN NH N
HN O NH
N N O NH 2 N H O
O N H HN NH
O H 2
H2 N NH N O O
N N N H
O H N N O N O
NH HN HN 2 N O N
H N O O N
O NH 2 N NH
H2 N HN O O O H2 N O N
NH N O H
O O NH O
N H N H N O O N N H2
NH NH N O H O H N
O H N NH N
NH 2 N N HN
N H2 HN HN O O
NH 2 H O
H2 N H2 N N H2 NH N H N O O
H2 N N N H2 H 2N H H NH O
O N O N N H2
NH 2 HN HN O N NH2 O H N N N
O O N
NH2 HN H N H N O N O H 2
N N
NH O 2 2 NH N N O N N H
H N NH HN NH 2 N HN N N N HN
2 NH NH H N H N O O N
HN O O NH O HN H H O
NH2 H N O O 2 O O
2 HN O O NH2 O NH NH O H
NH O HN O O O 2 NH N O
NH H2 N HN N H 2 NH NH
N H N NH2 O NH 2
O N H O H N NH2 O
H N O N O O N H N H2 HN O
O N NH NH H2 N O
H2 N HN 2
O NH NH O
H 2
N N H N N 2 H N C
2
N H2 N NH 2
N H O NH 2 NH
H N N 2 O
O N HN H2 N H 2
N O O N H2
HN NH O O NH NH2 H2 N
O H N O O
HN O O H N
H2 N NH H N
O O O HNO N
NH NH O NH2 H N
N H N N O O O H H
O H N H N
N N N N N
N O N N
H2 N O N O N NH
N O N H2 H2 N N 2
N O NHH O N H
O O H N H N O N N O
HN HN NH N H
HN O NH O O O NH 2
NH O O O H
H H N NH N H N H
H O O 2 N HN N H N
N H H2 N N
N N O N O O O NH O H
H2 N N O N H H
O N O N
N NH HN N
H2 N O O N H N N O O NH2
N O N N
N O O NH O N O O
HH HN N 2 N
O N H N O H N H2
N HN O N N N
HN HN O O H 2N
H O NH O H
H2 N O O H NH HNH
N N H O NH2 N H HN O O HN

THPC
O N O NH
H N N N HN H N N H
H2 N N H 2
N O O
N N O N N H N O
N N O N HN O
H N O N N
H H O N O NH 2
H O O N
N O O
NH N H H 2N NH N
O NH 2 N
O O HN
H N O N H HN
2 O HN O O
O O N H2
C H N H N O O
2 N H
O O N H
N H N
O NH NH N O
H2 N O O NH2 O H N
O O N
HN O
HN N H2
O HN N NH N HN
H N N NH 2
N O O H H O
N H N N N H N HN O N N H2

Mt
O N O O
N N H2 N O N O N H
H 2N N NH2 N
O N N H H N HN
H N H N O N N O NH
O HO O N H2 O HN
O O O O
O H NH 2 O NH N H2
N HN NH NH O O O N H2
H2 N N NH N H2 N HN NH
O O NH O H
H H NH O H N NH 2
O N NH 2 HN
HN O N NH NH
N N O NH 2 2
O N N NH
N O O H N
O H N NH2 2
O N N N H2 N NH 2
H2 N NH 2 NH
NH O H H 2
N H HN H2 N
O O HN H2 N
H N HN N H
H2 N O O N H NH
N O
O
N N NH
O N O 2
O
H2 N N H N
N
O H N
NH HN
HN O O NH2
HN O O O
H 2N NH
O O
N HN N H
NH NH N O
O H N
N
NH
2
N H N N HN NH 2
O
HN O N N H2
O O
H2 N O N O NH
N
N H H N HN
O H N
O
N H2 O O NH NH
O O O 2 N H2
H N HN N H
2 NH
NH N H O HN HN 2
2 N H
NH2
NH
H2 N
N H2
H2 N
N H2 NH2
H2 N H2 N

OMt DOMt-1

OH O CH3
monomer N O
OH

OH O CH3
N O
OH

boron acid monomer

FR-DOMt DOMt-3 boron acid DOMt-2

Scheme
Scheme1.1.Preparation processofofFR-DOMt.
Preparation process FR-DOMt.

110

100
(a) Mt
FR-DOMt (b) d=2.08 nm
Mt
FR-DOMt

90 d=1.40 nm
Intensity /cps
Mass /%

80 d=1.07 nm

70

60

50
100 200 300 400 500 600 2 4 6 8 10
 boron acid monomer

FR-DOMt DOMt-3 boron acid DOMt-2

Materials 2018, 11, 41 5 of 17

Scheme 1. Preparation process of FR-DOMt.

110

100
(a) Mt
FR-DOMt (b) d=2.08 nm
Mt
FR-DOMt

90 d=1.40 nm

Intensity /cps
Mass /%
80 d=1.07 nm

70

60

50
100 200 300 400 500 600 2 4 6 8 10

o 2/deg
Temperature / C

(c)
FR-DOMt
Mt
Transmittance/ %

Materials 2018, 11, 41 4000 3500 3000 2500 2000 1500 1000
5 of 17
-1
Wavenumber/cm

(d1) (d2)
Materials 2018, 11, 41 5 of 17

(d1) (d2)

Figure
Figure1.1.Mt
Mtand
andFR-DOMt
FR-DOMt(a)
(a)TGA,
TGA,(b)
(b)XRD,
XRD,(c)
(c)FTIR,
FTIR,(d1,d2)
(d1,d2)SEM.
SEM.
Figure 1. Mt and FR-DOMt (a) TGA, (b) XRD, (c) FTIR, (d1,d2) SEM.
OH
NH2
N H2
H 2N H2N H2N NH2

H2
NH2 HN
NH2 HN NH H2 N
NH O HN NH 2
H2N NH
NH2 HN O O O O N H2
H2N HN O O
NH O
NH H N
NH N NH2
HN O N O
O O O NH
H2N N HN
H2N O N NH 2
NH N
N
NH O

C CH2
O N HN HN N
HN NH O O NH NH2
O HN O O NH HN
H2N O O
NH NH N O NH2
HN O

H2
N N
H2 N O N O
N O NH2
O N O NH
HN HN O NH HN
HN O NH
NH O HN
H NH 2

+
OH
H O O
N NH2 N H
N HH
2 2N
N O N O
HO
N O N
H 2N 2N H2N NH2 N N NH

H2
NH2 H2 N O HN O N H
N O
NH2 HN
HH NH N H N O O N NH2
H2N NH O
NH
HNO 2 NH 2HN NH N
N HN

O
HN

C
NH2 O O O HN O N H2 HN O O
H2N HN O O O H O
NH H 2N O NH H N O H H NH O
NH
O N O N N
NH2 O N N H2
HN O N H N O O NH N N
O H2N N N

N
H2N O N N O HN N N H
H2N NH N N N NH 2
N N O N H
H H O N H O N
NH O

C CH2
O N HN HN N O NH
HN NH N O O NH NH2 NH NH O
O HN O
O NH2
H2N O O NH HN
O O H2 N O
NH NH N O NH2 O
HN O O

H3 C C C
H2
N N C
H2 N O N O
N O NH2
N O NH O
O
HN O H2N O NH O N H2
HN HN O NH HN O O
NH HN O HN
O HN
H NH 2

+
H O O O HN N
N N H
H 2N N O H N N N OO O H H
O N O O N
N N H N N NH N N H N
H2 N O O N H O N
N
N O N N NH2
HH
N HN O H2 N O
N N NH2
O O HN HN NH H N N N N H O
O

H
N N

O C
HN H HN O O O H OO NH 2
H 2N O O O NH H O
N
H
N H O N H2 O NH NH
O H N N O
H2N N N N HN NH N
N

NC CH2
H2N O O N NH O
N N
N O N
H N
N H N H O N HH
H N O O N
H H O HN O N

2
O N N N NH N O NH2
N NHO O
NH N O O NH2 N O
O O
O H O N N H2
H2 N H N O N N
O 2 NH O H

H3 C C C
C
HN H
NH O O HN
H2N O HN HN N H2
NH NH NH
O H2N O
O O N O
HN O O
O O
HN

O H2C
O HN N N N NH 2
H N O N O
N O O O H
O H H
N H N N H2N N
O NH N
N
N
H2 N N N
ON N NH2
O N NH N H HN HN
HN H N O N HN O O O

H2
H N NH2
O O O
H2 N HN O O O NH 2 O
N
O NH H NH O NH O
HN NH N NH
H2N N N HN

CHOH
H O O
O NH O NH H H NH N O
O N HN
HN ON N
N N N N H2 N O NH2
O N O O
O H NH N N H2 N N HN NH2
O N O
H2 N NN N

2
NH O HN O O H NH2
HN H O
NH O O H 2N HN O N O
HN HN NH N NH
H2N O N NH NH
O HN NH HN
O O
O HN

O H2
N N
NH 2 O O N O NH 2 O O NH NH2
O O O NH2
H2N NH N
H2 N HN O NH
O N
NH HN NH 2 NH HN O HN NH2
HN O O NH2 HN NH
H2 N HN O O O NH NH2
N O HN O NH NH
NH NH N O H2 N

OH
O HN H2 N NH 2
N H2
N N H2 NH 2
NH N N
O
HN NH2
H 2N H2 N
HN O O N NH2
H 2N O N O O
N NH
NH HN HN
O HN

THPC THPC
NH2 O O O NH NH2
O O O NH2
H2 N HN NH
NH 2 NH O HN NH2
HN NH NH2
NH
H2 N
H2 N NH 2
N H2 NH 2
H 2N H2 N

monomer
monomer G-1 G-1

monomer
monomer
NH 2
NH2
H2 N H 2N H2N NH 2
NH 2 HN
NH2 HN NH H2 N
NH O HN NH 2
H2N NH NH2
NH2 H N HN O O O O NH 2 NH2
2 HN O O O H2 N H 2N H 2N NH 2
NH NH HN NH2
NH N NH2 HN
HN O N O NH2 HN NH H 2N
O O O NH H 2N NH O HN NH 2
H2N N HN HN NH
H 2N O N NH 2 NH2 H N O O O O NH 2
NH N 2 HN O O O
N NH NH HN
NH O NH N NH2
HN HN O N O
O N HN N O O O NH
HN NH O O NH NH2 H 2N N HN
O HN H 2N
O
N NH 2
O O NH HN NH N
H 2N O O N
NH O
NH NH N O NH 2 N HN N
HN O HN
N N H2
NH2 O HN O
NH O O NH NH2
N HN O O HN
H2 N O N O H 2N H2N H 2N N H2
H2 N O NH
N NH 2
O O

monomer
HN
N H2
N O NH NH 2 NH NH N O NH 2

boric acid
HN H 2N
O O H 2N NH
NH O HN N H2
N
HN O
HN HN NH2 H N
HN
HN
O O NH 2 O
NH
O NH N H2
O NH HN N
NH 2
NH 2 NH2 NH
2 HN O
NH
O O
O NH H N
HN H2 N O N O
N O
H H2 N NH
HO 2N O N N H2
NH 2 O NH 2
NH 2
H 2N H 2N
H 2N NH 2
H HN O N
H2N NH O
2 O O NH
H O O O NH
N NH
NH2
HN
N N N
H 2N
O O
N
HN
N HN HN
HN
NH2
O NH HN
H2N NH
HN NH O
H2 N
NH 2 H 2N NH N
H2N NH N N
O
N H2
N O NH H2 N
NH2
H2 N NH2 O
NHHN
2 HN HN
H2N
N
NH2 H N O O O O NH 2
O O
N H H
NH2
NH 2
2 HN O O O N
NH
HN N N NH NH2 O HN
HN
H2 N O
NH2 H
NHHN NH HN
NH
H2 N O O
O
N NH HN NH2 N N H2 N NH O HN NH2

HN H 2 NN H H NH
HN
NH N NH 2 O O O NH N OH N HN
N O
NH H2 N O NH2
HN O N O
O O NH N HN O
O O
O N
NH2
HN
O O O
O N
HN
2 O O O
O H 2N HN NH NH HN

H2N N NHHN O O
NH NH 2 O
N
H 2N HN O O
N NH2
N NH
HH
NH N
H 2N O N NH 2 NH NH O
2 N H2 HN O
NNH
NHN
N O N
NH
N O HN O
NH N H2 N O O H2N N NO N
O O
H NH2
HN
HN
NH O
N O
N
HN NHNH2 N H2 N NH
O
N NH2
O NH
HN O
O N
NH HN
O
HN N
O NH NH2
NH2 H N HN OH N O N O
HN
N OO ON O
N
O O HH
N
HN
O NH
N
O O N NH2 2
HN
2 HN
HN O H O NH 2 O O N
NH
HN N
NH2
NH N H2 N H 2N NH 2
H2 N
O HN
O O
HN O O NH
O
H 2N O O
NH
O HN O
O NH O NH N
O
HN O HN H 2N
NH
HN
H O NH HN
O
O NH HN

NHN HN NH H
NH O NH 2 H2 N
NH N 2 HN HN HN O O
O O
HN O N O NH
NH2 O
NH2 H
NH NH
O N
O NH2

NH NH2
N NH2
HN HN
O
NH2
NH2
N
H N H
NH H2N H2N NH2 N H2 N
O

HN
ONH
NH2 O O
H2N

NO H 2N N
H 2N H 2N NH2
N O
NH N H
H 2N
O N O
O
2
H2N N O
H
HN
N O H2 N N
N
NH2

N
NH2 O
N NH 2
HN
NH 2 NH2
H 2N N O
HN H2 N

OO N
N O O
H 2N
NH O
NH2 HN H2 N
N O NHHN H2N NH NHHN NH2
O O N NH
N N
NH
NH
O
O N
O HN

HN N
O NH2 O
N N H
NH NH2
O
N N HN H 2N
HN NH

O O
H 2N NH NH2H N O O O
NH
N H HN HN
N
HN HN
N 2
HN O
N O NH
NH
H N O NH2 2
NH2 O O O
O O NHHN O O
NH HN N HN NH

O O O NHHN
O
HN NH
N NH
O
H 2N HN
H2 N O
N HN
NH2
N
O O O

H 2N
NH N
O NH H NH 2
HN
NH HN N
NH
N O O
H
NH O
HN HN O N H
H NH2 N
N O O
NH 2
NH2 O O NH

H 2NN
N O
O
NH
H
N N
N H
H
N

H O N
O
O N H2N

N
HN O HN N
O
H H N O N O N O N
O
O N H2
O O NH

NH
O H 2N N NH2 H 2N O
N
N
N
H
HH
NH N
N O
O HN N N
H 2N HN

H2N N H
N O N
N O
O
N NH2 O
N O O N
N
HN
H 2N
H 2N
N HN
NH N NH O N NH
NH
N O N
H O N
HN
N
HN
O
H2 N O N
N
O N HN N
O
O NH 2
O H
NH
O

H H O
NH
N NH HN NH NH2 N
NH2 H N O O
N O O O NH O
O
N
HN H NHN
O O O
N HN

NH 2
O HN O N O O NH2
H2 N O N H N

H 2N N H OO
NH NH2 O HN
O HN O O NH
H H2N O NH
H O HN
N O
O

N
N N
O O NH
HN NH
NH NH O
O
HN O HN NH2

NH
N HN
H 2N
N

NH NH NH
O HN
HN O
H 2N N H
N O O N NH 2
O 2 O O
O
H
O O

HH
HN HN O O
N
O
N
HN N N H2
O NH2
NH NH O N H2

N O
N H O
O H N O
NH N O H2 N O
N
N
OO N O O
NH NH
N O H2N H NH
N HN N N
NH NH HN
N H O
H
O NH2

N N
N NH N N NH2
O NH 2
N O O O
HN HN O O O NH O N
O
O N H N N
H2 N
HN HN HN
N
H2 N O HN O NH
NH2 N
H O N O NH
N N
NH O
N H H2N N
N O
NH2
H HN NH2

ON
O

O O
H 2N O O NH
O H NH H O O N N O N N H
H2 N N N
NH N
HN HN O NH HN
H O
NH
H N
N H
HN
N N NH2 N N
O N N H
ON
NH O N O N O O
O H2N H O N
NH NH 2

H
O ON N
HN
O N
H 2N H H
N O

O
H 2
NH 2
N N O
H 2N H2 N H N NH 2

H H
H O O N
H NO O
N NH
2

N NH 2 HN
H

HN O
N

HN
NH
H2N O O N H NH
H2N N
N N O
HN NH O H 2N

O N
H 2N N N O 2
H N NH NH 2
N O O

N NH
O
N O
NHHN

N N O O NH2
2

N N
N O O O NH
N
H HH NH NH
NH 2 O O O O NH 2

O
O NH N

O HN
N O N O HN
H 2N HN O O O

O O N H2
NHHN NH HN

N
H2 N O O HN O
NH
N N
N
O
N
NH 2

O
H N H N N HN NH N
O
NH NH
N

O
N O HN HN O O O
O O O NH

H O N
C
H 2N N HN
H O
O NH 2
NH O NH2
H H N O O
H N O N NH 2
HH O N NH2
O H2N O O NH H2 N
C
NH N
HN 2

N
O NH
N
H N O
NH N N H N H O NH2 O

HN
N O N HN HN N
O N O

OO O NH
NH H O
HN NH O O NH NH 2
N N
O
H 2N
HN O
H NHN O O N

HN
H HN
OO O O NH HN
H2N N
N O C
O

H2 N
2
N

O
HN NH

O
H 2N O NH NH N O
O NH 2
N N O N H
NH NH H
HN O

O
N N
N O NH2 N N N O N HNH
N
O NH 2 H O N
O N
O H N H2 N OO N O
N H H O
N

NH 2
O N O NH NH 2

HN
O
HN O NH

O
H N N
H 2N N N O O
HNO HN O NH HN
NH O HN
H N H2N NH2

O
N N O
O
OO
N NH NH O
N
H H NH 2
N O

O O
H 2N N N O
C
NH
N
N
O H
ON
O
N H O NH2
O
O2
HN N N O N O
H
O
H 2N NH 2
O

HN
O
O N O
H 2

O
N N NH
O HN O
H 2N NH2
H O H 2N O N H
H2 N

O O NH
N N O OO O NH
NH O HN

H 2N
O
HH HN N
O 2

O O N
N HN NH N
N

N
O HN
HN HN O O
NH NH

O
H O

C O NH2 C

O O HO O
H N
H2 N O O H H NH OO
O N N O N NH 2

OO
O
O
N O O H
H N N N

O
O

HN O O H
H2 N N N N H N

N N H2
H 2N N N O
ON N HNH

O H2N O O
O NH2 H N H N
O
H H N O N

N N N
H OO

HN
O
2
HN
N O O
O
O
O
O
NH
NH
C NH NH
HN O O N
HN
O N N
O 2

NH O NH 2
H 2N NH2
H N O

HN O
NH
O O O HN N N NH2
O

HN
2

H2 N
O

N
C
H N N
HN N
O O
O HN HN
O N O O H
O O H N H
O
H 2N O O NH2
HN O H

N
HN H N N O
H 2N O O NH 2
N H N

N
HN O O O
N N O N
N
N
O O

N
H
HN

O O HNN
O N

HN
H N O
HN
H N O HNH H
O HN N
N

HN
H N N O
H NN O H H
N NH2 O O NH2
O
N H N O N H N

H N
H N
N H2 N
N O N O
O N
O H NN
O HN
O
H N N N NH
HN H N N N H O O H
O
O N O HN NH NH2
O N N H
O N
N O H H
N 2 2

H NH NH
HN H N H O N N O

H N
O O H H
H N
O N
OO O OO NH 2

ON
O O NH2

HN N O
N N N N
O O O NH N
O O H
N H H

O O NH
N O H H H2 N N
NH2
N HN NH NH NH N
O H
HNH
O
N O O H
H 2N N O

N H
NH
N N N NH N
O N

H N
H O O O NH N HH
N HN

O H H
N N
H
N N N
H2N NH N O O
N NH O
N
N NH2
N H N HH
HN

N
N N O

N
O NH
H 2N O
O
N
N
H N O
N
N NH
2

N N O O O
O N H O N
N H2 N
HH
N
O H

NN H
N N
O N H O
O
HN H O NH N N 2
O N
N
H 2N O

H HN
H N
N N HN
O N
NH H

H N
O O NH2 N
N
N N
NH HN O O HN
HN O O
N H2 N
O
NH 2
N N N N
N O NH2
N O
HN HN NH NH NH
O N N O NH2
H 2N
O
H 2N O N O O
N
N
O H N
O
O 2 N N
HN
NH N H

NH N
N
N H 2N H2N N H2 O
N N NH

N O O
N O O
N H
HN
O N O O
NH2
O O

N H N
N
H 2N N NH 2
N

H 2N NH
HN NH N

HN H
O H NH2
HN H N H 2N N O
N N O
H2 N
N
O N
O
N

O N
2
O

O
O NH
ON H N H HN H2N O H NH2
O HN HN
N N
N
O

N
N
H O O H
N
N

N N
H O2
H O N
H N HN O O O

H2 N HO
NH O H
O O NH 2
OH
2 O NH O
H N N

N O O
N HN NHO

O
NH HN
O NH 2
HN

N
N N
O O HN
O NH NH N

N2 O
O O NH2

monomer
2
O NN
NH
O
O
HN

HO N H 2
NH2 HN H N NH H
N O
NH

O
O N N HN HN NH
O H2N O NH NH H
NH N N HN NH

H2 N HN H
2
O

O
N HN
ON
2
O

NH N
NH NH NH
HN O O

NH O NH 2
NHN NH 2
O H N O
N HN O O O HN
HN O NHN O O

N NH NH
O N

H O ON NH
N NHO
N
N
2
N
H 2N N NH N NH
NH HN HN

HN
H 2N

OH
HN HN
O HN
N O NH2

O
OO

NH
NH NH
H2
N O O NHO NH

H2 N N NH
O N

N ON H N
N
NH H

N H2 N O NH 2
O O O NH 2
O H2 N O

O 2
2
H
O

boric acid
O
H2 N NH
N H HN
O O NH N H
O
NH NH O HN NH 2
H2N NH N O
HN H OH N
O O H N
HH
N H 2N N
2 NH NH

O NH O
H
NH

O
N
O H
HN
HN HN N H
2

O O HN
H N
H 2N O NH
N
H
NH
O HN
H N NH 2
HN

N HN
2
O

O O
N NH 2 NH 2
N
H
2
O
N HN O O N NH 2
H N

H O
NH2
N
O

O O NH N H2
HN O O
H 2N 2

O H 2N NH NH
H2 N HN O O O N
NN
N N N
N O NH2 O

NH
NH 2 O NH O

OO NH NH 2
O
N
N
N
HN
O NH

HN HNH N
N N HN N

HN O
O
O N

HN
NH NH N O NH
O
N
2
N O O HN NH
O

ON N O N H2
H 2N NH

H2 N N
HN N
OHN N H2
O
N O
N N NN O HN
H
O HN
O H NH 2 NH2 H N
HN HNO NO
HN
O
NH HN NH2
NH
O N ONH
O NH
HN
O
HN O O NH2

O
N N NH2 HN O O
H2N N N
N NH2
O
O

NH NH
HN O O O
N O O O
NH HH
H 2N NH

O O H
O
HN O N

O
NH2 HN O O
O
O O
2 O
O N H2 H2 N
N
N
NH H
H2 N
O NH
O N
HN NH

NH H
H2N O N O

O N
N
H H2 NNH NH H N O
NH O O
N
NH NH O
NH 2 HN
O
N NH
NH N N
NHN
O
NH NH HN HN N HN
H2N N
HN

HN
O N
O HN O HN NH NH N O
NH 2 N
H
NH2
NHN NH
NH 2
O O
HN HN N H N NH2 O NH NH2
N H2 H
HN
O HN
O
O O
H
NH NH2
H 2N O NH NH NH N
O NH2 N
N NH
O

H HN O
H2N HN NH
H 2N H 2N O
N
O O
O NH
O NH N H H2H
HN O NH2
NH 2 N O NH2 NH
O N NH2
N O NH2
NH2
HN
O
O
O
O O HN
O HN
N

HN O
HN
H 2N
H 2N O O

O N
NH

O
NH
N N HN
NH

O NH N
NH2

H NH N NH2
O
N O
HN O O
HN

N O
NH HN NH
NH 2 N N O NH2 H 2NO O
H2N
NH N NH2

H
O HN HN O O

N N O O NH
NH
O
HN O N
HN
H2N
N
O O

N
2

HN
NH2 NH2 O
O
N HN
NH 2 O NH NH2
O
N
O O H2 N O N O
H 2N O NH
N
O NH2

O
H2N

HN HN
H 2N HN N H
N
O H NH 2
H2 N N NH2
N O O
N
H 2N NH HN
NH2
HN NH
NH2

O
HN
HN H2 N
O
NH 2 N H O HN
N
H 2N N N H2 NH
O N
HN
NH2
H2N N N H2
NH
NH O
NN N
N O NH2 O HN
O
N H2

O HN O
NH O N N N
NH

H2N NH NH 2 NH
HN
H 2N
O O
HN
N N O
N O N H2 N NH2 O O O
O O NH NH2
NH H2 N H2 N NH2
NHHN H2N
HN
H2 N NH2
NH 2 O NH2
O N N ONH
NH 2 NH 2
O
H H NH 2
H2 N HN NH
HN O O NH 2 H 2N HN O O
O N H 2N
O NH
N O NH NH2
H 2N
NH N O NH
NH2 H N O O
NH H
O HN 2
H
H2 N
O O O NH NH2 HN HN
2 HN O NH O O
NH HN
O
N
NH NH HN
N O
NH
O NH NH
HN HN N N O
HN
O
HN N
N NH 2 NH HN O O NH
NH NH2
HN NH2 O HN NH H2 N
H O
HN
H2 N O O
NH N HN O NH
N O HN
H2 N

NNH
NH NH2
NH O O NH2 N NH H2 N
O
N 2 H2 N NH2
NH N NH 2 NH 2 H2 N HN O 2 HN
O O NO
H NH H2 N HN O HN
H2 N
N H2 NH2
N NH OH N NHHN O
NH
NH2
N O
HN O
O
N O
O O NH
NH
HN O N
N N
O
HN
NH2
NH 2
N H 2N
HN O N
NH NH
O
O
NH NH
HN O HN
N O
O NH
O H H O
N H2 N
H2 N
N O NH2
2 HN
O O
NH
O
O O
O
O
NH HN O N
H 2N N HN O O
N N H NH O HNNH O O O O HN
O HN N NH 2 O NH
N NH
HH
NH
H 2N O
N N NH 2
H 2N O
N
N O NH
HN
N
O O N H2 N N HN O
ON O NH 2 N
N
O
NNH 2

NH
N
NH HN
O HN
HN
O HN
N H2
NH
HN
N HN N NH
N
O O
NH
HN NH2
NH N NH O H2 N O O O H2N N N
O O
HN
H
O N HN
NH
HN N
O NH 2
H 2N
O
HN
O O O
O
NH
O NH NH 2 NH2
N H2N O
N O N
N HN O O N HN N
O
NH2
O O H2 N NH N
N
N H2 N

O
NH
O
N N
N
NH2

O O NH2
HN O
HN
NH O O NH NH2 NH 2 NH O HN NH
HN NH 2
NH2 HN H2 N
H
O
HN
N O H N
O
2
NH H N
O
N
N
O
N
HN
O
O
NH N
NH
NH 2 O O NH
O N
HH OO HN HN O N HN HN
NH
HN N
O

N
N
H 2N O O NH HN NH
O O N O
OO
HN
O NH 2 HN N O HN O
NH O
HN
O NH NH2
NH
H 2N O
NH NH
H2N
O O HN HN NH2 NH
H O O NH HN O N O
HN
O O HN
O O2
H2 N NH 2
NH NH N O NH 2 NH 2 NH2 O HN
O O O
O NH
NH
H 2 NH 2 H 2N HN O O HN
H2 N
HN O
NH
O O
H 2NN NN NH2
HN H2N HN O NH NH NH NH O NH2
O H 2N
O NH H O
NH2
N NH NH2
HN NH 2 O O N HN
O
NH2
H2 N
O N O
H 2N
NH2
H 2N H 2N NH2 N
H N H
NH ONH 2

O
H2N H2N N H2 N H
H2N
N
NH2 O
HN NH
HN
N H N H2
NO
N H2 N
NH H N O NH
HN
N ON
NHO N
O H
N
O

NH O
H2N N HN O
H
HN
N O O HN 2
H2 N N
NH N
NH2
NHNH
N O
N NH 2
HN NH2
NH 2
H 2N N O HN NH2
HN H2 N
N
H 2N
N O O
NH O
NH2 HN NH H2 N
N O NHHN N
H2N NH NHHN 2
O H2 N
N O O N NH
O
HN O O N
O HN
N
OH
N N O
O NH2

N N O NH H
NH NH2
H2 N
O O N HN NH
N
H 2N NH NH2H N O O
2
HN HN NH2 H N O O O O NH NH2
O
N O
2 HN O NHHN O

O
O
NH HN N NHNH
2 NN H2 NH 2 NH 2 H HN
HN O
O NH
HN
N
HN NH
N NH
H 2N HN
H2 N
NH2 N
O HN O N
N O HN
O O O
O
H 2N H NH 2
N
NH N

H
NH HN

N
2
NH O
O
H2 N
O H HN
NH
HN NH NH
HN O
N H
N
H 2N
H NH2
N N NH 2 O O O
NH2 O O NH

N
N O
O
NH
H
N N
NNHN H
H
N

H O N
O
O O O OHO
HN O N H2N HN N
O
H H N O N N N
O
O N H2
O O NH
2N O
H 2N N NH2
N
O N
N H
HH NH N
NH N

N HN N O
N N
O HN
H 2N HN
N N H 2N
O
O N NH2
N O O
N
N HN O N O N
O H
H HN O N
H 2N NH N O
O 2 N NH
NH
NH
NH NH N O
N O N
O N
HN
O
N
N
O N HN
HN N
O H2 N O O N H
NH
O
N NH O H 2N O H H N
O
HN NH NH2
N
NH
N O O O NH O
H2 N O O HN
O N
N NH HN
O
HN N
O NH NH2
H HN H H2N H NHN OO
O
HN O O
NH HN O O O H N NH O N NH2
O
N H O
N O
O
N HN O HN O H 2N O
NH
N
NH N O
O
NH2
NH HN HN N HN NH N
NH
NH NH NH
O HN
HN O
H 2N N H
N O O N NH 2
O
O
H
O O

HH NH 2 N HN HN O O
N
HN N N H2
O NH2
NH NH O N H2

N O
N H O
O H N O
NH N O H2 N O
N
N
OO N
O HN O O
NH NH
N O H2N H NH
N HN N
H N N O NH2
N HN O H O
NH N
N NH
HN
N O
HN O O
O O NH
N N NH2 NH 2 O NH O N O N NH2
O NH 2
O
O
H2 N
H
N
O N
O
O NH
NH2
H2 N
N
HN HN

N
NH
HN O O NH HN
N H
N
O O O O H2N NH 2 H N N N
N
N O
H HN NH2
NH2
ON O
O
H 2N O O NH
O N N
O NH H N H
H N NH2 N O
O O

H2 N N N
HN HN HN
N
HN O NH
N H O NH2 N HN ON N H
O H H 2N HN NH N N N H
ON O
NH O N O N O
O O H O N
NH NH 2
H2N
H
O ON N
HN
O N
H 2 NHN H H
H 2
NH 2 N O
N N N O
H 2N H2 N H N NH 2

H H
O
NH2
H O
H NO O O NH
N NH

NH 2 NH
2

H
O HN
NH 2 HN
N

O
N NH
H2N O O N H NH
H2N N
N
H 2N
N
O N O O
HN NH O H 2N
H 2N N N O 2
H N NH NH 2
O N O O
N N O O NH2 N O
NHHN

O NH
2

N N N
H HH NH NH
NH 2 O O O O NH 2

O
O NH N
N O N O HN
NH
H 2N HN O O O

N
O O N H2
NHHN NH HN
NH N
N
N N N HN
O NH2
NH N NH 2
H2 N O O H
N O H N
HN O N O

NH NH
N O
N HN HN O O O
HN
O O O NH

H O N