Progress in Organic Coatings 78 (2015) 5558

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Synthesis of cyclohexanone-formaldehyde resin catalyzed by

rehydrated MgAl hydrotalcite
Guo Yang, Junqing Jiang, Yanwu Zhang
School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, China

a r t i c l e

i n f o

Article history:
Received 26 July 2014
Received in revised form
15 September 2014
Accepted 19 September 2014
Available online 22 October 2014
Keywords:
Aldol condensation
Cyclohexanone-formaldehyde resin
MgAl hydrotalcite
Solid base catalyst

a b s t r a c t
Cyclohexanone-formaldehyde resin (CFR) was synthesized over rehydrated MgAl hydrotalcite (HT).
Therein, MgAl HT was rehydrated from MgAl HT of good crystallinity using a liquid method. Rehydrated MgAl HT (HT-r) shows certain catalytic activity for aldol condensation and catalytic activity is
dramatically improved in the presence of hexadecyl trimethyl ammonium bromide (CTAB) because CTAB
as a phase transfer catalyst is helpful to enhance the mass transfer among three phases. Both higher temperature and longer reaction time are preferable to increase the molecular weight of CFR. Though the
catalytic activity of HT-r decreases as the reutilization cycle increases, the deactivated HT-r can be easily
regenerated upon calcining and rehydrating.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Ketone aldehyde resins are one kind of thermoplastic resins
through aldol condensation between ketones and aldehydes.
Therein, cyclohexanone-formaldehyde resin (CFR) with low molecular weight is produced though aldol condensation between
cyclohexanones and formaldehyde and widely applied in coating
and ink industry due to its excellent dissolution in polar and apolar
solvent. Because of unique compatibility with a variety of polymers,
CFR is used as a multifunctional additive to improve weathering
resistance and ller dispersion in polymer matrix [1,2]. Traditionally, aldol condensation is catalyzed by aqueous alkaline, which
involves corrosion of equipment, tedious separation and harm to
the environment.
In recent years, various solid base catalysts have attracted
much more attention during the development of green chemical
engineering. Among various solid base catalysts, hydrotalcite-like
compounds ([M2+ 1x M3+ x (OH)2 ]x+ An x/n mH2 O) and their derivatives such as double metal oxides have been focused because their
basicity can be tuned based on the diversity of cations and anions
[36]. The tuning methods include changing cations during the
synthesis and post anion exchange [711]. By now, hydrotalcitelike compounds and their derivatives have been used to catalyze

Corresponding author.
E-mail address: zhangyanwu@zzu.edu.cn (Y. Zhang).
http://dx.doi.org/10.1016/j.porgcoat.2014.09.020
0300-9440/ 2014 Elsevier B.V. All rights reserved.

aldol condensations, etherication reaction and transethericaion

reaction [1215].
In our previous research, LiAl hydrotalcite with strong basicity
is synthesized through replacing Mg2+ with Li+ and their corresponding double metal oxide is used to catalyze transestericaion
between ethylene glycol and soybean oil [16]. Herein, MgAl
hydrotalcite (HT) with stronger basicity are synthesized through
exchanging CO3 2 with OH and are used to catalyze aldol condensations in the preparation of CFR. To obtain high crystallinity,
MgAl HT was synthesized by a urea method in which pH of the
solution can be kept at a homogeneous level and agglomeration
can be avoided [17,18]. The exchanging CO3 2 with OH was realized through the liquid rehydration of MgAl HT [19]. Considering
liquidliquidsolid multi-phase reaction, the phase transfer catalyst CTAB was introduced to enhance the mass transfer. The effect
of reaction temperature, reaction time and catalyst loading on
catalytic activity were studied. Furthermore, the reutilization and
regeneration of the catalyst were investigated, too.
2. Experimental
2.1. Synthesis of HT
Mg(NO3 )2 6H2 O(15.38 g), Al(NO3 )3 9H2 O (7.50 g) and urea
(21.62 g) (nMg2+ : nAl3+ = 3; nurea : nNO3+ = 2 : 1) was dissolved in
deionized water (150 ml) and the solution was fed into a 250 ml
ask equipped with a condenser and a mechanical stirrer. The solution was agitated at 100 5 C under 400 rpm for 10 h and then aged

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G. Yang et al. / Progress in Organic Coatings 78 (2015) 5558

statically without agitation at the same temperature for another

20 h. The resulting slurry was ltrated and washed with deionized
water until the pH value was equal to 7. The solid was dried for 24 h
at 90 C and named as HT.
2.2. Rehydration of HT
HT was calcinated at 500 C under N2 for 8 h in the furnace.
The obtained MgAl mixed oxide was named as HT-c. Deionized
water (400 ml) was heated to 40 C in a 500 ml ask equipped with
a mechanical stirrer and bubbled with N2 for 30 min. Then HT-c
(4.00 g) was dispersed into it and the vigorous stirring continued
for 8 h under N2 . The suspension was ltrated to obtain solid rehydrated HT. After drying at 40 C in vacuum for 24 h, the product was
named as HT-r.
2.3. Synthesis of CFR
Formaldehyde aqueous solution (37%, 10.97 g), cyclohexanone
(10 ml), CTAB (0.50 g) and HT-r were fed into a three-necked 100 ml
ask equipped with a reux condenser and a mechanical stirrer.
The mixture was stirred at certain temperature under N2 to avoid
carbonation of HT-r for a period of time. After the reaction ended,
HT-r was collected by centrifugation. The product was extracted
with methylbenzene and then precipitated in ligarine. The solid
product was dried overnight in vacuum at 25 C.
2.4. Characterization
X-ray powdered diffraction patterns (XRD) were recorded
with a Shimadzu XRD-6000 powder diffractometer using Cu K
( = 0.1542 nm) radiation (40 kV and 30 mA). Transmission electron
microscopy (TEM) was performed using JEOL-JEM 1200 equipment operating at 100KV. FT-IR spectra were recorded from 400
to 4000 cm1 on a Thermo Nicolet IR 200 spectrometer. The rotational viscosity of CFR solution was determined by Rotating cylinder
viscometer LVDV-2 (Shanghai Jingtian Co.).
3. Results and discussion
3.1. Synthesis and rehydration of HT
According to Javier, MgAl HT with MgAl molar ratio of 3:1 has
proved to have higher catalytic activity [20]. Therefore, MgAl HT
of same composition was synthesized by a urea method. The XRD
pattern of synthesized HT is shown in Fig. 1a. The sharp and symmetric characteristic peaks indicate that HT has good crystallinity.
Upon calcinations, the disappearance of the characteristic peaks
corresponding to the layered structure indicates that the layered
structure of HT is destroyed and MgAl double mixed oxide forms

Fig. 1. XRD patterns of HT (a), HT-c (b) and HT-r (c).

(Fig. 1b). However, the layered structure is recovered after the rehydration (Fig. 1c). The microstructure of HT, HT-c and HT-r was
characterized with TEM and their images are shown in Fig. 2. As
shown in Fig. 2a, HT has a well-developed layered structure. Upon
calcination at 500 C for 8 h, a porous platelet structure forms which
indicate that HT is transformed to MgAl mixed oxide due to dehydration (Fig. 2b). When HT-c is rehydrated by a liquid method, the
layered structure is recovered (Fig. 2c). This is in agreement with
the results of XRD.
3.2. Aldol condensation catalyzed by HT-r
Due to easy volatility of formaldehyde, excess formaldehyde
was added in the reaction and the mole ratio between formaldehyde and cyclohexanone ratio was set as 1.4. Preparation of CFR
is different from simple aldol condensation because molecular
weight increases as aldol condensation proceeds. Herein, except
that the yield, CFR viscosity of toluene solution (30 wt%) was determined to indirectly characterize molecular weight of CFR. When the
reaction was catalyzed by HT-r, there existed liquidliquidsolid
three phases in the reaction system. To enhance mass transfer,
CTAB as a phase transfer catalyst was added. As shown in Table 1,
HT-r can catalyze the aldol condensation between formaldehyde
and cyclohexanone with low yield and the yield of CFR with the aid
of CTAB increases dramatically. CTAB itself has no catalytic activity
and just enhance the mass transfer among phases. FT-IR spectrum
of synthesized CFR is shown in the Fig. 3. The strong band at about
1711 cm1 is ascribed to C O absorption peak. The band at around
3449 cm1 is the absorption peak of OH. The band at 1448 cm1

Fig. 2. TEM images of HT (a), HT-c (b) and HT-r (c).

G. Yang et al. / Progress in Organic Coatings 78 (2015) 5558

57

Table 1
Yields of CFR for different catalysts.a
Run

CTAB (g)

HT-r (g)

Yield (%)

1
2
3

0
0.5
0.5

0.758
0
0.758

7.92
0
66.61

a
Reaction condition: reaction temperature 75 C, reaction time 20 h, catalyst
loading 8 wt%.

Fig. 4. Effect of reaction time on CFR yield and viscosity (reaction condition: 8 wt%
HT-r, 75 C, 0.5 g CTAB).

Fig. 3. FT-IR spectrum of synthesized CFR.

is the absorption peak of CH2 and the band at 2933 cm1 is the
absorption peak of CH.
According to synthetic mechanism of CFR, there involve two
elemental reactions (Scheme 1). One is the condensation between
cyclohexanone and formaldehyde to create 1-hydoxymethyl cyclohexanone, and the other is the condensation polymerization of
1-hydoxymethyl cyclohexanone through inter-molecule dehydration to form macromolecules. Reaction time and temperature play
important roles in synthesis of CFR. The yields and viscosities of CFR
for different reaction time are plotted in Fig. 4. When the reaction
time is beyond 5 h, the yield slightly decreases on the whole and the
viscosity increases. This indicates that the condensation between
cyclohexanone and formaldehyde can be nished in 5 h and prolongation of reaction time just increases the molecular weight. The
yields and viscosities of CFR for different reaction temperature are
plotted in Fig. 5. When the reaction temperature is beyond 75 C,
the yield calculated based on weight decreases slightly. This may
be ascribed to the decrease of weight caused by dehydration above
75 C. The viscosity increases as the reaction temperature increases,
which indicate that higher temperature is preferable to condensation.

Scheme 1. Synthetic mechanism of CFR.

Fig. 5. Effect of reaction temperature on CFR yield and viscosity (reaction condition:
8 wt% HT-r, 10 h, 0.5 g CTAB).

The effect of catalyst loading on aldol condensation was studied

too. The yields and viscosities for different catalyst loadings are
plotted in Fig. 6. Both the yield and viscosity of CFR increase as
the catalyst loading increases. When the catalyst loading is beyond
8 wt%, their increments are not obvious.

Fig. 6. Yields and viscosities of CFR for different catalyst loadings (reaction condition: 75 C, 20 h, 0.5 g CTAB).

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G. Yang et al. / Progress in Organic Coatings 78 (2015) 5558

can be recovered and interlayer CO3 2 was replaced by OH . Rehydrated HT (HT-r) shows catalytic activity for aldol condensation in
the preparation of CFR. With the help of CTAB, CFR can be synthesized over HT-r. Both the yield and viscosity of CFR increase as the
catalyst loading increases. Higher temperature and longer reaction
time are preferable to increase the molecular weight of CFR. After
the regeneration, catalytic activity of HT-r can be recovered to a
high level after the regeneration due to shape memory effect of HT.
Acknowledgment
This work was supported by National Natural Science Foundation of China (50903074) and Key Scientic Research Project of
Chinese Education Ministry (212107).
References

Fig. 7. Effect of reutilization times on yields.

Fig. 8. Effect of regeneration times on yields.

3.3. Reutilization and Regeneration of HT-r

To study the reutilization of HT-r, HT-r was collected and reused
directly at the same condition after one catalysis cycle. The yields
for three times are plotted in Fig. 7. The catalytic activity gradually
decreases as the reutilization time increases. This can be ascribed
to the deactivation of HT-r caused by CO2 during the application.
To study the generation behavior of HT-r, HT-r after one catalysis
cycle was calcined and rehydrated. Then the regenerated HT-r was
used at the same condition. The yields for three times are plotted
in Fig. 8. The yield after three regeneration cycles still reaches to
92.6% of the yield for fresh HT-r. This indicates that their catalytic
activity can be recovered to a high level after the regeneration due
to shape memory effect of HT.
4. Conclusions
MgAl HT with high crystallinity was synthesized by a urea
method. Upon calcination and rehydration, layered structure of HT

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