JOURNAL OF RARE EARTHS, Vol. 30, No. 9, Sep. 2012, P.

895

Zn-Al-La hydrotalcite-like compounds as heating stabilizer in PVC resin

WEN Runjuan (⏽⍺࿳)1, YANG Zhanhong (ᴼऴ㑶)1,2, CHEN Hongyan (䰜㑶➩)1, HU Youwang (㚵টᯎ)3, DUAN Ji’an (↉ঢ়ᅝ)3
(1. College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China; 2. Key Laboratory of Resource Chemistry of Nonferrous Metals,
Ministry of Education, Central South University, Changsha 410083, China; 3. College of Mechanical and Electrical Engineering, Central South University, Changsha
410083, China)

Received 19 December 2011; revised 28 May 2012

Abstract: ZnAlLa-CO3 layered double hydroxides (LDHs) with different Zn/Al/La molar ratios were prepared by the constant pH coprecipi-
tation method. The synthetic materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scan-
ning electron microscopy (SEM), Brunauer-Emmett-Teller method (BET) and particle analysis. The results showed that the hydrotalcite-like
materials had a layered structure. The ZnAlLa-CO3-LDHs as stabilizers were mixed with PVC resin. The tests of thermal aging, mass loss test
and Congo red for the PVC composites were carried out at 180±1 ºC, respectively. The results showed that ZnAlLa-CO3- LDHs used as sin-
gle thermal stabilizers could enhance both the long-term thermal stability and initial thermal stability of PVC, and 2.4 phr (parts per hundred
PVC resin) ZnAlLa-CO3-LDHs with Zn/Al/La (molar ratio)=20/8/2 had a better stabilizing effect on PVC than others. Compared with single
thermal stabilizers, the composite thermal stabilizers including 0.3 phr calcium stearate (CaSt2), 0.4 phr -diketone and 2.4 phr
ZnAlLa-CO3-LDHs significantly enhanced the thermal stability of PVC sample. And rare earth ion could optimize the conformation of PVC
and refrain the initiation of the thermal stability and the thermal stable time was over 220 min. The main reason could be concluded to the spe-
cial structure of rare earth ion, which had longer atom radius and more coordination numbers. So the rare earth ion (RE+) could react with the
labile chlorine atoms (Clr–) to form a stable coordinate complex.

Keywords: ZnAlLa-CO3-LDHs; thermal properties; poly(vinyl chloride); characterization; degradation; synergetic effect; rare earths

Chlorine-containing polymers such as poly(vinyl chloride)
(PVC) are widely used in many fields for their advantages of
non-flammable nature, good performance and low price[1].
However, PVC and its products are undesirable to decom-
pose. It is assumed that PVC, under the influence of tem-
peratures and energy rich radiation, undergoes an autocata-
lytic dehydrochlorination reaction and an initial reaction of
dehydrochlorination at a lower temperature probably auto-
accelerates the evolution of HCl[2,3]. Moreover, the degrada-
tion temperature and yield temperature of PVC are so close
that many problems would occur during further processing.
Therefore, it is necessary to utilize thermal stabilizers for
improving the thermal stability of PVC[4]. Currently, a
trend of thermal stabilizers with low toxicity or
non-toxicity, such as metal soaps, rare-earth stabilizers,
hydrotalcite-like materials, and other nontoxic thermal sta-
bilizers are developed[5].
Although metal soaps have excellent transparency and lu-
bricity[6], the thermal stability is not favorable when metal
soaps are used alone. So they are always used as the assistant
thermal stabilizers in combination with others[7,8]. As a
new-type thermal stabilizer with high efficiency, non-toxic
and a good synergetic effect with other stabilizer, rare earth
thermal stabilizers share a great research potential and a fas-
cinating prospect[9]. Unfortunately, rare earth stabilizers have
poor initial stabilization effects except for their combination
with other stabilizers to get a remarkably improved stabiliza-
tion effect[10,11].
Layered double hydroxides (LDHs) thermal stabilizers are
given a great research potential and application prospect for
their acidic and alkaline characteristics, memory effect, large
surface area, high anion exchange, and good thermal stabil-
ity[12–14]. The reason why LDHs served as efficient additives
to enhance PVC thermal stability is that HCl produced in the
degradation of PVC can be scavenged by the hydrotalcite
structure of LDHs.
According to the special structures and thermal stabilizing
mechanisms of rare earth elements and hydrotalcite-like ma-
terials, based on our previous work[15,16], the MgAl-CO3-
LDH can not react with labile chlorine atoms (such as allyl
chloride), so it is difficult to restrain the initial coloring and
prevent the growth of ‘‘polyolefin structure’’ when it is used
alone. Therefore, the initial coloring is very serious when the
MgAl-CO3-LDH is used as thermal stabilizer individually.
Compared with MgAl-CO3-LDH, the long-term thermal sta-
bility of the PVC samples with MgAlCe-CO3-LDH is en-
hanced although the initial coloring is restrained just a little.
As in the case of ZnAl-CO3-LDH served as thermal stabi-
lizer for PVC, it is significant for it to restrain the initial col-
oring and prevent the growth of "polyolefin structure" by

Foundation item: Project supported by National Natural Science Foundation of China (91023031)
Corresponding author: YANG Zhanhong (E-mail: zhyang@mail.csu.edu.cn; Tel.: +86-731-88879616)
DOI: 10.1016/S1002-0721(12)60151-3
896
reacting with allyl chloride. However, the long-term stabili-
zation effects of PVC composites containing ZnAl-CO3-
LDH are suppressed. The unsuitable production ZnCl2 could
catalyze the degradation of PVC, leading to the malignant
degradation of PVC and making PVC samples turn black
suddenly, i.e. "zinc burning"[17,18]. In order to satisfy both
initial coloring and long-term stabilization effect of PVC
composites, the rare earth element La[19,20] was introduced
into the ZnAl-CO3-LDH in this paper.
ZnAlLa-CO3-LDHs were prepared. As the thermal stabil-
ity of mixture of PVC, ZnAlLa-CO3-LDHs was examined
by static thermal aging test, mass loss test and Congo red test.
And the synergistic effect of ZnAlLa-CO3-LDHs with CaSt2
and -diketone, as well as the detailed thermal stabilizing
mechanisms of thermal stabilizers was discussed.
1 Experimental
1.1 Materials
The PVC resin (SG-5 type, suspension grade) was kindly
provided by Beijing Huaer Company Limited. All the
chemical reagents used in this study were of A.R. grade. The
deionized water was distilled twice to get rid of carbon di-
oxide (CO2).
1.2 Preparation of ZnAlLa-CO3-LDHs
The Zn(NO3)2·6H2O solution was added into an aqueous
mixture containing Al(NO3)3·9H2O and La(NO3)3·6H2O with
the total concentration fixed at 1 mol/L. Then, the aqueous
mixture above and a mixed solution containing NaOH and
Na2CO3 were added to the deionized water at a speed of 1
drop/s, respectively. The resultant solution was stirred for 4 h
at 85 ºC under a constant pH value of 10. Subsequently, the
resulting slurry was aged for 20 h at 65 °C. After being fil-
tered and washed, the precipitate was dried and ground to
fine powder.
1.3 Characterization techniques for ZnAlLa-CO3-LDHs
X-ray diffraction (XRD) was performed on a Rigaku
D500 (Siemens) diffractometer (36 kV, 30 mA) using Cu K
radiation at a scanning rate of 2=8(º)/min. FTIR spectra
were conducted on a Nicolet Nexus-670 FTIR spectrometer
(as KBr discs, with wavenumber 4004000 cm–1, resolution
0.09 cm–1, and the mass of measured sample 2 mg). The sur-
face morphology of as-synthesized ZnAlLa-CO3-LDHs was
observed using a scanning electron microscope (SEM,
JSM-6360LV).
1.4 Procedure for thermal stability
1.4.1 Static thermal aging test and mass loss test Mixtures
containing PVC powder, dioctylphthalate (DOP), different
LDHs, CaSt2 and -diketone (HSBM) were blended in a
double-roller mixer at 180±l ºC. The resulting composites
were molded to sheets with a thickness of 1.0 mm and cut
into 3 cm×2 cm strips. These strips were placed in a thermal
JOURNAL OF RARE EARTHS, Vol. 30, No. 9, Sep. 2012
aging test box at 180±l ºC and subjected to static thermal
aging. The strips were taken out of the box every 20 min and
subjected to visual examination. Synchronously, the mass
change determination was taken. The mass loss and time that
black decomposition started to emerge was defined as the
thermal stability time of PVC.
1.4.2 Congo red test PVC and other different stabilizers
were mixed absolutely in the mortar. The resultant mixtures
were put into a tube with Congo red test paper located at 2 cm
above the sample. The tube was immersed into an oil bath at
180±l ºC for evaluating static thermal stability of PVC com-
posites. The time required for the color change from red to
blue was taken to be the stability time. Each sample was
measured three times and the average time was obtained.
2 Results and discussion
2.1 Characterization of ZnAlLa-CO3-LDHs
2.1.1 XRD analysis of ZnAlLa-CO3-LDHs The XRD pat-
terns of ZnAlLa-CO3-LDHs are shown in Fig. 1. From Fig. 1,
the characteristic absorption peaks at 2=11.7°, 23.5°, 34.6°
and 61.7° of ZnAlLa-CO3-LDHs, which correspond to the
reflections of (003), (006), (009) and (110) respectively, in-
dicating that the as-grown ZnAlLa-CO3-LDHs share a hy-
drotalcite structure. These diffraction peaks are sharp, nar-
row and symmetrical with a low and stable baseline, sug-
gesting that the sample is well-crystallized. It can be found
that the XRD patterns of ZnAlLa-CO3-LDHs with different
Zn/Al/La molar ratios are similar. The results indicated that
the ZnAlLa-CO3-LDHs can be successfully synthesized with
different Zn/Al/La molar ratios. According to Fig. 1, the dif-
fraction peak of curves C and D are sharper than that of A
and B, indicating that the ZnAlLa-CO3-LDHs have high
crystallinity and integrated crystalline structures with M2+/
M3+=2/1. However, a higher diffraction peak of the sample
with Zn/Al/La=20/9/1 was located at about 56.5°, which can
be attributed to the characteristic peak of La(OH)3 (PDF06-
0585).
Fig. 1 XRD patterns of ZnAlLa-hydrotalcite samples with different
Zn/Al/La molar ratios
(1) Zn:Al:La=20:6:4; (2) Zn:Al:La=20:7:3; (3) Zn:Al:La=20:8:2;
(3) Zn:Al:La=20:9:1
WEN Runjuan et al., Zn-Al-La hydrotalcite-like compounds as heating stabilizer in PVC resin
2.1.2 FTIR analysis of ZnAlLa-CO3-LDHs Fig. 2 presents
the recorded FT-IR spectra of ZnAlLa-CO3-LDH and
ZnAl-CO3-LDH. It can be seen from Fig. 2 that there is a
hydroxyl vibrational peak at 3434 cm–1 for ZnAlLa-CO3-
LDHs, which shifts to a lower wavenumber in comparison
with the free hydroxyl group (3650 cm–1). The reason for
this is that the interlaminar H2O, CO32– or –OH in hydrotal-
cite structure react through the association of hydrogen-
bond[21,22]. The O–C–O asymmetric stretching vibration ap-
pears between 1350 and 1550 cm–1. And a considerably
lower shifted absorption peak at 1363 cm–1, as compared
with CO32– of CaCO3 (1430 cm–1), shows that there was an
intercalation between CO32– and interlayer H2O through the
strong hydrogen bonding. The lower wavenumber bands at
400–700 cm–1 is due to LDH lattice vibrations (Zn–O, Al–O,
La–O, La–O–Zn). The bands at 779 and 552 cm–1 can be as-
signed to Al–O stretching modes. These Al–O peaks of
ZnAlLa–CO3–LDHs are weaker than those of ZnAl–CO3–
LDH, which probably resulted from the partial replacement
of La3+. The strong band at 428 cm–1 belongs to the layered
skeleton structure of hydrotalcite. It was basically the same
as that of the LDHs containing no element La[23]. Hence, it is
safe to conclude that La had been introduced into the lattice
of hydrotalcite.
2.1.3 SEM analysis of ZnAlLa-CO3-LDHs Fig. 3 gives
SEM images for the ZnAlLa-CO3-LDHs sample. It is clear
that the as-obtained particles were in a well-distributed dis-
persion state on the whole and display a shape of sphericity.
And the particle size is assumed to be 2–20 m.
2.1.4 Particle size and BET analysis of ZnAlLa-CO3-LDHs
Fig. 2 FT-IR patterns of ZnAlLa-hydrotalcite and ZnAl-hydrotalcite
samples
(1) ZnAl-CO3-LDH; (2) ZnAlLa-CO3-LDH
Fig. 3 SEM images for samples prepared by aging style of hydro-
thermal treatment
897
The particle size distribution curve is shown in Fig. 4. It
can be observed that the particle size range is narrow and in
a normal distribution, which demonstrates that the as-syn-
thesized sample is very uniform and in accordance with
SEM images. Besides, the porous structure of ZnAlLa-CO3-
LDHs was measured by Brunauer-Emmett-Teller method.
The specific surface area is confirmed to be 31.5277 m2/g
with a pore volume of 0.2201 cm3/g.
2.2 Thermal stability testing of prepared PVC composites
2.2.1 Effect of ZnAlLa-CO3-LDHs with various Zn/Al/La
molar ratios on the thermal stability of PVC The effect of
mixtures containing 100 g PVC, 70g DOP, and 2.4 g
ZnAlLa-CO3-LDHs with different Zn/Al/La molar ratios on
the thermal stability of PVC are illustrated in Fig. 5 by static
thermal aging test and the Congo red test data of the mix-
tures with the same mass ratio are listed in Table 1. Syn-
chronously, the mass loss data are shown in Table 2.
As shown in Fig. 5(a), pure PVC without any stabilizer
begins to color and becomes black after only 20 min at 180±1
ºC. As shown in Table 2, the mass loss percentage is the
largest one and there is the maximum mass loss rate in this
sample, which indicated that loss of HCl made the greatest
increase in mass. It is well known that PVC, under the in-
fluence of temperatures and energy radiation, suffers from
the autocatalytic dehydrochlorination reaction and the
HCl-catalytic reaction, which is fulfilled by the ionic mecha-
nism[24]. At the beginning, the formation of a double bond
activates the subsequent chlorine atoms, i.e. allyl chloride,
and loss of HCl from an adjacent unit may form a conju-
gated bond system and cause mass loss of the PVC sample.
Secondly, the primary HCl molecule takes part in the forma-
tion of a dehydrochlorination transition state, which results
in an autocatalytic dehydrochlorination. These two processes
may be expressed as below:
(1) PVC autocatalytic dehydrochlorination reaction:
(1)
Fig. 4 Particle granularity analysis pattern of ZnAlLa-hydrotalcite
898 JOURNAL OF RARE EARTHS, Vol. 30, No. 9, Sep. 2012

Table 2 Mass-loss percentage (%) of ZnAlLa-CO3-LDHs with

different Zn/Al/La molar ratios on the thermal stabil-
ity of PVC (a) PVC; (b) Zn:Al:La=20:10:0; (c)
Zn:Al:La=20:6:4; (d) Zn:Al:La= 20:7:3; (e)
Zn:Al:La=20:8:2; (f) Zn:Al:La=20:9:1
Time/min (a) (b) (c) (d) (e) (f)
20 0.48 0.21 0.20 0.19 0.16 0.17
40 0.54 0.22 0.21 0.20 0.17 0.19
60 0.58 0.25 0.24 0.22 0.20 0.21
80 0.63 0.35 0.26 0.23 0.21 0.22
100 0.68 0.47 0.28 0.26 0.23 0.25
120 0.73 0.51 0.37 0.30 0.27 0.29
140 0.79 0.58 0.39 0.35 0.32 0.35
160 0.86 0.61 0.41 0.38 0.35 0.38
180 0.90 0.65 0.45 0.43 0.37 0.40
200 0.95 0.73 0.58 0.50 0.43 0.45

As stated above, it is necessary to add thermal stabilizers

to PVC resin to improve the thermal stability.
The thermal stability results for the PVC samples con-
taining ZnAl-CO3-LDH (Zn:Al=2:1) are shown in Fig. 5 (b).
The stability time is longer than pure PVC. The mass loss is
made some improvement. The initial coloring is lighter and
the mass loss is lower, but the PVC samples turn yellow
slightly only after 80 min and black all suddenly. Meanwhile,
the mass loss is aggravated, which indicates that the loss of
HCl is getting more and more serious. The blackening is ob-
served at 100 min.
As ZnAl-CO3-LDH served as thermal stabilizer for PVC,
the above mentioned detrimental reactions could be avoided
by the interaction between ZnAl-CO3-LDHs and unfavorable
HCl via a two-step process[25]. Firstly, the counterions such
Fig. 5 Effect of ZnAlLa-CO3-LDHs with different Zn/Al/La molar
as OH– between the LDH layers incline to react with the HCl,
ratios on the thermal stability of PVC.
which reveals the long-term stabilization. Secondly, the
(a) PVC; (b) Zn:Al:La=20:10:0; (c) Zn:Al:La=20:6:4;
LDH itself reacts with the HCl, resulting in the complete
(d) Zn:Al:La=20:7:3; (e) Zn:Al:La=20:8:2; (f) Zn:Al:La=20:9:1
destruction of the LDH structure and formation of metal
Table 1 Effect of ZnAlLa-CO3-LDHs with different Zn/Al/La chlorides. It is important for ZnAl-CO3-LDHs to restrain the
molar ratios on the thermal stability of PVC at 180 ± l ºC initial coloring and prevent the growth of "polyolefin struc-
(as determined by Congo red test) ture" by reacting with allyl chloride. The process may be ex-
PVC composite Zn/Al/La molar ratio Thermal stable time of pressed as below:
PVC composite/min
PVC – 15
PVC+ ZnAl-CO3-LDHs 20:10:0 75
PVC+ZnAlLa-CO3-LDHs 20:6:4 120 (3)
PVC+ZnAlLa-CO3-LDHs 20:7:3 133 The unsuitable production of the reaction is the ZnCl2,
PVC+ZnAlLa-CO3-LDHs 20:8:2 186 which is thought as a high-efficiency catalyst in the dehy-
PVC+ZnAlLa-CO3-LDHs 20:9:1 135 drochlorination reaction of PVC, leading to the malignant
degradation of PVC and making PVC samples turn black
The conjugated polyene sequence is a chromophore. And suddenly, i.e. "zinc burning"[17,18], which is the reason why
the discoloration of PVC resin results from the formation of PVC samples turned black suddenly only after 100 min.
conjugated polyene sequences of more than 6 double bonds. Consequently, the long-term stabilization effect of PVC
(2) HCl catalytic reaction: composites containing ZnAl-CO3-LDH are suppressed.
The thermal stabilities of mixtures containing PVC resin,
DOP, and ZnAlLa-CO3-LDHs with different Zn/Al/La mo-
lar ratios are shown in Fig. 5 (c–f), respectively. Compared
(2) with Fig. 5 (b), the long-term thermal stability are more ex-
WEN Runjuan et al., Zn-Al-La hydrotalcite-like compounds as heating stabilizer in PVC resin 899

cellent. The thermal stability of the PVC samples becomes reported in Fig. 6 and listed in Table 3, Table 4, respec-
better with the increasing of Zn/Al/La molar ratio. When the tively.
ratios of Zn/Al/La became higher than 20/8/2, however, As shown in Table 3 and Fig. 6, the discoloration time of
there was a slight decrease in thermal stability. The result is PVC is prolonged with the increasing amounts of ZnAlLa-
consistent with that in Congo red tests and the mass loss tests. CO3-LDHs from 1.2 to 3.0 phr (parts per hundred PVC res-
So it is suggested that the optimum molar ratio of Zn/Al/La ins), revealing that the thermal stability of PVC is improved
is 20/8/2. And the mass-loss percentage and mass loss rate significantly. However, further increment of ZnAlLa-CO3-
are the entire minimum. LDHs in PVC cannot enhance the thermal stability any more,
Compared with the PVC strips containing ZnAl-CO3- but weaken it instead, suggesting that the optimum amount
LDH, the long-term stabilization effect of PVC composites
containing ZnAlLa-CO3-LDHs are more excellent. The main
reason is attributed to the strong complexation property of
rare-earth elements which have longer atom radius and more
coordination numbers[26]. So the rare earth ion (RE+) can
react with the labile chlorine atoms (Clr–) to form a stable
coordinate complex[27]. After chlorine atoms coordinates
with rare earths, the catalysis effect of HCl is refrained.
Consequently, ZnAlLa-CO3-LDHs are very effective in co-
ordinating with allylic chlorine atoms and suppressing deg-
radation of PVC resin. As stated previously, the rare earth
ions enhance effectively the initial thermal stability. Simul-
taneously, it is worthy noticing that the undesirable ZnCl2
could be consumed by an exchange reaction between ZnCl2
and La3+. Conversely, LaCl3 production does not promote
rapidly dehydrochlorination. The synergistic effect might be
expressed as below:
3ZnCl2+2La3+3Zn2++2LaCl3 (4)
Relevantly, the synergistic effect might be explained by
the orbit theory[28]. Bonding orbitals including 6s, 6p, 5d and
a large ionic radius in rare earth ions La endow them more
coordination number, which form ionic coordination bonds
by electrostatic interaction. The outermost d orbitals of La3+
are "unoccupied orbitals", on which there are no electrons.
Conversely, the 3d orbitals of Zn2+ are full of electrons,
which are called "occupied orbitals". It is clear that the ther-
mal stability is excellent when the "unoccupied orbitals" are
combined with the "occupied orbitals". According to the
Hund’s Rule, the relatively stable complex is probably due
to the fact that the outermost d orbitals of La3+ are combined
with the 3d orbitals of Zn2+. In the complexes, the d orbitals
were all under the condition of "half-occupied". Conse-
quently, the unsuitable zinc chloride was changed into a
more stable d-d complex. Thus, the time of "zinc burning"
Fig. 6 Effects of different amounts of ZnAlLa-CO3-LDHs on ther-
was delayed effectively. According to the unique synergetic
mal stability of PVC composites
effect of rare earth La3+, it is not sufficient for excessively
(a) 1.2 phr; (b) 1.8 phr; (c) 2.4 phr; (d) 3.0 phr
low dosage of La to produce a desired synergetic effect and
excessive La addition leads to damage on the structure of Table 3 Effect of various amounts of ZnAlLa-CO3-LDHs on the
LDHs. Consequently, it is indicated that the optimum molar thermal stability of PVC at 180± l ºC (as determined by
ratio of Zn/Al/La is 20/8/2 and the sample with this Congo red test)
Zn/Al/La molar ratio has the most integrated crystalline PVC composite Amount of Thermal stable time of
structure as demonstrated clearly in Fig. 1. ZnAlLa-CO3-LDHs/phr PVC composite/min
2.2.2 Effect of various amounts of ZnAlLa-CO3-LDHs on PVC+ZnAlLa-CO3-LDHs 1.2 138
the stability of PVC 100 g PVC, 70 g DOP and various PVC+ZnAlLa-CO3-LDHs 1.8 157
amounts of ZnAlLa-CO3-LDHs with the optimum molar ra- PVC+ZnAlLa-CO3-LDHs 2.4 186
tio of Zn/Al/La (20/8/2) were mixed. The results of static PVC+ZnAlLa-CO3-LDHs 3.0 158
thermal aging test Congo red test, and mass loss test are
900 JOURNAL OF RARE EARTHS, Vol. 30, No. 9, Sep. 2012

Table 4 Mass-loss percentage (%) of different amounts of ZnAlLa-

CO3-LDHs on the thermal stability of PVC composites.
(a) 1.2 phr, (b) 1.8 phr, (c) 2.4 phr, (d) 3.0 phr
Time/min (a) (b) (c) (d)
20 0.16 0.17 0.16 0.16
40 0.17 0.18 0.17 0.17
60 0.25 0.21 0.20 0.19
80 0.30 0.27 0.22 0.29
100 0.33 0.30 0.24 0.32
120 0.35 0.32 0.28 0.34
140 0.37 0.34 0.32 0.35
160 0.41 0.37 0.35 0.37
180 0.43 0.42 0.38 0.43
200 0.48 0.45 0.41 0.47

of ZnAlLa-CO3-LDHs fillers is 2.4 phr, which is consistent

with that in Congo red test. And the mass loss test reveals
the same result in Table 4.

2.3 Effect of composite thermal stabilizers on the sta-

bility of PVC
According to the above test, the introduced La in the
ZnAlLa-CO3-LDHs could delay the time of "zinc burning",
but it is too difficult to prevent completely the reaction. Both
of CaSt2 and E-diketones can effectively prevent the "zinc
burning" to improve the long-term stabilization of PVC.
Thus, we made a research in detail on them.
2.3.1 Effect of various amounts of E-diketones (HSBM) on
the stability of PVC 100 g PVC, 70 g DOP, 2.4 g ZnAlLa-
CO3-LDHs with the optimum molar ratio of Zn/Al/La, 0.3 g
CaSt2 and various amounts of E-diketones (in the range of
0–0.5 phr) were mixed. The results of mass loss test and the
static thermal aging test are shown in Table 5 and Fig. 7, re- Fig. 7 Effects of different amounts of -diketones on thermal stabil-
spectively. ity of PVC composites
As shown in Fig. 7, the effect of E-diketones on the ther- (a) 0.0 phr; (b) 0.1 phr; (c) 0.2 phr; (d) 0.3 phr; (e) 0.4 phr; (f) 0.5 phr
mal stability of PVC is the most efficient when the dosage of
E-diketones increases to 0.4 phr. In Table 5, the mass loss of E-diketones in PVC could not enhance the thermal stabil-
has been improved remarkably. However, further increment ity any more. So the optimum amount of E-diketones is 0.4
Table 5 Mass-loss percentage (%) of different amount of - phr, which is revealed in Table 5.
diketones on the thermal stability of PVC composites Although E-diketones alone have no thermal stability, it
(a) 0.0 phr, (b) 0.1 phr, (c) 0.2 phr, (d) 0.3 phr, (e) 0.4 can suppress the initial coloring of PVC composites and en-
phr, (f) 0.5 phr hance the long-term stabilization thereof with thermal stabi-
Time/min (a) (b) (c) (d) (e) (f)
lizer containing Zn combined. As the co-stabilizer,
E-diketones are expected to effectively displace allylic chlo-
20 0.11 0.12 0.11 0.11 0.09 0.11
rine atoms of PVC resin which is catalyzed by Zn2+. This
40 0.12 0.13 0.12 0.12 0.10 0.12
process may be expressed as below:
60 0.12 0.13 0.13 0.12 0.10 0.12
80 0.13 0.14 0.13 0.13 0.10 0.13
100 0.14 0.15 0.14 0.13 0.12 0.14 (5)
120 0.15 0.16 0.14 0.14 0.12 0.15
140 0.17 0.18 0.15 0.14 0.13 0.16
In addition, an enhanced photostability of PVC resin could
160 0.25 0.20 0.17 0.15 0.14 0.20
be obtained with E-diketones used, which is known as an ul-
180 0.28 0.21 0.19 0.16 0.15 0.22
traviolet absorber. To sum up, the combination of
200 0.30 0.27 0.23 0.18 0.17 0.27
E-diketones system with ZnAlLa-CO3-LDHs stabilizer dis-
220 0.42 0.29 0.29 0.24 0.19 0.30
plays a favorable synergistic effect in stabilization of PVC.
240 0.45 0.30 0.30 0.26 0.22 0.31
WEN Runjuan et al., Zn-Al-La hydrotalcite-like compounds as heating stabilizer in PVC resin 901

2.3.2 Effect of various amounts of CaSt2 on the stability of Table 6 Mass-loss percentage (%) of different amount of cal-
PVC 100 g PVC, 70 g DOP, 2.4 g ZnAlLa-CO3-LDHs cium stearate on the thermal stability of PVC compos-
with the optimum molar ratio of Zn/Al/La, 0.4 g E-diketones ites (a) 0.0 phr; (b) 0.1 phr; (c) 0.2 phr; (d) 0.3 phr; (e)
0.4 phr
and various amounts of CaSt2 (in the range of 0–0.4 phr)
were mixed. The results of the static thermal aging test and Time/min (a) (b) (c) (d) (e)

mass loss test are presented in Fig. 8 and Table 6. 20 0.11 0.10 0.11 0.09 0.10
From Fig. 8, it can be found that there is a remarkable im- 40 0.12 0.11 0.12 0.10 0.11
provement in thermal stability of PVC with the increasing 60 0.12 0.12 0.13 0.10 0.11
amount of CaSt2 from 0.1 to 0.4 phr (parts per hundred res- 80 0.13 0.13 0.13 0.10 0.12
ins). The same result is shown in Table 6. However, further 100 0.13 0.14 0.14 0.12 0.13
increment of CaSt2 in PVC can not enhance the thermal sta- 120 0.14 0.15 0.14 0.12 0.14
bility any more, suggesting that the optimum amount of 140 0.17 0.16 0.15 0.13 0.15
CaSt2 is 0.3 phr. On this occasion, the mass loss is the opti- 160 0.18 0.17 0.16 0.14 0.15
mal. 180 0.28 0.19 0.17 0.14 0.16
200 0.30 0.24 0.19 0.16 0.19
220 0.33 0.26 0.23 0.17 0.23
240 0.35 0.30 0.27 0.18 0.26

However, it should be noted that the element La that ex-

isted in ZnAlLa-CO3-LDHs would not be quantitatively
enough to consume ZnCl2 generated by the reaction in the
PVC- ZnAlLa-LDHs systems. Hence, the introduction of
CaSt2 which has synergistic effect and presents favorable
stabilization could be of great expectation. The CaSt2 not
only absorbs HCl produced during dehydrochlorination of
PVC and handicaps the catalysis of HCl, but also exchanges
ions with ZnCl2 in the PVC-ZnAlLa-LDHs systems, which
can result in a malignant dehydrochlorination of PVC. This
process may be expressed as below:

(6)

The stabilization is fulfilled by this mechanism. Conse-

quently, the combination of CaSt2 system with ZnAlLa-CO3-
LDHs stabilizer has favorable synergistic effect in stabiliza-
tion of PVC. Based on the common effect of CaSt2, E-dike-
tone, and ZnAlLa-CO3-LDHs, the PVC composites present
favorable stabilization.

Fig. 8 Effects of different amounts of calcium stearate on thermal
stability of PVC composites
(a) 0.0 phr; (b) 0.1 phr; (c) 0.2 phr; (d) 0.3 phr; (e) 0.4 phr
3 Conclusions
ZnAlLa-CO3-LDHs were prepared by co-precipitation
method under constant pH. And the results showed that the
hydrotalcite had a layered structure. The PVC composites
containing ZnAlLa-CO3-LDHs only showed a better thermal
stability when the amount of ZnAlLa-CO3-LDHs filler was
2.4 phr and the molar ratio of Zn/Al/La was 20/8/2. The
PVC composites containing 100 g PVC, 70 g DOP, 0.3 g
CaSt2, 0.4 g E-diketones and 2.4 g ZnAlLa-CO3-LDHs pre-
sented a significant enhancement in the thermal stability.
The reason could be that ZnAlLa-CO3-LDHs was very ef-
fective in coordinating with allylic chlorine atoms and sup-
pressing degradation of PVC resin. Simultaneously, it could
suppress the catalysis of HCl. On the other hand, it could op-
902
timize the stability of PVC.
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