Polymer Degradation and Stability 92 (2007) 1565e1571 www.elsevier.

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Metal dicarboxylates as thermal stabilizers for PVC

Yan-Bin Liu a,b, Wei-Qu Liu a,*, Meng-Hua Hou a,b
a

Guangzhou Institute of Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China b Graduate University of Chinese Academy of Sciences, Beijing 100049, China Received 26 January 2007; received in revised form 26 April 2007; accepted 5 May 2007 Available online 18 May 2007

Abstract Different metal dicarboxylates such as calcium glutarate, zinc glutarate, calcium sebacate and zinc sebacate were investigated in this paper as thermal stabilizers (without and with calcium stearate and pentaerythritol as costabilizers) of poly(vinyl chloride) (PVC). The thermal stability of the PVC lms was determined by two different methods which are visual color comparison and measurement of HCl release from heated pellets. Both zinc dicarboxylates and calcium dicarboxylates exhibited good thermal stability. With respect to stabilizing performance, zinc glutarate (ZnGa) was more effective than zinc sebacate (ZnSe), particularly in the presence of a large amount of pentaerythritol. Similarly, calcium glutarate (CaGa) was more effective than calcium sebacate (CaSe). And the relative order of stabilizing effectiveness of metal dicarboxylates was as follows: CaGa > CaSe > ZnGa > ZnSe. Moreover, the CaeZn complex thermal stabilizer and the PeeZn complex thermal stabilizer were also studied. It was found that no more than 20% of the zinc compound exhibited better stabilizing performance. 2007 Elsevier Ltd. All rights reserved.
Keywords: PVC; Thermal stabilizer; Metal dicarboxylates; Pentaerythritol; Calcium stearate

1. Introduction It is well known that poly(vinyl chloride) (PVC) is an important thermoplastic material on account of its versatility and low cost. However, one major drawback of PVC is that it decomposes at a temperature lower than its processing temperature. Thermal degradation of PVC is the result of a process called zipper dehydrochlorination, which generates polyene sequences in polymer chains that may produce an undesirable color in the material [1]. The color changes from white to yellow, brown, and nally to black while the properties of the material deteriorate. It is generally accepted that thermooxidative degradation of PVC can be blocked or retarded by thermal stabilizers which must perform at least two basic functions: substitute stable groups for labile chlorine atoms in PVC chains (e.g., allylic or tertiary chlorine atoms) and react with HCl generated by the

* Corresponding author. Tel./fax: 86 20 85231660. E-mail address: liuwq@gic.ac.cn (W.-Q. Liu). 0141-3910/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.polymdegradstab.2007.05.003

degradation process [2,3]. The most important stabilizers of PVC are different metal soaps like Pb-, Cd-, Ba-, Ca-, and Zn-carboxylates and some mono-alkyltin compounds, e.g., carboxylates and mercaptides. While the thermal stabilizers based on tin and lead are most effective, in some cases, they are not used any more since they are poisonous and are substituted by calciumezinc stabilizers which are nontoxic. Ca-carboxylate which has no Lewis acidity is a HCl scavenger (secondary stabilizer) and Zn-carboxylate, which has stronger Lewis acidity, is able to scavenge HCl and react with labile chlorine atoms. An undesirable effect of the stabilizing action of zinc stearate (ZnSt2) is the ZnCl2 production, which can promote a sudden dehydrochlorination of PVC [1]. The effectiveness of ZnCl2 in the degradation reaction can be explained on the basis that it has a tendency to form HZnCl 3 [4], thus creating labile chlorine in the PVC chain. However, it has been claimed that such sudden dehydrochlorination occurs only after ZnCl2 concentrations reach a certain level [1,4e6]. Conversely, CaCl2 does not promote the sudden dehydrochlorination. Pentaerythritol (Pe) is a compound widely used to delay the degradation time considerably for PVC. In the catalytic

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presence of ZnCl2, pentaerythritol reacts with such chloride to produce a chemical compound [7]:

Cl Zn Cl

H H O CH2 H2C O C O CH2 H2C O H H Zn

Cl Cl
b

In this way, ZnCl2 is inactivated and consequently there will be no free ZnCl2 to catalyze the dehydrochlorination. Generally speaking, pentaerythritol is used in great excess to hinder the detrimental effect of ZnCl2. Although the use of metal carboxylates as stabilizers for PVC has been extensively studied, reports on the utilization of derivatives of dicarboxylic acids as stabilizers for PVC are scanty. Ikhuoria [8] has reported that metal soaps of dicarboxylic acids are fairly heat stable and may be suitable as stabilizer of PVC. Some metal dicarboxylates (e.g., zinc glutarate) has been studied a lot in other elds. It is well known that zinc glutarate prepared from the reaction of ZnO and glutaric acid has a very high catalytic activity [9], and it has been found to be the most effective and economically feasible catalyst for the production of poly(propylene carbonate) with a high molecular weight from CO2 and propylene oxide [9e13]. Therefore, based on its character, zinc glutarate may show good stabilizing performance in PVC. But there is no any such study which has reported zinc glutarate as thermal stabilizers for PVC. In this study, we choose zinc glutarate, zinc sebacate, calcium glutarate and calcium sebacate to investigate systemically the stabilizing performance of metal dicarboxylates for PVC. 2. Experimental 2.1. Materials PVC resin from Shenyang Chemical Co., Ltd. (PSM-31) was used to prepare the compounds. DOP and pentaerythritol were purchased from Shanxi Sanwei Group Co., Ltd. Calcium stearate (CaO assay 9.1e10.4%) was acquired from Wenzhou Tiansheng Plastics Additives Co., Ltd. 2.2. Preparation of zinc dicarboxylate (ZnDC) and calcium dicarboxylate (CaDC) Zinc glutarate was synthesized from zinc oxide (ZnO) and glutaric acid as described elsewhere [14]. That is, glutaric acid of 0.10 mol was dissolved in 150 mL of toluene in a round bottom ask (250 mL) equipped with a DeaneStark trap and a reux condenser with a drying tube. Then, 0.10 mol ZnO was added into the glutaric acid in toluene. After the addition was completed, the slurried mixture was stirred vigorously at 50  C for 4 h. After cooled to room temperature, the reaction mixture was ltered off and washed with acetone several times, giving zinc glutarate in powder form. The powdered zinc glutarate was dried in a vacuum at 100  C for 24 h. The reaction yield was 99.8%. Calcium glutarate was prepared in the same way as zinc glutarate.

4000

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3000

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1500

1000

500

Wavenumber cm-1
Fig. 1. IR spectrum of calcium sebacate (a) and sebacic acid (b).

Calcium sebacate was prepared in the following way: calcium hydroxide (0.02 mol) was at rst dissolved in water and then the solution was added into sebacic acid (4.04 g, 0.02 mol in 100 mL boiling water). The precipitate was ltered, washed with water three times, and dried at 100  C. The reaction yield was 99.5%. Zinc sebacate was prepared from zinc hydroxide [Zn(OH)2] and sebacic acid in a procedure similar to calcium sebacate. 2.3. FTIR analysis of metal dicarboxylates The transmission IR spectra of metal dicarboxylates were taken using FTIR 740 infrared spectrophotometer. 2.4. Preparation and testing of PVC lms Films were prepared from PVC (100 parts), DOP (50 parts) and varying amounts of stabilizers by mixing at 25  C and gelation at 120  C for 20 min.

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500

Wavenumber cm-1
Fig. 2. IR spectrum of zinc glutarate (a) and glutarate (b).

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3

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ZnDo: 1.0 phr Pe: 0 phr gHCl/100 g PVC

3 2

ZnDo: 0.5 phr Pe: 2 phr gHCl/100 g PVC

2

ZnDo: 1.0 phr Pe: 2 phr

ZnDo: 1.5 phr Pe: 2 phr

0 0 1 2 3 4 5 6 3 0 1 2 3 4 5 6

time, h ZnDo: 1.0 phr Pe: 3 phr g HCl/100 g PVC

2

time, h

0 0 1 2 3 4 5 6

time, h
Fig. 3. HCl evolution curves, as a function of time, for formulations stabilized with zinc sebacate e- or zinc glutarate e,.

To compare zinc glutarate with zinc sebacate, formulations with the following Pe/ZnDC ratios (phr/phr) were considered: (a) 2/0.5, (b) 2/1, (c) 2/1.5, (d) 0/1 and (e) 3/1. To investigate the stabilizing performance of calcium dicarboxylate as stabilizers for PVC, formulations with the following CaDC contents (phr) were considered: 0.5, 1.0 and 1.5. To analyze synergistic stabilizing action of the mixtures of CaSt2 and ZnDC, the following CaSt2/ZnDC ratios (phr/phr) were used: (a) 1.0/0.0, (b) 0.8/0.2, (c) 0.6/0.4, (d) 0.4/0.6, (e) 0.2/0.8 and (f) 0.0/1.0. The thermal stability was determined by the following means. (a) Visual color comparison of PVC strips (1 1 cm). These strips were heated in a thermal aging test box at 170  C and subjected to static thermal aging according to the ISO standard [15]. Strips were removed every 10 min. (b) Measurement of the HCl released by 4.5 g of PVC pellets

that were maintained at 180  C in a homemade equipment described elsewhere [16]. 3. Results and discussion 3.1. FTIR studies As shown in Figs. 1 and 2, a wide peak at the wave number of 3200e2500 cm1 corresponded to the carboxyl of dicarboxylic acids, which were due to the dimer expansion and contraction vibration. In addition, two sharp peaks at 1420e1250 cm1 resulted from the hydroxyl surface bending vibrations of the carbonyl and the coupling of the expansion and contraction vibration. However, when the hydrogen ions were replaced by metal ions in carboxylic acid molecules, there was no hydroxyl. So the phenomenon which mentioned above could not be observed.

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(a)
0.5 phr g HCl/100 g PVC

(b)
1.0 phr

(c)
1.5 phr

0 0 1 2 3 4 5 6 0 1 2 3 4 5 6 0 1 2 3 4 5 6

time, h

time, h

time, h

Fig. 4. HCl evolution curves, as a function of time, for formulations stabilized with calcium sebacate e- or calcium glutarate e,; the concentration of stabilizer: (a) 0.5 phr, (b) 1.0 phr, and (c) 1.5 phr.

Clearly, the single carbonyl (C]O) absorption observed at 1680e1750 cml for two dicarboxylic acids had disappeared after the formation of the metal dicarboxylates. Instead, it was replaced by two new bands between 1360e1480 cm1 and 1500e 1650 cm1. These two peaks corresponded to the symmetrical and antisymmetrical vibrations of the COO. The replacement of C]O band with two new ones was due to the ionization of the dicarboxylic acids resulting in the equilibration of the two oxygen atoms attached to the carbon [17]. In addition, the vibration-plane swing of the anti-methene of dicarboxylate resulted in a weak and broad absorption peak at 700e800 cm1, which was attributed to the cyclic molecular structure. 3.2. Formulations stabilized with metal dicarboxylates As shown in Fig. 3, in the absence of Pe, both the formulations released HCl quickly at the very beginning and neglectable differences in the time at which the rst sudden HCl release occurs (ts) can be observed. The similar behaviors were also observed in the formulations containing 1.5 phr of zinc dicarboxylate and 2.0 phr of Pe. But with the concentration of the zinc dicarboxylate and the Pe/ZnDC ratio in the

formulations increasing, zinc glutarate produced a more considerable decrease in the amount of HCl released at a specic degradation time and more increment in the characteristic ts values when compared to their equivalent zinc sebacate formulations. The above behaviors suggested that zinc dicarboxylates (zinc glutarate and zinc sebacate) had stronger Lewis acidity and were able to scavenge HCl (reaction (1)) and react with labile chlorine atoms (reaction (2)), just like ZnSt2 [18]. The reaction of zinc dicarboxylates with the labile chlorines of PVC occurred if stabilizers and PVC were mixed at the molecular level, which was very difcult to achieve. This results in the non-uniform distribution of the zinc dicarboxylates in PVC lms. HCl that was eliminated from regions poor of zinc dicarboxylates could accelerate the dehydrochlorination of PVC and react with zinc dicarboxylates, which might cause increasing amount of Lewis acid (ZnCl2) simultaneously. In this case, auto-acceleration of dehydrochlorination occurred. The detrimental effect of ZnCl2 was particularly severe and hindered the stabilizing performance of both zinc dicarboxylates because of high zinc content in zinc glutarate and zinc sebacate. That was why neither zinc dicarboxylate showed good stabilizing performance (no induction period was observed and

(a)

3 ZnGa CaGa

(b)
ZnSe CaSe

g HCl/100 g PVC

0 0 1 2 3 4 5 6 0 1 2 3 4 5 6

time, h

time, h

Fig. 5. HCl evolution curves, as a function of time, for formulations stabilized with metal dicarboxylates; the concentration of stabilizer: 1.0 phr.

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HCl evolution occurred with extremely high rates) in the absence of Pe. When there was enough Pe to inactivate ZnCl2 [19], HCl evolution curves were only determined by the kind of zinc dicarboxylate. Because zinc glutarate had higher catalytic activity than zinc sebacate, the degraded formulation containing 1.0 phr of zinc glutarate and 3.0 phr of Pe released less amount of HCl and had a higher ts value than the formulation containing equivalent zinc sebacate and Pe at a specic degradation time. OOC-R-COOZn HCl/HOOC-RCOOH ZnCl2 1

180  C, which was due to the catalytic effect of ZnCl2 on the dehydrochlorination of PVC. ZnCl2 was formed in the reaction between ZnDC and HCl even in the very early stages of degradation. Since CaCl2 formed during the reaction between CaDC and HCl was not a dehydrochlorination catalyst, CaDC contributed to a considerable increment in the characteristic induction period compared to equivalent ZnDC. As to CaGa and CaSe, the amount of free HCl released from PVC strips increased very slowly. According to Figs. 3e5, the relative order of stabilizing effectiveness of metal dicarboxylates was as follows: CaGa > CaSe > ZnGa > ZnSe. Therefore, CaGa and CaSe were efcient stabilizers, while ZnGa and ZnSe could not be used without any costabilizer.

CH CH CH CH2 Cl

+ (OOC-R-COO)Zn
3.4. Synergetic thermal stabilizing effect of Pe and CaSt2 In order to carry out the static thermal aging tests via observing the color change of the samples, the PVC strips blended with stabilizers were placed in a thermal aging test box at 170  C. The thermal stability of PVC was dened by the time taken for the black decomposition products to appear. The results were illustrated in Fig. 6. As shown in Fig. 6a and b, the color of PVC strips containing ZnGa alone began to change even during the gelating process and became completely black after only 10 min at 170  C. The thermal stability of PVC strips became better with increasing Pe/ZnGa ratio and CaSt2/ZnGa ratio. In addition, CaSt2 resulted in a little better thermal stability than Pe initially, and then the situation of CaSt2 got worse with equivalent Pe/ZnGa ratio and CaSt2/ZnGa ratio. Similar behaviors with above ZnSe could be observed in Fig. 6c and d. It was proved that CaSt2 and Pe had different mechanisms of synergetic action with ZnDC. As we know, dehydrochlorination catalyst, ZnCl2, formed in reactions (1) and (2) might be transformed to other inactive substances. With the addition of Pe, the activation of ZnCl2 was decreased by reaction (3).

CH CH CH CH2 O O C-R-COO

+ ZnCl2

(2)

Fig. 4 showed that the formulations stabilized by calcium sebacate released a larger amount of HCl at a specic degradation time than their equivalent formulations stabilized by calcium glutarate. However, with different contents of these calcium dicarboxylates (calcium glutarate or calcium sebacate), there was a negligible difference in their HCl evolution curves. The above-described behaviors suggested that both calcium dicarboxylates took part in the reaction of acceptance of hydrogen chloride without additional inuence on the kinetic rate of its degradation (except the elimination of HCl catalytic inuence) [20]. As the calcium content of calcium glutarate was more than that of calcium sebacate, the former showed better stabilizing performance. 3.3. Effect of the type of metal on the stabilizing performance of dicarboxylates The contents of free HCl evolution as a function of time for the degradation of PVC strips under inert atmosphere with

HO CH2 H2C OH 2ZnCl2 + C HO CH2H2C OH

Cl Cl

H H O CH2 H2C O Zn C O CH2H2C O H H Zn

Cl Cl (3)

1.0 phr of ZnGa, CaGa, ZnSe, and CaSe were shown in Fig. 5, respectively. As shown in Fig. 5, there were signicant induction periods for the appearance of free HCl for the PVC strips with calcium dicarboxylates. When ZnGa or ZnSe was added to the PVC strips, no induction period was observed, and HCl evolution occurred with extremely high rates. The PVC strips with 1.0 phr ZnDC had 2% weight loss in 1 h at

CaOOCR2 ZnCl2 /CaCl2 ZnOOCR2

When CaSt2, reacted with ZnCl2, calcium chloride and zinc stearate were produced, as shown in reaction (4). Since zinc stearate, which was also an effective stabilizer used commercially, was capable of substituting active chlorine atoms and thus prolonged the stabilizing action, the samples

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(a)
Ca/ZnGa ratio, phr/phr 1.0/0.0 0.8/0.2 0.6/0.4 0.4/0.6 0.2/0.8 0.0/1.0 Degradation time, 10 min 0 1 2 3 4 5 6 7 8 9

(b)
Pe/ZnGa ratio, phr/phr 1.0/0.0 0.8/0.2 0.6/0.4 0.4/0.6 0.2/0.8 0.0/1.0 Degradation time, 10 min 0 1 2 3 4 5 6 7 8 9

(c)
Ca/ZnSe ratio, phr/phr 1.0/0.0 0.8/0.2 0.6/0.4 0.4/0.6 0.2/0.8 0.0/1.0 Degradation time, 10 min 0 1 2 3 4 5 6 7 8 9

(d)
Pe/ZnSe ratio, phr/phr 1.0/0.0 0.8/0.2 0.6/0.4 0.4/0.6 0.2/0.8 0.0/1.0 Degradation time, 10 min 0 1 2 3 4 5 6 7 8 9

Fig. 6. Color evolution, as a function of time, of PVC strips heated at 170  C.

containing CaSt2 had better performance in the rst stage than the ones with equivalent Pe. However, once CaSt2 and Pe were consumed out, the degradation became as it was without the costabilizer. Reaction (3) could induce the reduction of the nal concentration of ZnCl2 in the PVC samples, while reaction (4) had no effect on its nal concentration (because zinc stearate could be transformed into ZnCl2 with the further degradation of PVC). Therefore, Pe produced better long-term thermal stability for PVC than CaSt2. Moreover, it has been reported that the concentration of the zinc compound in the stabilizer must be sufcient for the substitution of active chlorine atoms at a proper speed, but it could not exceed the capacity of CaSt2 and Pe to convert ZnCl2 into zinc stearate [2]. Therefore, in the complex stabilizer, the CaSt2/ZnDC ratio and the Pe/ZnDC ratio should be 4/1 or more.

4. Both Pe and CaSt2 can hinder a sudden dehydrochlorination of PVC due to their synergetic thermal stabilizing effect with zinc dicarboxylates. 5. The percent of the zinc compound in the mixture which mixed with the zinc compound and costabilizer (CaSt2 or Pe) should not be more than 20%.

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4. Conclusions 1. Zinc glutarate and zinc sebacate are good stabilizers for PVC in the presence of pentaerythritol and zinc glutarate is more effective. 2. Calcium glutarate shows better thermal stabilizing performance than calcium stearate. 3. The relative order of effectiveness of metal dicarboxylates for restricting thermal dehydrochlorination of PVC under inert atmosphere is as follows: CaGa > CaSe > ZnGa > ZnSe.

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