J Polym Res (2011) 18:22212227 DOI 10.

1007/s10965-011-9634-2

ORIGINAL PAPER

PET synthesis in the presence of new aluminum catalysts

Bin Xiao & Liping Wang & Renhao Mei & Gongying Wang

Received: 16 October 2010 / Accepted: 19 May 2011 / Published online: 31 May 2011 # Springer Science+Business Media B.V. 2011

Abstract A new polycondensation catalyst (ethylene glycol aluminum) was synthesized and applied in PET synthesis. It has been characterized by spectral studies (IR, NMR). The catalytic activity of organic aluminum compound was discussed in this paper. In this investigation, the synthesis of poly(ethylene terephthalate) (PET) is presented using ethylene glycol (EG) and terephthalic acid (TPA). The result proved that ethylene glycol aluminum was the real catalytic material. And it was proved to be the most efficient catalyst for the polycondesation reaction among the organic aluminum compounds. Similar catalytic activity has been observed for ethylene glycol aluminum compared to ethylene glycol antimony. The esterification reaction was monitored by measuring the distilled water as a function of time and the modeling of this process was carried out from these data. The received PET samples were characterized by viscometry, carboxyl end-group content and diethylene glycol (DEG) content. A mechanism of aluminum catalysis has been proposed to explain these observations. Keywords Aluminum alkoxide . PET . Polycondensation . Catalyst . Ethylene glycol . Terephthalic acid
B. Xiao : L. Wang : G. Wang (*) Chengdu Institute of Organic Chemistry, The Chinese Academy of Sciences, Chengdu 610041( Sichuan, China e-mail: gywang@cioc.ac.cn B. Xiao e-mail: bxwisdom_886@yahoo.com.cn R. Mei Changzhou Key Laboratory of Green Chemistry and Technology, Changzhou Institute of Chemistry, Changzhou 213164( Jiangsu, China

Introduction Poly(ethylene terephthalate) (PET) is used as a commodity as well as engineering product for diverse applications. Its main end products are fibers, packaging articles and films [1, 2]. PET has one of the fastest growing markets and will continue this trend in the future boosted by world economic growth and continuous development of new application fields. In the production of high molecular weight PET by the polycondensation of ethylene terephthalate, the presence of a catalyst is essential. Although the large number of papers and reviews is published in the literature on the kinetic and catalytic aspects of PET synthesis [36], the report is rare which aluminum alkoxide is used as the polycondensation catalyst. The mechanism of the reaction in the presence of different metals is still the object of controversial interpretations owing to difficulties in the kinetic treatment of polycondensation. In this study, EG was used to prepare PET directly from TPA in presence of several aluminum alkoxides. Aluminum alkoxides were too sensitive to water, so they were added in the polycondensation process. The catalytic activity of different aluminum alkoxides was similar. In order to compare other organic aluminum compound catalytic acitivity, different aluminum -diketones and -ketoesters were used both as esterification and polycondensation catalyst because they were not sensitive to water. Their acitivity was lower than aluminum alkoxide. In mechanism tests, the process of esterification was examined. Additionallly, specific strategy for designing the real catalytic material on the polycondensation process has been also discussed. The result showed that ethylene glycol aluminum was produced for using organic aluminum compounds as catalyst and it was the real role of catalytic material. The new catalyst (ethylene glycol aluminum) was synthesized

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by the reaction of EG and aluminum isopropoxide. The influence of the new catalyst on the polycondensation process was also investigated.

Experimental Materials TPA (99%) and EG (99%) were obtained from China Resource Company, suitable for polyester synthesis. Aluminum isopropoxide (Chinese Medicine Company, 99%), aluminum nitrate (Chinese Medicine Company, 99%), dibenzoylmethanate (Alfa Aesar, 99%), benzoylacetone (Alfa Aesar, 99%), aluminum acetylacetonate (Shanghai Qincheng Company, 99%), EG (Alfa Aesar, 99%), trifluoroacetic acid (TFA) (Chinese Medicine Company, 99%), phenol (Jiangsu Yonghua Chemical Company, 99%), tetrachloroethane (Jiangsu Qiangsheng Chemical Company) were used as received. The compounds were used as catalysts in the polymerization reaction, including aluminum alkoxides, aluminum -ketoesters, titanium glycolate, ethylene glycol antimony and all were of analytical grade without further purification. Synthesis of catalysts Aluminum isopropoxide was added to ethylene glycol at room temperature. The mixture was the heated under reflux at 190 C for 9 h. Then the glycol was removed by vacuum distillation at 190 C. The solution was cooled and toluene was added. The product precipitated out as a white solid and the mixture was filtered. Then the white solid sample was dried in vacuum at room temperature [7]. The product was characterized by NMR and IR spectroscopy. The product was characterized by NMR. 1 H-NMR ( [ppm], CD4O, 20 C): 4.94 (t, 1 H, -OH), 3.31/ 3.60 (d, 12 H, -CH2-). 13C-NMR ( [ppm], CD4O, 20 C): 62.91 (CH2-), 49.59 (CD4O). EI-MS (70 eV): m/z 297 [M+]. Elemental Anal. Calc. for C8H18Al2O8: C,32.43; H, 6.08; Al,18.24%. Found: C, 32.65; H, 6.23; Al, 18.68%. Melting point (Tm) 153 C. Aluminum dibenzoylmethanate: An amount of 0.01 mol aluminum nitrate was dissolved in 10 mL of ethanol and the solution of dibenzoylmethanate 6.72 g in 25 mL trichloromethane was slowly added. Then pH was adjusted to 7 by adding ammonia water. After 5 h of stirring the product precipitated from the reaction solution was filtered, washed with ethanol and a white solid was obtained [8]. 1H-NMR ( [ppm], (CD3)2CO, 20 C): 8.16/8.15 (m, 12 H, phenyl), 7.567.43 (m, 18 H, phenyl), 7.22 (s, 3 H, -CO-CH-CO-). 13 C-NMR ( [ppm], (CD3)2CO, 20 C): 186.23 (CO-), 139.70129.15 (phenyl), 95.10 (CH-). EI-MS (70 eV): m/z 697 [M+]. Elemental Anal. Calc. for C45H33AlO6: C,77.59;

H, 4.74; Al,3.88%. Found: C, 77.82; H, 4.90; Al, 3.69%. Melting point (Tm) 279 C. Aluminum benzoylacetone: An amount of 0.01 mol aluminum nitrate nonahydrate was dissolved in 50 mL of water and the solution of benzoylacetone 4.8 g in 75 mL methanol was slowly added. Then pH was adjusted to 7 by adding ammonia water. After 9 h of stirring the product precipitated from the reaction solution was filtered. The received product was washed with ethanol and a white solid was obtained [9]. 1H-NMR ( [ppm], (CD3)2CO, 20 C): 7.957.94 (m, 6 H, phenyl), 7.517.39 (m, 12 H, phenyl), 6.426.38 (m, 3 H, -CH-), 2.872.84 (s, 9 H, -CH3). 13CNMR ( [ppm], (CD3)2CO, 20 C): 194.75194.47 (CO-), 184.15183.80 (CH3-CO-), 139.30128.82 (phenyl), 98.35 (OC-CH-CO-), 27.91 (CH3-CO-). EI-MS (70 eV): m/z 511 [M+]. Elemental Anal. Calc. for C30H27AlO6: C,70.59; H, 5.29; Al,5.29%. Found: C, 70.72; H, 5.34; Al, 5.11%. Melting point (Tm) 221 C. Synthesis of PET TPA and EG in a molar ratio of EG/TPA =1.2 were charged into a 1 L stainless-steel batch reactor equipped with a paddle agitator (50 Hz). The first step (esterification) is considered to be completed after the collection of 95% of the theoretical amount of water, which was removed from the reaction mixture by distillation and collected in a graduated cylinder. In the second step, the polycondensation catalyst was added. After the polycondensation reaction was completed, the product was unloaded into cold water with a pressure of nitrogen, and dried 12 h in a vacuum oven at 100 C and reduced pressure. 1H-NMR ( [ppm], CDCl3-TFA (95:5 by weight), 20 C): 10.30 (s, 1 H, -COOH), 6.91 (m, 4 H, phenyl), 3.593.45 (m, 2 H, -CH2-). Characterization Intrinsic viscosity (IV) measurements were performed in an Ubbelohde viscometer at 25 C using a mixture of phenol/ 1,1,2,2-tetrachloroethane (60:40 by weight). IV was calculated using Moore equation [10]. Carboxyl end-group content (COOH) of the resins was determined according to Pohls method [11] by titrating a solution of the resin in phenol/chloroform with standard KOH in ethanol in the presence of bromophenol blue as indicator. After the polymer samples were saponified by sodium hydroxide and methanol, the content of DEG was measured on Shanghai Precision & Scientific Instrument Co. Ltd. gas chromatographic instrument [12]. The esterification water was measured by the internal standard method on GC instrument, and the internal standard substance was pentanediol [13].

PET synthesis in the presence of new aluminum catalysts

2223

FT-IR spectra were recorded with an infrared spectrophotometer (Nicolet 560). NMR data was obtained from AVANCE III 500 MHz (Bruker company), using CD3OD or CD Cl3 mixture with TFA (95:5, by weight) as the solvents. Thermal analysis of the catalysts was performed on Perkin-Elmer Pyris 1 differential scanning calorimeter at a rate of 10 C/min. Elemental analyses were recorded on an elemental Carlo Erba 1106 spectrometer. Mass spectras were obtained using electron impact (EI-MS) and LDI-1700 (Linear Scientific Inc.).

methylene group. The multiplets at 49.59 ppm are attributed to the solvent CD4O. From FT-IR and NMR spectrums, we can justify the received sample is ethylene glycol aluminum. Catalytic activity of different aluminum alkoxides The synthesis of PET samples was performed by twostep melt polymerization method, that is, by the direct esterification of TPA with EG and subsequent polycondensation of the oligomers produced. In order to compare the acitivity of the polycondensation catalysts, different aluminum alkoxides were used. Samples were tested for the IV after reaction. The carboxyl contents were determined only for the base polymer according to the Pohls method [3]. As can be seen from the results presented in Table 1, values of the IV of PET synthesized with aluminum alkoxides are different. DEG and carboxyl end-group content are also similar. Another character of catalytic activity is the polycondensation time and they are listed in Tables 1 and 2. It is tested the time of the stirring powder (from 40 W to 70 W) at a constant stirring frequency (50 Hz). After the material is added, the batch reactor is manipulated by a computer. The stirring powder is tested every three minutes by computer. Among aluminum alkoxides, the second stage reaction time of ethylene glycol aluminum is 39 min and it is the shortest among aluminum alkoxides. The second stage reaction time of ethylene glycol antimony and titanium glycolate are 45 and 30 min. From this aspect, we can see the catalytic activity of ethylene glycol aluminum is higher than ethylene glycol antimony and lower than titanium glycolate. The stirring powder of aluminum phenoxide and 8-hydroxyquinoline aluminum did not reach 70 W after 60 min. The catalytic activity of aluminum phenoxide and 8hydroxyquinoline aluminum is the lowest among aluminum compounds in Table 1. This phenomenon could be caused by three reason. Firstly, the catalytic activity of aluminum alkoxide is related to Lewis acidity of aluminum. Alcoholic group is donor group. Among these aluminum alkoxides, the electron-donating power of alcoholic group is different: (CH3)3CO- (CH3)2CHO- CH3CH2O- CH3O- [14]. Lewis acidity of aluminum is reverse. Each aluminum atom in aluminium alkoxide becomes highly electrophilic because of the stronger electron- attracting inductive effect of the conjoint O atoms, and thereby improves the Lewis acidity of the active center (Al atom). Secondly, the steric hindrance of different alkoxide is different. When the steric hindrance is higher, the catalytic activity is lower. Thirdly, the conjugated p- bond is formed for the conjugated bond of phenyl with O atom because the conjugated effect is stronger than the inductive effect. Lewis acidity of

Results and discussion Synthesis of Ethylene Glycol Aluminum FT-IR absorption bands from ethylene glycol aluminum (see Fig. 1) have been empirically assigned by comparison with the spectra of EG, because EG molecule is the part of the structure. Appearance of the peaks at 3,320 cm1 and 1,589 cm1 corresponds to O-H and O-H. These peaks become weak in the spectrum of ethylene glycol aluminum at 2,939 cm1, 2,880 cm1 and 1,4601,250 cm1 due to the bond of C-H and C-H. This implies that the glycolate anion cannot move freely in ethylene glycol aluminum. It can be seen that the presence of Al-O and C-O bands at 658 and 1,090 cm1. The IR spectroscopic data is coincided with those of Wangs paper [8]. 1 H-NMR spectrum data of ethylene glycol aluminum in CD4O is shown above. The singlets at 3.60 and 3.31 ppm are attributed to the proton in methylene group and CD4O. The triplets at 4.94 ppm are attributed to the proton in hydroxyl group or water in CD4O. In the 13C-NMR spectrum, two signals were observed including the solvents. The singlet at 62.91 ppm is attributed to the carbon in

Fig. 1 FT-IR of ethylene glycol aluminum and EG

2224 Table 1 Effect of different aluminum alkoxides on PET characters Catalyst Symbol Polycondensation time a /min IV (dL/g) -COOH (mol/g) DEG (mol/t)

B. Xiao et al.

Sample color L* a* 0.2 0.8 0.3 2.3 0.1 0.5 2.0 0.2 3.0 b* 14.2 15.6 10.9 16.8 9.0 14.6 15.3 16.2 29.3

Aluminum methoxide Aluminum ethoxide Aluminum isopropoxide Aluminum tert-butoxide Ethylene glycol aluminum Aluminum phenoxide 8-Hydroxyquinoline aluminum Ethylene glycol antimony Titanium glycolate
a

Al-OMe Al-OEt Al-OPr Al-OBu Al-EG Al-OPh Al-OQ Sb-EG Ti-EG

42 45 45 48 39 60 60 45 30

0.86 0.84 0.86 0.85 0.87 0.56 0.59 0.86 0.89

29.3 25.0 19.3 21.5 23.0 28.9 25.7 29.3 26.6

8.5 7.2 8.1 6.1 8.2 9.4 7.8 9.3 6.8

60.4 60.8 55.7 59.9 53.8 60.4 63.4 60.4 73.4

Polycondensation time was measured by computer. For Al-OMe, Al-OEt, Al-OPr, Al-OBu, Al-EG, Sb-EG and Ti-EG, polycondensation time is tested the time of the stirring powder (from 40 W to 70 W) at a constant stirring frequency (50 Hz). For Al-OPh and Al-OQ, the stirring powder did not reach 70 W after bis(hydroxyethyl) terephthalate was polycondensed 60 min

aluminum of aluminum phenoxide and 8-hydroxyquinoline aluminum is lower than other aluminum alkoxides. The IV data in Table 1 illustrates that the catalytic activity of titanium glycolate is higher than ethylene glycol aluminum and ethylene glycol antimony and it is similar between ethylene glycol aluminum and ethylene glycol antimony. This phenomenon could be caused by the coordinative ability of Ti to create some kinds of coordinative network in the polymer melt that results in enhanced values of melt viscosity; Al and Sb are unable to form such network and, as a consequence, lead to lower values of IV, which can be considered a further advantage in their application. It is worthwhile noting that when titanium compounds are used for the production of PET, the polymer becomes markedly yellowish [1013]. The data of b* is usually used as the criterion of sample color comparing with L* and a*.
Table 2 Effect of different aluminum compounds on PET synthesis Catalyst Symbol Polycondensation time a/min

From b* values of color measurement of PET samples of this work (Table 1), the PET sample of titanium glycolate showed a clear visible yellow discoloration (b*=29.3) due to titanium glycolate adding. A visible yellow discoloration showed the samples with b* values >4.5, and all the other samples showed sensible discoloration. But the samples of aluminum compounds are whiter than the sample of titanium glycolate and b* values are lower. So, aluminum alkoxides worked better in the case, where they were new catalyst for the polycondensation. Catalytic activity of aluminum -diketones and -ketoesters In order to detect other organic aluminum compound acitivity, different aluminum -diketones and -ketoesters were used. As shown in Table 2, IV distribution of PET

IV (dL/g)

-COOH (mol/g)

DEG (mol/t)

Sample color L* a* 1.0 0.8 2.2 1.2 1.5 0.7 0.9 b* 14.5 13.0 14.1 12.9 12.0 15.6 10.9

Aluminum Aluminum Aluminum Aluminum Aluminum Aluminum Aluminum

a

methylacetoacetate ethylacetoacetate isopropylacetoacetate tertbutylacetonate acetylacetonate benzoylacetonate dibenzoyl methane

Al(meac)3 Al(etac)3 Al(ipac)3 Al(tbuac)3 Al(AAc)3 Al(BAc)3 Al(DBA)3

60 60 60 60 54 60 60

0.82 0.81 0.79 0.80 0.83 0.65 0.59

66.36 67.96 69.80 63.40 71.50 69.25 64.10

8.5 7.2 7.8 6.3 6.9 5.4 7.9

60.4 65.2 61.4 65.9 60.5 61.4 55.7

Polycondensation time was measured by computer. For Al(meac)3, Al(etac)3, Al(ipac)3, Al(tbuac)3 and Al(AAc)3, polycondensation time is tested the time of the stirring powder (from 40 W to 70 W) at a constant stirring frequency (50 Hz). For Al(BAc)3 and Al(DBA)3, the stirring powder did not reach 70 W after bis(hydroxyethyl) terephthalate was polycondensed 60 min

PET synthesis in the presence of new aluminum catalysts

2225

samples synthesized with aluminum chelates was found to be different to each other. DEG and carboxyl end-group content are similar. The stirring powder can reach 70 W after the reaction except Al(BAc)3 and Al(DBA)3. From the data of IV and the second stage reaction time in Table 2, we can conclude that the catalytic activity of aluminum ketoesters and Al(AAc)3 is similar. The catalytic activity of Al(DBA)3 and Al(BAc)3 is the lowest. This phenomenon could be caused by two reason. The quantity had obvious effect on the polycondensation, but all the quantity of the catalysts is 0.5% of TPA mole. The first reason is the steric hindrance of different ligands. When the steric hindrance is higher, the catalytic activity is lower. The second reason is Lewis acidity of aluminum. It is different when the ligand is different. Each aluminum atom in aluminium -diketones or -ketoester molecule becomes highly electrophilic because of the stronger electron- attracting inductive effect of the conjoint O atoms, and thereby improves the Lewis acidity of the active center (Al atom). There is also AlO bond and electron attracting effect in aluminium -diketones molecules, but it is not so strong because of the weaker inductive effect of the higher steric hindrance ligand (-diketones) that results in the lower Lewis acidity of active center (Al). From b* values of color measurement of PET samples (Table 2), the PET sample showed a yellow discoloration and the result of sample color was similar to aluminum alkoxides. There is no significantly difference in PET sample color. Although aluminum -diketones and -ketoesters can be used as esterification and polycondensation catalysts, their catalytic activity is lower than aluminum alkoxide. So they are limited in their application. PET structure The Fig. 2 of PET FT-IR was complicated, but the characteristic absorption peaks were ester conformation and benzene ring. The IR spectrpscopic data was coincided with those of Biswass paper [15]. 1,300 cm1 and 1,090 cm1 are due to stretching vibration of C-O. 1,720 cm1 and 725 cm1 were assigned to the band of the carboxyl and benzene ring. The absorbencies of the signals at 3430 and at 872 cm1 were due to the end-group. 1 H-NMR spectrum data of the sublimate in CDCl3-TFA (95:5 by weight) mixture is shown above The multiplet observed in the 3.453.59 ppm region has been assigned to the protons of methylene groups present in PET [16]. The singlests observed at 6.91 ppm and 10.30 ppm have been assigned to the protons of the phenyl groups and terminal carboxyl groups. The 1H-NMR spectrpscopic data was coincided with those of Ma Ys paper [16]. It can be concluded that the received sample is PET from the spectrum of FT-IR and 1H-NMR.

Fig. 2 FT-IR of PET

Mechanism In order to find the real catalytic material, blank test was done. Eight aluminum compouds (0.5 mol) were reacted with EG (200 mL) in a reactor equipped with a nitrogen inlet, a condenser and a mechanical stirrer. The temperature is 200 C. The conversion of ligand was listed in Table 3. Data presented in Table 3 showed that these aluminum compounds were reacted with EG and the corresponding ligands were produced. It was detected by GC. We choosed aluminum -diketone as an example and the reaction mechanism was listed in Scheme 1. The aluminum chelates with -diketones or -ketoesters reversible exchange of -diketones or -ketoesters with EG. It can be concluded that aluminum glycolate may be the real catalytic material. B. Apicella [17] reported a mechanism of ethylene glycol antimony. Aluminum and antimony are both trivalent metal. The spatial structure of ethylene glycol antimony and ethylene glycol aluminum is similar, so the catalytic mechanism should be similar to ethylene glycol antimony. According to this author trivalent metal catalysts
Table 3 The reaction of catalyst (0.5 mol) and EG (200 mL) at 200 C No. 1 2 3 4 5 6 7 8 Catalyst Al(meac)3 Al(etac)3 Al(ipac)3 Al(tbuac)3 Al(AAc)3 Al-OEt Al-OPr Al-OBu Ligand produced (%) 31.8 29.3 26.5 33.5 25.9 45.5 49.1 40.3

2226 Scheme 1 The ethylene glycol aluminum mechanism of polycondensation

B. Xiao et al.

attack the carbonylic oxygen in the following way: BHET favors a successive nucleophilic attack of a glycoxide oxygen to the carboxylic carbon atom. In this case, the metal has a strong inductive, effect and influences the resonance of the aromatic ring. For this reason para-substituent strongly affects the performances of the catalyst, as shown in a previous paper [18]. On the contrary, trivalent metals are coordinated to the acylic oxygen, and this favors the nucleophilic attack to carbon from the alkoxide coordinated to the metal [19], in a four-step mechanism. The reaction mechanism in Scheme 1 can be divided into four steps. Firstly, the ligand of organic aluminum compounds exchange with EG at the Al atom. Secondly, organic aluminum compounds have appropriate Lewis acidity. Each aluminum atom in organic aluminum compound molecule becomes highly electrophilic because of the stronger electron-attracting inductive effect of the conjoint O atoms, and thereby improves the Lewis acidity of the active center (Al atom). Thus, the O atom in carbonyl group of TPA is easier to coordinate on the aluminum center and then accelerate the reaction. Thirdly, the C atom in carboxyl group of TPA, which is coordinate to the aluminum center, becomes highly electrophilic, and thereby the hydroxyl of EG is easier to coordinate on the carboxyl C atom. Meanwhile, the hydroxyl H atom coordinates on hydroxyl of carboxyl and water is produced. Lastly, AlO bond is not so strong because of the weaker inductive effect of ligand that results in the lower Lewis acidity of active

center (Al). The produced functional group removes from Al atom and it is the end of one circle. The listed Scheme 1 is for the esterification process and the polycondensation process is similar. This suggests that the mechanism of the reaction is similar in the case of trivalent ones. Moreover, the mechanism of condensation is probably very similar to that of polycondensation. On the other hand, the mechanism of BHET polycondensation has been already proposed by other author in the literature [20], even though different catalyst is used to justify the analogy.

Conclusions A series of PET have been synthesized using TPA and EG in presence of different aluminum alkoxides. The use of ethylene glycol aluminum as catalyst has the major advantage to be effective in polycondensation step. No addition of another catalyst is added in esterification step in order to make sure the catalytic activity. Ethylene glycol aluminum is synthesized and applied to PET synthesis. It is a new catalyst in polyester polycondesation. Comparing with titanium glycolate and ethylene glycol antimony, the catalytic activity is similar to ethylene glycol antimony, but is lower than titanium glycolate. The reason for this phenomenon is discussed. Finally, ethylene glycol aluminum does not give any rise to environmental problems and is available at reasonable

PET synthesis in the presence of new aluminum catalysts

2227 7. Gainsford GJ, Kemmitt T, Milestone NB (1995) Inorg Chem 34:52445251 8. Gao D, Bian Z, Wang K (2003) J Alloy Comp 358:188192 9. Manuel AV, Reis MV (1983) J Chem Thermodyn 15:957863 10. Wijayathunga VN, Lawrence CA, Blackburn RS (2007) Opt Laser Technol 39:13011309 11. Karayannidis GP, Roupakias CP, Bikiaris DN (2003) Polymer 44:931942 12. Qu MH, Wang YZ, Wang C (2005) Eur Polym J 41:2569 2574 13. Kang C, Lee B, Ihm D (1996) J Appl Polym Sci 60:20072015 14. Herreros B, Barr TL, Klinowski J (1994) J Phys Chem 98:738 741 15. Biswas S, Lotha D (1999) Nucl Instrum Methods Phys Res B 159:4051 16. Ma Y, Agarwal US, Sikkema DJ (2003) Polymer 44:4085 4096 17. Apicella B, Serio MD, Fiocca L (1998) J Appl Polym Sci 69:24232433 18. Apicella B, Santacesaria E, Serio MD (1999) Stud Surf Sci Catal 122:431434 19. Serio MD, Tesser R, Ferrara A (2004) J Mol Catal A: Chem 212:251257 20. Serio MD, Apicella B, Grieco G (1998) J Mol Catal A: Chem 130:233240

cost. Its polycondensation mechanism has been recognized. The compound is a trivalent metal compound and the polycondesation mechanism is similar to ethylene glycol antimony.
Acknowledgement The authors would like to thank co-workers (Changzhou Chemistry Institute) for experimental supporting. This study has been supported by the Analytical&Testing Center Jiangsu Institute of Technology, P.R.China.

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