21 2 No.2 Vol Journal of Chemical Engineering of Chinese Universities Apr PET/ATO

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1 21 2 No.2 Vol Journal of Chemical Engineering of Chinese Universities Apr (2007) PET/ATO,, (, ) (ATO) (EG) EG (TPA) (PET)/ATO SEM DSC XRD FTIR TGA ATO PET PET/ATO PET/ATO ATO PET 100~150 nm ATO PET PET ATO PET PET PET ATO PET 1%ATO PET Ω cm ATO TQ TQ TQ TQ A Preparation and Crystalline Behavior of PET/ATO Nanocomposites Prepared by In-Situ Polymerization CHEN Xiao-lei, SHAO Wei, LI Chun-zhong (School of Materials Science and Engineering, Key Laboratory for Ultrafine Materials of Ministry of Education, East China University of Science and Technology, Shanghai , China) Abstract: Poly(ethylene terephathalate) / antimony doped tin oxide (PET/ATO) nanocomposites were prepared by means of esterization and condensation reactions of terephathalic acid and ethyl glycol in the presence of ATO nanoparticles. The dispersion of ATO in PET matrix and the effects of ATO on the intrinsic viscosity of PET, the crystallization and thermal behavior of PET were investigated by SEM, DSC, XRD, FTIR and TGA. It was found that ATO nanoparticles are well dispersed in the PET matrix, and the introduction of ATO increases the intrinsic viscosity of PET nanocomposites. ATO nanoparticles behave as the nucleating agent. Compared with the neat PET, adding ATO nanoparticles, the crystallization rate and crystallization temperature of the PET nanocomposites increase, in addition, the crystallinity of the nanocomposites also increases and their crystallite size decreases. The thermal stability of the nanocomposites is slightly enhanced by the addition of ATO nanoparticles. The specific resistance of the fibers prepared by the PET/ATO nanocomposites (with 1 wt% of ATO) is about Ω cm, which is much lower than that of the neat PET fibers (about Ω cm), and the hybrid fibers show a better anti-static property. Key words: poly(ethylene terephathalate); antimony doped tin oxide; in-situ polymerization; crystallization; anti-static; nanocomposites 1 (PET) ( ) (04DZ14002) (04DZ DZ22302) (0452nm nm047 05nm05001) (1980-) czli@ecust.edu.cn

2 21 2 PET/ATO 335 [1~3] PET PET PET [4] / 22% 10 5 Ω cm [5] / 2% PET Ω cm PET (ATO) ATO [6] [7] ATO >10 12 Ω Ω PET PET ATO PET PET PET PET PET ATO PET ATO PET ATO [8] 20 nm 65 m 2 g -1 1~5 Ω cm (TPA) (EG) (TMP) ( ) 2.2 PET 830 g TPA 403 g EG 14 µl g g 2 L N MPa h Pa 3.5 h PET/ATO ATO EG PET/ATO 1 EG with modified ATO TPA Catalyst Stabilizing agent Agitating for 15 min at 25 Mixture 0.25 MPa, 240 Esterifying for 1 h Fractionating H 2 O PET/ATO nanocomposite Cooling and cutting Condensation polymerization for 3h 70 Pa 280 Ethylene terephthalate 1 PET/ATO Fig.1 Flow chart of in-situ polymerizing PET/ATO nanocomposites 2.3 1:1 0.5 g dl 1 25 PET

3 PET/ATO (JEM-6700F JEOL ) ATO PET (WRT-2 ) 10 min ATO PET (Model CRY-Y ) N 2 10 min min 10 min min (1) Hc X c (%) = 100 (1) (1 Φ ) Hm H m 100% PET H m 140 J g 1 H c Ф [9] X (D/MAX-2550PC ) Cu K α 40 kv 100 ma 5 min 1 XRD PET PET/ATO (Nicolet Fq Irsx ) PET ABE-25 YG PET/ATO TPA/EG PET/ATO 1 1 PET/ATO ATO PET/ATO PET ATO PET ATO 65 m 2 g 1 PET PET ATO ATO PET (2a) ATO Sn PET ATO PET ( (2b) ) PET [10~12] ATO ATO OH RO C O Sn O RO C O HO Sn (2) 1 ATO PET/ATO Table 1 Effect of ATO on intrinsic viscosity of nanocomposites Mass fraction of ATO / % Intrinsic viscosity / dl g ATO PET ATO PET 2 2 ATO PET 2 ATO PET 100~150 nm ATO ATO EG

4 21 2 PET/ATO 337 ATO ATO ATO ATO ATO PET ATO PET [13,14] 2 PET/ATO Fig.2 FESEM micrographs of PET/ATO nanocomposites. PET/1%ATO PET/2.5%ATO 3.3 PET/ATO 3 PET PET/ATO DSC 3 2 t 1/2 (2) t1/2 = ( Ton Tc )/ χ (2) T on T c χ 2 PET/ATO (d) T c PET ATO 2.5% PET/ATO 198 Temperature / o C 3 PET/ATO DSC Fig.3 Cooling measurement of DSC trace for PET/ATO nanocomposites pure PET PET/1%ATO PET/0.5%ATO (d) PET/2.5%ATO ATO PET PET/ATO 2 PET/ATO Table 2 DSC Data for PET/ATO nanocomposites Nanocomposite Melting Crystallization (PET/ATO) T m / T m / H m / J g 1 T onset / T c / T c / t 1/2 / min H c / J g 1 X c / % T c / 100/ / / / T c 2 PET/ATO T c PET (30 ) ATO T c ATO 2.5% PET/ATO T c 16 T c T c PET/ATO ATO PET PET Endo

5 H c t 1/2 T c H c H c t 1/2 t 1/2 T c T m T c T c T c 2 PET/ATO t 1/2 T c PET ATO t 1/2 T c ATO 2.5% t 1/2 T c PET 1.5 min 60 C 0.8 min 54 PET/ATO H c PET (35.7 J g 1 ) ATO H c 2.5% PET/ATO H c (40.8 J g 1 ) ATO PET [15,16] 4 PET PET/ATO DSC ATO T m PET/ATO PET 3.6% ATO PET 4 ATO PET/ATO ATO PET [17,18] Groeninckx [19] PET (100~150 ) ( ) DSC DSC 4 Ι ATO PET ATO Endo (d) Intensity / CPS I II (d) Temperature Temperature / / o C Theta / o 4 PET/ATO DSC Fig.4 Heating measurement of DSC trace for PET/ATO nanocomposites pure PET PET/0.5%ATO PET/1%ATO (d) PET/2.5%ATO 5 PET/ATO XRD Fig.5 XRD patterns of PET and PET/ATO nanocomposites pure PET PET/0.5%ATO PET/1%ATO (d) PET/2.5%ATO 3.4 ATO PET XRD PET PET/ATO 5 5 PET ATO PET ATO PET

6 21 2 PET/ATO 339 ATO PET 1% 2.5% ATO PET 6 PET [20] 6 1% 2.5%ATO PET cm 1 1% 2.5%ATO PET 2.5%ATO PET cm 1 1%ATC PET ATO PET/ATO ATO PET Weight / % PET/ATO Fig 6 FTIR spectra of PET/ATO nanocomposites PET/1%ATO PET/2.5%ATO Temperature / o C 7 PET PET/ATO Fig.7 TG curves of PET/ATO nanocomposites pure PET PET/2.5%ATO PET/5%ATO 3.5 PET/ATO 7 PET PET/ATO 7 PET 1%ATO PET 5%ATO PET ATO PET ATO PET 3.6 ATO PET PET ATO 8 8 ATO ATO ATO ATO / %(wt) 8 ATO PET Fig.8 Effect of ATO contents on the specific resistance of the hybrid fibers ATO ATO ATO ATO ATO 8 1%ATO PET Ω cm PET ( Ω cm) 4 Specific resistance / Ω cm (1) ATO EGPET/ATO

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