액상촉매를 사용한 PET 중합에 관한 연구(1) - Sb<sub>2</sub>O<sub>3</sub>를 Glycol에 용해한 용액촉매의 영향 -

손해식; 임상규; 박광현; 손태원; 윤원식

Polymer(Korea), Vol.22, No.1, 23-32, January, 1998

Export Citation

액상촉매를 사용한 PET 중합에 관한 연구(1) - Sb₂O₃를 Glycol에 용해한 용액촉매의 영향 -

Polymerization of PET Using Liquid-Phase Catalysts(1)-Effect of Sb₂O₃ Solution in Glycol Solvents-

손해식, 임상규, 박광현, 손태원, 윤원식

초록

Sb₂O₃ 분말을 glycol[ethylene glycol (EG), neopenthyl glycol(NPG), ethylene glycol-neopenthyl glycol (EG-NPG(5:1)), ethylene glycol- eopenthyl glycol (EG-NPG(1:5))]에 용해시킨 Sb계 액상촉매를 bis(2-hydroxyethyl) erephthalate (BHET)에 투입하여 poly (ethylene terephthalate) (PET)를 중합하고, 중합과정에서 일어나는 반응성과 중합된 PET의 특성을 조사하였다. 반응속도에 있어서는 Sb계 액상촉매를 사용한 경우가 Sb₂O₃ 분말촉매를 사용한 경우보다 초기반응 속도가 증가하였고 액상촉매중에서도 용액을 안정화시킨 용액계가 보다 효과적으로 초기반응 속도를 증가시켰다. 또한 액상촉매를 사용한 경우는 2시간 이내에 중합속도와 분해속도가 평형을 이루고, 고유점도가 0.65dL/g정도의 PET를 얻기 위해서는 액상촉매를 사용하는 것이 중합시간을 단축시키는데 유리하였다. DSC 열곡선에서 PET시료의 용융점 (T_m) 및 냉각시 결정화온도(T_c)가 중합도의 증가와 함께 감소하는 경향을 보이고 있었으며, NPG를 함유한 액상촉매를 사용한 경우에는 NPG의 영향으로 T_m에서 약 3℃정도 감소하였으며, T_c에서는 5℃ 정도 감소함을 알 수 있었다.

In order to investigate the influence of the physical state of the catalyst on polymerization of poly(ethylene terephthalate) (PET), liquid-phase catalysts of Sb₂O₃ solutions such as Sb₂O₃ dissolved in EG-based glycol [ethylene glycol (EG), neopenthyl glycol (NPG), ethylene glycol-neopenthyl glycol (EG-NPG)] was utilized In Polycondensation reaction using bis(2-hydroxyethyl)terephthalate (BHET). Reaction using Sb₂O₃ Powder as catalysts was also carried out for comparison with the liquid-phase catalyst, the rate of polycondensation reaction markedly increased in the early state compared to that of Sb₂O₃ powder-catalyzed case. The liquid-phase catalyst accelarated more effectively both the condensation and the decomposition during polycondensation than Sb₂O₃ powder catalyst. PET with intrinsic viscosity of up to 0.65 dL/g could be obtained by the polycondensation using liquid-phase catalyst in shorter time than by that using powder solid catalyst. The properties of the resultant PET were measured. The DSC thermogram showed melting point of PET at 254℃, and cooling crystallization temperature, at 196℃. PET prepared using catalysts with NPG showed that NPG decreased T_m by 3℃ and T_c by 5℃.

Keywords:Liquid-phase catalyst;PET polycondensation;degree of reaction;thermal analysis

[References]

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Tomita K, Ida H, Polymer, 16, 185 (1975)
Tomita K, Polymer, 17, 221 (1976)
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Hovenkamp SG, J. Polym. Sci. A: Polym. Chem., 9, 3671 (1971)
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U.S. Patent, 3,833,630 (1974)
U.S. Patent, 3,415,860 (1968)
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Spera S, Po R, Abis L, Polymer, 34, 3381 (1993)
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[Referenced By]

[1] Park LS, Yoon JH, Polym.(Korea), 18(5), 693 (1994)

[2] Tomita K, Ida H, Polymer, 16, 185 (1975)

[3] Tomita K, Polymer, 17, 221 (1976)

[4] Stevenson RW, Nettleton HR, J. Polym. Sci. A: Polym. Chem., 20, 205 (1982)

[5] Hovenkamp SG, J. Polym. Sci. A: Polym. Chem., 9, 3671 (1971)

[6] Offenlegungsschrift, 1,950,553 (1970)

[7] U.S. Patent, 3,833,630 (1974)

[8] U.S. Patent, 3,415,860 (1968)

[9] Manaresi P, Munari A, Polymer, 27, 956 (1986)

[10] Spera S, Po R, Abis L, Polymer, 34, 3381 (1993)

[11] Spera S, Po R, Abis L, Polymer, 37(5), 729 (1996)

[12] Solomon OF, Ciuta IZ, J. Appl. Polym. Sci., 6, 683 (1962)

[13] Berkowitz SA, J. Appl. Polym. Sci., 29, 4353 (1984)

[14] Flory PJ, "Principles of Polymer Chemistry," p. 79, Cornell University Press, New York (1953)

[15] Billmeyer FW, "Textbook of Polymer Science," p. 36, Wiley, New York (1984)

[16] Odian G, "Principles of Polymerization," p. 68, Wiley, New York (1991)

[17] Tomita K, Polymer, 14, 51 (1973)