Article
  • Olefins Polymerization with MgCl2/2-Ethyl-1-hexanol/TiC14-Triethylaluminum Catalyst System; 3. Copolymerization of Ethylene and 1-Hexene
  • Lee DH, Kim JT, Yoon KB, Min KE, Park LS, Lim JC, Um DH
  • MgCl2/2-Ethyl-1-hexanol/TiCl4-Triethylaluminum 촉매에 의한 올레핀의 중합; 3. 에틸렌과 1-헥센의 공중합
  • 이동호, 김진태, 윤근병, 민경은, 박이순, 임정철, 엄달호
Abstract
The copolymerization of ethylene and 1-hexene with MgCl2/EHA/TiC14-TEA catalyst system in hexane has been studied in which MgCl2 was dissolved in 2-ethyl-1-hexanol(EHA). In the catalyst preparation, mole ratio of MgCl2/EHA was fixed to be 1/6 and reaction temperature and time were 30℃ and 2h, respectively. The effects of catalyst retreatment with TiC14, mole ratio of catalyst components, feed ratio of monomers and addition of Lewis bases, diisobutylphthalate(DIBP) and phenyltriethoxysilane(PTES), on the activity and composition of copolymers have been investigated. For ethylene/1-hexene copolymerzation, activity increased with (TEA)/[Ti] (>25) and 1-hexene content gave a maximum at [TEA]/[Ti]=100. With addition of Lewis bases, the activity and 1-hexene contents in copolymer decreased. The reactivity ratios obtained by Kelen-Tudos method were rE=53.8, rH=0.18 for MgCl2/EHA/DIBP/TiC14-TEA/ catalyst system and rE=70.8, rH=0.08 for MgCl2/EHA/DIBP/TiC14-TEA/PTES catalyst system. Thermal and mechanical properties of copolymer were also investigated with 1-hexene contents.

염화마그네슘을 2-Ethyl-1-hexanol(EHA)에 녹인 용액으로부터 제조한 사염화티탄 담지촉매로 에틸렌/1-헥센 공중합체를 합성하였다. 이때 촉매의 제조에서 MgCl2/EHA의 몰비는 1/6, 반응온도는 30℃, 반응시간은 2시간으로 고정하였다. 촉매의 TiC14 재처리 및 중합조건 즉 촉매성분 농도비, 단량체의 공급비 등에 따른 촉매의 활성과 공중합체의 조성을 조사하였으며, 아울러 Lewis 염기인 diisobutylphthalate(DIBP) 및 phenyltriethoxysilane(PTES)의 영향도 조사하였다. 에틸렌/1-헥센 공중합시는 (TEA)/[Ti]의 농도가 증가할수록 활성은 증가하였고 [TEA]/[Ti]=25이하에서는 중합이 되지 않았다. 그리고 공중합체의 1-헥센의 함량은 [TEA]/[Ti]의 농도비가 100에서 최대를 나타내었다. Lewis염기를 첨가함에 따라 촉매의 활성과 1-헥센의 함량은 감소하였으며, Kelen-Tudos 방법으로 구한 단량체의 반응성비는 MgCl2/EHA/DIBP/TiC14-TEA/PTES 촉매계에서는 각각 rE=70.8, rH=0.08 이었다. 1-헥센의 함량에 변화에 따른 공중합체의 열적 및 기계적 성질도 조사하였다.

References
  • 1. Boor JZiegler-Natta Catalysts and Polymerization, Academic Press, New York, p. 264 (1979)
  •  
  • 2. Keil T, Soga KCatalytic Olefin Polymerization, Kodansa, Tokyo (1990)
  •  
  • 3. Lee DH, Min KE, Ahn TO, Polym. J., 8, 973 (1987)
  •  
  • 4. Do JG, Jeong YT, Lee DH, Polym.(Korea), 14(3), 240 (1990)
  •  
  • 5. Lee DH, Song KC, Jeong YT, Ha KR, Polym.(Korea), 16(1), 61 (1992)
  •  
  • 6. Lee DH, Kim JT, Jeong YT, Polym.(Korea), 16(4), 451 (1992)
  •  
  • 7. Nowlin TE, Kissin YV, Wagner KP, J. Polym. Sci. A: Polym. Chem., 26, 755 (1988)
  •  
  • 8. Lindeman LP, Adams JQ, Anal. Chem., 43, 1245 (1971)
  •  
  • 9. 안태완, 이동호, 조원제고분자 화학실험, 형설출판사, 서울, p. 120 (1984)
  •  
  • 10. Jeong YT, Lee DH, Soga K, Makromol. Chem. Rapid Commun., 12, 5 (1991)
  •  
  • 11. Chien JCW, Hsieh JTT, J. Polym. Sci. A: Polym. Chem., 14, 1915 (1976)
  •  
  • 12. Busico V, Corradini P, DeMartino L, Proto A, Savino V, Makromol. Chem., 186, 1279 (1985)
  •  
  • 13. Soga K, Yanagihara H, Lee DH, Makromol. Chem., 190, 995 (1989)
  •  
  • 14. Soga K, Lee DH, Yanagihara H, Makromol. Chem., 190, 37 (1989)
  •  
  • 15. Elias HGMacromolecules, 2nd Ed., Plenum Press, p. 760 (1984)
  •  
  • 16. Lee DH, Min KE, Kim CW, J. Korean Chem. Soc., 31, 110 (1987)
  •  
  • 17. Stehling FC, Mandelkern L, Macromolecules, 3, 247 (1970)
  •  
  • 18. Foly PJPrinciples of Polymer Chemistry, Cornell University Press, London, p. 568 (1953)
  •  
  • 19. The Infrared Spectra Atlas of Monomers and Polymers, Sadtler Research Lab., Philadelphia, p. 5 (1984)
  •  
  • 20. 안태완, 이동호, 박이순, 이상원, 정한모고분자물성, 대광문화사, p. 425 (1989)
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2022 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 1992; 16(6): 721-728

    Published online Nov 25, 1992