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Nghiên cứu so sánh về quá trình polymer hóa etylen bằng các chất xúc tác bis(aminotropone) Ti
Tóm tắt
Một loạt các phức hợp titan aminotropone có cặp ligand chelating [O–N] đã được tổng hợp và sử dụng thành công trong quá trình polymer hóa etylen. Các phản ứng polymer hóa etylen đã được thực hiện dưới các điều kiện khác nhau bằng cách sử dụng các chất xúc tác đã chuẩn bị. Hoạt động polymer hóa etylen phụ thuộc rõ rệt vào cấu trúc của chất xúc tác. Hoạt động polymer hóa tăng lên với sự gia tăng cả áp suất monomer và tỷ lệ [MAO]:[Ti]. Hoạt động cao nhất của các chất xúc tác đạt được ở khoảng 30–40 °C. Điều này cho thấy, trái với các chất xúc tác Ti–FI hiệu suất cao, các chất xúc tác bis(aminotropone) Ti không yêu cầu sự hiện diện của khối lượng steric gần kề với nhóm oxy. Việc giới thiệu thay thế alkyl cồng kềnh bên cạnh nhóm oxy làm giảm hoạt động của các chất xúc tác. Các nghiên cứu về Lý thuyết chức năng mật độ (DFT) cho thấy các loài hoạt tính phát sinh từ những chất xúc tác này thường sở hữu tính điện tích cao hơn so với những loài được sản xuất từ các chất xúc tác bis(phenoxy-imine) Ti (các chất xúc tác Ti–FI). Hydro được sử dụng làm tác nhân chuyển chuỗi. Hoạt động của các chất xúc tác tăng lên với nồng độ hydro ở một mức độ nào đó, nhưng giá trị Mv của các polymer thu được lại giảm. Tính tinh thể và nhiệt độ nóng chảy của polymer thu được nằm trong khoảng 42–62% và 102–124 °C, tương ứng. Áp suất cao hơn làm tăng cả tính tinh thể và giá trị Mv của các polymer thu được. Chất xúc tác 8a cũng sản xuất PE với độ phân bố hẹp gần như (1,10–2,55) như là đặc trưng cho các chất xúc tác một vị trí. Tuy nhiên, PDI đã tăng rộng theo thời gian.
Từ khóa
#polymer hóa etylen #bis(aminotropone) #chất xúc tác titan #lý thuyết chức năng mật độ #hoạt động xúc tác #polymerTài liệu tham khảo
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