Nd(acac)_3-Al(i-Bu)_3催化邻苯二甲酸酐与环氧氯丙烷交替共聚

RING OPENTING ALTERNATING COPOLYMERIZATION OF PHTHALIC ANHYDRIDE AND EPICHLOROHYDRIN BY Nd(acac) 3 Al(i Bu) 3

研究了 Ｎｄ（ａｃａｃ）３  Ａｌ（ｉ Ｂｕ）３ 催化剂催化邻苯二甲酸酐（ Ｐ Ａ）和环氧氯丙烷（ Ｅ Ｃ Ｈ）交替共聚合。考察了共聚反应的聚合特征，用红外光谱、核磁共振表征了共聚物结构。共聚反应动力学研究表明共聚反应与单体浓度呈一级关系，与催化剂浓度呈一级关系，表观活化能为１１２．０ ｋ Ｊ／ｍ ｏｌ。

The Nd(acac) 3 Al(i Bu) 3 was found to be a good catalyst for the alternating copolymerization of phthalic anhydride with epichlorohydrin. The structure of the copolymer was studied with IR and 1H NMR. The copolymer is a product of high alternation. There is more than 42% phthalic anhydride in the copolymer by calculating the ratio of peak area of 1H NMR from the copolymer obtained from different monomer ratio. The copolymerization can be realized in the solvents such as aromatic hydrocarbon and alkane. The yield and [η] are higher in aromatic hydrocarbon than in other solvnets. In toluene, the yield is 89.8%. [η] =0.083 dL/g. The way of adding the raw materials to the reaction system influences the yield. The better order is PA→sol.→ECH→cat.. The more suitalbe concentration of catalysts is [Nd]=1.0×10 -2 mol/L, [Al]/[Nd]=6~8. The higher is the temperature of copolymerization, the higher are the yield and [η] . The more suitable temperature is 80 ℃. The kinetic studies indicate that the copolymerization reaction is first order with respect to both monomer concentration and catalyst concentration. Δ E =112.0 kJ/mol.