MoCl5/TBP/AlEt3体系引发丁二烯聚合制备含结晶的高乙烯基聚丁二烯
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山东省自然科学基金资助项目(ZR2016EMM03)


Polymerization of Butadiene Initiated by MoCl5/TBP/AlEt3 to Prepare High Crystalline Vinyl Polybutadiene
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    摘要:

    以五氯化钼(MoCl5)为主催化剂,磷酸三丁酯(TBP)为配体,三乙基铝(AlEt3)为助催化剂的配位聚合催化体系引发丁二烯(Bd)聚合,研究催化体系配比和聚合温度对丁二烯聚合活性的影响。结果表明,随Mo/Bd摩尔比和Al/Mo摩尔比增大,聚合活性显著增加,聚合物特性黏数和相对分子质量均呈现先升高后降低的趋势,相对分子质量分布略有变窄;聚合温度升高,聚合速度加快,聚合物特性黏数先增大后减小。MoCl5/TBP/AlEt3催化体系引发丁二烯聚合可得1,2-结构含量高于75%的无规1,2-聚丁二烯,聚合物的立构规整性受聚合温度的变化影响较小,随Al/Mo摩尔比增加,定向性增加,聚合物1,2-结构含量在78%~84%的范围内增加,聚合物中出现少量微晶结构。结晶结构的存在对橡胶材料力学性能的提升具有显著意义。

    Abstract:

    The polymerization of butadiene (Bd) was initiated by coordination catalysis system,which consists of molybdenum chloride (MoCl5) as main catalyst, tributyl phosphate as ligand (TBP) and triethyl aluminum (AlEt3) as cocatalyst. The effect of catalytic system ratio and polymerization temperature on the polymerization activity of butadiene was studied . The results show that with increase of the Mo/Bd mole ratio and the Al/Mo mole ratio, the polymerization activity increases significantly, the intrinsic viscosity and molecular weight of the polymer show the trend of first increasing and then decreasing, the molecular weight distribution slightly becomes narrow; with the polymerization temperature increased, the polymerization speed increases, the intrinsic viscosity of the polymer first increases and then decreases. The polymerization of butadiene initiated by MoCl5/TBP/AlEt3 catalytic system can prepare the random 1,2-polybutadiene of which the 1,2-structure content is more than 75%, and the stereoregularity of the polymer is less affected by change of the polymerization temperature. With increase of the Al/Mo mole ratio, the orientation increases, the content of 1,2-structure of polymer increases between the range of 78%~84%, and a small amount of microcrystalline structure appears in the polymer. The existence of the crystal structure is of great significance to improvement of the mechanical properties of rubber materials.

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赵 煊,刘金慧,华 静. MoCl5/TBP/AlEt3体系引发丁二烯聚合制备含结晶的高乙烯基聚丁二烯[J].高分子材料科学与工程,2019,35(1):7-12.

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  • 在线发布日期: 2019-02-13
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