Zielger-Natta复合催化剂的制备及其乙烯聚合的研究
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摘要
负载型Ziegler-Natta烯烃聚合催化剂的载体一般以无机物为主,如SiO、MgCl2和沸石等。同无机物载体相比,有机物载体可以大幅度减少烯烃聚合产物中的无机灰分,提高聚烯烃产品的性能,还可以较容易地引入官能团,有效地控制催化活性中心在载体上的分布,从而更好地调控烯烃聚合过程以及聚合产物的形貌。因此,将无机/有机载体复合制备催化剂成为新型聚烯烃催化剂的重要方向。目前制备无机/有机复合材料的方法主要有乳液聚合法、悬浮聚合法及层层组装法等,但是这些方法制备过程比较繁琐,同时也引入了其它一些极性物质,不适用于烯烃聚合催化剂的制备过程。相转化法是膜材料领域常用的一类简单易行的成膜方法。本文首先考察了相转化法制备硅胶/聚(苯乙烯-co-丙烯酸)(PSA)复合载体的基本实验条件,然后将该方法引入复合Ziegler-Natta催化剂的制备,用PSA包覆以硅胶为载体的TiCl3催化剂(SLC-S催化剂),再负载MgCl2/TiCl4络合物制得核壳结构的复合催化剂,聚合反应后得到了分子量分布较宽的聚乙烯产品,研究结果对于单反应器内制备宽/双峰聚乙烯具有重要的意义。
论文主要进行了以下几个方面的研究：(1)基于相转化法成膜机理制备硅胶/聚(苯乙烯-co-丙烯酸)(PSA)核壳型微球,并确定制备复合微球的基本实验条件；(2)依据确定的相转化法成膜的条件制备Ziegler-Natta复合催化剂,并分别用乙烯气相聚合和淤浆聚合考察氢气含量及有机膜的厚度对催化剂的聚合活性及其聚乙烯性能的影响；(3)对复合催化剂中壳层部分的催化剂进行了改进,并考察了催化剂的性能。具体的工作成果如下：
1.提出采用相转化法制备具有良好分散性的无机/有机复合载体颗粒,并考察了非溶剂的蒸发速度、聚合物的浓度、硅胶粒径及聚(苯乙烯-co-丙烯酸)的类型等因素对复合载体的表面形貌及粒径的影响。非溶剂的蒸发速度越慢,复合载体的分散性越好,但为兼顾生产效率与覆膜效果,蒸发速度采用1 ml/min;聚合物浓度越大,复合载体表面越粗糙；硅胶的粒径越大,复合载体表面越蓬松；而聚(苯乙烯-co-丙烯酸)的分子量以及官能团的含量基本不影响复合载体的形貌以及粒径分布。另外,复合载体表面包覆的PSA膜较致密,与单独的硅胶载体相比,其比表面积、孔体积及孔径明显减小
2.利用相转化法制备了同时包含无机载体和有机载体的复合Ziegler-Natta催化剂,研究了该催化剂乙烯气相聚合反应的聚合活性和聚合产物的性能。复合催化剂具有较高的活性,活性高达3000克聚乙烯／克催化剂(9.0 bar聚合压力),且复合催化剂的动力学可调。膜厚为3微米的复合催化剂聚合活性高于核层的SLC-S催化剂,且具有带诱导期的平稳型动力学曲线,而膜厚为1.5微米的复合催化剂的活性接近于SLC-S催化剂,且其具有相似的衰减型动力学曲线。同时,不同的膜厚还能够调节复合催化剂的氢调性能及所得聚乙烯的分子量分布,得到宽峰分子量分布的聚乙烯。
3.对Ziegler-Natta复合催化剂进行了乙烯淤浆聚合的研究,考察了不同覆膜厚度的催化剂对乙烯淤浆聚合活性和聚合产物性能的影响。研究发现,复合催化剂淤浆聚合的活性明显高于气相聚合。SLC-S催化剂和HC-5催化剂的动力学曲线由气相聚合中的快速衰减型转变为淤浆聚合中的平稳型的曲线类型,而HC-20催化剂的动力学曲线则有平稳型变为淤浆聚合中的缓慢衰减型。淤浆聚合中随着膜厚的增加Mn和Mw逐渐依次增大,与其气相聚合的规律相同,但MWD则逐渐变窄。同时,催化剂淤浆聚合所得聚乙烯的堆密度略低于气相聚合。
4.为了改善催化剂的性能,采用BuMgCl代替MgCl2进行反应制得了一系列的复合载体催化剂,主要研究了TiCl4加入量对壳层催化剂的聚合活性及聚乙烯分子量分布的影响。随着TiCl4加入量的增加,催化剂的活性逐渐升高,且几乎呈线性的增加趋势。同时,其聚合动力学曲线的类型由快速衰减型逐渐过渡为缓慢衰减型,MWD逐渐减小,聚合反应所得聚乙烯的堆密度则逐渐增加。
Most of the support materials successfully used in Ziegler-Natta catalysts have been inorganic compounds, such as silica gel, magnesium chloride and zeolite. Compared with the inorganic carriers, organic carriers can greatly reduce inorganic residues to improve the performance of polyolefin products. Therefore, inorganic/organic carrier of the composite catalyst has become an important direction of new polyolefin catalysts. The current preparation method of inorganic/organic composite are complicated and introduces a number of other polar substances, not being suitable for the catalyst of olefin polymerization. A phase inversion method was introduced for hybrid Ziegler-Natta Catalyst preparation.
This thesis focused on the following three aspects:(1) the preparation of silica/poly (styrene-co-acrylic acid) (PSA) core-shell microspheres; (2) the study of hybrid Ziegler-Natta catalysts for gas phase and slurry phase ethylene polymerization; (3) the improvement of hybrid Ziegler-Natta catalysts for slurry ethylene polymerization. Specific works are as follows:
1. Inorganic/organic composite carrier particles were prepared based on phase inversion method. The influences of several factors on the composite surface morphology and particle size were studied, such as evaporation rate of the non-solvent, polymer concentration, the size of silica gel particle and different poly (styrene-co-acrylic acid). The slower of the non-solvent evaporation rate was, the better the dispersion of composite carrier became, and 1 ml/min was chosen as the suitable non-solvent evaporation rate. The influences of other factors on the particle size distribution of composite carriers were quite small. In addition, the specific surface area, pore volume and pore size of the composite supports were significantly reduced compared to silica gel.
2. Hybrid Ziegler-Natta catalysts were prepared based on phase inversion method. Ethylene polymerizations were conducted in a gas phase reactor. Composite catalyst has high activity (3000 g polyethylene/g catalyst) (9.0 bar pressure). HC-20 catalyst had a good ethylene polymerization activity and its kinetic curve was stable with an inductive period, while HC-5 catalyst demonstrated a fast decay during polymerization and its activity and kinetic curve both resembled SLC-S catalyst. What's more, the thickness of membrane could affect the hydrogen response of the hybrid catalysts and the molecular weight distribution of resultant polyethylene.
3. The hybrid Ziegler-Natta catalysts were employed for ethylene slurry polymerization. The activities of the composite catalysts in slurry polymerization were significantly higher than the activities in the gas phase polymerization. In the slurry polymerization, the kinetic profiles of SLC-S catalyst, HC-5 catalyst and HC-20 catalyst were relatively stable then with a small decay. With the increase of the thickness of hybrid catalysts, Mn and Mw of the obtained polyethylene gradually increased, but their MWD became narrow. Meanwhile, the bulk density of the polyethylene obtained from slurry polymerization was slightly lower than that from gas phase polymerization.
4. In order to improve the performance of the catalyst, MgCl2 was replaced by BuMgCl to obtain a series of catalysts. With the increase of the amount of TiCl4, catalyst activity gradually increased with a linearly trend. At the same time, the kinetic profiles were in the gradual transition from the rapid decay type to the slowly decaying type, MWD decreased and the bulk density increased.
论文主要进行了以下几个方面的研究：(1)基于相转化法成膜机理制备硅胶/聚(苯乙烯-co-丙烯酸)(PSA)核壳型微球,并确定制备复合微球的基本实验条件；(2)依据确定的相转化法成膜的条件制备Ziegler-Natta复合催化剂,并分别用乙烯气相聚合和淤浆聚合考察氢气含量及有机膜的厚度对催化剂的聚合活性及其聚乙烯性能的影响；(3)对复合催化剂中壳层部分的催化剂进行了改进,并考察了催化剂的性能。具体的工作成果如下：
1.提出采用相转化法制备具有良好分散性的无机/有机复合载体颗粒,并考察了非溶剂的蒸发速度、聚合物的浓度、硅胶粒径及聚(苯乙烯-co-丙烯酸)的类型等因素对复合载体的表面形貌及粒径的影响。非溶剂的蒸发速度越慢,复合载体的分散性越好,但为兼顾生产效率与覆膜效果,蒸发速度采用1 ml/min;聚合物浓度越大,复合载体表面越粗糙；硅胶的粒径越大,复合载体表面越蓬松；而聚(苯乙烯-co-丙烯酸)的分子量以及官能团的含量基本不影响复合载体的形貌以及粒径分布。另外,复合载体表面包覆的PSA膜较致密,与单独的硅胶载体相比,其比表面积、孔体积及孔径明显减小
2.利用相转化法制备了同时包含无机载体和有机载体的复合Ziegler-Natta催化剂,研究了该催化剂乙烯气相聚合反应的聚合活性和聚合产物的性能。复合催化剂具有较高的活性,活性高达3000克聚乙烯／克催化剂(9.0 bar聚合压力),且复合催化剂的动力学可调。膜厚为3微米的复合催化剂聚合活性高于核层的SLC-S催化剂,且具有带诱导期的平稳型动力学曲线,而膜厚为1.5微米的复合催化剂的活性接近于SLC-S催化剂,且其具有相似的衰减型动力学曲线。同时,不同的膜厚还能够调节复合催化剂的氢调性能及所得聚乙烯的分子量分布,得到宽峰分子量分布的聚乙烯。
3.对Ziegler-Natta复合催化剂进行了乙烯淤浆聚合的研究,考察了不同覆膜厚度的催化剂对乙烯淤浆聚合活性和聚合产物性能的影响。研究发现,复合催化剂淤浆聚合的活性明显高于气相聚合。SLC-S催化剂和HC-5催化剂的动力学曲线由气相聚合中的快速衰减型转变为淤浆聚合中的平稳型的曲线类型,而HC-20催化剂的动力学曲线则有平稳型变为淤浆聚合中的缓慢衰减型。淤浆聚合中随着膜厚的增加Mn和Mw逐渐依次增大,与其气相聚合的规律相同,但MWD则逐渐变窄。同时,催化剂淤浆聚合所得聚乙烯的堆密度略低于气相聚合。
4.为了改善催化剂的性能,采用BuMgCl代替MgCl2进行反应制得了一系列的复合载体催化剂,主要研究了TiCl4加入量对壳层催化剂的聚合活性及聚乙烯分子量分布的影响。随着TiCl4加入量的增加,催化剂的活性逐渐升高,且几乎呈线性的增加趋势。同时,其聚合动力学曲线的类型由快速衰减型逐渐过渡为缓慢衰减型,MWD逐渐减小,聚合反应所得聚乙烯的堆密度则逐渐增加。
Most of the support materials successfully used in Ziegler-Natta catalysts have been inorganic compounds, such as silica gel, magnesium chloride and zeolite. Compared with the inorganic carriers, organic carriers can greatly reduce inorganic residues to improve the performance of polyolefin products. Therefore, inorganic/organic carrier of the composite catalyst has become an important direction of new polyolefin catalysts. The current preparation method of inorganic/organic composite are complicated and introduces a number of other polar substances, not being suitable for the catalyst of olefin polymerization. A phase inversion method was introduced for hybrid Ziegler-Natta Catalyst preparation.
This thesis focused on the following three aspects:(1) the preparation of silica/poly (styrene-co-acrylic acid) (PSA) core-shell microspheres; (2) the study of hybrid Ziegler-Natta catalysts for gas phase and slurry phase ethylene polymerization; (3) the improvement of hybrid Ziegler-Natta catalysts for slurry ethylene polymerization. Specific works are as follows:
1. Inorganic/organic composite carrier particles were prepared based on phase inversion method. The influences of several factors on the composite surface morphology and particle size were studied, such as evaporation rate of the non-solvent, polymer concentration, the size of silica gel particle and different poly (styrene-co-acrylic acid). The slower of the non-solvent evaporation rate was, the better the dispersion of composite carrier became, and 1 ml/min was chosen as the suitable non-solvent evaporation rate. The influences of other factors on the particle size distribution of composite carriers were quite small. In addition, the specific surface area, pore volume and pore size of the composite supports were significantly reduced compared to silica gel.
2. Hybrid Ziegler-Natta catalysts were prepared based on phase inversion method. Ethylene polymerizations were conducted in a gas phase reactor. Composite catalyst has high activity (3000 g polyethylene/g catalyst) (9.0 bar pressure). HC-20 catalyst had a good ethylene polymerization activity and its kinetic curve was stable with an inductive period, while HC-5 catalyst demonstrated a fast decay during polymerization and its activity and kinetic curve both resembled SLC-S catalyst. What's more, the thickness of membrane could affect the hydrogen response of the hybrid catalysts and the molecular weight distribution of resultant polyethylene.
3. The hybrid Ziegler-Natta catalysts were employed for ethylene slurry polymerization. The activities of the composite catalysts in slurry polymerization were significantly higher than the activities in the gas phase polymerization. In the slurry polymerization, the kinetic profiles of SLC-S catalyst, HC-5 catalyst and HC-20 catalyst were relatively stable then with a small decay. With the increase of the thickness of hybrid catalysts, Mn and Mw of the obtained polyethylene gradually increased, but their MWD became narrow. Meanwhile, the bulk density of the polyethylene obtained from slurry polymerization was slightly lower than that from gas phase polymerization.
4. In order to improve the performance of the catalyst, MgCl2 was replaced by BuMgCl to obtain a series of catalysts. With the increase of the amount of TiCl4, catalyst activity gradually increased with a linearly trend. At the same time, the kinetic profiles were in the gradual transition from the rapid decay type to the slowly decaying type, MWD decreased and the bulk density increased.
引文
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