乙烯选择性三聚与串联共聚催化体系制备LLDPE
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摘要
本文以HN(C_2H_4SR)_2·CrCl_3／MAO为催化体系，实验考察了反应条件对乙烯三聚的选择性、活性及其动力学特性的影响，建立了相应的模型，并进一步实验考察了催化剂负载化对其活性和选择性的影响规律；又以HN(C_2H_4SC_(12)H_(25))_2·CrCl_3／Et(Ind)_2ZrCl_2／MAO为串联催化体系催化乙烯三聚及共聚制备线性低密度聚乙烯(LLDPE)——乙烯／1-己烯共聚物，实验并建模考察了反应条件对乙烯三聚选择性、乙烯／1-己烯共聚活性、齐聚与共聚动力学特性以及产物性能等的影响；考察了催化体系的负载化对串联反应过程及其产物性能的影响。
HN(C_2H_4SR)_2·CRCl_3催化乙烯齐聚实验发现该催化剂在低压和较低的MAO用量下有非常高的三聚选择性(>99％)。当R基为-C_2H_5时，1atm下65℃时活性最高可达550kg hexene／(mol Crh)，提高反应压力有助于得到更高的活性，但是会降低催化剂的选择性；当R基为-C_(12)H_(25)时，1atm下75℃时活性最高可达450kg hexene／(mol Crh)。实验发现，该类催化剂的最佳反应温度区间在55-75℃之间。将HN(C_2H_4SR)_2·CrCl_3催化剂负载于SiO_2上，发现负载化对催化剂的三聚选择性没有影响，但是催化剂的活性有所下降，动力学曲线则更趋平缓。当R基为-C_2H_5时，负载型催化剂活性相对于均相催化剂下降了1 00 kg hexene／(mol Cr．h)左右；而当R基为-C_(12)H_(25)时，活性下降到其均相时的1／4。负载化对两种催化剂活性的影响程度不同，是由于R基为-C_(12)H_(25)时催化剂本身的位阻基团比较大，催化剂负载化加剧了位阻对乙烯配位、络合及插入的影响。
三聚催化剂HN(C_2H_4SC_(12)H_(25))_2·CrCl_3(1)与茂金属催化剂Et(Ind)_2ZrCl_2(2)配合组成串联催化剂体系，以乙烯为唯一原料，在同一个反应器中催化剂1催化乙烯选择性三聚生成1-己烯，而催化剂2催化乙烯与原位生成的1-己烯共聚生成乙烯／1-己烯共聚物。共聚物的性能可通过催化剂配比、反应温度等条件控制。~(13)C-NMR表征发现，聚合物只含有C4支链，表明三聚催化剂的选择性在串联共聚时保持不变。当反应温度较低或者Cr／Zr较高时，串联催化体系得到的共聚物的DSC曲线分布较宽，甚至出现双峰分布。1-己烯的浓度累积与漂移是造成这一现象的主要原因，采用预齐聚的方法抑制这种漂移，得到结构更均一的共聚物。
针对HN(C_2H_4SR)_2·CrCl_3催化剂，应用金属成环中间体三聚机理，建立了相应的动力学模型，导出了常压下该类催化剂催化乙烯三聚的反应速率方程：R_p=k_1.ka.C_E~2/k_a-k_d(e~(-k_dt)-e~(-k_at))．M_w，获得了对应的动力学参数。针对HN(C_2H_4SC_(12)H_(25))_2·CrCl_3／Et(Ind)_2ZrCl_2／MAO串联催化体系，基于简化的金属成环中间体三聚机理和乙烯／1-己烯共聚机理，建立了一个半连续乙烯串联反应制备LLDPE的数学模型。该模型可以很好的预测反应速率、共聚单体浓度、共聚物组成、产物分子量及分子量分布等。串联催化反应实验和仿真研究发现，反应过程中三聚反应和共聚反应存在着速度差；正是这一速度差导致了反应过程中1-己烯的浓度从零起不断累积增大；采用预齐聚的方法可使1-己烯先在短期内累积到比较高的浓度，进而使其消耗的速率与生成的速率达到平衡，得到组成结构更均一的共聚物。
使用均相或负载化HN(C_2H_4SC_(12)H_(25))_2·CrCl_3与均相或负载化Et(Ind)_2ZrCl_2组合成的不同的串联催化体系进行乙烯的化学反应，研究发现，共聚催化剂Et(Ind)_2ZrCl_2负载化对其活性和1-己烯的插入都有影响。固定Cr／Zr比条件下，串联催化体系的活性取决于共聚催化剂负载与否，与三聚催化剂的负载与否则没有关系；采用均相共聚催化剂，其聚合产物的分子量较小，分子量分布窄，DSC曲线呈单峰分布；采用负载型共聚催化剂，由于其具有多活性中心，产物分子量高，分子量分布宽，DSC曲线比较复杂。使用双负载型串联催化剂活性比较高，产物中只有C4支链，熔点介于95℃到120℃之间，是典型的LLDPE。在相同的反应条件下，双负载催化体系得到的聚合物分子量最大。负载三聚催化剂降低了体系中1-己烯的浓度，而负载型共聚催化剂降低了链转移速率和β-氢消除速率，这两种作用共同影响了产物的分子量。
In this study, the ethylene trimerization catalyst system, HN(C_2H_4SR)_2·CrCl_3/MAO, was studied under various reaction conditions on the selectivity, activity, and dynamic evolution. The effect of SiO_2 support on the catalyst selectivity and activity was also studied. A simplified metallacyclic intermediates model was applied to describe trimerization mechanism. A tandem catalysis system composed of HN(C_2H_4S C_(12)H_(25))_2·CrCl_3and Et(Ind)_2ZrCl_2 was used to synthesize ethylene-1-hexene copolymers. A mathematical model was developed to describe ethylene/1-hexene copolymerization with this tandem catalysis system based on a simplified trimerization model and an ethylene/a-olefin copolymerization model. The effect of reaction conditions, on trimerization catalyst selectivity, copolymerization catalyst activity, polymerization kinetics, and polymer properties were investigated both by experiment and simulation. HN(C_2H_4S C_(12)H_(25))_2·CrCl_3 and Et(Ind)_2ZrCl_2 were supported on SiO_2 and the effects of different supporting strategies on trimerization selectivity, 1-hexene incorporation efficiency and copolymerization activity were studied and compared to the homogeneous system.
The selectivity of HN(C_2H_4SR)_2·CrCl_3 were high (>99%) with small amount of MAO at atmosphere pressure. The highest activity is 550 kg hexene/(mol Cr h) for HN(C_2H_4SC_2H_5)_2·CrCl3 at 65℃, while 450 kg hexene/(mol Cr h) for HN(C_2H_4SC_(12)H_(25))_2·CrCl_3 at 75℃. Supporting HN(C_2H_4SR)_2·CrCl_3 on SiO_2 did not change the trimerization selectivity, but a decrease of activity and improved catalyst stability were found. The activity for supported HN(C_2H_4SC_2H_5)_2·CrCl_3 dropped about 100 kg hexene/ (mol Cr. h) at each condition compared to its homogeneous counterpart, while the activity for supported HN(C_2H_4SC_(12)H_(25))_2·CrCl_3 only remained 1/4. The different effect of support on trimerization catalyst activity was due to the hindrance of the ligand imposed to the active site, which might block off ethylene coupling, coordination, and insertion.
Ethylene-1-hexene copolymers were synthesized with a tandem catalysis system that consisted of HN(C_2H_4SC_(12)H_(25))_2·CrCl_3/MAO (1/MAO) and Et(Ind)_2ZrCl_2/MAO (2/MAO) at atmosphere pressure. Catalyst 1 trimerized ethylene with high activity and excellent selectivity, while catalyst 2 incorporated the 1-hexene content and produced ethylene-1-hexene copolymer from an ethylene-only stock in the same reactor. Adjusting the Cr/Zr ratio and reaction temperature yielded various branching densities and thus melting temperatures. Only C4 side chain was found in the copolymer. However, broad DSC curves were observed when low temperatures and/or high Cr/Zr ratios were employed due to an accumulation of 1-hexene component and composition drifting during the copolymerization. It was found that applying a short time period of pre-trimerization resulted in more homogeneous materials that gave unimodal DSC curves.
A simplified metallacyclic intermediate model was applied to describe trimerization mechanism of HN(C_2H_4SR)_2·CrCl_3, taking a first order catalyst activation, a first order deactivation, and a second order ethylene chelating intoaccount. The reaction rate can be described as R_p=k_1.k_a.C_E~2/k_a-k_d(e~(-k_dt)-e~(-k_at)).M_w.Based on this expression and an ethylene/a-olefin copolymerization kinetic model, a mathematical model was developed to describe ethylene/1-hexene copolymerization with HN(C_2H_4SC_(12)H_(25))_2·CrCl_3/Et(Ind)_2ZrCl_2/MAO system. The model could predict the reaction rate, 1-hexene concentration in the liquid phase, copolymer composition, and molecular weight. A series of semi-batch polymerization runs were carried out to verify the model. Both experimentation and modeling showed that adjusting the Cr/Zr ratio yielded various branching densities and thus melting temperatures, as well as molecular weights and polydispersities. Broad composition distributions and thus broad DSC curves were observed at high Cr/Zr ratios. Modeling results elucidated that this is due to an accumulation of 1-hexene component and to composition drifting during the copolymerization. It was also found that applying a short time period of pre-trimerization improved homogeneity in chain microstructure and minimized broadening in DSC curves.
Catalysts 1 and 2 were supported on silica particles and the effects of different supporting strategies on trimerization selectivity, 1-hexene incorporation efficiency and copolymerization activity were studied and compared to the homogeneous system. Supporting 2 resulted in a reduction in both catalytic activity and incorporation ability of 1-hexene because of a hindrance effect. At fixed Cr/Zr ratio, the activity of tandem system depended on if 2 was supported, but was not affected by 1 supporting. Homogeneous 2 yielded lower molecular weight copolymers with lower polydispersity index and having narrow DSC curves. Supported 2 gave higher molecular weight, higher polydispersity, and broader DSC curves because of its multiple-site nature. The tandem action of supported 1 and supported 2 gave high activities at a 10~7 g/(mol Zr h) level. The resulting copolymers contained only C4 side chains with melting temperature ranged from 95℃to 120℃, similar to commercial LLDPE. The samples had the highest molecular weight among the four catalysis systems under similar reaction conditions. This could be attributed to the lower 1-hexene concentration generated by supported 1 and the lower rate constants of chain transfer andβ-hydrogen elimination of supported 2.
HN(C_2H_4SR)_2·CRCl_3催化乙烯齐聚实验发现该催化剂在低压和较低的MAO用量下有非常高的三聚选择性(>99％)。当R基为-C_2H_5时，1atm下65℃时活性最高可达550kg hexene／(mol Crh)，提高反应压力有助于得到更高的活性，但是会降低催化剂的选择性；当R基为-C_(12)H_(25)时，1atm下75℃时活性最高可达450kg hexene／(mol Crh)。实验发现，该类催化剂的最佳反应温度区间在55-75℃之间。将HN(C_2H_4SR)_2·CrCl_3催化剂负载于SiO_2上，发现负载化对催化剂的三聚选择性没有影响，但是催化剂的活性有所下降，动力学曲线则更趋平缓。当R基为-C_2H_5时，负载型催化剂活性相对于均相催化剂下降了1 00 kg hexene／(mol Cr．h)左右；而当R基为-C_(12)H_(25)时，活性下降到其均相时的1／4。负载化对两种催化剂活性的影响程度不同，是由于R基为-C_(12)H_(25)时催化剂本身的位阻基团比较大，催化剂负载化加剧了位阻对乙烯配位、络合及插入的影响。
三聚催化剂HN(C_2H_4SC_(12)H_(25))_2·CrCl_3(1)与茂金属催化剂Et(Ind)_2ZrCl_2(2)配合组成串联催化剂体系，以乙烯为唯一原料，在同一个反应器中催化剂1催化乙烯选择性三聚生成1-己烯，而催化剂2催化乙烯与原位生成的1-己烯共聚生成乙烯／1-己烯共聚物。共聚物的性能可通过催化剂配比、反应温度等条件控制。~(13)C-NMR表征发现，聚合物只含有C4支链，表明三聚催化剂的选择性在串联共聚时保持不变。当反应温度较低或者Cr／Zr较高时，串联催化体系得到的共聚物的DSC曲线分布较宽，甚至出现双峰分布。1-己烯的浓度累积与漂移是造成这一现象的主要原因，采用预齐聚的方法抑制这种漂移，得到结构更均一的共聚物。
针对HN(C_2H_4SR)_2·CrCl_3催化剂，应用金属成环中间体三聚机理，建立了相应的动力学模型，导出了常压下该类催化剂催化乙烯三聚的反应速率方程：R_p=k_1.ka.C_E~2/k_a-k_d(e~(-k_dt)-e~(-k_at))．M_w，获得了对应的动力学参数。针对HN(C_2H_4SC_(12)H_(25))_2·CrCl_3／Et(Ind)_2ZrCl_2／MAO串联催化体系，基于简化的金属成环中间体三聚机理和乙烯／1-己烯共聚机理，建立了一个半连续乙烯串联反应制备LLDPE的数学模型。该模型可以很好的预测反应速率、共聚单体浓度、共聚物组成、产物分子量及分子量分布等。串联催化反应实验和仿真研究发现，反应过程中三聚反应和共聚反应存在着速度差；正是这一速度差导致了反应过程中1-己烯的浓度从零起不断累积增大；采用预齐聚的方法可使1-己烯先在短期内累积到比较高的浓度，进而使其消耗的速率与生成的速率达到平衡，得到组成结构更均一的共聚物。
使用均相或负载化HN(C_2H_4SC_(12)H_(25))_2·CrCl_3与均相或负载化Et(Ind)_2ZrCl_2组合成的不同的串联催化体系进行乙烯的化学反应，研究发现，共聚催化剂Et(Ind)_2ZrCl_2负载化对其活性和1-己烯的插入都有影响。固定Cr／Zr比条件下，串联催化体系的活性取决于共聚催化剂负载与否，与三聚催化剂的负载与否则没有关系；采用均相共聚催化剂，其聚合产物的分子量较小，分子量分布窄，DSC曲线呈单峰分布；采用负载型共聚催化剂，由于其具有多活性中心，产物分子量高，分子量分布宽，DSC曲线比较复杂。使用双负载型串联催化剂活性比较高，产物中只有C4支链，熔点介于95℃到120℃之间，是典型的LLDPE。在相同的反应条件下，双负载催化体系得到的聚合物分子量最大。负载三聚催化剂降低了体系中1-己烯的浓度，而负载型共聚催化剂降低了链转移速率和β-氢消除速率，这两种作用共同影响了产物的分子量。
In this study, the ethylene trimerization catalyst system, HN(C_2H_4SR)_2·CrCl_3/MAO, was studied under various reaction conditions on the selectivity, activity, and dynamic evolution. The effect of SiO_2 support on the catalyst selectivity and activity was also studied. A simplified metallacyclic intermediates model was applied to describe trimerization mechanism. A tandem catalysis system composed of HN(C_2H_4S C_(12)H_(25))_2·CrCl_3and Et(Ind)_2ZrCl_2 was used to synthesize ethylene-1-hexene copolymers. A mathematical model was developed to describe ethylene/1-hexene copolymerization with this tandem catalysis system based on a simplified trimerization model and an ethylene/a-olefin copolymerization model. The effect of reaction conditions, on trimerization catalyst selectivity, copolymerization catalyst activity, polymerization kinetics, and polymer properties were investigated both by experiment and simulation. HN(C_2H_4S C_(12)H_(25))_2·CrCl_3 and Et(Ind)_2ZrCl_2 were supported on SiO_2 and the effects of different supporting strategies on trimerization selectivity, 1-hexene incorporation efficiency and copolymerization activity were studied and compared to the homogeneous system.
The selectivity of HN(C_2H_4SR)_2·CrCl_3 were high (>99%) with small amount of MAO at atmosphere pressure. The highest activity is 550 kg hexene/(mol Cr h) for HN(C_2H_4SC_2H_5)_2·CrCl3 at 65℃, while 450 kg hexene/(mol Cr h) for HN(C_2H_4SC_(12)H_(25))_2·CrCl_3 at 75℃. Supporting HN(C_2H_4SR)_2·CrCl_3 on SiO_2 did not change the trimerization selectivity, but a decrease of activity and improved catalyst stability were found. The activity for supported HN(C_2H_4SC_2H_5)_2·CrCl_3 dropped about 100 kg hexene/ (mol Cr. h) at each condition compared to its homogeneous counterpart, while the activity for supported HN(C_2H_4SC_(12)H_(25))_2·CrCl_3 only remained 1/4. The different effect of support on trimerization catalyst activity was due to the hindrance of the ligand imposed to the active site, which might block off ethylene coupling, coordination, and insertion.
Ethylene-1-hexene copolymers were synthesized with a tandem catalysis system that consisted of HN(C_2H_4SC_(12)H_(25))_2·CrCl_3/MAO (1/MAO) and Et(Ind)_2ZrCl_2/MAO (2/MAO) at atmosphere pressure. Catalyst 1 trimerized ethylene with high activity and excellent selectivity, while catalyst 2 incorporated the 1-hexene content and produced ethylene-1-hexene copolymer from an ethylene-only stock in the same reactor. Adjusting the Cr/Zr ratio and reaction temperature yielded various branching densities and thus melting temperatures. Only C4 side chain was found in the copolymer. However, broad DSC curves were observed when low temperatures and/or high Cr/Zr ratios were employed due to an accumulation of 1-hexene component and composition drifting during the copolymerization. It was found that applying a short time period of pre-trimerization resulted in more homogeneous materials that gave unimodal DSC curves.
A simplified metallacyclic intermediate model was applied to describe trimerization mechanism of HN(C_2H_4SR)_2·CrCl_3, taking a first order catalyst activation, a first order deactivation, and a second order ethylene chelating intoaccount. The reaction rate can be described as R_p=k_1.k_a.C_E~2/k_a-k_d(e~(-k_dt)-e~(-k_at)).M_w.Based on this expression and an ethylene/a-olefin copolymerization kinetic model, a mathematical model was developed to describe ethylene/1-hexene copolymerization with HN(C_2H_4SC_(12)H_(25))_2·CrCl_3/Et(Ind)_2ZrCl_2/MAO system. The model could predict the reaction rate, 1-hexene concentration in the liquid phase, copolymer composition, and molecular weight. A series of semi-batch polymerization runs were carried out to verify the model. Both experimentation and modeling showed that adjusting the Cr/Zr ratio yielded various branching densities and thus melting temperatures, as well as molecular weights and polydispersities. Broad composition distributions and thus broad DSC curves were observed at high Cr/Zr ratios. Modeling results elucidated that this is due to an accumulation of 1-hexene component and to composition drifting during the copolymerization. It was also found that applying a short time period of pre-trimerization improved homogeneity in chain microstructure and minimized broadening in DSC curves.
Catalysts 1 and 2 were supported on silica particles and the effects of different supporting strategies on trimerization selectivity, 1-hexene incorporation efficiency and copolymerization activity were studied and compared to the homogeneous system. Supporting 2 resulted in a reduction in both catalytic activity and incorporation ability of 1-hexene because of a hindrance effect. At fixed Cr/Zr ratio, the activity of tandem system depended on if 2 was supported, but was not affected by 1 supporting. Homogeneous 2 yielded lower molecular weight copolymers with lower polydispersity index and having narrow DSC curves. Supported 2 gave higher molecular weight, higher polydispersity, and broader DSC curves because of its multiple-site nature. The tandem action of supported 1 and supported 2 gave high activities at a 10~7 g/(mol Zr h) level. The resulting copolymers contained only C4 side chains with melting temperature ranged from 95℃to 120℃, similar to commercial LLDPE. The samples had the highest molecular weight among the four catalysis systems under similar reaction conditions. This could be attributed to the lower 1-hexene concentration generated by supported 1 and the lower rate constants of chain transfer andβ-hydrogen elimination of supported 2.
引文
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