WO2014100924A1

WO2014100924A1 - Polypropylene intra-autoclave alloy having carbon nanotubes, preparation method for the alloy, and applications thereof

Info

Publication number: WO2014100924A1
Application number: PCT/CN2012/001773
Authority: WO
Inventors: 董金勇; 王宁; 秦亚伟
Original assignee: 中国科学院化学研究所
Priority date: 2012-12-31
Filing date: 2012-12-31
Publication date: 2014-07-03

Abstract

Disclosed are a polypropylene intra-autoclave alloy having carbon nanotubes, a preparation method for the alloy, and applications thereof. The intra-autoclave alloy comprises the carbon nanotubes, a homopolymer polypropylene resin, and an ethylene-α olefin random copolymer. The preparation method is completed by utilizing a catalyst-polymer particle form-copying effect for in situ catalysis of a copolymerization reaction of propylene monomers and comonomers on a nanotube-loaded transitional metal catalyst that is spherical in terms of particle superficial form. Interface enhancement is implemented for the carbon nanotubes and a polymer substrate by introducing to the surfaces of the carbon nanotubes a double bond that can participate in a polymerization reaction. The carbon nanotube/polypropylene intra-autoclave alloy prepared with the method is spherical in terms of particle form; this not only implements the goals that the polymer is non-stick to an autoclave, flows easily, and is easy to transport, but, given that the carbon nanotubes in a single form are evenly distributed in a resin substrate, that a rubber phase is evenly distributed and is less than 0.2 microns in size, and that the carbon nanotubes and the substrate are provided with a strong interfacial interaction, also implements the preparation of the high performance polypropylene intra-autoclave alloy. The carbon nanotube/polypropylene intra-autoclave alloy resin provided in the present invention has broad application prospects in the fields of automotive spare parts, packaging materials, barrier materials, flame retardant materials, and electrically-conductive materials.

Description

含有碳纳米管的聚丙烯釜内合金及其制备方法与应用技术领域 Polypropylene autoclave alloy containing carbon nanotubes and preparation method and application thereof

本发明涉及一种含有碳纳米管的聚丙烯釜内合金及其制备方法与应用。 The invention relates to a polypropylene inner cylinder alloy containing carbon nanotubes and a preparation method and application thereof.

背景技术 Background technique

聚丙烯是一种通用树脂，具有良好的绝缘、加工以及耐化学品腐蚀等性能。但单一规整的高分子链结构在赋予聚丙烯高强度的同时，却使其韧性大大下降，从而限制了其在常温和低温环境的应用。目前，科研领域和工业领域普遍通过引入橡胶或弹性体来增韧聚丙烯。具有高附加值的共聚聚丙烯比均聚聚丙烯的性能更优良，应用领域更广阔。通过对聚丙烯共聚改性，增强抗冲击性能，不仅可以得到高附加值的聚丙烯合金产品，而且可以全面提升聚丙烯树脂的性能，广泛替代其它塑料品种。 Polypropylene is a general-purpose resin with good insulation, processing and chemical resistance. However, the single regular polymer chain structure gives the polypropylene high strength while reducing its toughness, which limits its application in normal temperature and low temperature environments. At present, the introduction of rubber or elastomers in the research and industrial fields is generally used to toughen polypropylene. Copolymerized polypropylene with high added value has better performance than homopolypropylene and has a wider application field. By copolymerizing polypropylene to enhance impact resistance, not only high value-added polypropylene alloy products can be obtained, but also the performance of polypropylene resin can be comprehensively improved, and other plastic varieties can be widely replaced.

近年来，随着聚丙烯及其共聚物的消费量日益增加，对其性能的要求也不断提高。众多的聚合物高性能化研究结果表明，以无机纳米粒子与聚合物进行复合，制备纳米复合材料，是具有高度经济性和有效性的最佳途径之一（M. Alexandre and P. Dubois, Materials Science and Engineering, R: Reports 2000, 28, (1-2), 1-63 ) 。聚合物纳米复合材料通过分散相和连续相之间的偶合作用将无机纳米材料的高强度、高刚度、高硬度、高热稳定性与聚合物的高韧性、可加工性等糅合在一起，利用纳米材料具有的独特的体积效应、表面效应、量子尺寸效应、宏观量子隧道效应，在很少填充量的情况下，即可赋予聚合物优异的力学、电学、磁学、热学等性质（Qin, Y. W. ; Dong, J. Y., Chinese Science Bulletin 2009, 54, (1), 38-45 )。在众多的纳米材料中，碳纳米管是一维纳米材料，具有低密度、高长径比和高比表面积等特点，其杨氏模量高达 1.2TPa，拉伸断裂强度达到 50-200GPa，是聚合物理想的纳米填充材料。将碳纳米管均匀分散于聚丙烯基体中，实现与聚丙烯树脂的纳米复合，已经成为聚丙烯树脂高性能化的重要手段。而且，近年来碳纳米管已实现规模化生产，为大规模制备高性能聚丙烯 /碳纳米管纳米复合材料带来契机。 In recent years, as the consumption of polypropylene and its copolymers has increased, the performance requirements have been increasing. Numerous high-performance polymer research results show that the combination of inorganic nanoparticles and polymers to prepare nanocomposites is one of the most economical and effective methods (M. Alexandre and P. Dubois, Materials Science and Engineering, R: Reports 2000, 28, (1-2), 1-63). The polymer nanocomposite combines the high strength, high rigidity, high hardness, high thermal stability of the inorganic nano material with the high toughness and processability of the polymer by the coupling between the dispersed phase and the continuous phase, and utilizes the nanometer. The unique volume effect, surface effect, quantum size effect, and macroscopic quantum tunneling effect of the material can give the polymer excellent mechanical, electrical, magnetic, thermal and other properties (Qin, YW). Dong, JY, Chinese Science Bulletin 2009, 54, (1), 38-45). Among many nanomaterials, carbon nanotubes are one-dimensional nanomaterials with low density, high aspect ratio and high specific surface area. The Young's modulus is as high as 1.2TPa and the tensile strength at break is 50-200GPa. The ideal nanofiller for polymers. The uniform dispersion of carbon nanotubes in a polypropylene matrix to achieve nanocomposite with a polypropylene resin has become an important means for improving the performance of polypropylene resins. Moreover, in recent years, carbon nanotubes have been mass-produced, which brings opportunities for large-scale preparation of high-performance polypropylene/carbon nanotube nanocomposites.

在制备碳纳米管复合聚丙烯或共聚物树脂的众多方法中，原位聚合技术被认为是最行之有效的方法之一。该技术是通过碳纳米管负载过渡催化剂的催化活性中心催化丙烯单体聚合反应，避免了由聚丙烯和碳纳米管极性差异而导致的热力学的苛刻要求，进而成功制备纳米增强聚丙烯树脂。同时，原位聚合技术允许在复合过程中对聚丙烯基体进行分子设计，因此不但可以通过改变聚烯烃催化剂或共聚合反应灵活调节聚丙烯组成与结构，获得基体性质不同的纳米复合材料，扩大性能范围；针对无机纳米粒子与聚合物界面作用弱的缺点，原位聚合技术还可以通过在碳纳米管表面引入反应性双键，使碳纳米管与聚合物基体形成强烈界面相互作用，从而对界面进行设计，实现碳纳米管对釜内合金性能改善。截至目前，通过原位聚合技术制备纳米复合聚烯烃的研究较多（US661371 1B2、 CN101235169A US646554313 K US5830820 ) ，但通过引入碳纳米管实现釜内合金的高性能化的研究未见报道。另夕卜，在原位聚合技术的实施过程中，必须值得关注的问题是釜内合金的颗粒表观形态。制备具有良好颗粒形态的聚烯烃颗粒，不但有利于避免因聚合物颗粒表观形态较差而引起的粘釜及传输困难等问题的发生，而且有利于满足现有聚丙烯生产工艺，促进原位聚合技术制备碳纳米管 /聚丙烯釜内合金的工业化实施。 Among the many methods for preparing carbon nanotube composite polypropylene or copolymer resins, in-situ polymerization technology is considered to be one of the most effective methods. The technology catalyzes the polymerization of propylene monomer through the catalytic active center of the carbon nanotube-supported transition catalyst, avoids the thermodynamic requirements caused by the difference in polarity between the polypropylene and the carbon nanotube, and succeeds in preparing the nano-reinforced polypropylene resin. At the same time, the in-situ polymerization technology allows the molecular design of the polypropylene matrix in the compounding process. Therefore, the polypropylene composition and structure can be flexibly adjusted by changing the polyolefin catalyst or the copolymerization reaction, and the nanocomposites with different matrix properties can be obtained, and the performance can be expanded. Scope; In view of the shortcomings of weak interaction between inorganic nanoparticles and polymers, in-situ polymerization technology can also form a strong interfacial interaction between carbon nanotubes and polymer matrix by introducing reactive double bonds on the surface of carbon nanotubes. Designed to improve the performance of the carbon nanotubes in the autoclave. Up to now, there have been many studies on the preparation of nanocomposite polyolefins by in-situ polymerization technology (US661371 1B2, CN101235169A US646554313 K US5830820), but the research on the high performance of alloys in the autoclave by introducing carbon nanotubes has not been reported. Another In addition, in the implementation of in-situ polymerization technology, the problem that must be paid attention to is the apparent morphology of the alloy in the autoclave. The preparation of polyolefin particles with good particle morphology not only helps to avoid problems such as sticky kettle and transmission difficulties caused by poor appearance of polymer particles, but also helps to meet the existing polypropylene production process and promote in situ. Polymerization technology for the industrial implementation of carbon nanotube/polypropylene autoclave alloys.

发明公开 Invention disclosure

本发明的目的是提供含有碳纳米管的聚丙烯釜内合金及其制备方法与应用。本发明提供的含有碳纳米管的聚丙烯釜内合金，包括碳纳米管、均聚聚丙烯树脂和乙烯 -α烯烃无规共聚物。 The object of the present invention is to provide a polypropylene inner cylinder alloy containing carbon nanotubes and a preparation method and application thereof. The carbon nanotube-containing polypropylene in-cylinder alloy provided by the present invention comprises carbon nanotubes, a homopolypropylene resin and an ethylene-α-olefin random copolymer.

该含有碳纳米管的聚丙烯釜内合金可只由上述组分组成。 The carbon nanotube-containing polypropylene in-cylinder alloy may be composed only of the above components.

所述均聚聚丙烯树脂选自等规聚丙烯、间规聚丙烯和无规聚丙烯树脂中的至少一种；所述均聚聚丙烯树脂的重均分子量为 20000-1000000g/mol，具体为 The homopolypropylene resin is selected from at least one of isotactic polypropylene, syndiotactic polypropylene and random polypropylene resin; the homopolypropylene resin has a weight average molecular weight of 20000-1000000 g/mol, specifically

200000-800000 g/mol, 更具体为 725000g/mol、 260000g/moK 200000g/moK 200000-800000 g/mol, more specifically 725000g/mol, 260000g/moK 200000g/moK

150000g/mol、 300000g/moK 250000g/mol 220000g/moK 180000g/mol 21 OOOOg/mol 220000g/moK 215000g/moK 280000g/mol 255000g/mol或 240000g/mol; 150000g/mol, 300000g/moK 250000g/mol 220000g/moK 180000g/mol 21 OOOOg/mol 220000g/moK 215000g/moK 280000g/mol 255000g/mol or 2400000g/mol;

所述乙烯 -a烯烃无规共聚物中， a烯烃选自丙烯、 1-丁烯、 1-戊烯、 1-己烯、 In the ethylene-a olefin random copolymer, the a olefin is selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene,

1-辛烯、 1-壬烯和 1-癸烯中的至少一种； At least one of 1-octene, 1-decene, and 1-decene;

所述乙烯 -a烯烃无规共聚物具体为乙烯 /丙烯无规共聚物、乙烯 /丁烯无规共聚物或乙烯 /辛烯无规共聚物。所述 a-烯烃占所述乙烯 -a烯烃无规共聚物的质量百分含量为 0.5-80.0%, 具体为 5-50%； The ethylene-a olefin random copolymer is specifically an ethylene/propylene random copolymer, an ethylene/butene random copolymer or an ethylene/octene random copolymer. The a-olefin comprises the ethylene-a olefin random copolymer in a mass percentage of 0.5-80.0%, specifically 5-50%;

所述均聚聚丙烯树脂与所述乙烯 -a烯烃共聚物的质量比为 40.0 99.0: 1.0-60.0, 具体为 60-75: 25-40；更具体为 79.0: 20.0或 89.0: 10.0或 80.9: 18.1或 89.2: 9.6 或 83.9: 15.2或 78.7: 20.7或 88.9: 10.3或 95.5: 2.5或 94.4: 5.1或 83.0: 15.5或 94.6： 5.1或 94.6: 5.1或 92.9: 6.0或 84.0-88.1 : 10.8-15.4； The mass ratio of the homopolypropylene resin to the ethylene-a olefin copolymer is 40.0 99.0: 1.0-60.0, specifically 60-75: 25-40; more specifically 79.0: 20.0 or 89.0: 10.0 or 80.9: 18.1 or 89.2: 9.6 or 83.9: 15.2 or 78.7: 20.7 or 88.9: 10.3 or 95.5: 2.5 or 94.4: 5.1 or 83.0: 15.5 or 94.6: 5.1 or 94.6: 5.1 or 92.9: 6.0 or 84.0-88.1: 10.8-15.4;

所述碳纳米管占所述含有碳纳米管的聚丙烯釜内合金的质量百分含量为 0.01-25%, 具体为 0.02-5.0%，具体为 1.00%或 0.91%或 1.17%或 0.90%或 0.64%或 0.48%或 1.25%或 0.33%或 0.76%或 0.56-1.42%或 0.64-1.34%。 The carbon nanotubes comprise 0.01-25% by mass, specifically 0.02-5.0%, specifically 1.00% or 0.91% or 1.17% or 0.90% of the carbon nanotube-containing polypropylene in-cavity alloy. 0.64% or 0.48% or 1.25% or 0.33% or 0.76% or 0.56-1.42% or 0.64-1.34%.

所述碳纳米管的粒径为 10-20nm，具体为 20nm，长度为 0.5-50μιη，具体为 0.5μιη 或 5μιη或 0.5-5μιη，长径比为 50-1000，具体为 50或 250或 50-250。 The carbon nanotubes have a particle diameter of 10-20 nm, specifically 20 nm, a length of 0.5-50 μm, specifically 0.5 μm or 5 μm or 0.5-5 μm, and an aspect ratio of 50-1000, specifically 50 or 250 or 50- 250.

所述含有碳纳米管的聚丙烯釜内合金的颗粒表观形态为球形或类球形，粒径为 10~10000μιη, 具体为 10-500μιη_; 所述碳纳米管在所述聚丙烯釜内合金中以单一分散的形式存在。 The particle shape of the carbon nanotube-containing polypropylene in-cylinder alloy is spherical or spheroidal, and the particle diameter is 10 to 10000 μm, specifically 10 to 500 μm _; the carbon nanotube is in the alloy in the polypropylene kettle. It exists in a single dispersion.

上述含有碳纳米管的聚丙烯釜内合金也可为按照如下方法制备而得的产物。本发明提供的制备上述含有碳纳米管的聚丙烯釜内合金的方法，包括如下步骤: The above-mentioned polypropylene in-cylinder alloy containing carbon nanotubes may also be a product obtained by the following method. The method for preparing the above-mentioned carbon nanotube-containing polypropylene in-cavity alloy provided by the invention comprises the following steps:

1 ) 将丙烯单体、碳纳米管负载过渡金属催化剂、助催化剂在有机溶剂中进行淤浆聚合反应，得到中间产物； 1) slurry polymerization of a propylene monomer, a carbon nanotube-supported transition metal catalyst, and a cocatalyst in an organic solvent to obtain an intermediate product;

或者，将丙烯单体、碳纳米管负载过渡金属催化剂、助催化剂进行本体聚合反应，得到中间产物； Alternatively, the propylene monomer, the carbon nanotube-supported transition metal catalyst, and the cocatalyst are subjected to bulk polymerization to obtain an intermediate product;

2) 向所述步骤 1 ) 所得含有中间产物的反应体系中加入乙烯和 a-烯烃单体，于有机溶剂中进行淤浆聚合反应，反应完毕得到所述含有碳纳米管的聚丙烯釜内合金； 2) adding ethylene and a-olefin monomer to the reaction system containing the intermediate product obtained in the step 1), Slurry polymerization in an organic solvent, the reaction is completed to obtain the carbon nanotube-containing polypropylene in-cavity alloy;

或者，向所述步骤 1 )所得含有中间产物的反应体系中加入乙烯和 α-烯烃单体进行聚合反应，反应完毕得到所述含有碳纳米管的聚丙烯釜内合金。 Alternatively, ethylene and an α-olefin monomer are added to the reaction system containing the intermediate product obtained in the step 1) to carry out a polymerization reaction, and the reaction is completed to obtain the carbon nanotube-containing polypropylene in-cylinder alloy.

该方法中，所述助催化剂选自 C1-C4的烷基铝和 C1-C4的烷氧基铝化合物中的至少一种，具体选自三甲基铝、三乙基铝、三异丁基铝和甲基铝氧烷中的至少一种； In the method, the promoter is at least one selected from the group consisting of a C1-C4 alkyl aluminum and a C1-C4 alkoxy aluminum compound, specifically selected from the group consisting of trimethyl aluminum, triethyl aluminum, and triisobutyl. At least one of aluminum and methylaluminoxane;

所述 α烯烃选自丙烯、 1-丁烯、 1-戊烯、 1-己烯、 1-辛烯、 1-壬烯和 1-癸烯中的至少一种； The alpha olefin is selected from at least one of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene and 1-decene;

所述有机溶剂选自 C5 C10的烷烃和 C6-C8的芳香烃中的至少一种，具体选自庚烷、己烷和甲苯中的至少一种。 The organic solvent is at least one selected from the group consisting of a C5 C10 alkane and a C6-C8 aromatic hydrocarbon, and is specifically selected from at least one of heptane, hexane and toluene.

所述步骤 1 ) 中，助催化剂中的烷基铝与碳纳米管负载过渡金属催化剂中的过渡金属元素钛的摩尔比为 1 5000: 1，具体为 10-2000: 1，更具体为 600: 1或 150: 或 150-600: 1。助催化剂中的烷氧基铝化合物与碳纳米管负载过渡金属催化剂中的过渡金属元素锆的摩尔比为 1 5000: 1，具体为 2000: 1。 In the step 1), the molar ratio of the aluminum alkyl in the cocatalyst to the transition metal element titanium in the carbon nanotube-supported transition metal catalyst is 15000:1, specifically 10-2000: 1, more specifically 600: 1 or 150: or 150-600: 1. The molar ratio of the alkoxyaluminum compound in the cocatalyst to the transition metal element zirconium in the carbon nanotube-supported transition metal catalyst is 15,000:1, specifically 2000:1.

碳纳米管负载过渡金属催化剂的加入量为丙烯单体质量的 0.1-5.0%，具体为 0.1-0.4%, 更具体为 0.33%或 1.25%或 0.4%或 0.33%-1.25%或 0.4%-1.25%或 The carbon nanotube-supported transition metal catalyst is added in an amount of 0.1 to 5.0% by mass based on the mass of the propylene monomer, specifically 0.1 to 0.4%, more specifically 0.33% or 1.25% or 0.4% or 0.33% to 1.25% or 0.4% to 1.25. % or

0.33%-0.4%； 0.33%-0.4%;

所述淤浆聚合反应和本体聚合反应的温度均为 30°C〜90°C，优选 40°C~80°C，更具体为 70°C，时间均为 0.05〜10.0小时，优选 0.1 2.0小时，更具体为 0.2或 0.5 或 0.2-0.5小时；压强均为 0-4MPa，具体为 0.5-3.5MPa，所述压强不为 0，更具体为 0.5或 1.0或 0.5-1.0 MPa; The temperature of the slurry polymerization reaction and the bulk polymerization reaction are both 30 ° C to 90 ° C, preferably 40 ° C to 80 ° C, more specifically 70 ° C, and the time is 0.05 to 10.0 hours, preferably 0.1 2.0 hours. , more specifically 0.2 or 0.5 or 0.2-0.5 hours; pressure is 0-4MPa, specifically 0.5-3.5MPa, the pressure is not 0, more specifically 0.5 or 1.0 or 0.5-1.0 MPa;

所述步骤 2) 中，乙烯的加入量为乙烯和 α-烯烃单体总重的 1.0-100.0%，具体为 5.0-50.0%，具体为 25%或 20%或 20-25%或 50%或 20-50%或 25-50%; In the step 2), the ethylene is added in an amount of 1.0-100.0%, specifically 5.0-50.0%, specifically 25% or 20% or 20-25% or 50% or more, based on the total weight of the ethylene and the α-olefin monomer. 20-50% or 25-50%;

α-烯烃单体的加入量为所述步骤 1 )所得中间产物总重的 20-200%，具体为 75% 或 42%或 67%或 78%或 64%或 49%或 56%或 30%或 89%或 28%或 27%或 31%或 27-89%或 28-78%或 30-75%或 31-67%或 42-64%或 49-56%； The α-olefin monomer is added in an amount of 20-200%, specifically 75% or 42% or 67% or 78% or 64% or 49% or 56% or 30%, based on the total weight of the intermediate product obtained in the step 1). Or 89% or 28% or 27% or 31% or 27-89% or 28-78% or 30-75% or 31-67% or 42-64% or 49-56%;

所述淤浆聚合反应和聚合反应的温度均为 60°C〜120°C，优选 75 °C~95 °C，更具体为 70°C或 80°C或 90°C或 80-90°C或 70-90°C或 70-80 °C , 时间均为 0.1-10.0小时，优选 0.05~2.0小时，更具体为 0.5或 0.3或 0.2或 0.2-0.3或 0.2-0.5或 0.3-0.5 小时；压强均为 0-4MPa，具体为 0.5-3.5MPa，更具体为 l .OMPa, 所述压强不为 0。 The temperature of the slurry polymerization reaction and the polymerization reaction are both 60 ° C to 120 ° C, preferably 75 ° C to 95 ° C, more specifically 70 ° C or 80 ° C or 90 ° C or 80-90 ° C. Or 70-90 ° C or 70-80 ° C, the time is 0.1-10.0 hours, preferably 0.05-2.0 hours, more specifically 0.5 or 0.3 or 0.2 or 0.2-0.3 or 0.2-0.5 or 0.3-0.5 hours; Both are 0-4 MPa, specifically 0.5-3.5 MPa, more specifically 1.0 MPa, and the pressure is not zero.

所述方法还包括如下步骤： The method further includes the following steps:

在所述步骤 1 )淤浆聚合反应或本体聚合反应之前，向反应体系中加入结构通式为 R4._nSiCOR';)_n的给电子体； Before the step 1) slurry polymerization or bulk polymerization, an electron donor having a structural formula of R4. _n SiCOR'; _n is added to the reaction system;

所述 I _nSi(OR')_n中， n为 1-3的整数， R与 R'均选自 C1-C8的烷基、 C5-C10 的环烷基和 C6-C10的芳基中的至少一种，具体选自二苯基二甲基硅烷、二环己基二甲基硅烷和苯基三甲基硅烷中的至少一种；或， In the I _n Si(OR') _n , n is an integer of 1-3, and R and R' are each selected from a C1-C8 alkyl group, a C5-C10 cycloalkyl group, and a C6-C10 aryl group. At least one selected from the group consisting of at least one of diphenyldimethylsilane, dicyclohexyldimethylsilane, and phenyltrimethylsilane; or

所述给电子体与所述助催化剂中烷基铝的摩尔比为 0.01-1.0: 1，具体为 0.1-1.0: 1； The molar ratio of the electron donor to the aluminum alkyl in the cocatalyst is 0.01-1.0:1, specifically 0.1-1.0: 1;

所述方法还包括如下步骤：在所述步骤 1 )淤浆聚合反应或本体聚合反应之前，向反应体系中通入氢气；其中，氢气的加入量为丙烯单体质量的 0.001%-0.5%，具体为 0.005-0.08%，更具体为 0.067%或 0.08%或 0.067%-0.08%，且所述氢气的加入量不为 0; The method further comprises the steps of: introducing hydrogen into the reaction system before the step 1) slurry polymerization or bulk polymerization; wherein the hydrogen is added in an amount of 0.001% to 0.5% by mass of the propylene monomer, Specifically, it is 0.005-0.08%, more specifically 0.067% or 0.08% or 0.067%-0.08%, and the hydrogen is not added in an amount of 0;

所述方法还包括如下步骤：在所述步骤 2)淤浆聚合反应或聚合反应之前，向反应体系中通入氢气；其中，氢气的加入量为乙烯和 α-烯烃单体总重的 0-5.0%，具体为 0.01-0.07%,更具体为 0.0125%、 0.050%、 0.625%、 0.060%、 0.0125%-0.060% 0.0125%-0.625% 0.050%-0.625%或 0.060%-0.625%，且所述氢气的加入量不为 0。 The method further comprises the steps of: introducing hydrogen into the reaction system before the step 2) slurry polymerization or polymerization; wherein the hydrogen is added in an amount of 0 - the total weight of the ethylene and the α-olefin monomer 5.0%, specifically 0.01-0.07%, more specifically 0.0125%, 0.050%, 0.625%, 0.060%, 0.0125%-0.060% 0.0125%-0.625% 0.050%-0.625% or 0.060%-0.625%, and The amount of hydrogen added is not zero.

此外，该方法中，所用碳纳米管负载过渡金属催化剂即为申请号为 In addition, in the method, the carbon nanotube-supported transition metal catalyst used is the application number

201110095036.9的中国专利申请中的以碳纳米管为载体的聚烯烃催化剂，该催化剂是由碳纳米管催化剂载体、过渡金属化合物、金属化合物和内给电子体组成； A carbon nanotube-supported polyolefin catalyst in a Chinese patent application of 201110095036.9, which is composed of a carbon nanotube catalyst carrier, a transition metal compound, a metal compound and an internal electron donor;

其中，所述碳纳米管催化剂载体下述步骤 1 )所得成形的碳纳米管载体或步骤 2) 所得双键功能化的碳纳米管，具体制备方法包括如下步骤： Wherein, the carbon nanotube catalyst carrier comprises the formed carbon nanotube carrier obtained in the following step 1) or the double bond functionalized carbon nanotube obtained in the step 2), and the specific preparation method comprises the following steps:

1 ) 将碳纳米管于介质中分散后进行喷雾干燥，压力为 0.05~0.20MPa，进风温度 100~180°C，进料速度为 10~30.0ml/min，得到成形的碳纳米管载体； 1) dispersing the carbon nanotubes in a medium and then performing spray drying, the pressure is 0.05~0.20 MPa, the inlet air temperature is 100-180 ° C, and the feed rate is 10~30.0 ml/min, to obtain a formed carbon nanotube carrier;

所述步骤 1 ) 中，所述介质选自水、丙酮、乙醇、异丙醇和正丁醇中的至少一种；碳纳米管与介质的质量比为 0.01 0.1 : 1 ; 所述成形的碳纳米管载体的粒径为 5~100μιη，比表面积为 100~200m²/g，平均孔径为 15~25nm，平均孔容为 0.35~0.72cm³/g, 堆密度为 0.1~0.3g/ml。 In the step 1), the medium is at least one selected from the group consisting of water, acetone, ethanol, isopropanol and n-butanol; the mass ratio of the carbon nanotube to the medium is 0.01 0.1:1; the shaped carbon nano The tube carrier has a particle diameter of 5 to 100 μm, a specific surface area of 100 to 200 m ² /g, an average pore diameter of 15 to 25 nm, an average pore volume of 0.35 to 0.72 cm ³ /g, and a bulk density of 0.1 to 0.3 g/ml.

2 ) 将步骤 1 ) 所得成形的碳纳米管载体分散于介质中后，加入固体光气于 30~50°C进行活化反应 4~24小时后，将所述介质用真空泵抽干，加入 C_nH_2n_₂0₂所示烯酸或 C_nH_2nO所示烯醇于 30~50°C反应 4~24小时，之后将介质用真空泵抽干，使用甲醇洗涤若干次，得到所述双键功能化的碳纳米管； 2) After dispersing the formed carbon nanotube carrier obtained in the step 1) in the medium, adding the solid phosgene to the activation reaction at 30 to 50 ° C for 4 to 24 hours, then draining the medium with a vacuum pump and adding C _n The enolic acid represented by H _2n _ ₂ 0 ₂ or the enol represented by C _n H _2n O is reacted at 30 to 50 ° C for 4 to 24 hours, after which the medium is vacuum-dried and washed several times with methanol to obtain the double. Key functionalized carbon nanotubes;

所述步骤 2) 中，所述介质选自己烷、庚烷、 ***和丁醚中的至少一种；所述成形的碳纳米管载体与介质的质量比为 0.01 0.5: 1 ; 成形的碳纳米管载体与固体光气的质量比为 0.01~0.5: 1；所述 C_nH_{2l 2}0₂和 C_nH_2nO中， n≥3，具体均为 3-20的整数；碳纳米管与烯酸或烯醇的质量比为 0.01~0.5: 1； In the step 2), the medium is at least one selected from the group consisting of hexane, heptane, diethyl ether and dibutyl ether; the mass ratio of the formed carbon nanotube carrier to the medium is 0.01 0.5:1; shaped carbon nano The mass ratio of the tube carrier to the solid phosgene is 0.01 to 0.5:1; in the C _n H _{2l 2} 0 ₂ and C _n H _2n O, n≥3, specifically an integer of 3-20; The mass ratio of the olefinic acid or the enol is 0.01 to 0.5:1;

该步骤是对步骤 1 )所得成形碳纳米管载体进行进一步功能化，即在碳纳米管表面引入双键。 This step is to further functionalize the shaped carbon nanotube support obtained in the step 1), that is, to introduce a double bond on the surface of the carbon nanotube.

该双键功能化的碳纳米管颗粒的粒径为 5~100μιη，比表面积为 100~200m²/g，平均孔径为 15~25nm，平均孔容为 0.35~0.72cm³/g，堆密度为 0.1~0.3g/ml，反应性基团也即碳碳双键占所述双键功能化的碳纳米管的质量百分含量为 5.0 30.0%; 所述过渡金属化合物选自 Ziegler-Natta催化剂、茂金属催化剂和非茂金属催化剂中的至少一种； The double-bonded functionalized carbon nanotube particles have a particle diameter of 5 to 100 μm, a specific surface area of 100 to 200 m ² /g, an average pore diameter of 15 to 25 nm, an average pore volume of 0.35 to 0.72 cm ³ /g, and a bulk density of 0.1~0.3g/ml, the reactive group, that is, the carbon-carbon double bond accounts for 5.030.0% by mass of the double-bond functionalized carbon nanotube; the transition metal compound is selected from the Ziegler-Natta catalyst, At least one of a metallocene catalyst and a non-metallocene catalyst;

其中，所述 Ziegler-Natta催化剂所用的四卤化钛为 TiCl₄、 TiBr₄或 Til_4; 所用烷氧基钛为 Ti(OEt)Cl₃、 Ti(OEt)₂Cl₂、 Ti(OEt)₃Cl、 Ti(OEt)₄或 Ti(OBu)_4; Wherein, the titanium tetrahalide used in the Ziegler-Natta catalyst is TiCl ₄ , TiBr ₄ or Til _4; the titanium alkoxide used is Ti(OEt)Cl ₃ , Ti(OEt) ₂ Cl ₂ , Ti(OEt) ₃ Cl , Ti(OEt) ₄ or Ti(OBu) _4;

所述茂金属催化剂的结构通式如式 I所示，

The structural formula of the metallocene catalyst is as shown in Formula I,

(式 I) (Formula I)

所述式 I中， M选自 Ti、 Zr、 Hf、 V、 Fe、 Y、 Sc和镧系金属中的至少一种；所述 Cp¹和 Cp¹¹代表环戊二烯基或含有取代基的环戊二烯基，所述含有取代基的环戊二烯基中，取代基为 d~C₆的烷基、 C₃~C₁₈的环烷基或 C₆~C₁₈的芳香基；所述 R¹和 1 ²为11、卤原子、碳原子数为 1~8的烷基、碳原子数为 1~8的烷氧基、碳原子数为 6~20的芳基、 d~C₁₅烷基取代的碳原子数为 6~20的芳基、碳原子数为 1~8 的酰氧基、烯丙基或 d~C₁₅的硅烷基;所述 B代表烷基桥或硅烷基桥，优选 -C(R³R⁴)- 或 -Si(R³R⁴)-; R³和 1 ⁴为11、碳原子数为 1~4的烷基或碳原子数为 6~10的芳基； e 为 1、 2或 3 ; a禾 P b为 0、 1或 2，其中 a+b=2; In the formula I, M is at least one selected from the group consisting of Ti, Zr, Hf, V, Fe, Y, Sc, and a lanthanide metal; and the Cp ¹ and Cp ¹¹ represent a cyclopentadienyl group or a substituent-containing group. a cyclopentadienyl group, wherein the substituent is a cyclopentadienyl group, the substituent is a d-C ₆ alkyl group, a C ₃ -C ₁₈ cycloalkyl group or a C ₆ -C ₁₈ aryl group; R ¹ and 1 ² are 11, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, and d~C ₁₅ An alkyl group-substituted aryl group having 6 to 20 carbon atoms, an acyloxy group having 1 to 8 carbon atoms, an allyl group or a silyl group having d to C ₁₅ ; and said B represents an alkyl bridge or a silane bridge , preferably -C(R ³ R ⁴ )- or -Si(R ³ R ⁴ )-; R ³ and ¹⁴ are 11, an alkyl group having 1 to 4 carbon atoms or an aromatic group having 6 to 10 carbon atoms; Base; e is 1, 2 or 3; a and P b are 0, 1 or 2, where a + b = 2;

所述茂金属催化剂具体为 C₂H₄(Ind)₂ZrCl₂、 C₂H₄(H₄Ind)₂ZrCl₂、 Me₂Si(Ind)₂ZrCl₂、 Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂ Me₂Si(Me₄Cp)₂ZrCl₂、 Me₂Si(Flu)₂ZrCl₂ The metallocene catalyst is specifically C ₂ H ₄ (Ind) ₂ ZrCl ₂ , C ₂ H ₄ (H ₄ Ind) ₂ ZrCl ₂ , Me ₂ Si(Ind) ₂ ZrCl ₂ , Me ₂ Si (2-Me-4) -Ph-Ind) ₂ ZrCl ₂ Me ₂ Si(Me ₄ Cp) ₂ ZrCl ₂ , Me ₂ Si(Flu) ₂ ZrCl ₂

Me₂Si(2-Me-4-Naph-Ind)₂ZrCl₂或 Ph₂Si(Ind)₂ZrCl₂，其中， Me为甲基， Ph为苯基，为环戊二烯基， Ind为茚基， H₄Ind为 4,5,6,7-四氢化茚， Flu为芴基， Naph为萘所述非茂金属催化剂的结构通 II所示，

Me ₂ Si(2-Me-4-Naph-Ind) ₂ ZrCl ₂ or Ph ₂ Si(Ind) ₂ ZrCl ₂ , wherein Me is a methyl group, Ph is a phenyl group, a cyclopentadienyl group, and Ind is a fluorene a structure in which H ₄ Ind is 4,5,6,7-tetrahydroanthracene, Flu is a fluorenyl group, and Naph is a naphthalene-based non-metallocene catalyst.

(式 II) (Formula II)

所述式 II中， M选自 Zr、 Ti、 V和 Hf中的至少一种， I ¹、 R²和 1 ³为11、卤原子、碳原子数为 1~8的烷基、碳原子数为 1~8的烷氧基、碳原子数为 6~20的芳基、 d~C₆的烷基取代的芳基、 c₃~c₁₈的环烷基取代的芳基或 c₆~c₁₈的芳香基取代的芳基、碳原子数为 1~8的酰氧基、烯丙基或 d~C₁₅的硅烷基； n=2; In the formula II, M is at least one selected from the group consisting of Zr, Ti, V and Hf, and I ¹ , R ² and ¹³ are 11, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and a carbon number. Is an alkoxy group of 1 to 8, an aryl group having 6 to 20 carbon atoms, an alkyl group-substituted aryl group of d-C _{6 ,} a cycloalkyl-substituted aryl group of c ₃ to c ₁₈ or c ₆ -c ₁₈ aryl substituted aryl, 1-8 acyloxy, allyl or d~C ₁₅ silane; n=2;

所述非茂金属催化剂具体为二 [N-(3-叔丁基亚水杨基；)苯胺基]二氯化锆、二 The non-metallocene catalyst is specifically bis [N-(3-tert-butyl salicylidene;) anilino] zirconium dichloride, two

[N-(3-甲基亚水杨基；)苯胺基]二氯化锆、二 [N-(3-异丙基亚水杨基；)苯胺基]二氯化锆或二 [N-(3-金刚烷基 -5-甲基亚水杨基；)苯胺基]二氯化锆。 [N-(3-methyl salicylidene;) anilino]zirconium dichloride, bis[N-(3-isopropylsalicylidene)-anilino]zirconium dichloride or di[N- (3-adamantyl-5-methyl salicylidene;) anilino]zirconium dichloride.

所述金属化合物为含镁化合物和 /或含铝化合物；所述含镁化合物为分子式为 MgX₂的卤化镁或结构通式为 RMgX的格氏试剂；所述 MgX₂中， X为氟、氯、溴或碘元素，优选 X为氯；所述 RMgX中， R为碳原子数为 1-10的烷基，优选甲基、乙基、丙基、异丙基、丁基或异丁基， X为氟、氯、溴或碘；所述含铝化合物为 Al(OR')„R₃-„, 0<n<3 , R和 R'碳原子数为 2~10的烷基，优选三甲基铝、三乙基铝、三异丁基铝或甲基铝氧烷； The metal compound is a magnesium-containing compound and/or an aluminum-containing compound; the magnesium-containing compound is a magnesium halide having a molecular formula of MgX ₂ or a Grignard reagent having a structural formula of RMgX; in the MgX ₂ , X is fluorine or chlorine. Or bromine or an iodine element, preferably X is chlorine; in the RMgX, R is an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group. X is fluorine, chlorine, bromine or iodine; the aluminum-containing compound is Al(OR') „R ₃ —„, 0<n<3, R and R′ are 2 to 10 carbon atoms, preferably three Methyl aluminum, triethyl aluminum, triisobutyl aluminum or methyl aluminoxane;

所述内给电子体为邻苯二甲酸二异丁酯、芴二醚、苯甲酸甲酯或邻苯二甲酸二丁酯； The internal electron donor is diisobutyl phthalate, decane diether, methyl benzoate or dibutyl phthalate;

所述碳纳米管催化剂载体在所述碳纳米管负载过渡金属催化剂中的质量百分含量为 70.0~99.0%，，具体为 75.0-95.0%; The mass percentage of the carbon nanotube catalyst carrier in the carbon nanotube-supported transition metal catalyst is 70.0-99.0%, specifically 75.0-95.0%;

所述金属化合物中的金属元素和所述过渡金属化合物中的过渡金属元素的总和在所述碳纳米管负载过渡金属催化剂中所占质量百分含量为 1.0~30.0%，具体为 1.0-25.0%； a total of a metal element in the metal compound and a transition metal element in the transition metal compound And the mass percentage of the carbon nanotube-supported transition metal catalyst is 1.0 to 30.0%, specifically 1.0 to 25.0%;

所述金属化合物为含镁化合物时，所述过渡金属化合物中的过渡金属元素在所述碳纳米管负载过渡金属催化剂中的质量百分含量为 0.5~5.0%，具体为 0.5-4.0%; 所述金属化合物为含铝化合物时，所述过渡金属化合物中的过渡金属元素在所述碳纳米管负载过渡金属催化剂中的质量百分含量为 0.05~2.0%，具体为 0.1-2.0%; 所述金属化合物为含镁化合物和含铝化合物时，所述过渡金属化合物中的过渡金属元素在所述碳纳米管负载过渡金属催化剂中的质量百分含量为 0.55-7.0%，具体为 0.55-5.0%。 When the metal compound is a magnesium-containing compound, the mass percentage of the transition metal element in the transition metal compound in the carbon nanotube-supported transition metal catalyst is 0.5 to 5.0%, specifically 0.5 to 4.0%; When the metal compound is an aluminum-containing compound, the mass percentage of the transition metal element in the transition metal compound in the carbon nanotube-supported transition metal catalyst is 0.05 to 2.0%, specifically 0.1 to 2.0%; When the metal compound is a magnesium-containing compound and an aluminum-containing compound, a mass percentage of the transition metal element in the transition metal compound in the carbon nanotube-supported transition metal catalyst is 0.55 to 7.0%, specifically 0.55 to 5.0%. .

所述内给电子体在所述碳纳米管负载过渡金属催化剂中的质量百分含量为 The mass percentage of the internal electron donor in the carbon nanotube-supported transition metal catalyst is

2.50-15.0%。 2.50-15.0%.

所述碳纳米管负载过渡金属催化剂的颗粒表观形态为球形；粒径为 5~100μιη，比表面积为 100~200m²/g，平均孔径为 10~30nm，孔容为 0.22 0.66cm³/g，堆密度 0.1~0.3g/ml;所述过渡金属元素均匀分布于所述碳纳米管催化剂载体的表面及内部。 The surface morphology of the carbon nanotube-supported transition metal catalyst is spherical; the particle diameter is 5 to 100 μm, the specific surface area is 100 to 200 m ² /g, the average pore diameter is 10 to 30 nm, and the pore volume is 0.22 0.66 cm ³ /g. The bulk density is 0.1 to 0.3 g/ml; and the transition metal element is uniformly distributed on the surface and inside of the carbon nanotube catalyst carrier.

另外，上述本发明提供的含有碳纳米管的聚丙烯釜内合金在制备汽车用零部件、包装材料、阻隔材料、阻燃材料、电器材料和电导材料中至少一种的应用，也属于本发明的保护范围。 In addition, the application of the carbon nanotube-containing polypropylene in-cell alloy provided by the present invention in preparing at least one of automotive parts, packaging materials, barrier materials, flame retardant materials, electrical materials, and electrically conductive materials also belongs to the present invention. The scope of protection.

附图说明 DRAWINGS

图 1 为实施例 1中碳纳米管 /聚丙烯合金颗粒表观形态。 Figure 1 shows the apparent morphology of the carbon nanotube/polypropylene alloy particles in Example 1.

图 2为实施例 1中碳纳米管 /聚丙烯合金颗粒中碳纳米管的单一分散。 Figure 2 is a single dispersion of carbon nanotubes in the carbon nanotube/polypropylene alloy particles of Example 1.

图 3为实施例 1中碳纳米管 /聚丙烯合金经二甲苯刻蚀后橡胶相分布与尺寸。图 4为实施例 1中碳纳米管负载过渡金属催化剂的表观形态。 3 is a rubber phase distribution and size of the carbon nanotube/polypropylene alloy after etching through xylene in Example 1. 4 is an apparent morphology of a carbon nanotube-supported transition metal catalyst in Example 1.

图 5为实施例 1中碳纳米管载体的颗粒形态。 Fig. 5 is a view showing the particle form of the carbon nanotube carrier in Example 1.

图 6为实施例 1中功能化碳纳米管载体的颗粒形态。 Figure 6 is a graph showing the particle morphology of the functionalized carbon nanotube support of Example 1.

图 7为实施例 1中步骤 1 ) 所得均聚聚丙烯的升温核磁碳谱图。 Figure 7 is a graph showing the temperature-raised nuclear magnetic carbon spectrum of the homopolypropylene obtained in the step 1) of Example 1.

图 8为实施例 1中步骤 2)所得烯烃聚合物（乙烯丙烯无规共聚物）的升温核磁碳谱图。 Figure 8 is a graph showing the temperature-raising nuclear magnetic spectrum of the olefin polymer (ethylene propylene random copolymer) obtained in the step 2) of Example 1.

实施发明的最佳方式 The best way to implement the invention

下面对本发明作进一步说明，所述原料如无特别说明，均能共公开商业途径购买得到，所述方法如无特别说明均为常规方法。钛元素和锆元素的含量均用紫外分光光度法测得，镁元素和铝元素的含量均用滴定法测得。本发明着重于对碳纳米管 /釜内合金颗粒形态的控制和碳纳米管在基体中的分散，故对产物的表征主要通过两个手段：扫描电镜测试和透射电镜测试。力学性能按照标准 IS0527-2-5A (拉伸测试）， ASTM 638-V (弯曲测试）以及 ASTMD256-02 (冲击性能测试）制样并测试。下述实施例中各反应均在惰性气氛中进行。 The present invention is further illustrated by the following, and the raw materials can be commercially obtained commercially, unless otherwise specified, and the methods are conventional unless otherwise specified. The contents of titanium and zirconium were measured by ultraviolet spectrophotometry, and the contents of magnesium and aluminum were measured by titration. The invention focuses on the control of the morphology of the carbon nanotube/cavity alloy particles and the dispersion of the carbon nanotubes in the matrix, so the product is characterized by two means: scanning electron microscopy and transmission electron microscopy. The mechanical properties were prepared and tested according to the standard IS0527-2-5A (tensile test), ASTM 638-V (bending test) and ASTMD256-02 (impact performance test). Each of the reactions in the following examples was carried out under an inert atmosphere.

实施例 1 Example 1

1 )将 300g液态丙烯加入至反应釜中， 30°C下依次加入 0.23mol助催化剂三乙基铝、 0.033mol甲基铝氧烷及 l .Og碳纳米管负载过渡金属催化剂（三乙基铝和催化剂中过渡金属元素钛的摩尔比为 600: 1；助催化剂甲基铝氧烷与催化剂中过渡金属元素锆的摩尔比为 2000: 1 ) 以及氢气 0.2g，压强为 3.1MPa，升温至 70°C，反应 0.2个小时，得到中间产物聚合物 80.0g，直接进行下一步反应。 1) Add 300g of liquid propylene to the reaction kettle, and add 0.23mol of cocatalyst to the third batch at 30 °C. Base aluminum, 0.033 mol methyl aluminoxane and 1.0 g carbon nanotube supported transition metal catalyst (the molar ratio of triethyl aluminum to transition metal element titanium in the catalyst is 600:1; cocatalyst methyl aluminoxane and catalyst The medium transition metal element zirconium has a molar ratio of 2000: 1 ) and hydrogen gas of 0.2 g, a pressure of 3.1 MPa, a temperature rise to 70 ° C, and a reaction time of 0.2 hours to obtain an intermediate product polymer of 80.0 g, which is directly subjected to the next reaction.

2) 将上述步骤 1 ) 中的反应釜内残留的丙烯放空并降温至 30°C，再通入 20g 乙烯和 60g丙烯的混合气，通入氢气 0.05g，压强为 l .OMPa, 升温至 80°C，反应 0.3 个小时，最终得到碳纳米管 /聚丙烯釜内合金 100.0g。 2) The propylene remaining in the reaction vessel in the above step 1) was vented and cooled to 30 ° C, and then a mixture of 20 g of ethylene and 60 g of propylene was introduced, and 0.05 g of hydrogen was introduced thereto, and the pressure was 1.0 MPa, and the temperature was raised to 80. At °C, the reaction was carried out for 0.3 hours, and finally 100.0 g of a carbon nanotube/polypropylene inner alloy was obtained.

该碳纳米管 /聚丙烯釜内合金由碳纳米管、重均分子量为 725000g/mol的均聚等规聚丙烯树脂和乙烯 /丙烯无规共聚物组成；碳纳米管、乙烯 /丙烯无规共聚物、均聚聚丙烯树脂的质量比为 1.0: 20.0： 79。碳纳米管的粒径为 10nm，长度为 0.5μιη，长径比为 50。 The carbon nanotube/polypropylene inner alloy is composed of carbon nanotubes, a homopolymeric isotactic polypropylene resin having a weight average molecular weight of 725000 g/mol, and an ethylene/propylene random copolymer; carbon nanotubes, ethylene/propylene random copolymerization The mass ratio of the homopolymeric polypropylene resin was 1.0: 20.0:79. The carbon nanotubes have a particle diameter of 10 nm, a length of 0.5 μm, and an aspect ratio of 50.

碳纳米管 /聚丙烯合金颗粒表观形态为球形，如图 1所示，颗粒粒径大小为 50~500μιη; 透射电镜照片（图 2)表明，碳纳米管以单一分散的纳米片层的形式存在。通过扫描电镜观察其经二甲苯刻蚀断面，发现橡胶相分散均匀，且橡胶相的尺寸小于 0.2微米，如图 3所示。由步骤 1 ) 所得复合物中等规聚丙烯的分子结构由升温核磁碳谱确定，如图 7所示。由步骤 2) 所得烯烃聚合物（乙烯 /丙烯无规共聚物的分子结构由升温核磁碳谱确定，如图 8所示。 The apparent morphology of the carbon nanotube/polypropylene alloy particles is spherical, as shown in Fig. 1, the particle size is 50~500μιη; the transmission electron micrograph (Fig. 2) shows that the carbon nanotubes are in the form of a single dispersed nanosheet. presence. The cross section of the xylene was observed by scanning electron microscopy to find that the rubber phase was uniformly dispersed, and the rubber phase was less than 0.2 μm, as shown in Fig. 3. The molecular structure of the isotactic polypropylene in the composite obtained in the step 1) is determined by the temperature-raising nuclear magnetic carbon spectrum, as shown in Fig. 7. The molecular structure of the olefin polymer obtained from the step 2) (the ethylene/propylene random copolymer is determined by the temperature-raising nuclear magnetic carbon spectrum, as shown in Fig. 8.

其中，所用碳纳米管负载过渡金属催化剂按照下述方法制备而得： Wherein, the carbon nanotube-supported transition metal catalyst used is prepared according to the following method:

1 )将 2.0g无水氯化镁 MgCl₂与 5.5ml异辛醇分散于 20ml癸烷中，加热至 110 °C，形成透明溶液，于 110°C下反应 4.0个小时。 1) 2.0 g of anhydrous magnesium chloride MgCl ₂ and 5.5 ml of isooctanol were dispersed in 20 ml of decane, heated to 110 ° C to form a transparent solution, and reacted at 110 ° C for 4.0 hours.

将上述氯化镁醇合物滴加入 3.0g球形碳纳米管载体 /100ml癸烷的悬浮液中，于 90°C下恒温反应 12.0个小时，然后滤除液体，滤出的固体用癸烷洗涤 3次，干燥后得到碳纳米管载体的镁复合物。 The above magnesium chloride alcoholate was added dropwise to a suspension of 3.0 g of spherical carbon nanotube support/100 ml of decane, and the reaction was carried out at 90 ° C for 12.0 hours, and then the liquid was filtered off, and the filtered solid was washed 3 times with decane. After drying, a magnesium composite of a carbon nanotube support is obtained.

2)向 -20°C的 100ml四氯化钛溶液中加入 lO.Og球形碳纳米管载体的镁复合物，并于 -20°C下恒温反应 1.0个小时。缓慢升温至 60°C，加入 2.0ml邻苯二甲酸二异丁酯，然后于 110°C下恒温反应 2.0个小时，反应完成后滤除液体，再次加入 100ml 四氯化钛溶液，于 120°C下恒温反应 2.0个小时。最后，用己烷洗涤 3~6次，干燥后得到碳纳米管负载钛化合物。 2) To a 100 ml titanium tetrachloride solution at -20 ° C, a magnesium complex of lO.Og spherical carbon nanotube support was added and reacted at -20 ° C for 1.0 hour at a constant temperature. Slowly raise the temperature to 60 ° C, add 2.0 ml of diisobutyl phthalate, and then react at a constant temperature of 110 ° C for 2.0 hours. After the reaction is completed, filter the liquid and add 100 ml of titanium tetrachloride solution at 120 °. The reaction was carried out under constant temperature for 2.0 hours. Finally, it was washed 3 to 6 times with hexane, and dried to obtain a carbon nanotube-supported titanium compound.

3 )取 5.0g球形碳纳米管负载钛化合物分散于 50ml甲苯中，然后加入含 O. lmol 甲基铝氧烷的甲苯溶液 30ml，于 90°C下反应 4.0个小时，然后用甲苯洗涤 5次，干燥后得到活化的碳纳米管负载催化剂。 3) Take 5.0 g of spherical carbon nanotube-supported titanium compound and disperse it in 50 ml of toluene, then add 30 ml of a toluene solution containing 0.1 mol of methylaluminoxane, react at 90 ° C for 4.0 hours, and then wash 5 times with toluene. After drying, an activated carbon nanotube-supported catalyst is obtained.

4)将 0.10g过渡金属化合物 Et(Ind)₂ZrCl₂加入至含有 O. lOmol甲基铝氧烷的甲苯溶液 40ml中，于 20°C下反应 4.0个小时，得到活化的催化剂溶液。 4) 0.10 g of a transition metal compound Et(Ind) ₂ ZrCl _{2 was} added to 40 ml of a toluene solution containing 0.1 mol of methyl aluminoxane, and reacted at 20 ° C for 4.0 hours to obtain an activated catalyst solution.

5 ) 将此催化剂溶液滴加入至含有 5.0g所述步骤 3 ) 制备所得活化的碳纳米管负载催化剂的 50ml甲苯悬浮液中，于 90°C下反应 4.0个小时。反应完成后，用甲苯洗涤 5次，干燥后得到本发明提供的碳纳米管负载的过渡金属催化剂。 5) The catalyst solution was dropwise added to a suspension of 5.0 g of the activated carbon nanotube-supported catalyst prepared in the above step 3) in 50 ml of toluene, and reacted at 90 ° C for 4.0 hours. After completion of the reaction, it was washed 5 times with toluene, and after drying, the carbon nanotube-supported transition metal catalyst provided by the present invention was obtained.

该碳纳米管负载过渡金属催化剂为球形颗粒，如图 4所示，由碳纳米管催化剂载体、过渡金属化合物 Et(Ind)₂ZrCl₂、四氯化钛、氯化镁、甲基铝氧烷和内给电子体邻苯二甲酸二异丁酯组成；其中钛元素、镁元素、锆元素和铝元素的含量分别为 1.81wt% 3.56wt% 0.15 ％和 8.75wt%，邻苯二甲酸二异丁酯的质量百分含量为 9.85wt%。该催化剂的比表面积为 106.6m²/g，孔容为 0.25cm³/g，平均孔径为 15.6nm 其中，所用碳纳米管催化剂载体按照下述方法制备而得： The carbon nanotube-supported transition metal catalyst is a spherical particle, as shown in FIG. 4, comprising a carbon nanotube catalyst carrier, a transition metal compound Et(Ind) ₂ ZrCl ₂ , titanium tetrachloride, magnesium chloride, methyl aluminoxane and inner Giving electronics The composition of diisobutyl phthalate; wherein the contents of titanium, magnesium, zirconium and aluminum are 1.81% by weight, 3.56wt%, 0.15% and 8.75wt%, respectively, and the quality of diisobutyl phthalate The percentage is 9.85 wt%. The catalyst has a specific surface area of 106.6 m ² /g, a pore volume of 0.25 cm ³ /g, and an average pore diameter of 15.6 nm. The carbon nanotube catalyst carrier used is prepared according to the following method:

1 ) 将 5.0g碳纳米管 (碳纳米管的粒径为 10 长度为 0.5μιη，长径比 50，羟基含量 3.06% (w/w) ；)经超声分散于 150毫升水和 150毫升乙醇的混合溶液中形成悬浮液，搅拌 0.5小时后，喷雾干燥成型制备得到碳纳米管催化剂载体，喷雾干燥的压力为 O. lMPa, 干燥进风温度 180°C，进料速度为 20.0ml/min，得到成形的碳纳米管载体；该载体颗粒形态为球形，如图 5所示，其颗粒粒径大小为 10~30μιη，比表面积为 150.1m²/g，孔容为 0.36cm³/g，平均孔径为 18.4nm 1) 5.0 g of carbon nanotubes (having a diameter of 10 carbon nanotubes of 0.5 μm, an aspect ratio of 50, and a hydroxyl group content of 3.06% (w/w);) were ultrasonically dispersed in 150 ml of water and 150 ml of ethanol. The suspension is formed in the mixed solution, and after stirring for 0.5 hours, the carbon nanotube catalyst carrier is prepared by spray drying, and the spray drying pressure is 0.1 MPa, the dry inlet air temperature is 180 ° C, and the feed rate is 20.0 ml/min. The formed carbon nanotube carrier; the carrier particle shape is spherical, as shown in Fig. 5, the particle size is 10~30μιη, the specific surface area is 150.1m ² /g, the pore volume is 0.36cm ³ /g, and the average pore diameter is Is 18.4nm

2) 将步骤 1 ) 所得成形的碳纳米管载体分散于庚烷中，碳纳米管与分散介质的质量比为 0.06: 1；加入固体光气于 30°C活化 24小时，碳纳米管与固体光气的质量比为 0.1 : 1，之后将介质用真空泵抽干，加入十一烯酸 30°C反应 24小时，碳纳米管与十一烯酸的质量比为 0.1 : 1，之后将介质用真空泵抽干，甲醇洗涤若干次，得到碳纳米管催化剂载体，颗粒形态为球形，如图 6所示，粒径为 5~100μιη，比表面积为 120.1m²/g，平均孔径为 15.1nm，平均孔容为 0.32cm³/g，堆密度为 0.19g/ml 带有反应性双键的基团也即碳碳双键占该碳纳米管催化剂载体的含量为 24.2wt% 实施例 1 2 6和 11所制备的含有碳纳米管的聚丙烯釜内合金的力学性能测试时，分别按照标准 IS0527-2-5A (拉伸测试）， ASTM 638-V (弯曲测试）以及 ASTMD256-02 (冲击性能测试）制样并测试。测试结果如表 1所示： 2) The formed carbon nanotube carrier obtained in the step 1) is dispersed in heptane, the mass ratio of the carbon nanotube to the dispersion medium is 0.06:1; the solid phosgene is activated at 30 ° C for 24 hours, the carbon nanotubes and the solid The mass ratio of phosgene is 0.1:1, and then the medium is vacuumed by a vacuum pump, and undecylenic acid is added at 30 ° C for 24 hours. The mass ratio of carbon nanotubes to undecylenic acid is 0.1:1, and then the medium is used. The vacuum pump was drained and washed with methanol several times to obtain a carbon nanotube catalyst carrier. The particle shape was spherical, as shown in Fig. 6, the particle size was 5 to 100 μm, the specific surface area was 120.1 m ² /g, and the average pore diameter was 15.1 nm. The pore volume is 0.32 cm ³ /g, and the bulk density is 0.19 g/ml. The group having a reactive double bond, that is, the carbon-carbon double bond accounts for 24.2% by weight of the carbon nanotube catalyst carrier. Example 1 2 6 The mechanical properties of the prepared carbon nanotube-containing polypropylene in-cavity alloy were tested according to the standard IS0527-2-5A (tensile test), ASTM 638-V (bending test) and ASTM D256-02 (impact performance test). ) Sample preparation and testing. The test results are shown in Table 1:

表 1、含有碳纳米管的聚丙烯釜内合金的力学性能测试结果 Table 1. Test results of mechanical properties of polypropylene alloy containing carbon nanotubes

力学性能结果显示，本发明提供的含有碳纳米管的聚丙烯釜内合金具有较高的模量和冲击韧性，从而同时实现了高模量和高韧性的目标，得到了性能优异的聚丙烯釜内合金。与不含碳纳米管的聚丙烯釜内合金相比，其各项力学性能均得到不同程度地提高，特别是在低温冲击方面，可以大幅提高釜内合金的性能。 The results of mechanical properties show that the carbon nanotube-containing polypropylene in-cylinder alloy provided by the invention has high modulus and impact toughness, thereby achieving the goals of high modulus and high toughness at the same time, and obtaining a polypropylene kettle with excellent performance. Inner alloy. Compared with the polypropylene in-cylinder alloy containing no carbon nanotubes, the mechanical properties of the alloy are improved to some extent, especially in terms of low temperature impact, and the performance of the alloy in the autoclave can be greatly improved.

其中，该对比样品的制备方法如下： 1 ) 真空状态下，将 20g丙烯单体充入反应釜中，依次加入 50ml溶剂己烷、含 1.5mmol助催化剂三乙基铝的庚烷溶液 3.5ml 及 0.02克氯化镁负载过渡金属催化剂（助催化剂三乙基铝中铝元素与氯化镁负载的过渡金属催化剂中过渡金属元素钛之间的摩尔比为 150: 1 )，釜内压强恒定在 0.7MPa，反应温度为 70°C，进行淤浆聚合反应 0.5小时，得到均聚聚丙烯 15.0g，然后，停止通入丙烯单体； The preparation method of the comparative sample is as follows: 1) 20 g of propylene monomer is charged into the reaction kettle under vacuum, and then 50 ml of solvent hexane, 3.5 ml of 1.5 mmol of a cocatalyst triethylaluminum heptane solution and 0.02 g of magnesium chloride supported transition metal catalyst (cocatalyst triethyl aluminum in aluminum and magnesium chloride supported The molar ratio of the transition metal element titanium in the transition metal catalyst is 150:1), the pressure in the autoclave is constant at 0.7 MPa, the reaction temperature is 70 ° C, and slurry polymerization is carried out for 0.5 hour to obtain 15.0 g of homopolypropylene. Then, the passage of the propylene monomer is stopped;

2) 向步骤 1 ) 反应釜中通入乙烯与丙烯的混合气（其中乙烯与丙烯的摩尔比为 1 : 2) 5g，继续反应 0.2小时，釜内压强恒定为 0.5MPa，反应温度为 70°C，反应完成后，加入酸化乙醇终止聚合反应，使用去离子水和乙醇洗涤， 60°C下真空干燥，得到 17.0克聚丙烯釜内合金；该聚丙烯釜内合金由质量比为 88.24%和 11.76% 的均聚聚丙烯树脂和乙烯 /丙烯无规共聚物组成。 2) In step 1), a mixture of ethylene and propylene (in which the molar ratio of ethylene to propylene is 1:2) 5 g is introduced into the reaction vessel, and the reaction is continued for 0.2 hours. The pressure in the autoclave is constant at 0.5 MPa, and the reaction temperature is 70°. C. After the reaction is completed, the polymerization reaction is terminated by adding acidified ethanol, washed with deionized water and ethanol, and dried under vacuum at 60 ° C to obtain 17.0 g of an alloy in a polypropylene kettle; the mass ratio of the alloy in the polypropylene is 88.24% by mass and 11.76% of a homopolypropylene resin and an ethylene/propylene random copolymer.

其中，所用氯化镁负载的过渡金属催化剂按照如下方法制备而得： Among them, the magnesium chloride-supported transition metal catalyst is prepared by the following method:

1 )将 2.0g无水氯化镁 MgCl₂与 5.5ml异辛醇分散于 50ml癸烷中，加热至 1301) Disperse 2.0 g of anhydrous magnesium chloride MgCl ₂ and 5.5 ml of isooctanol in 50 ml of decane and heat to 130

°C，形成透明溶液，于 130°C下反应 2.0小时，得到氯化镁醇合物； °C, a clear solution was formed and reacted at 130 ° C for 2.0 hours to obtain a magnesium chloride alcoholate;

2)向 -20°C的 100ml四氯化钛溶液中滴加入步骤 1 )所得将上述氯化镁醇合物，并于 -20°C下恒温反应 1.0小时。缓慢升温至 120°C，加入 0.2ml邻苯二甲酸二异丁酯，之后于 120°C下恒温反应 1.5小时，反应完成后滤除液体，再次加入 100ml四氯化钛溶液，于 120°C下恒温反应 2.0小时。最后，用己烷洗涤 3~6次，干燥后得到氯化镁负载的过渡金属催化剂。该氯化镁负载过渡金属催化剂由氯化镁、四氯化钛和内给电子体邻苯二甲酸二异丁酯组成；钛元素、镁元素的含量分别为 2.32wt%、 17.56wt%, 邻苯二甲酸二异丁酯的含量为 9.88 wt%。 2) To the 100 ml of titanium tetrachloride solution at -20 ° C, the above magnesium chloride alcoholate was added dropwise to the step 1), and the reaction was carried out at a constant temperature of -20 ° C for 1.0 hour. Slowly raise the temperature to 120 ° C, add 0.2 ml of diisobutyl phthalate, then react at 120 ° C for 1.5 hours. After the reaction is completed, filter the liquid and add 100 ml of titanium tetrachloride solution at 120 ° C. The reaction was carried out under constant temperature for 2.0 hours. Finally, it was washed 3 to 6 times with hexane, and dried to obtain a transition metal catalyst supported by magnesium chloride. The magnesium chloride supported transition metal catalyst is composed of magnesium chloride, titanium tetrachloride and internal electron donor diisobutyl phthalate; the content of titanium element and magnesium element is 2.32wt%, 17.56wt%, respectively, phthalic acid II The content of isobutyl ester was 9.88 wt%.

实施例 2 Example 2

1 ) 真空状态下，将 8.0g丙烯单体充入反应釜中，依次加入 100ml己烷、含 1) Under vacuum, 8.0 g of propylene monomer was charged into the reaction vessel, and 100 ml of hexane was added in sequence, including

5.5mmol三乙基铝的庚烷溶液 3.0ml、 O.Olmol甲基铝氧烷及 O. lg碳纳米管负载过渡金属催化剂（三乙基铝与碳纳米管负载过渡金属催化剂中的过渡金属元素钛的摩尔比为 150: 1，甲基铝氧烷与碳纳米管负载过渡金属催化剂中的过渡金属元素锆的摩尔比为 2000: 1 ) ，釜内压力恒定在 0.7MPa，反应温度为 70°C，聚合反应 0.5个小时，停止通入丙烯单体，得到中间产物 9.0g; 5.5mmol of triethylaluminum heptane solution 3.0ml, O.Olmol methylaluminoxane and O.lg carbon nanotube supported transition metal catalyst (transition metal element in triethylaluminum and carbon nanotube supported transition metal catalyst) The molar ratio of titanium is 150: 1, the molar ratio of methylaluminoxane to the transition metal element zirconium in the carbon nanotube-supported transition metal catalyst is 2000: 1 ), the pressure in the autoclave is constant at 0.7 MPa, and the reaction temperature is 70°. C, polymerization reaction for 0.5 hours, the propylene monomer was stopped, and 9.0 g of an intermediate product was obtained;

2)向步骤 1 )的反应釜中通入乙烯与丙烯的混合气（其中乙烯 1.25g，丙烯 3.75g) 5.0g，继续反应 0.5个小时，釜内压强恒定为 0.5MPa，反应温度为 70°C，反应完成后，加入酸化乙醇终止聚合反应，使用去离子水和乙醇洗涤， 60°C下真空干燥，得到 10.0g碳纳米管 /聚丙烯釜内合金； 2) To the reactor of step 1), a mixed gas of ethylene and propylene (including 1.25 g of ethylene and 3.75 g of propylene) was introduced into 5.0 g, and the reaction was continued for 0.5 hour. The pressure in the autoclave was constant at 0.5 MPa, and the reaction temperature was 70 °. C, after the reaction is completed, the polymerization reaction is terminated by adding acidified ethanol, washed with deionized water and ethanol, and dried under vacuum at 60 ° C to obtain 10.0 g of carbon nanotube/polypropylene in-cylinder alloy;

该碳纳米管 /聚丙烯釜内合金由碳纳米管、重均分子量为 260000g/mol的均聚等规聚丙烯树脂和乙烯 /丙烯无规共聚物组成；碳纳米管、乙烯 /丙烯无规共聚物、均聚聚丙烯树脂的质量比为 1.0: 10.0: 89，表观形态为球形，碳纳米管的粒径为 10nm，长度为 0.5μιη，长径比 50。 The carbon nanotube/polypropylene inner alloy is composed of carbon nanotubes, a homopolymeric isotactic polypropylene resin having a weight average molecular weight of 260,000 g/mol, and an ethylene/propylene random copolymer; carbon nanotubes, ethylene/propylene random copolymerization The mass ratio of the homopolypropylene resin is 1.0: 10.0: 89, and the apparent morphology is spherical. The carbon nanotube has a particle diameter of 10 nm, a length of 0.5 μm, and an aspect ratio of 50.

其中，所用碳纳米管负载过渡金属催化剂是按照下述方法进行制备的： Among them, the carbon nanotube-supported transition metal catalyst used is prepared according to the following method:

1 )将 2.0g无水氯化镁 MgCl₂与 5.5ml异辛醇分散于 20ml癸烷中，加热至 110°C，形成透明溶液，于 110°C下反应 4.0个小时。 1) 2.0 g of anhydrous magnesium chloride MgCl ₂ and 5.5 ml of isooctanol were dispersed in 20 ml of decane, heated to 110 ° C to form a transparent solution, and reacted at 110 ° C for 4.0 hours.

将上述氯化镁醇合物滴加入 3.0g球形碳纳米管载体 /100ml癸烷的悬浮液中，于 90°C下恒温反应 12.0个小时，然后滤除液体，滤出的固体用癸烷洗涤 3次，干燥后得到碳纳米管催化剂载体的镁复合物。 The above magnesium chloride alcoholate was added dropwise to a suspension of 3.0 g of spherical carbon nanotube support/100 ml of decane, and the reaction was carried out at 90 ° C for 12.0 hours, and then the liquid was filtered off, and the filtered solid was washed 3 times with decane. Dry After drying, a magnesium composite of a carbon nanotube catalyst carrier is obtained.

2) 向 -20°C的 100ml四氯化钛溶液中加入 lO.Og球形所述碳纳米管催化剂载体的镁复合物，并于 -20°C下恒温反应 1.0个小时。缓慢升温至 80°C，加入 2.0ml邻苯二甲酸二异丁酯后于 110°C下恒温反应 2.0个小时，反应完成后滤除液体，再次加入 100ml四氯化钛溶液，于 120°C下恒温反应 2.0个小时。最后，用己烷洗涤 3~6 次，干燥后得到碳纳米管负载钛化合物。 2) To 100 ml of a titanium tetrachloride solution at -20 ° C, 10 g of a magnesium complex of the spherical carbon nanotube catalyst carrier was added and reacted at -20 ° C for 1.0 hour at a constant temperature. Slowly raise the temperature to 80 ° C, add 2.0 ml of diisobutyl phthalate and react at 110 ° C for 2.0 hours. After the reaction is completed, filter the liquid and add 100 ml of titanium tetrachloride solution at 120 ° C. The reaction was carried out under constant temperature for 2.0 hours. Finally, it was washed 3 to 6 times with hexane, and dried to obtain a carbon nanotube-supported titanium compound.

3 )取 5.0g所述球形碳纳米管负载钛化合物分散于 100ml甲苯中，然后加入含 O. lmol甲基铝氧烷的甲苯溶液 30ml，于 110°C下反应 4.0个小时，然后用甲苯洗涤 5次，干燥后得到活化的碳纳米管催化剂。 3) 5.0 g of the spherical carbon nanotube-supported titanium compound was dispersed in 100 ml of toluene, and then 30 ml of a toluene solution containing 0.1 mol of methylaluminoxane was added, and the reaction was carried out at 110 ° C for 4.0 hours, followed by washing with toluene. Five times, an activated carbon nanotube catalyst was obtained after drying.

4)将 0.20g过渡金属化合物 Et(Ind)₂ZrCl₂加入至含有 0.20mol甲基铝氧烷的甲苯溶液 80ml中，于 20°C下反应 4.0个小时，得到活化的催化剂溶液。 4) 0.20 g of a transition metal compound Et(Ind) ₂ ZrCl _{2 was} added to 80 ml of a toluene solution containing 0.20 mol of methylaluminoxane, and reacted at 20 ° C for 4.0 hours to obtain an activated catalyst solution.

5 ) 将此催化剂溶液滴加入至含有 5.0g所述步骤 3 ) 制备所得活化的碳纳米管催化剂的 50ml甲苯悬浮液中，于 90°C下反应 4.0个小时。反应完成后，用甲苯洗涤 5次，干燥后得到本发明提供的碳纳米管负载的过渡金属催化剂。 5) This catalyst solution was dropwise added to a suspension of 5.0 g of the activated carbon nanotube catalyst prepared in the above step 3), and reacted at 90 ° C for 4.0 hours. After the completion of the reaction, the mixture was washed with toluene 5 times, and dried to obtain a carbon nanotube-supported transition metal catalyst provided by the present invention.

该碳纳米管负载过渡金属催化剂为球形颗粒，由碳纳米管催化剂载体、过渡金属化合物 Et(Ind)₂ZrCl₂、四氯化钛、氯化镁、甲基铝氧烷和内给电子体邻苯二甲酸二异丁酯组成;其中钛元素、镁元素、锆元素、铝元素的含量分别为 1.80wt%、2.58%、 0.50%、 15.48%, 邻苯二甲酸二异丁酯的含量为 6.0wt%。该催化剂的比表面积为 112.3m²/g, 孔容为 0.25cm³/g，平均孔径为 12.7nm。 The carbon nanotube-supported transition metal catalyst is a spherical particle composed of a carbon nanotube catalyst carrier, a transition metal compound Et(Ind) ₂ ZrCl ₂ , titanium tetrachloride, magnesium chloride, methyl aluminoxane and an internal electron donor phthalic acid. The composition of diisobutyl formate; wherein the content of titanium element, magnesium element, zirconium element and aluminum element is 1.80 wt%, 2.58%, 0.50%, 15.48%, respectively, and the content of diisobutyl phthalate is 6.0 wt%. . The catalyst had a specific surface area of 112.3 m ² /g, a pore volume of 0.25 cm ³ /g, and an average pore diameter of 12.7 nm.

其中，所用碳纳米管催化剂载体与实施例 1相同。 Among them, the carbon nanotube catalyst carrier used was the same as in Example 1.

实施例 3 Example 3

1 )将 250g液态丙烯加入至反应釜中， 30°C下依次加入 0.16mol助催化剂三乙基铝、 0.066mol甲基铝氧烷及 l .Og碳纳米管负载过渡金属催化剂（三乙基铝和催化剂中过渡金属元素钛的摩尔比为 600: 1；甲基铝氧烷与催化剂中过渡金属元素锆的摩尔比为 2000: 1 )以及氢气 0.2g，压强为 3.0MPa，升温至 70°C，反应 0.2个小时，得到中间产物聚合物 90.0g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.16 mol of cocatalyst triethylaluminum, 0.066 mol of methylaluminoxane and 1.0 g of carbon nanotube-supported transition metal catalyst (triethylaluminum) were sequentially added at 30 ° C. The molar ratio of the transition metal element titanium to the catalyst is 600:1; the molar ratio of methylaluminoxane to the transition metal element zirconium in the catalyst is 2000: 1 ) and the hydrogen gas is 0.2 g, the pressure is 3.0 MPa, and the temperature is raised to 70 ° C. After reacting for 0.2 hours, 90.0 g of an intermediate product polymer was obtained, and the next reaction was directly carried out.

2) 将上述步骤 1 ) 中的反应釜内残留的丙烯放空并降温至 30°C，再通入 20g 乙烯和 60gl-丁烯的混合气，通入氢气 0.05g，压强为 l .OMPa, 升温至 80°C，反应 0.3个小时，最终得到碳纳米管 /聚丙烯釜内合金 110.0g。 2) The propylene remaining in the reaction vessel in the above step 1) was vented and cooled to 30 ° C, and then a mixture of 20 g of ethylene and 60 g of butene was introduced, and 0.05 g of hydrogen was introduced thereto, and the pressure was 1.0 MPa. The reaction was carried out at 80 ° C for 0.3 hours to finally obtain 110.0 g of a carbon nanotube/polypropylene inner alloy.

该碳纳米管 /聚丙烯釜内合金由碳纳米管、重均分子量为 200000g/mol的均聚等规聚丙烯树脂和乙烯 /丁烯无规共聚物组成；碳纳米管、乙烯 /丁烯无规共聚物、均聚聚丙烯树脂的质量比为 0.91 : 18.1： 80.99。颗粒表观形态为球形，颗粒粒径大小为 50~500μιη; 碳纳米管的粒径为 50nm，长度为 ΙΟμιη, 长径比 200。 The carbon nanotube/polypropylene inner alloy is composed of carbon nanotubes, a homopolymeric isotactic polypropylene resin having a weight average molecular weight of 200,000 g/mol, and an ethylene/butene random copolymer; carbon nanotubes, ethylene/butene-free The mass ratio of the copolymer and the homopolypropylene resin was 0.91: 18.1: 80.99. The apparent morphology of the particles is spherical, and the particle size is 50-500 μm; the diameter of the carbon nanotubes is 50 nm, the length is ΙΟμιη, and the aspect ratio is 200.

2 ) 向 -20°C的 100ml四氯化钛溶液中加入 lO.Og球形所述碳纳米管催化剂载体的镁复合物，并于 -20°C下恒温反应 1.0个小时。缓慢升温至 80°C，加入 2.0g芴二醚然后于 1 10°C下恒温反应 2.0个小时，反应完成后滤除液体，再次加入 100ml四氯化钛溶液，于 120°C下恒温反应 2.0个小时。最后，用己烷洗涤 3~6次，干燥后得到碳纳米管负载钛化合物。 2) To 100 ml of a titanium tetrachloride solution at -20 ° C, 10 g of a magnesium complex of the spherical carbon nanotube catalyst carrier was added and reacted at -20 ° C for 1.0 hour at a constant temperature. Slowly raise the temperature to 80 ° C, add 2.0 g of decyl diether and then react at a constant temperature of 10 ° C for 2.0 hours. After the reaction is completed, the liquid is filtered off, and 100 ml of titanium tetrachloride solution is added again, and the reaction is kept at 120 ° C at a constant temperature of 2.0. Hours. Finally, it was washed 3 to 6 times with hexane, and after drying, a carbon nanotube-supported titanium compound was obtained.

3 )取 5.0g所述球形碳纳米管负载钛化合物分散于 100ml甲苯中，然后加入含 O. lmol甲基铝氧烷的甲苯溶液 30ml，于 1 10°C下反应 4.0个小时，然后用甲苯洗涤 5次，干燥后得到活化的碳纳米管催化剂。 3) taking 5.0 g of the spherical carbon nanotube-supported titanium compound dispersed in 100 ml of toluene, and then adding 30 ml of a toluene solution containing 0.1 mol of methylaluminoxane, reacting at 10 ° C for 4.0 hours, and then using toluene After washing 5 times, the activated carbon nanotube catalyst was obtained after drying.

4 )将 0.20g过渡金属化合物 Et(Ind)₂ZrCl₂加入至含有 0.20mol甲基铝氧烷的甲苯溶液 80ml中，于 20°C下反应 4.0个小时，得到活化的催化剂溶液。 4) 0.20 g of a transition metal compound Et(Ind) ₂ ZrCl _{2 was} added to 80 ml of a toluene solution containing 0.20 mol of methylaluminoxane, and reacted at 20 ° C for 4.0 hours to obtain an activated catalyst solution.

该碳纳米管负载过渡金属催化剂为球形颗粒，由碳纳米管催化剂载体、过渡金属化合物 Et(Ind)₂ZrCl₂、四氯化钛、氯化镁、甲基铝氧烷和内给电子体芴二醚组成；其中钛元素、镁元素、锆元素、铝元素的含量分别为 1.34wt%、 2.89wt% 0.30wt% 14.68wt%, 芴二醚的含量为 9.42wt%。该催化剂的比表面积为 1 13.9m²/g，孔容为 0.27cm³/g，平均孔径为 16.7nm。 The carbon nanotube-supported transition metal catalyst is a spherical particle, which is composed of a carbon nanotube catalyst carrier, a transition metal compound Et(Ind) ₂ ZrCl ₂ , titanium tetrachloride, magnesium chloride, methyl aluminoxane and internal electron donor deuterated diether. Composition; wherein the content of titanium element, magnesium element, zirconium element, and aluminum element is 1.34 wt%, 2.89 wt%, 0.30 wt%, 14.68 wt%, and the content of the sebacic ether is 9.42 wt%, respectively. The catalyst had a specific surface area of 1 13.9 m ² /g, a pore volume of 0.27 cm ³ /g, and an average pore diameter of 16.7 nm.

其中，所用碳纳米管催化剂载体，是按照下述方法制备的：将 5.0g碳纳米管 (碳纳米管的粒径为 50nm，长度为 ΙΟμιη, 长径比 200)经超声分散于 300毫升乙醇中形成悬浮液，搅拌 0.5小时后，喷雾干燥成型制备得到碳纳米管催化剂载体，喷雾干燥的压力为 0.15MPa，干燥进风温度 100°C，进料速度为 20.0ml/min。该碳纳米管载体颗粒形态为球形，其颗粒粒径为 8~30μιη。由氮气吸附测试可知，碳纳米管载体比表面积为 148.0m²/g，平均孔容为 0.54cm³/g，平均孔径为 18.5nm，堆密度 0.17g/ml。 Wherein, the carbon nanotube catalyst carrier used is prepared according to the following method: 5.0 g of carbon nanotubes (having a particle diameter of 50 nm of carbon nanotubes, a length of ΙΟμιη, and an aspect ratio of 200) are ultrasonically dispersed in 300 ml of ethanol. The suspension was formed, stirred for 0.5 hours, and spray-dried to prepare a carbon nanotube catalyst carrier. The spray drying pressure was 0.15 MPa, the dry inlet air temperature was 100 ° C, and the feed rate was 20.0 ml/min. The carbon nanotube carrier particle has a spherical shape and a particle size of 8 to 30 μm. From the nitrogen adsorption test, the carbon nanotube carrier had a specific surface area of 148.0 m ² /g, an average pore volume of 0.54 cm ³ /g, an average pore diameter of 18.5 nm, and a bulk density of 0.17 g/ml.

实施例 4 Example 4

1 )将 250g液态丙烯加入至反应釜中， 30°C下依次加入 0.24mol助催化剂三乙基铝、 0.055mol甲基铝氧烷、 0.024mol二甲基二苯基硅烷及 l .Og碳纳米管负载过渡金属催化剂（三乙基铝和催化剂中过渡金属元素钛之间摩尔比为 600: 1；甲基铝氧烷与催化剂中过渡金属元素锆的摩尔比为 2000: 1 )以及氢气 0.2g，压强为 3.0MPa，升温至 70°C，反应 0.2个小时，得到中间产物聚合物 76.8g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.24 mol of promoter triethylaluminum, 0.055 mol of methylaluminoxane, 0.024 mol of dimethyldiphenylsilane and 1.0 g of carbon nanoparticle were sequentially added at 30 ° C. Pipe-loaded transition metal catalyst (the molar ratio between triethylaluminum and the transition metal element titanium in the catalyst is 600:1; the molar ratio of methylaluminoxane to the transition metal element zirconium in the catalyst is 2000:1) and hydrogen gas 0.2g The pressure was 3.0 MPa, the temperature was raised to 70 ° C, and the reaction was carried out for 0.2 hours to obtain 76.8 g of an intermediate polymer, which was directly subjected to the next reaction.

2 ) 将上述步骤 1 ) 中的反应釜内残留的丙烯放空并降温至 30°C，再通入 20g 乙烯和 60gl-辛烯，通入氢气 0.05g，压强为 l .OMPa, 升温至 80°C，反应 0.3个小时，最终得到碳纳米管 /聚丙烯釜内合金 85.0g。 2) The propylene remaining in the reaction vessel in the above step 1) is vented and cooled to 30 ° C, and then 20 g of ethylene and 60 g of octene are introduced, 0.05 g of hydrogen gas is introduced, the pressure is 1.0 MPa, and the temperature is raised to 80 °. C, the reaction was carried out for 0.3 hours, and finally 85.0 g of a carbon nanotube/polypropylene inner alloy was obtained.

该碳纳米管 /聚丙烯釜内合金由碳纳米管、重均分子量为 150000g/mol的均聚等规聚丙烯树脂和乙烯 /辛烯无规共聚物组成；碳纳米管、乙烯 /辛烯无规共聚物、均聚聚丙烯树脂的质量比为 1.17: 9.6： 89.23。颗粒表观形态为球形，颗粒粒径大小为 50~500μιη; 碳纳米管的粒径为 10nm，长度为 0.5μιη，长径比 50。其中，所用碳纳米管负载过渡金属催化剂是按照下述方法进行制备的： The carbon nanotube/polypropylene inner alloy is composed of carbon nanotubes, a homopolymeric isotactic polypropylene resin having a weight average molecular weight of 150,000 g/mol, and an ethylene/octene random copolymer; carbon nanotubes, ethylene/octene-free The mass ratio of the copolymer and the homopolypropylene resin was 1.17: 9.6: 89.23. The apparent morphology of the particles is spherical, and the particle size is 50-500 μm; the carbon nanotubes have a particle size of 10 nm, a length of 0.5 μm, and a length to diameter ratio of 50. Among them, the carbon nanotube-supported transition metal catalyst used is prepared according to the following method:

将上述氯化镁醇合物滴加入 3.0g球形碳纳米管载体 /100ml癸烷的悬浮液中，于 90°C下恒温反应 12.0个小时，然后滤除液体，滤出的固体用癸烷洗涤 3次，干燥后得到碳纳米管催化剂载体的镁复合物。 The above magnesium chloride alcoholate was added dropwise to a suspension of 3.0 g of spherical carbon nanotube support/100 ml of decane, and the reaction was carried out at 90 ° C for 12.0 hours, and then the liquid was filtered off, and the filtered solid was washed 3 times with decane. After drying, a magnesium composite of a carbon nanotube catalyst carrier is obtained.

2) 向 -20°C的 100ml四氯化钛溶液中加入 lO.Og球形所述碳纳米管催化剂载体的镁复合物，并于 -20°C下恒温反应 1.0个小时。缓慢升温至 110°C，加入 1.0ml邻苯二甲酸二异丁酯，然后于 110°C下恒温反应 2.0个小时，反应完成后滤除液体，再次加入 100ml四氯化钛溶液，于 120°C下恒温反应 2.0个小时。最后，用己烷洗涤 3~6次，干燥后得到碳纳米管负载钛化合物。 2) To 100 ml of a titanium tetrachloride solution at -20 ° C, 10 g of a magnesium complex of the spherical carbon nanotube catalyst carrier was added and reacted at -20 ° C for 1.0 hour at a constant temperature. Slowly raise the temperature to 110 ° C, add 1.0 ml of diisobutyl phthalate, and then react at a constant temperature of 110 ° C for 2.0 hours. After the reaction is completed, the liquid is filtered off, and 100 ml of titanium tetrachloride solution is added again at 120 °. The reaction was carried out under constant temperature for 2.0 hours. Finally, it was washed with hexane for 3 to 6 times, and after drying, a carbon nanotube-supported titanium compound was obtained.

3 ) 取 5.0g所述球形碳纳米管负载钛化合物分散于 50ml甲苯中，然后加入含 0.05mol甲基铝氧烷的甲苯溶液 30ml，于 90°C下反应 10.0个小时，然后用甲苯洗涤 5次，干燥后得到活化的碳纳米管催化剂。 3) Take 5.0 g of the spherical carbon nanotube-supported titanium compound and disperse it in 50 ml of toluene, then add 30 ml of a toluene solution containing 0.05 mol of methylaluminoxane, react at 90 ° C for 10.0 hours, and then wash with toluene 5 Second, an activated carbon nanotube catalyst is obtained after drying.

4)将 0.15g过渡金属化合物 rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂加入至含有 0. lOmol 甲基铝氧烷的甲苯溶液 40ml中，于 0°C下反应 4.0个小时，得到活化的催化剂溶液。 4) 0.15g of transition metal compound rac-Me ₂ Si(2-Me-4-PhInd) ₂ ZrCl _{2 was} added to 40 ml of toluene solution containing 0.1 mol of methyl aluminoxane, and reacted at 0 ° C for 4.0 In an hour, an activated catalyst solution was obtained.

该碳纳米管负载过渡金属催化剂为球形颗粒，由碳纳米管催化剂载体、过渡金属化合物 rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂、四氯化钛、氯化镁、甲基铝氧烷和内给电子体邻苯二甲酸二异丁酯组成；其中钛元素、镁元素、锆元素、铝元素的含量分别为 2.01wt%、 3.51wt% 0.25wt% 8.53wt%,邻苯二甲酸二异丁酯的含量为 9.2wt%。该催化剂的比表面积为 145m²/g，孔容为 0.55cm³/g，平均孔径为 20.5nm，堆密度 0.23g/ml。 The carbon nanotube-supported transition metal catalyst is a spherical particle composed of a carbon nanotube catalyst carrier, a transition metal compound rac-Me ₂ Si(2-Me-4-PhInd) ₂ ZrCl ₂ , titanium tetrachloride, magnesium chloride, methyl aluminum The composition of the oxane and the internal electron donor diisobutyl phthalate; wherein the content of the titanium element, the magnesium element, the zirconium element, and the aluminum element is 2.01 wt%, 3.51 wt%, 0.25 wt%, 8.53 wt%, respectively. The content of diisobutyl formate was 9.2% by weight. The catalyst had a specific surface area of 145 m ² /g, a pore volume of 0.55 cm ³ /g, an average pore diameter of 20.5 nm, and a bulk density of 0.23 g/ml.

其中，所用碳纳米管催化剂载体按照下述方法制备而得： Wherein, the carbon nanotube catalyst carrier used is prepared according to the following method:

1 )将 5.0g碳纳米管 (碳纳米管的粒径为 10nm，长度为 0.5μιη，长径比 50)经超声分散于 300毫升水中形成悬浮液，搅拌 0.5小时后，喷雾干燥成型制备得到碳纳米管催化剂载体，喷雾干燥的压力为 0.05MPa，干燥进风温度 180°C，进料速度为 23.0ml/min, 得到成形的碳纳米管载体；该载体颗粒形态为球形，其颗粒粒径大小为 15~50μιη，比表面积为 180.0m²/g，平均孔容为 0.66cm³/g，平均孔径为 24.2nm，堆密度 0.20g/ml。 1) 5.0 g of carbon nanotubes (having a particle diameter of 10 nm, a length of 0.5 μm, and a length to diameter ratio of 50) were ultrasonically dispersed in 300 ml of water to form a suspension, and after stirring for 0.5 hours, the carbon was prepared by spray drying. The nanotube catalyst carrier has a spray drying pressure of 0.05 MPa, a dry inlet air temperature of 180 ° C, and a feed rate of 23.0 ml/min, to obtain a shaped carbon nanotube carrier; the carrier particle shape is spherical, and the particle size thereof It is 15 to 50 μm, has a specific surface area of 180.0 m ² /g, an average pore volume of 0.66 cm ³ /g, an average pore diameter of 24.2 nm, and a bulk density of 0.20 g/ml.

2) 将步骤 1 ) 所得成形的碳纳米管载体分散于***中，碳纳米管与分散介质的质量比为 0.1 : 1；加入固体光气于 30°C活化 24小时，碳纳米管与固体光气的质量比为 0.1 : 1，之后将介质用真空泵抽干，加入十一烯酸 30°C反应 24小时，碳纳米管与十一烯酸的质量比为 0.1 : 1，之后将介质用真空泵抽干，甲醇洗涤若干次，得到碳纳米管催化剂载体，颗粒形态为球形，粒径为 5~100μιη，比表面积为 113m²/g，平均孔径为 18.1nm，平均孔容为 0.45cm³/g，堆密度为 0.25g/ml，带有反应性双键的基团也即碳碳双键占该碳纳米管催化剂载体的含量为 25.0wt%。 2) The formed carbon nanotube carrier obtained in the step 1) is dispersed in diethyl ether, and the mass ratio of the carbon nanotube to the dispersion medium is 0.1:1; the solid phosgene is activated at 30 ° C for 24 hours, and the carbon nanotubes and the solid light are activated. The mass ratio of gas is 0.1:1, and then the medium is vacuumed by a vacuum pump, and undecylenic acid is added at 30 ° C for 24 hours. The mass ratio of carbon nanotubes to undecylenic acid is 0.1:1, and then the medium is vacuum pump. Draining, washing with methanol several times, to obtain a carbon nanotube catalyst carrier, the particle shape is spherical, the particle size is 5~100μιη, the specific surface area is 113m ² /g, the average pore diameter is 18.1nm, and the average pore volume is 0.45cm ³ /g. , bulk density of 0.25g/ml, with reactive double bonds The group, that is, the carbon-carbon double bond, accounts for 25.0% by weight of the carbon nanotube catalyst carrier.

实施例 5 Example 5

1 )将 250g液态丙烯加入至反应釜中， 30°C下依次加入 0.23mol助催化剂三乙基铝、 0.033mol甲基铝氧烷及 l.Og碳纳米管负载过渡金属催化剂（三乙基铝和催化剂中过渡金属元素钛之间摩尔比为 600: 1；甲基铝氧烷与催化剂中过渡金属元素锆的摩尔比为 2000: 1 ) 以及氢气 0.2g，压强为 3.0MPa，升温至 70°C，反应 0.2个小时，得到中间产物聚合物 94.1g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.23 mol of promoter triethylaluminum, 0.033 mol of methylaluminoxane and 1.0 g of carbon nanotube-supported transition metal catalyst (triethylaluminum) were sequentially added at 30 ° C. The molar ratio of the transition metal element titanium to the catalyst is 600:1; the molar ratio of methylaluminoxane to the transition metal element zirconium in the catalyst is 2000:1) and the hydrogen gas is 0.2g, the pressure is 3.0MPa, and the temperature is raised to 70°. C, the reaction was carried out for 0.2 hours to obtain 94.1 g of an intermediate product polymer, which was directly subjected to the next reaction.

2) 将上述步骤 1 ) 中的反应釜内残留的丙烯放空并降温至 30°C，再通入 20g 乙烯和 60g丙烯的混合气，通入氢气 0.05g，压强为 l.OMPa, 升温至 90°C，反应 0.2 个小时，最终得到碳纳米管 /聚丙烯釜内合金 111.0g。 2) The propylene remaining in the reaction vessel in the above step 1) was vented and cooled to 30 ° C, and then a mixture of 20 g of ethylene and 60 g of propylene was introduced, and 0.05 g of hydrogen was introduced thereto, and the pressure was 1.0 MPa, and the temperature was raised to 90. At °C, the reaction was carried out for 0.2 hours, and finally 111.0 g of a carbon nanotube/polypropylene inner alloy was obtained.

该碳纳米管 /聚丙烯釜内合金由碳纳米管、重均分子量为 300000g/mol的均聚等规聚丙烯树脂和乙烯 /丙烯无规共聚物组成；碳纳米管、乙烯 /丙烯无规共聚物、均聚聚丙烯树脂的质量比为 0.90: 15.2： 83.9。颗粒表观形态为球形，颗粒粒径为 50~500μιη; 碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250。 The carbon nanotube/polypropylene inner alloy is composed of carbon nanotubes, a homopolymeric isotactic polypropylene resin having a weight average molecular weight of 300,000 g/mol, and an ethylene/propylene random copolymer; carbon nanotubes, ethylene/propylene random copolymerization The mass ratio of the homopolymeric polypropylene resin was 0.90: 15.2: 83.9. The apparent morphology of the particles is spherical, and the particle size is 50-500 μm; the carbon nanotubes have a particle size of 20 nm, a length of 5 μm, and an aspect ratio of 250.

2)向 -20°C的 100ml四氯化钛溶液中加入 lO.Og球形碳纳米管载体的镁复合物，并于 -20°C下恒温反应 1.0个小时。缓慢升温至 60°C，加入 2.0g芴二醚，然后于 110°C 下恒温反应 2.0个小时，反应完成后滤除液体，再次加入 100ml四氯化钛溶液，于 120°C下恒温反应 2.0个小时。最后，用己烷洗涤 3~6次，干燥后得到碳纳米管负载钛化合物。 2) To a 100 ml titanium tetrachloride solution at -20 ° C, a magnesium complex of lO.Og spherical carbon nanotube support was added and reacted at -20 ° C for 1.0 hour at a constant temperature. Slowly raise the temperature to 60 ° C, add 2.0 g of decyl diether, and then react at a constant temperature of 110 ° C for 2.0 hours. After the reaction is completed, the liquid is filtered off, and 100 ml of titanium tetrachloride solution is added again, and the reaction is kept at 120 ° C at a constant temperature of 2.0. Hours. Finally, it was washed 3 to 6 times with hexane, and dried to obtain a carbon nanotube-supported titanium compound.

3 )取 5.0g球形碳纳米管负载钛化合物分散于 50ml甲苯中，然后加入含 O. lmol 甲基铝氧烷的甲苯溶液 30ml，于 90°C下反应 4.0个小时，然后用甲苯洗涤 5次，干燥后得到活化的碳纳米管催化剂。 3) Take 5.0 g of spherical carbon nanotube-supported titanium compound and disperse it in 50 ml of toluene, then add 30 ml of a toluene solution containing 0.1 mol of methylaluminoxane, react at 90 ° C for 4.0 hours, and then wash 5 times with toluene. After drying, an activated carbon nanotube catalyst is obtained.

该碳纳米管负载过渡金属催化剂为球形颗粒由碳纳米管催化剂载体、过渡金属化合物 Et(Ind)₂ZrCl₂、四氯化钛、氯化镁、甲基铝氧烷和内给电子体芴二醚组成；其中钛元素、镁元素、锆元素、铝元素的含量分别为 1.81%、 3.32%、 0.15%、 8.27%, 内给电子体芴二醚的含量为 11.6wt%。该催化剂的比表面积为 132m²/g，孔容为 0.33cm³/g, 平均孔径为 18.7nm。其中，所用碳纳米管催化剂载体按照下述方法制备而得： The carbon nanotube-supported transition metal catalyst is composed of a carbon nanotube catalyst carrier, a transition metal compound Et(Ind) ₂ ZrCl ₂ , titanium tetrachloride, magnesium chloride, methyl aluminoxane and an internal electron donor decane. The content of titanium element, magnesium element, zirconium element and aluminum element is 1.81%, 3.32%, 0.15%, 8.27%, respectively, and the content of the internal electron donor sebacon is 11.6 wt%. The catalyst had a specific surface area of 132 m ² /g, a pore volume of 0.33 cm ³ /g, and an average pore diameter of 18.7 nm. Wherein, the carbon nanotube catalyst carrier used is prepared according to the following method:

1 )将 5.0g碳纳米管 (碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250)经超声分散于 300毫升乙醇中形成悬浮液，搅拌 0.5小时后，喷雾干燥成型制备得到碳纳米管催化剂载体，喷雾干燥的压力为 0.2MPa，干燥进风温度 120°C，进料速度为 lO.Oml/min, 得到成形的碳纳米管载体；该载体颗粒形态为球形，其颗粒粒径大小为 8~20μιη，比表面积为 165.0m²/g，平均孔容为 0.55cm³/g，平均孔径为 20.0nm，堆密度 0.18g/ml。 1) 5.0 g of carbon nanotubes (having a particle diameter of 20 nm, a length of 5 μm, and a length to diameter ratio of 250) were ultrasonically dispersed in 300 ml of ethanol to form a suspension, stirred for 0.5 hours, and spray-dried to prepare carbon. The nanotube catalyst carrier has a spray drying pressure of 0.2 MPa, a dry inlet air temperature of 120 ° C, a feed rate of 10 mL/min, and a shaped carbon nanotube carrier is obtained; the carrier particle shape is spherical, and the particle size thereof is The size is 8-20 μm, the specific surface area is 165.0 m ² /g, the average pore volume is 0.55 cm ³ /g, the average pore diameter is 20.0 nm, and the bulk density is 0.18 g/ml.

2) 将步骤 1 ) 所得成形的碳纳米管载体分散于丁醚中，碳纳米管与分散介质的质量比为 0.2: 1；加入固体光气于 30°C活化 24小时，碳纳米管与固体光气的质量比为 0.5 : 1，之后将介质用真空泵抽干，加入丙烯酸 30°C反应 24小时，碳纳米管与丙烯酸的质量比为 0.5 : 1，之后将介质用真空泵抽干，甲醇洗涤若干次，得到碳纳米管催化剂载体，颗粒形态为球形，粒径为 5~100μιη，比表面积为 138.3m²/g，平均孔径为 18.1nm，平均孔容为 0.45cm³/g，堆密度为 0.25g/ml，带有反应性双键的基团也即碳碳双键占该碳纳米管催化剂载体的含量为 6.5wt%。 2) The formed carbon nanotube carrier obtained in the step 1) is dispersed in the dibutyl ether, the mass ratio of the carbon nanotube to the dispersion medium is 0.2:1; the solid phosgene is activated at 30 ° C for 24 hours, the carbon nanotubes and the solid The mass ratio of phosgene is 0.5:1, and then the medium is vacuumed by a vacuum pump, and the reaction is carried out at 30 ° C for 24 hours. The mass ratio of carbon nanotubes to acrylic acid is 0.5:1, and then the medium is vacuum-dried and washed with methanol. Several times, a carbon nanotube catalyst carrier was obtained, the particle shape was spherical, the particle size was 5 to 100 μm, the specific surface area was 138.3 m ² /g, the average pore diameter was 18.1 nm, the average pore volume was 0.45 cm ³ /g, and the bulk density was At 0.25 g/ml, the group having a reactive double bond, that is, the carbon-carbon double bond, accounts for 6.5 wt% of the carbon nanotube catalyst carrier.

实施例 6 Example 6

1 )将 250g液态丙烯加入至反应釜中， 30°C下依次加入 0.23mol助催化剂三乙基铝、 0.033mol甲基铝氧烷及 l .Og碳纳米管负载过渡金属催化剂（三乙基铝和催化剂中过渡金属元素钛之间摩尔比为 600: 1；甲基铝氧烷与催化剂中过渡金属元素锆的摩尔比为 2000: 1 ) 以及氢气 0.2g，压强为 3.0MPa，升温至 70°C，反应 0.2个小时，得到中间产物聚合物 123.7g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.23 mol of promoter triethylaluminum, 0.033 mol of methylaluminoxane and 1.0 g of carbon nanotube-supported transition metal catalyst (triethylaluminum) were sequentially added at 30 ° C. The molar ratio of the transition metal element titanium to the catalyst is 600:1; the molar ratio of methylaluminoxane to the transition metal element zirconium in the catalyst is 2000:1) and the hydrogen gas is 0.2g, the pressure is 3.0MPa, and the temperature is raised to 70°. C, the reaction was carried out for 0.2 hours to obtain 123.7 g of an intermediate polymer, which was directly subjected to the next reaction.

2) 将上述步骤 1 ) 中的反应釜内残留的丙烯放空并降温至 30°C，再通入 20g 乙烯和 60g丙烯的混合气，通入氢气 0.05g，压强为 l .OMPa, 升温至 90°C，反应 0.2 个小时，最终得到碳纳米管 /聚丙烯釜内合金 156.0g。 2) The propylene remaining in the reaction vessel in the above step 1) was vented and cooled to 30 ° C, and then a mixture of 20 g of ethylene and 60 g of propylene was introduced, and 0.05 g of hydrogen gas was introduced thereto, and the pressure was 1.0 MPa, and the temperature was raised to 90 ° At °C, the reaction was carried out for 0.2 hours, and finally 156.0 g of a carbon nanotube/polypropylene inner alloy was obtained.

该碳纳米管 /聚丙烯釜内合金由碳纳米管、重均分子量为 250000g/mol的均聚等规聚丙烯树脂和乙烯 /丙烯无规共聚物组成；碳纳米管、乙烯 /丙烯无规共聚物、均聚聚丙烯树脂的质量比为 0.64: 20.7： 78.66。颗粒表观形态为球形，颗粒粒径大小为 50~500μιη_; 碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250。 The carbon nanotube/polypropylene inner alloy is composed of carbon nanotubes, a homopolymeric isotactic polypropylene resin having a weight average molecular weight of 250,000 g/mol, and an ethylene/propylene random copolymer; carbon nanotubes, ethylene/propylene random copolymerization The mass ratio of the homopolymeric polypropylene resin was 0.64: 20.7: 78.66. The apparent morphology of the particles is spherical, and the particle size is 50-500 μm _; the diameter of the carbon nanotubes is 20 nm, the length is 5 μιη, and the aspect ratio is 250.

2)向 -20°C的 100ml四氯化钛溶液中加入 lO.Og球形碳纳米管载体的镁复合物，并于 -20°C下恒温反应 1.0个小时。缓慢升温至 60°C，加入 2.0g芴二醚，然后于 110°C 下恒温反应 2.0个小时，反应完成后滤除液体，再次加入 100ml四氯化钛溶液，于 120°C下恒温反应 2.0个小时。最后，用己烷洗涤 3~6次，干燥后得到碳纳米管负载钛化合物。 3 )取 5.0g球形碳纳米管负载钛化合物分散于 50ml甲苯中，然后加入含 O. lmol 甲基铝氧烷的甲苯溶液 30ml，于 90°C下反应 4.0个小时，然后用甲苯洗涤 5次，干燥后得到活化的碳纳米管催化剂。 2) To a 100 ml titanium tetrachloride solution at -20 ° C, a magnesium complex of 10 g of a spherical carbon nanotube support was added, and reacted at -20 ° C for 1.0 hour at a constant temperature. Slowly raise the temperature to 60 ° C, add 2.0 g of decyl diether, and then react at a constant temperature of 110 ° C for 2.0 hours. After the reaction is completed, the liquid is filtered off, and 100 ml of titanium tetrachloride solution is added again, and the reaction is kept at 120 ° C at a constant temperature of 2.0. Hours. Finally, it was washed 3 to 6 times with hexane, and dried to obtain a carbon nanotube-supported titanium compound. 3) Take 5.0 g of spherical carbon nanotube-supported titanium compound and disperse it in 50 ml of toluene, then add 30 ml of a toluene solution containing 0.1 mol of methylaluminoxane, react at 90 ° C for 4.0 hours, and then wash 5 times with toluene. After drying, an activated carbon nanotube catalyst is obtained.

该碳纳米管负载过渡金属催化剂为球形颗粒由碳纳米管催化剂载体、过渡金属化合物 Et(Ind)₂ZrCl₂、四氯化钛、氯化镁、甲基铝氧烷和内给电子体芴二醚组成；其中钛元素、镁元素、锆元素、铝元素的含量分别为 1.81wt%、 3.52wt% 0.15wt%、 8.45wt%，内给电子体芴二醚的含量为 11.52wt%。该碳纳米管负载过渡金属催化剂的比表面积为 115m²/g，孔容为 0.32cm³/g，平均孔径为 18.4nm。 The carbon nanotube-supported transition metal catalyst is composed of a carbon nanotube catalyst carrier, a transition metal compound Et(Ind) ₂ ZrCl ₂ , titanium tetrachloride, magnesium chloride, methyl aluminoxane and an internal electron donor decane. The content of the titanium element, the magnesium element, the zirconium element, and the aluminum element is 1.81 wt%, 3.52 wt%, 0.15 wt%, and 8.45 wt%, respectively, and the content of the internal electron donor sebacon is 11.52 wt%. The carbon nanotube-supported transition metal catalyst had a specific surface area of 115 m ² /g, a pore volume of 0.32 cm ³ /g, and an average pore diameter of 18.4 nm.

其中，所用碳纳米管催化剂载体，是按照下述方法制备的： Among them, the carbon nanotube catalyst carrier used was prepared as follows:

将 5.0g碳纳米管 (碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250)经超声分散于 300毫升乙醇中形成悬浮液，搅拌 0.5小时后，喷雾干燥成型制备得到碳纳米管催化剂载体，喷雾干燥的压力为 0.05MPa，干燥进风温度 180°C，进料速度为 30.0ml/min。该碳纳米管载体颗粒形态为球形，其颗粒粒径大小为 15~45μιη。由氮气吸附测试可知，碳纳米管载体比表面积为 188.0m²/g，平均孔容为 0.72cm³/g，平均孔径为 24.5nm。 5.0 g of carbon nanotubes (having a particle diameter of 20 nm, a length of 5 μm, and a length to diameter ratio of 250) were ultrasonically dispersed in 300 ml of ethanol to form a suspension, stirred for 0.5 hours, and spray-dried to prepare carbon nanotubes. The catalyst carrier had a spray drying pressure of 0.05 MPa, a dry inlet air temperature of 180 ° C, and a feed rate of 30.0 ml/min. The carbon nanotube carrier particle has a spherical shape and a particle size of 15 to 45 μm. As a result of nitrogen gas adsorption test, the carbon nanotube carrier had a specific surface area of 188.0 m ² /g, an average pore volume of 0.72 cm ³ /g, and an average pore diameter of 24.5 nm.

实施例 7 Example 7

1 )将 250g液态丙烯加入至反应釜中， 30°C下依次加入 0.23mol助催化剂三乙基铝、 0.033mol甲基铝氧烷及 l .Og碳纳米管负载过渡金属催化剂（三乙基铝和催化剂中过渡金属元素钛之间摩尔比为 600: 1；甲基铝氧烷与催化剂中过渡金属元素锆的摩尔比为 2000: 1 ) 以及氢气 0.2g，压强为 3.0MPa，升温至 70°C，反应 0.2个小时，得到中间产物聚合物 107.7g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.23 mol of promoter triethylaluminum, 0.033 mol of methylaluminoxane and 1.0 g of carbon nanotube-supported transition metal catalyst (triethylaluminum) were sequentially added at 30 ° C. The molar ratio of the transition metal element titanium to the catalyst is 600:1; the molar ratio of methylaluminoxane to the transition metal element zirconium in the catalyst is 2000:1) and the hydrogen gas is 0.2g, the pressure is 3.0MPa, and the temperature is raised to 70°. C, the reaction was carried out for 0.2 hours to obtain 107.7 g of an intermediate polymer, which was directly subjected to the next reaction.

2) 将上述步骤 1 ) 中的反应釜内残留的丙烯放空并降温至 30°C，再通入 20g 乙烯和 60g丙烯的混合气，通入氢气 0.05g，压强为 l .OMPa, 升温至 90°C，反应 0.2 个小时，最终得到碳纳米管 /聚丙烯釜内合金 120.0g。 2) The propylene remaining in the reaction vessel in the above step 1) was vented and cooled to 30 ° C, and then a mixture of 20 g of ethylene and 60 g of propylene was introduced, and 0.05 g of hydrogen gas was introduced thereto, and the pressure was 1.0 MPa, and the temperature was raised to 90 ° At °C, the reaction was carried out for 0.2 hours, and finally 120.0 g of a carbon nanotube/polypropylene inner alloy was obtained.

该碳纳米管 /聚丙烯釜内合金由碳纳米管、重均分子量为 220000g/mol的均聚等规聚丙烯树脂和乙烯 /丙烯无规共聚物组成；碳纳米管、乙烯 /丙烯无规共聚物、均聚聚丙烯树脂的质量比为 0.83 : 10.3： 88.87。颗粒表观形态为球形，颗粒粒径大小为 50~500μιη_; 碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250。 The carbon nanotube/polypropylene inner alloy is composed of carbon nanotubes, a homopolymeric isotactic polypropylene resin having a weight average molecular weight of 220,000 g/mol, and an ethylene/propylene random copolymer; carbon nanotubes, ethylene/propylene random copolymerization The mass ratio of the homopolymeric polypropylene resin was 0.83: 10.3: 88.87. The apparent morphology of the particles is spherical, and the particle size is 50-500 μm _; the diameter of the carbon nanotubes is 20 nm, the length is 5 μιη, and the aspect ratio is 250.

将上述氯化镁醇合物滴加入 3.0g球形碳纳米管载体 /100ml癸烷的悬浮液中，于 90°C下恒温反应 12.0个小时，然后滤除液体，滤出的固体用癸烷洗涤 3次，干燥后得到碳纳米管载体的镁复合物。 The above magnesium chloride alcoholate was added dropwise to a suspension of 3.0 g of spherical carbon nanotube support/100 ml of decane, and the reaction was carried out at 90 ° C for 12.0 hours, and then the liquid was filtered off, and the filtered solid was washed 3 times with decane. Dry After drying, a magnesium composite of a carbon nanotube support is obtained.

2)向 -20°C的 100ml四氯化钛溶液中加入 lO.Og球形碳纳米管载体的镁复合物，并于 -20°C下恒温反应 1.0个小时。缓慢升温至 60°C，加入 3.0g芴二醚，然后于 110°C 下恒温反应 2.0个小时，反应完成后滤除液体，再次加入 100ml四氯化钛溶液，于 120°C下恒温反应 2.0个小时。最后，用己烷洗涤 3~6次，干燥后得到碳纳米管负载钛化合物。 2) To a 100 ml titanium tetrachloride solution at -20 ° C, a magnesium complex of lO.Og spherical carbon nanotube support was added and reacted at -20 ° C for 1.0 hour at a constant temperature. Slowly raise the temperature to 60 ° C, add 3.0 g of decyl diether, and then react at a constant temperature of 110 ° C for 2.0 hours. After the reaction is completed, the liquid is filtered off, and 100 ml of titanium tetrachloride solution is added again, and the reaction is kept at 120 ° C at a constant temperature of 2.0. Hours. Finally, it was washed 3 to 6 times with hexane, and dried to obtain a carbon nanotube-supported titanium compound.

该碳纳米管负载过渡金属催化剂为球形颗粒，由碳纳米管催化剂载体、过渡金属化合物 Et(Ind)₂ZrCl₂、四氯化钛、氯化镁、甲基铝氧烷和内给电子体芴二醚组成；其中钛元素、镁元素、锆元素、铝元素的含量分别为 1.81wt%、 3.52wt% 0.15wt%、 8.45wt%，芴二醚的含量为 10.32wt%。该碳纳米管负载过渡金属催化剂的比表面积为 122.5m²/g，孔容为 0.23cm³/g，平均孔径为 14.7nm。 The carbon nanotube-supported transition metal catalyst is a spherical particle, which is composed of a carbon nanotube catalyst carrier, a transition metal compound Et(Ind) ₂ ZrCl ₂ , titanium tetrachloride, magnesium chloride, methyl aluminoxane and internal electron donor deuterated diether. The content of the titanium element, the magnesium element, the zirconium element, and the aluminum element is 1.81 wt%, 3.52 wt%, 0.15 wt%, and 8.45 wt%, respectively, and the content of the sebacic ether is 10.32 wt%. The carbon nanotube-supported transition metal catalyst had a specific surface area of 122.5 m ² /g, a pore volume of 0.23 cm ³ /g, and an average pore diameter of 14.7 nm.

1 )将 5.0g碳纳米管 (碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250)经超声分散于 300毫升乙醇中形成悬浮液，搅拌 0.5小时后，喷雾干燥成型制备得到碳纳米管催化剂载体，喷雾干燥的压力为 0.15MPa，干燥进风温度 120°C，进料速度为 10.0ml/min，得到成形的碳纳米管载体；该载体颗粒形态为球形，其颗粒粒径大小为 8~20μιη，比表面积为 175.1m²/g，平均孔容为 0.55cm³/g，平均孔径为 20.0nm，堆密度 0.18g/ml。 1) 5.0 g of carbon nanotubes (having a particle diameter of 20 nm, a length of 5 μm, and a length to diameter ratio of 250) were ultrasonically dispersed in 300 ml of ethanol to form a suspension, stirred for 0.5 hours, and spray-dried to prepare carbon. The nanotube catalyst carrier, the spray drying pressure is 0.15 MPa, the dry inlet air temperature is 120 ° C, the feed rate is 10.0 ml/min, and the formed carbon nanotube carrier is obtained; the carrier particle shape is spherical, and the particle size thereof It is 8-20 μm, has a specific surface area of 175.1 m ² /g, an average pore volume of 0.55 cm ³ /g, an average pore diameter of 20.0 nm, and a bulk density of 0.18 g/ml.

2) 将步骤 1 ) 所得成形的碳纳米管载体分散于己烷中，碳纳米管与分散介质的质量比为 0.05 : 1；加入固体光气于 30°C活化 24小时，碳纳米管与固体光气的质量比为 0.2: 1，之后将介质用真空泵抽干，加入十八烯酸 30°C反应 24小时，碳纳米管与十八烯酸的质量比为 0.05 : 1，之后将介质用真空泵抽干，甲醇洗涤若干次，得到碳纳米管催化剂载体，颗粒形态为球形，粒径为 5~100μιη，比表面积为 148.1m²/g，平均孔径为 18.1nm，平均孔容为 0.45cm³/g，堆密度为 0.25g/ml，带有反应性双键的基团也即碳碳双键占该碳纳米管催化剂载体的含量为 26.7wt%。 2) Dispersing the formed carbon nanotube carrier obtained in the step 1) in hexane, the mass ratio of the carbon nanotube to the dispersion medium is 0.05:1; adding solid phosgene to activate at 30 ° C for 24 hours, carbon nanotubes and solid The mass ratio of phosgene is 0.2: 1, and then the medium is vacuumed by a vacuum pump, and octadecanoic acid is added at 30 ° C for 24 hours. The mass ratio of carbon nanotubes to oleic acid is 0.05: 1, and then the medium is used. The vacuum pump was drained and washed with methanol several times to obtain a carbon nanotube catalyst carrier. The particle shape was spherical, the particle size was 5 to 100 μm, the specific surface area was 148.1 m ² /g, the average pore diameter was 18.1 nm, and the average pore volume was 0.45 cm ^{3 .} /g, the bulk density is 0.25 g/ml, and the group having a reactive double bond, that is, the carbon-carbon double bond accounts for 26.7 wt% of the carbon nanotube catalyst carrier.

实施例 8 Example 8

1 )将 250g液态丙烯加入至反应釜中， 30°C下依次加入 0.24mol助催化剂三乙基铝、 0.033mol甲基铝氧烷及 l .Og碳纳米管负载过渡金属催化剂（三乙基铝和催化剂中过渡金属元素钛之间摩尔比为 600: 1；甲基铝氧烷与催化剂中过渡金属元素锆的摩尔比为 2000: 1 ) 以及氢气 0.2g，压强为 3.0MPa，升温至 70°C，反应 0.2个小时，得到中间产物聚合物 199.3g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.24 mol of promoter triethylaluminum, 0.033 mol of methylaluminoxane and 1.0 g of carbon nanotube-supported transition metal catalyst (triethylaluminum) were sequentially added at 30 ° C. The molar ratio of the transition metal element titanium to the catalyst is 600:1; the molar ratio of methylaluminoxane to the transition metal element zirconium in the catalyst is 2000:1) and the hydrogen gas is 0.2g, the pressure is 3.0MPa, and the temperature is raised to 70°. C, the reaction is 0.2 small At this time, 199.3 g of an intermediate product polymer was obtained, and the next reaction was directly carried out.

2) 将上述步骤 1 ) 中的反应釜内残留的丙烯放空并降温至 30°C，再通入 20g 乙烯和 60g丙烯的混合气，通入氢气 0.05g，压强为 l .OMPa, 升温至 90°C，反应 0.2 个小时，最终得到碳纳米管 /聚丙烯釜内合金 210g。 2) The propylene remaining in the reaction vessel in the above step 1) was vented and cooled to 30 ° C, and then a mixture of 20 g of ethylene and 60 g of propylene was introduced, and 0.05 g of hydrogen gas was introduced thereto, and the pressure was 1.0 MPa, and the temperature was raised to 90 ° At °C, the reaction was carried out for 0.2 hours, and finally 210 g of a carbon nanotube/polypropylene inner alloy was obtained.

该碳纳米管 /聚丙烯釜内合金由碳纳米管、重均分子量为 180000g/mol的均聚等规聚丙烯树脂和乙烯 /丙烯无规共聚物组成；碳纳米管、乙烯 /丙烯无规共聚物、均聚聚丙烯树脂的质量比为 0.48: 5.1： 94.42。颗粒表观形态为球形，颗粒粒径大小为 50~500μιη_; 碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250。 The carbon nanotube/polypropylene inner alloy is composed of carbon nanotubes, a homopolymeric isotactic polypropylene resin having a weight average molecular weight of 180,000 g/mol, and an ethylene/propylene random copolymer; carbon nanotubes, ethylene/propylene random copolymerization The mass ratio of the homopolymeric polypropylene resin was 0.48: 5.1: 94.42. The apparent morphology of the particles is spherical, and the particle size is 50-500 μm _; the diameter of the carbon nanotubes is 20 nm, the length is 5 μιη, and the aspect ratio is 250.

该碳纳米管负载过渡金属催化剂为球形颗粒，由碳纳米管催化剂载体、过渡金属化合物 Et(Ind)₂ZrCl₂、四氯化钛、氯化镁、甲基铝氧烷和内给电子体芴二醚组成；其中钛元素、镁元素、锆元素、铝元素的含量分别为 1.82%、 3.52%、 0.15%、 8.45%, 芴二醚的含量为 11.21%。该碳纳米管负载过渡金属催化剂的比表面积为 103.2m²/g，孔容为 0.22cm³/g，平均孔径为 12.7nm。 The carbon nanotube-supported transition metal catalyst is a spherical particle, which is composed of a carbon nanotube catalyst carrier, a transition metal compound Et(Ind) ₂ ZrCl ₂ , titanium tetrachloride, magnesium chloride, methyl aluminoxane and internal electron donor deuterated diether. Composition; wherein the content of titanium element, magnesium element, zirconium element and aluminum element is 1.82%, 3.52%, 0.15%, 8.45%, respectively, and the content of sebacic ether is 11.21%. The carbon nanotube-supported transition metal catalyst had a specific surface area of 103.2 m ² /g, a pore volume of 0.22 cm ³ /g, and an average pore diameter of 12.7 nm.

1 )将 5.0g碳纳米管 (碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250)经超声分散于 300毫升乙醇中形成悬浮液，搅拌 0.5小时后，喷雾干燥成型制备得到碳纳米管催化剂载体，喷雾干燥的压力为 0.15MPa，干燥进风温度 120°C，进料速度为 10.0ml/min，得到成形的碳纳米管载体；该载体颗粒形态为球形，其颗粒粒径大小为 8~20μιη，比表面积为 175.0m²/g，平均孔容为 0.55cm³/g，平均孔径为 20.0nm，堆密度 0.18g/ml。 1) 5.0 g of carbon nanotubes (having a particle diameter of 20 nm, a length of 5 μm, and a length to diameter ratio of 250) were ultrasonically dispersed in 300 ml of ethanol to form a suspension, stirred for 0.5 hours, and spray-dried to prepare carbon. The nanotube catalyst carrier, the spray drying pressure is 0.15 MPa, the dry inlet air temperature is 120 ° C, the feed rate is 10.0 ml/min, and the formed carbon nanotube carrier is obtained; the carrier particle shape is spherical, and the particle size thereof It is 8~20μιη, has a specific surface area of 175.0m ² /g, an average pore volume of 0.55cm ³ /g, and an average pore diameter of 20.0nm. The bulk density was 0.18 g/ml.

2) 将步骤 1 ) 所得成形的碳纳米管载体分散于丁醚中，碳纳米管与分散介质的质量比为 0.05: 1；加入固体光气于 30°C活化 24小时，碳纳米管与固体光气的质量比为 0.2: 1，之后将介质用真空泵抽干，加入辛烯醇 30°C反应 24小时，碳纳米管与辛烯醇的质量比为 0.05: 1，之后将介质用真空泵抽干，甲醇洗涤若干次，得到碳纳米管催化剂载体，颗粒形态为球形，粒径为 5~100μιη，比表面积为 148.4m²/g，平均孔径为 18.1nm，平均孔容为 0.45cm³/g，堆密度为 0.25g/ml，带有反应性双键的基团也即碳碳双键占该碳纳米管催化剂载体的含量为 15.8wt%。 2) The formed carbon nanotube carrier obtained in the step 1) is dispersed in the dibutyl ether, the mass ratio of the carbon nanotube to the dispersion medium is 0.05:1; the solid phosgene is activated at 30 ° C for 24 hours, the carbon nanotubes and the solid The mass ratio of phosgene is 0.2:1, and then the medium is vacuumed by a vacuum pump, and octene alcohol is added at 30 ° C for 24 hours. The mass ratio of carbon nanotubes to octenol is 0.05: 1, and then the medium is vacuum pumped. Dry, methanol washing several times to obtain a carbon nanotube catalyst carrier, the particle shape is spherical, the particle size is 5~100μιη, the specific surface area is 148.4m ² /g, the average pore diameter is 18.1nm, and the average pore volume is 0.45cm ³ /g. The bulk density is 0.25 g/ml, and the group having a reactive double bond, that is, the carbon-carbon double bond accounts for 15.8 wt% of the carbon nanotube catalyst carrier.

实施例 9 Example 9

1 )将 250g液态丙烯加入至反应釜中， 30°C下依次加入 0.23mol助催化剂三乙基铝、 0.033mol甲基铝氧烷及 l.Og碳纳米管负载过渡金属催化剂（三乙基铝和催化剂中过渡金属元素钛之间摩尔比为 600: 1；甲基铝氧烷与催化剂中过渡金属元素锆的摩尔比为 2000: 1 ) 以及氢气 0.2g，压强为 3.1MPa，升温至 70°C，反应 0.2个小时，得到中间产物聚合物 67.6g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.23 mol of promoter triethylaluminum, 0.033 mol of methylaluminoxane and 1.0 g of carbon nanotube-supported transition metal catalyst (triethylaluminum) were sequentially added at 30 ° C. The molar ratio of the transition metal element titanium to the catalyst is 600:1; the molar ratio of methylaluminoxane to the transition metal element zirconium in the catalyst is 2000: 1 ) and the hydrogen gas is 0.2 g, the pressure is 3.1 MPa, and the temperature is raised to 70°. C, the reaction was carried out for 0.2 hours to obtain 67.6 g of an intermediate polymer, which was directly subjected to the next reaction.

2) 将上述步骤 1 ) 中的反应釜内残留的丙烯放空并降温至 30°C，再通入 20g 乙烯和 60g丙烯的混合气，通入氢气 0.05g，压强为 l.OMPa, 升温至 90°C，反应 0.2 个小时，最终得到碳纳米管 /聚丙烯釜内合金 80.0g。 2) The propylene remaining in the reaction vessel in the above step 1) was vented and cooled to 30 ° C, and then a mixture of 20 g of ethylene and 60 g of propylene was introduced, and 0.05 g of hydrogen was introduced thereto, and the pressure was 1.0 MPa, and the temperature was raised to 90. At °C, the reaction was carried out for 0.2 hours, and finally 80.0 g of a carbon nanotube/polypropylene inner alloy was obtained.

该碳纳米管 /聚丙烯釜内合金由碳纳米管、重均分子量为 210000g/mol的均聚等规聚丙烯树脂和乙烯 /丙烯无规共聚物组成；碳纳米管、乙烯 /丙烯无规共聚物、均聚聚丙烯树脂的质量比为 1.25: 15.5： 83.25。颗粒表观形态为球形，颗粒粒径大小为 50~500μιη_; 碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250。 The carbon nanotube/polypropylene inner alloy is composed of carbon nanotubes, a homopolymeric isotactic polypropylene resin having a weight average molecular weight of 210,000 g/mol, and an ethylene/propylene random copolymer; carbon nanotubes, ethylene/propylene random copolymerization The mass ratio of the homopolymeric polypropylene resin was 1.25: 15.5: 83.25. The apparent morphology of the particles is spherical, and the particle size is 50-500 μm _; the diameter of the carbon nanotubes is 20 nm, the length is 5 μιη, and the aspect ratio is 250.

5 ) 将此催化剂溶液滴加入至含有 5.0g所述步骤 3 ) 制备所得活化的碳纳米管催化剂的 50ml甲苯悬浮液中，于 90°C下反应 4.0个小时。反应完成后，用甲苯洗涤 5次，干燥后得到本发明提供的碳纳米管负载的过渡金属催化剂。 5) adding the catalyst solution to the activated carbon nanotubes prepared by containing 5.0 g of the step 3) The catalyst was reacted in a 50 ml toluene suspension at 90 ° C for 4.0 hours. After completion of the reaction, it was washed 5 times with toluene, and dried to obtain a carbon nanotube-supported transition metal catalyst provided by the present invention.

该碳纳米管负载过渡金属催化剂为球形颗粒，由碳纳米管催化剂载体、过渡金属化合物 Et(Ind)₂ZrCl₂、四氯化钛、氯化镁、甲基铝氧烷和内给电子体芴二醚组成；其中钛元素、镁元素、锆元素、铝元素的含量分别为 1.81wt%、 3.42wt% 0.15wt%、 8.25wt%, 内给电子体芴二醚的含量为 10.33wt%。该碳纳米管负载过渡金属催化剂的比表面积为 128.6m²/g，孔容为 0.30cm³/g，平均孔径为 20.5nm。 The carbon nanotube-supported transition metal catalyst is a spherical particle, which is composed of a carbon nanotube catalyst carrier, a transition metal compound Et(Ind) ₂ ZrCl ₂ , titanium tetrachloride, magnesium chloride, methyl aluminoxane and internal electron donor deuterated diether. The content of the titanium element, the magnesium element, the zirconium element, and the aluminum element is 1.81% by weight, 3.42% by weight, 0.15% by weight, and 8.25% by weight, respectively, and the content of the internal electron donor sebacon is 10.33% by weight. The carbon nanotube-supported transition metal catalyst had a specific surface area of 128.6 m ² /g, a pore volume of 0.30 cm ³ /g, and an average pore diameter of 20.5 nm.

1 )将 5.0g碳纳米管 (碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250)经超声分散于 300毫升乙醇中形成悬浮液，搅拌 0.5小时后，喷雾干燥成型制备得到碳纳米管催化剂载体，喷雾干燥的压力为 0.05MPa，干燥进风温度 100°C，进料速度为 10.0ml/min，得到成形的碳纳米管载体；该载体颗粒形态为球形，其颗粒粒径大小为 8~20μιη，比表面积为 185.0m²/g，平均孔容为 0.65cm³/g，平均孔径为 23.0nm，堆密度 0.15g/ml。 1) 5.0 g of carbon nanotubes (having a particle diameter of 20 nm, a length of 5 μm, and a length to diameter ratio of 250) were ultrasonically dispersed in 300 ml of ethanol to form a suspension, stirred for 0.5 hours, and spray-dried to prepare carbon. The nanotube catalyst carrier has a spray drying pressure of 0.05 MPa, a dry inlet air temperature of 100 ° C, and a feed rate of 10.0 ml/min, to obtain a shaped carbon nanotube carrier; the carrier particle shape is spherical, and the particle size thereof It is 8 to 20 μm, has a specific surface area of 185.0 m ² /g, an average pore volume of 0.65 cm ³ /g, an average pore diameter of 23.0 nm, and a bulk density of 0.15 g/ml.

2) 将步骤 1 ) 所得成形的碳纳米管载体分散于丁醚中，碳纳米管与分散介质的质量比为 0.05 : 1；加入固体光气于 30°C活化 24小时，碳纳米管与固体光气的质量比为 0.05 : 1，之后将介质用真空泵抽干，加入癸烯醇 40°C反应 24小时，碳纳米管与癸烯醇的质量比为 0.1 : 1，之后将介质用真空泵抽干，甲醇洗涤若干次，得到碳纳米管催化剂载体，颗粒形态为球形，粒径为 5~100μιη，比表面积为 139.2m²/g，平均孔径为 21.1nm，平均孔容为 0.56cm³/g，堆密度为 0.17g/ml，带有反应性双键的基团也即碳碳双键占该碳纳米管催化剂载体的含量为 21.5wt%。 2) The formed carbon nanotube carrier obtained in the step 1) is dispersed in the dibutyl ether, the mass ratio of the carbon nanotube to the dispersion medium is 0.05:1; the solid phosgene is activated at 30 ° C for 24 hours, the carbon nanotubes and the solid The mass ratio of phosgene is 0.05:1, and then the medium is vacuumed by a vacuum pump, and the terpene alcohol is added at 40 ° C for 24 hours. The mass ratio of carbon nanotubes to terpene alcohol is 0.1:1, and then the medium is vacuum pumped. Dry, methanol washing several times to obtain a carbon nanotube catalyst carrier, the particle shape is spherical, the particle size is 5~100μιη, the specific surface area is 139.2m ² /g, the average pore diameter is 21.1nm, and the average pore volume is 0.56cm ³ /g. The bulk density is 0.17 g/ml, and the group having a reactive double bond, that is, the carbon-carbon double bond accounts for 21.5 wt% of the carbon nanotube catalyst carrier.

实施例 10 Example 10

1 )将 250g液态丙烯加入至反应釜中， 30°C下依次加入 0.23mol助催化剂三乙基铝、 0.033mol甲基铝氧烷及 l .Og碳纳米管负载过渡金属催化剂（三乙基铝和催化剂中过渡金属元素钛之间摩尔比为 600: 1；甲基铝氧烷与催化剂中过渡金属元素锆的摩尔比为 2000: 1 ) 以及氢气 0.2g，压强为 3.1MPa，升温至 70°C，反应 0.2个小时，得到中间产物聚合物 143.3g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.23 mol of promoter triethylaluminum, 0.033 mol of methylaluminoxane and 1.0 g of carbon nanotube-supported transition metal catalyst (triethylaluminum) were sequentially added at 30 ° C. The molar ratio of the transition metal element titanium to the catalyst is 600:1; the molar ratio of methylaluminoxane to the transition metal element zirconium in the catalyst is 2000: 1 ) and the hydrogen gas is 0.2 g, the pressure is 3.1 MPa, and the temperature is raised to 70°. C, the reaction was carried out for 0.2 hours to obtain 143.3 g of an intermediate polymer, which was directly subjected to the next reaction.

2) 将上述步骤 1 ) 中的反应釜内残留的丙烯放空并降温至 30°C，再通入 10g 乙烯和 40g丙烯的混合气，通入氢气 0.03g，压强为 l .OMPa, 升温至 90°C，反应 0.2 个小时，最终得到碳纳米管 /聚丙烯釜内合金 151.0g。 2) The propylene remaining in the reaction vessel in the above step 1) was vented and cooled to 30 ° C, and then a mixture of 10 g of ethylene and 40 g of propylene was introduced, and 0.03 g of hydrogen gas was introduced thereto, and the pressure was 1.0 MPa, and the temperature was raised to 90. At °C, the reaction was carried out for 0.2 hours, and finally 151.0 g of a carbon nanotube/polypropylene inner alloy was obtained.

该碳纳米管 /聚丙烯釜内合金由碳纳米管、重均分子量为 220000g/mol的均聚等规聚丙烯树脂和乙烯 /丙烯无规共聚物组成；碳纳米管、乙烯 /丙烯无规共聚物、均聚聚丙烯树脂的质量比为 0.33 : 5.1： 94.57。颗粒表观形态为球形，颗粒粒径大小为 50~500μιη_; 碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250。 The carbon nanotube/polypropylene inner alloy is composed of carbon nanotubes, a homopolymeric isotactic polypropylene resin having a weight average molecular weight of 220,000 g/mol, and an ethylene/propylene random copolymer; carbon nanotubes, ethylene/propylene random copolymerization The mass ratio of the homopolymeric polypropylene resin was 0.33: 5.1: 94.57. The apparent morphology of the particles is spherical, and the particle size is 50-500 μm _; the diameter of the carbon nanotubes is 20 nm, the length is 5 μιη, and the aspect ratio is 250.

将上述氯化镁醇合物滴加入 3.0g球形碳纳米管载体 /100ml癸烷的悬浮液中，于 90°C下恒温反应 12.0个小时，然后滤除液体，滤出的固体用癸烷洗涤 3次，干燥后得到碳纳米管载体的镁复合物。 The above magnesium chloride alcoholate was added dropwise to a suspension of 3.0 g of spherical carbon nanotube support/100 ml of decane. The reaction was carried out at a constant temperature of 12.0 hours at 90 ° C, and then the liquid was filtered off, and the filtered solid was washed three times with decane, and dried to obtain a magnesium complex of a carbon nanotube support.

该碳纳米管负载过渡金属催化剂为球形颗粒，由碳纳米管催化剂载体、过渡金属化合物 Et(Ind)₂ZrCl₂、四氯化钛、氯化镁、甲基铝氧烷和内给电子体芴二醚组成；其中钛元素、镁元素、锆元素、铝元素的含量分别为 1.81wt%、 3.52wt% 0.15wt%、 8.22wt%, 内给电子体芴二醚的含量为 13.53wt%。该碳纳米管负载过渡金属催化剂的比表面积为 105.8m²/g，孔容为 0.24cm³/g，平均孔径为 15.1nm。 The carbon nanotube-supported transition metal catalyst is a spherical particle, which is composed of a carbon nanotube catalyst carrier, a transition metal compound Et(Ind) ₂ ZrCl ₂ , titanium tetrachloride, magnesium chloride, methyl aluminoxane and internal electron donor deuterated diether. The content of the titanium element, the magnesium element, the zirconium element, and the aluminum element is 1.81 wt%, 3.52 wt%, 0.15 wt%, and 8.22 wt%, respectively, and the content of the internal electron donor sebacon is 13.53 wt%. The carbon nanotube-supported transition metal catalyst had a specific surface area of 105.8 m ² /g, a pore volume of 0.24 cm ³ /g, and an average pore diameter of 15.1 nm.

1 )将 5.0g碳纳米管 (碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250)经超声分散于 300毫升乙醇中形成悬浮液，搅拌 0.5小时后，喷雾干燥成型制备得到碳纳米管催化剂载体，喷雾干燥的压力为 0.2MPa，干燥进风温度 100°C，进料速度为 lO.Oml/min, 得到成形的碳纳米管载体；该载体颗粒形态为球形，其颗粒粒径大小为 8~30μιη，比表面积为 145.0m²/g，平均孔容为 0.35cm³/g，平均孔径为 17.0nm，堆密度 0.20g/ml。 1) 5.0 g of carbon nanotubes (having a particle diameter of 20 nm, a length of 5 μm, and a length to diameter ratio of 250) were ultrasonically dispersed in 300 ml of ethanol to form a suspension, stirred for 0.5 hours, and spray-dried to prepare carbon. The nanotube catalyst carrier has a spray drying pressure of 0.2 MPa, a dry inlet air temperature of 100 ° C, a feed rate of 10 mL/min, and a shaped carbon nanotube carrier is obtained; the carrier particle shape is spherical, and the particle size thereof is The size is 8 to 30 μm, the specific surface area is 145.0 m ² /g, the average pore volume is 0.35 cm ³ /g, the average pore diameter is 17.0 nm, and the bulk density is 0.20 g/ml.

2) 将步骤 1 ) 所得成形的碳纳米管载体分散于丁醚中，碳纳米管与分散介质的质量比为 0.05 : 1；加入固体光气于 30°C活化 24小时，碳纳米管与固体光气的质量比为 0.05 : 1，之后将介质用真空泵抽干，加入庚烯醇 40°C反应 24小时，碳纳米管与庚烯醇的质量比为 0.2: 1，之后将介质用真空泵抽干，甲醇洗涤若干次，得到碳纳米管催化剂载体，颗粒形态为球形，粒径为 5~100μιη，比表面积为 117.5m²/g，平均孔径为 15.7nm，平均孔容为 0.28cm³/g，堆密度为 0.24g/ml，带有反应性双键的基团也即碳碳双键占该碳纳米管催化剂载体的含量为 14.0wt%。 2) The formed carbon nanotube carrier obtained in the step 1) is dispersed in the dibutyl ether, the mass ratio of the carbon nanotube to the dispersion medium is 0.05:1; the solid phosgene is activated at 30 ° C for 24 hours, the carbon nanotubes and the solid The mass ratio of phosgene was 0.05:1, and then the medium was vacuum-dried, and the reaction was carried out by adding heptyl alcohol at 40 ° C for 24 hours. The mass ratio of carbon nanotubes to heptyl alcohol was 0.2:1, and then the medium was vacuum pumped. Dry, methanol washing several times, to obtain a carbon nanotube catalyst carrier, the particle shape is spherical, the particle size is 5~100μιη, the specific surface area is 117.5m ² /g, the average pore diameter is 15.7nm, and the average pore volume is 0.28cm ³ /g. The bulk density was 0.24 g/ml, and the group having a reactive double bond, that is, the carbon-carbon double bond, accounted for 14.0% by weight of the carbon nanotube catalyst carrier.

实施例 11 Example 11

1 )将 250g液态丙烯加入至反应釜中， 30°C下依次加入 0.23mol助催化剂三乙基铝、 0.033mol甲基铝氧烷及 l .Og碳纳米管负载过渡金属催化剂（三乙基铝和催化剂中过渡金属元素钛之间摩尔比为 600: 1；甲基铝氧烷与催化剂中过渡金属元素锆的摩尔比为 2000: 1 ) 以及氢气 0.2g，压强为 3.1MPa，升温至 70°C，反应 0.2个小时，得到中间产物聚合物 110.8g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.23 mol of promoter triethylaluminum, 0.033 mol of methylaluminoxane and 1.0 g of carbon nanotube-supported transition metal catalyst (triethylaluminum) were sequentially added at 30 ° C. And the molar ratio between the transition metal element titanium in the catalyst is 600: 1; methyl aluminoxane and the transition metal element zirconium in the catalyst The molar ratio was 2000: 1 ) and hydrogen gas was 0.2 g, the pressure was 3.1 MPa, the temperature was raised to 70 ° C, and the reaction was carried out for 0.2 hours to obtain 110.8 g of an intermediate polymer, which was directly subjected to the next reaction.

2) 将上述步骤 1 ) 中的反应釜内残留的丙烯放空并降温至 50°C，再通入 30g 乙烯和 30g丙烯的混合气，通入氢气 0.03g，压强为 l .OMPa, 升温至 90°C，反应 0.2 个小时，最终得到碳纳米管 /聚丙烯釜内合金 131.0g。 2) The propylene remaining in the reaction vessel in the above step 1) was vented and cooled to 50 ° C, and then a mixture of 30 g of ethylene and 30 g of propylene was introduced, and 0.03 g of hydrogen was introduced thereto, and the pressure was 1.0 MPa, and the temperature was raised to 90. At °C, the reaction was carried out for 0.2 hours, and finally 131.0 g of a carbon nanotube/polypropylene inner alloy was obtained.

该碳纳米管 /聚丙烯釜内合金由碳纳米管、重均分子量为 215000g/mol的均聚等规聚丙烯树脂和乙烯 /丙烯无规共聚物组成；碳纳米管、乙烯 /丙烯无规共聚物、均聚聚丙烯树脂的质量比为 0.76: 15.4： 94.6。颗粒表观形态为球形，颗粒粒径大小为 50~500μιη_; 碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250。 The carbon nanotube/polypropylene autoclave alloy is composed of carbon nanotubes, a homopolymeric isotactic polypropylene resin having a weight average molecular weight of 215,000 g/mol, and an ethylene/propylene random copolymer; carbon nanotubes, ethylene/propylene random copolymerization The mass ratio of the homopolymeric polypropylene resin was 0.76: 15.4: 94.6. The apparent morphology of the particles is spherical, and the particle size is 50-500 μm _; the diameter of the carbon nanotubes is 20 nm, the length is 5 μιη, and the aspect ratio is 250.

该碳纳米管负载过渡金属催化剂为球形颗粒，由碳纳米管催化剂载体、过渡金属化合物 Et(Ind)₂ZrCl₂、四氯化钛、氯化镁、甲基铝氧烷和内给电子体芴二醚组成；其中钛元素、镁元素、锆元素、铝元素的含量分别为 1.81wt%、 3.52wt% 0.15wt%、 8.45wt%，内给电子体芴二醚的含量为 11.38wt%。该碳纳米管负载过渡金属催化剂的比表面积为 114.4m²/g，孔容为 0.22cm³/g，平均孔径为 16.7nm。 The carbon nanotube-supported transition metal catalyst is a spherical particle, which is composed of a carbon nanotube catalyst carrier, a transition metal compound Et(Ind) ₂ ZrCl ₂ , titanium tetrachloride, magnesium chloride, methyl aluminoxane and internal electron donor deuterated diether. The content of the titanium element, the magnesium element, the zirconium element, and the aluminum element is 1.81 wt%, 3.52 wt%, 0.15 wt%, and 8.45 wt%, respectively, and the content of the internal electron donor sebacon is 11.38 wt%. The carbon nanotube-supported transition metal catalyst had a specific surface area of 114.4 m ² /g, a pore volume of 0.22 cm ³ /g, and an average pore diameter of 16.7 nm.

1 )将 5.0g碳纳米管 (碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250)经超声分散于 300毫升乙醇中形成悬浮液，搅拌 0.5小时后，喷雾干燥成型制备得到碳纳米管催化剂载体，喷雾干燥的压力为 O. lMPa, 干燥进风温度 110°C，进料速度为 lO.Oml/min, 得到成形的碳纳米管载体；该载体颗粒形态为球形，其颗粒粒径大小为 15~30μιη，比表面积为 165.0m²/g，平均孔容为 0.35cm³/g，平均孔径为 17.9nm，堆密度 0.20g/ml。 1) 5.0 g of carbon nanotubes (having a particle diameter of 20 nm, a length of 5 μm, and a length to diameter ratio of 250) were ultrasonically dispersed in 300 ml of ethanol to form a suspension, stirred for 0.5 hours, and spray-dried to prepare carbon. The nanotube catalyst carrier, the spray drying pressure is O. lMPa, the dry inlet air temperature is 110 ° C, the feed rate is lO.Oml/min, and the formed carbon nanotube carrier is obtained; the carrier particle shape is spherical, and the particle is granulated. Path size It is 15 to 30 μm, has a specific surface area of 165.0 m ² /g, an average pore volume of 0.35 cm ³ /g, an average pore diameter of 17.9 nm, and a bulk density of 0.20 g/ml.

2) 将步骤 1 ) 所得成形的碳纳米管载体分散于丁醚中，碳纳米管与分散介质的质量比为 0.02: 1；加入固体光气于 30°C活化 24小时，碳纳米管与固体光气的质量比为 0.02: 1，之后将介质用真空泵抽干，加入十二烯醇 50°C反应 24小时，碳纳米管与十二烯醇的质量比为 0.2: 1，之后将介质用真空泵抽干，甲醇洗涤若干次，得到碳纳米管催化剂载体，颗粒形态为球形，粒径为 5~100μιη，比表面积为 117。 2) The formed carbon nanotube carrier obtained in the step 1) is dispersed in the dibutyl ether, the mass ratio of the carbon nanotube to the dispersion medium is 0.02:1; the solid phosgene is activated at 30 ° C for 24 hours, the carbon nanotubes and the solid The mass ratio of phosgene is 0.02:1, and then the medium is vacuum-dried, and the dodecenol is added at 50 ° C for 24 hours. The mass ratio of carbon nanotubes to dodecenol is 0.2:1. The vacuum pump was drained and washed with methanol several times to obtain a carbon nanotube catalyst carrier. The particle shape was spherical, the particle size was 5 to 100 μm, and the specific surface area was 117.

6m²/g，平均孔径为 17.7nm，平均孔容为 0.28cm³/g，堆密度为 0.24g/ml，带有反应性双键的基团也即碳碳双键占该碳纳米管催化剂载体的含量为 22.6wt%。 6m ² /g, the average pore diameter is 17.7nm, the average pore volume is 0.28cm ³ /g, the bulk density is 0.24g/ml, and the group having a reactive double bond, that is, the carbon-carbon double bond accounts for the carbon nanotube catalyst. The content of the carrier was 22.6 wt%.

实施例 12 Example 12

1 )将 250g液态丙烯加入至反应釜中， 30°C下依次加入 0.23mol助催化剂三乙基铝、 0.033mol甲基铝氧烷及 l .Og碳纳米管负载过渡金属催化剂（三乙基铝和催化剂中过渡金属元素钛的摩尔比为 600: 1；甲基铝氧烷与催化剂中过渡金属元素锆的摩尔比为 2000: 1 )以及氢气 0.2g，压强为 3.1MPa，升温至 70°C，反应 0.2个小时，得到中间产物聚合物 97.8g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.23 mol of promoter triethylaluminum, 0.033 mol of methylaluminoxane and 1.0 g of carbon nanotube-supported transition metal catalyst (triethylaluminum) were sequentially added at 30 ° C. The molar ratio of the transition metal element titanium to the catalyst is 600:1; the molar ratio of methylaluminoxane to the transition metal element zirconium in the catalyst is 2000:1) and the hydrogen gas is 0.2g, the pressure is 3.1 MPa, and the temperature is raised to 70 °C. After reacting for 0.2 hours, 97.8 g of an intermediate product polymer was obtained, and the next reaction was directly carried out.

2) 将上述步骤 1 ) 中的反应釜内残留的丙烯放空并降温至 50°C，再通入 30g 乙烯和 30g丙烯的混合气，通入氢气 0.03g，压强为 l .OMPa, 升温至 90°C，反应 0.2 个小时，最终得到碳纳米管 /聚丙烯釜内合金 115.0g。 2) The propylene remaining in the reaction vessel in the above step 1) was vented and cooled to 50 ° C, and then a mixture of 30 g of ethylene and 30 g of propylene was introduced, and 0.03 g of hydrogen was introduced thereto, and the pressure was 1.0 MPa, and the temperature was raised to 90. At °C, the reaction was carried out for 0.2 hours, and finally 115.0 g of a carbon nanotube/polypropylene inner alloy was obtained.

该碳纳米管 /聚丙烯釜内合金由碳纳米管、重均分子量为 280000g/mol的均聚等规聚丙烯树脂和乙烯 /丙烯无规共聚物组成；碳纳米管、乙烯 /丙烯无规共聚物、均聚聚丙烯树脂的质量比为 0.87: 15.1： 84.03。颗粒表观形态为球形，颗粒粒径大小为 50~500μιη_; 碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250。 The carbon nanotube/polypropylene inner alloy is composed of carbon nanotubes, a homopolymeric isotactic polypropylene resin having a weight average molecular weight of 280,000 g/mol, and an ethylene/propylene random copolymer; carbon nanotubes, ethylene/propylene random copolymerization The mass ratio of the homopolymeric polypropylene resin was 0.87: 15.1: 84.03. The apparent morphology of the particles is spherical, and the particle size is 50-500 μm _; the diameter of the carbon nanotubes is 20 nm, the length is 5 μιη, and the aspect ratio is 250.

4)将 0.10g过渡金属化合物 Et(Ind)₂ZrCl₂加入至含有 O. lOmol甲基铝氧烷的甲苯溶液 40ml中，于 20°C下反应 4.0个小时，得到活化的催化剂溶液。 5 ) 将此催化剂溶液滴加入至含有 5.0g所述步骤 3 ) 制备所得活化的碳纳米管催化剂的 50ml甲苯悬浮液中，于 90°C下反应 4.0个小时。反应完成后，用甲苯洗涤 5次，干燥后得到本发明提供的碳纳米管负载的过渡金属催化剂。 4) 0.10 g of a transition metal compound Et(Ind) ₂ ZrCl _{2 was} added to 40 ml of a toluene solution containing 0.1 mol of methyl aluminoxane, and reacted at 20 ° C for 4.0 hours to obtain an activated catalyst solution. 5) This catalyst solution was dropwise added to a suspension of 5.0 g of the activated carbon nanotube catalyst prepared in the above step 3), and reacted at 90 ° C for 4.0 hours. After completion of the reaction, it was washed 5 times with toluene, and dried to obtain a carbon nanotube-supported transition metal catalyst provided by the present invention.

该碳纳米管负载过渡金属催化剂为球形颗粒，由碳纳米管催化剂载体、过渡金属化合物 Et(Ind)₂ZrCl₂、四氯化钛、氯化镁、甲基铝氧烷和内给电子体芴二醚组成；其中钛元素、镁元素、锆元素、铝元素的含量分别为 1.81wt%、 3.52wt% 0.15wt%、 8.45wt%, 内给电子体芴二醚的含量为 10.66wt%。该碳纳米管负载过渡金属催化剂的比表面积为 119.5m²/g，孔容为 0.32cm³/g，平均孔径为 16.7nm。 The carbon nanotube-supported transition metal catalyst is a spherical particle, which is composed of a carbon nanotube catalyst carrier, a transition metal compound Et(Ind) ₂ ZrCl ₂ , titanium tetrachloride, magnesium chloride, methyl aluminoxane and internal electron donor deuterated diether. The content of the titanium element, the magnesium element, the zirconium element, and the aluminum element is 1.81 wt%, 3.52 wt%, 0.15 wt%, and 8.45 wt%, respectively, and the content of the internal electron donor sebacon is 10.66 wt%. The carbon nanotube-supported transition metal catalyst had a specific surface area of 119.5 m ² /g, a pore volume of 0.32 cm ³ /g, and an average pore diameter of 16.7 nm.

1 )将 5.0g碳纳米管 (碳纳米管的粒径为 20nm，长度为 5μιη，长径比 250)经超声分散于 300毫升乙醇中形成悬浮液，搅拌 0.5小时后，喷雾干燥成型制备得到碳纳米管催化剂载体，喷雾干燥的压力为 O. lMPa, 干燥进风温度 110°C，进料速度为 20.0ml/min, 得到成形的碳纳米管载体；该载体颗粒形态为球形，其颗粒粒径大小为 15~30μιη，比表面积为 168.0m²/g，平均孔容为 0.45cm³/g，平均孔径为 18.9nm，堆密度 0.16g/ml。 1) 5.0 g of carbon nanotubes (having a particle diameter of 20 nm, a length of 5 μm, and a length to diameter ratio of 250) were ultrasonically dispersed in 300 ml of ethanol to form a suspension, stirred for 0.5 hours, and spray-dried to prepare carbon. The nanotube catalyst carrier, the spray drying pressure is O. lMPa, the dry inlet air temperature is 110 ° C, the feed rate is 20.0 ml / min, and the formed carbon nanotube carrier is obtained; the carrier particle shape is spherical, and the particle diameter thereof The size is 15 to 30 μm, the specific surface area is 168.0 m ² /g, the average pore volume is 0.45 cm ³ /g, the average pore diameter is 18.9 nm, and the bulk density is 0.16 g/ml.

2) 将步骤 1 ) 所得成形的碳纳米管载体分散于丁醚中，碳纳米管与分散介质的质量比为 0.02: 1；加入固体光气于 30°C活化 24小时，碳纳米管与固体光气的质量比为 0.02: 1，之后将介质用真空泵抽干，加入 ^一烯醇 50°C反应 24小时，碳纳米管与十一烯醇的质量比为 005: 1，之后将介质用真空泵抽干，甲醇洗涤若干次，得到碳纳米管催化剂载体，颗粒形态为球形，粒径为 5~100μιη，比表面积为 147.1m²/g，平均孔径为 17.7nm，平均孔容为 0.38cm³/g，堆密度为 0.19g/ml，带有反应性双键的基团也即碳碳双键占该碳纳米管催化剂载体的含量为 17.2wt%。 2) The formed carbon nanotube carrier obtained in the step 1) is dispersed in the dibutyl ether, the mass ratio of the carbon nanotube to the dispersion medium is 0.02:1; the solid phosgene is activated at 30 ° C for 24 hours, the carbon nanotubes and the solid The mass ratio of phosgene is 0.02: 1, and then the medium is vacuum-dried, and the reaction is carried out at 50 ° C for 24 hours. The mass ratio of carbon nanotubes to undecenol is 005: 1, and then the medium is used. The vacuum pump was drained and washed with methanol several times to obtain a carbon nanotube catalyst carrier. The particle shape was spherical, the particle size was 5 to 100 μm, the specific surface area was 147.1 m ² /g, the average pore diameter was 17.7 nm, and the average pore volume was 0.38 cm ^{3 .} /g, the bulk density is 0.19 g/ml, and the group having a reactive double bond, that is, the carbon-carbon double bond accounts for 17.2% by weight of the carbon nanotube catalyst carrier.

工业应用 Industrial application

本发明利用催化剂-聚合物粒子形态复制效应，在颗粒表观形态为球形或类球形的碳纳米管负载过渡金属催化剂上原位催化丙烯单体与其他单体进行聚合反应而制得碳纳米管 /聚丙烯釜内合金树脂。本发明具有以下优点： The invention utilizes the catalyst-polymer particle morphology replication effect to in situ catalyze the polymerization of propylene monomer with other monomers on the carbon nanotube-supported transition metal catalyst with an apparent morphology or spherical shape to obtain carbon nanotubes. / Polypropylene autoclave alloy resin. The invention has the following advantages:

1、本发明着重于对碳纳米管 /聚丙烯釜内合金的颗粒形态进行控制，提供了一种能够制备得到具有球形颗粒表观形态的含有碳纳米管的聚丙烯釜内合金的方法。由于产物为球形形态，具有较大的堆密度，在聚合过程中不会造成聚合物粘附于釜壁上的现象，因而易于流动和传输；否则，如果产物是无定形状态，则其堆密度较小，易于粘附于釜壁上，从而影响聚合物的传输，从而限制了其后续应用前景。 1. The present invention focuses on the control of the particle morphology of the carbon nanotube/polypropylene alloy, and provides a method for preparing a carbon nanotube-containing polypropylene in-cylinder alloy having an apparent morphology of spherical particles. Since the product has a spherical shape and a large bulk density, it does not cause the polymer to adhere to the wall of the kettle during the polymerization, so that it is easy to flow and transport; otherwise, if the product is in an amorphous state, its bulk density Smaller, easy to adhere to the wall of the kettle, thus affecting the transport of the polymer, thus limiting its future application prospects.

2、本发明提供的碳纳米管 /聚丙烯釜内合金中，碳纳米管以单一分散的形式均匀分散于树脂基体中，碳纳米管贯穿于橡胶相和聚丙烯相两相之间，由于碳纳米管功能化增强了碳纳米管与两相的界面作用，有效限制了橡胶相的聚集，将橡胶相的尺寸控制在 0.2微米以下，可知本发明通过原位聚合方法成功制备得到了高性能的聚丙烯釜内合金树脂。 2. In the carbon nanotube/polypropylene inner alloy provided by the present invention, the carbon nanotubes are uniformly dispersed in the resin matrix in a single dispersion form, and the carbon nanotubes penetrate between the rubber phase and the polypropylene phase due to carbon The functionalization of the nanotubes enhances the interfacial interaction between the carbon nanotubes and the two phases, effectively limiting the aggregation of the rubber phase, and controlling the size of the rubber phase to be less than 0.2 μm. It is known that the present invention successfully prepares high performance by the in-situ polymerization method. Polycarbonate alloy resin in the kettle.

本发明提供的碳纳米管 /聚丙烯釜内合金树脂，在汽车用零部件、包装材料、阻隔材料、阻燃材料、电器材料和电导材料等领域，均具有广泛的应用前景。 The carbon nanotube/polypropylene inner alloy resin provided by the invention has wide application prospects in the fields of automobile parts, packaging materials, barrier materials, flame retardant materials, electrical materials and electrical conductivity materials.

Claims

权利要求 Rights request

1、一种含有碳纳米管的聚丙烯釜内合金，包括碳纳米管、均聚聚丙烯树脂和乙烯 -α烯烃无规共聚物。 A polypropylene inner cylinder alloy comprising carbon nanotubes, comprising carbon nanotubes, a homopolypropylene resin and an ethylene-alpha olefin random copolymer.

2、根据权利要求 1所述的聚丙烯釜内合金，其特征在于：所述均聚聚丙烯树脂选自等规聚丙烯、间规聚丙烯和无规聚丙烯树脂中的至少一种；或， 2. The polypropylene in-cavity alloy according to claim 1, wherein: the homopolypropylene resin is at least one selected from the group consisting of isotactic polypropylene, syndiotactic polypropylene, and random polypropylene resin; or ,

所述均聚聚丙烯树脂的重均分子量为 20000-1000000g/mol，具体为 The weight average molecular weight of the homopolypropylene resin is 20000-1000000 g/mol, specifically

200000-800000 g/mol; 或， 200000-800000 g/mol; or,

所述乙烯 -α烯烃无规共聚物中， α烯烃选自丙烯、 1-丁烯、 1-戊烯、 1-己烯、 1-辛烯、 1-壬烯和 1-癸烯中的至少一种；或， In the ethylene-α-olefin random copolymer, the α-olefin is at least selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene and 1-decene. One; or,

所述 α-烯烃占所述乙烯 -α烯烃无规共聚物的质量百分含量为 0.5-80.0%; 所述均聚聚丙烯树脂与所述乙烯 -α烯烃共聚物的质量比为 40.0〜99.0： 1.0-60.0；所述碳纳米管占所述含有碳纳米管的聚丙烯釜内合金的质量百分含量为 0.01-25%。 The α-olefin accounts for 0.5-80.0% by mass of the ethylene-α-olefin random copolymer; the mass ratio of the homopolypropylene resin to the ethylene-α-olefin copolymer is 40.0~99.0 1.0-60.0; The carbon nanotubes accounted for 0.01-25% by mass of the carbon nanotube-containing polypropylene in-cylinder alloy.

3、根据权利要求 1或 2所述的聚丙烯釜内合金，其特征在于：所述碳纳米管的粒径为 10-20nm，长度为 0.5-50μιη，长径比为 50-1000; 或， The polypropylene in-cylinder alloy according to claim 1 or 2, wherein the carbon nanotubes have a particle diameter of 10-20 nm, a length of 0.5-50 μm, and an aspect ratio of 50-1000;

所述含有碳纳米管的聚丙烯釜内合金的颗粒表观形态为球形，粒径为 The surface morphology of the carbon nanotube-containing polypropylene in-cylinder alloy is spherical, and the particle size is

10~10000μηι, 具体为 10-500μπι; 10~10000μηι, specifically 10-500μπι;

所述碳纳米管在所述含有碳纳米管的聚丙烯釜内合金中均以单一分散的形式存在。 The carbon nanotubes are present in a single dispersed form in the carbon nanotube-containing polypropylene in-cylinder alloy.

4、一种制备权利要求 1-3任一所述含有碳纳米管的聚丙烯釜内合金的方法，包括如下步骤： A method for preparing a carbon nanotube-containing polypropylene in-cylinder alloy according to any one of claims 1 to 3, comprising the steps of:

1 ) 将丙烯单体、碳纳米管负载过渡金属催化剂和助催化剂在有机溶剂中进行淤浆聚合反应，得到中间产物； 1) slurry polymerization of a propylene monomer, a carbon nanotube-supported transition metal catalyst and a cocatalyst in an organic solvent to obtain an intermediate product;

或者，将丙烯单体、碳纳米管负载过渡金属催化剂和助催化剂进行本体聚合反应，得到中间产物； Alternatively, a bulk polymerization reaction is carried out by reacting a propylene monomer, a carbon nanotube-supported transition metal catalyst, and a cocatalyst to obtain an intermediate product;

2) 向所述步骤 1 ) 所得含有中间产物的反应体系中加入乙烯和 α-烯烃单体，于有机溶剂中进行淤浆聚合反应，反应完毕得到所述含有碳纳米管的聚丙烯釜内合金； 2) adding ethylene and an α-olefin monomer to the reaction system containing the intermediate product obtained in the step 1), performing slurry polymerization in an organic solvent, and completing the reaction to obtain the carbon nanotube-containing polypropylene in-cavity alloy ;

5、根据权利要求 4所述的方法，其特征在于：所述助催化剂选自 C1-C4的垸基铝和 C1-C4的烷氧基铝化合物中的至少一种，具体选自三甲基铝、三乙基铝、三异丁基铝和甲基铝氧垸中的至少一种； 5. The method according to claim 4, wherein: the cocatalyst is at least one selected from the group consisting of C1-C4 bismuth aluminum and C1-C4 alkoxy aluminum compound, specifically selected from trimethyl. At least one of aluminum, triethyl aluminum, triisobutyl aluminum, and methyl aluminoxane;

所述 α烯烃选自丙烯、 1-丁烯、 1-戊烯、 1-己烯、 1-辛烯、 1-壬烯和 1-癸烯中的至少一种。 The α-olefin is at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene and 1-decene.

6、根据权利要求 4或 5所述的方法，其特征在于：所述步骤 1 ) 中，助催化剂中的烷基铝与碳纳米管负载过渡金属催化剂中的过渡金属元素钛的摩尔比为 1-5000： 1 , 具体为 10-2000： 1；或， 6. The method according to claim 4 or 5, wherein in the step 1), the molar ratio of the aluminum alkyl in the cocatalyst to the transition metal element titanium in the carbon nanotube-supported transition metal catalyst is 1 -5000: 1 , specifically 10-2000: 1; or,

所述助催化剂中的垸氧基铝化合物与碳纳米管负载过渡金属催化剂中的过渡 Transition in the promoter of the aluminum oxyhydroxide compound and the carbon nanotube-supported transition metal catalyst

24 twenty four

替换页（细则第 26条）金属元素锆的摩尔比为 1~5000_: 1，具体为 2000: 1；碳纳米管负载过渡金属催化剂的加入量为丙烯单体质量的 0.1-5.0%，具体为 0.1-0.4%。 Replacement page (Article 26) The molar ratio of the metal element zirconium is from 1 to 5,000 _: 1, specifically 2000:1; the amount of the carbon nanotube-supported transition metal catalyst is from 0.1 to 5.0%, specifically from 0.1 to 0.4%, based on the mass of the propylene monomer.

7、根据权利要求 4或 5所述的方法，其特征在于：所述步骤 2) 中，乙烯的加入量为乙烯和 α-烯烃单体总重的 1.0-100.0%，具体为 5.0-50.0%; 或， The method according to claim 4 or 5, wherein in the step 2), the amount of ethylene added is 1.0-100.0%, specifically 5.0-50.0%, of the total weight of the ethylene and the α-olefin monomer. ; or,

乙烯和 α-烯烃单体的加入量为所述步骤 1 )所得中间产物总重的 20-200%，具体为 34.9-1 18.4%。 The ethylene and the α-olefin monomer are added in an amount of from 20 to 200% by weight based on the total weight of the intermediate product obtained in the step 1), and specifically from 34.9 to 18.4%.

8、根据权利要求 6所述的方法，其特征在于：所述步骤 2 ) 中，乙烯的加入量为乙烯和 α-烯烃单体总重的 1.0-100.0%，具体为 5.0-50.0%; 或， 8. The method according to claim 6, wherein: in the step 2), the amount of ethylene added is 1.0-100.0%, specifically 5.0-50.0%, based on the total weight of the ethylene and the α-olefin monomer; ,

乙烯和 a-烯烃单体的加入量为所述步骤 1 )所得中间产物总重的 20-200%，具体为 34.9-118.4%。 The ethylene and a-olefin monomers are added in an amount of from 20 to 200% by weight based on the total weight of the intermediate product obtained in the step 1), and specifically from 34.9 to 118.4%.

9、根据权利要求 4或 5所述的方法，其特征在于：所述步骤 1 ) 中，所述淤浆聚合反应和本体聚合反应的温度均为 30°C〜90°C，时间均为 0.05〜10.0小时；压强均为 0-4MPa，具体为 0.5-3.5MPa，所述压强不为 0; 或， The method according to claim 4 or 5, wherein in the step 1), the temperature of the slurry polymerization reaction and the bulk polymerization reaction are both 30 ° C to 90 ° C, and the time is 0.05. ~10.0 hours; pressure is 0-4MPa, specifically 0.5-3.5MPa, the pressure is not 0; or,

所述步骤 2 ) 中，所述淤浆聚合反应和聚合反应的温度均为 60°C〜12(rC , 时间均为 0.1~10.0小时，压强均为 0-4MPa，具体为 0.5-3.5MPa，所述压强不为 0。 In the step 2), the temperature of the slurry polymerization reaction and the polymerization reaction are both 60 ° C to 12 (rC, the time is 0.1 to 10.0 hours, the pressure is 0-4 MPa, specifically 0.5-3.5 MPa, The pressure is not zero.

10、根据权利要求 6所述的方法，其特征在于：所述步骤 1 ) 中，所述淤桨聚合反应和本体聚合反应的温度均为 301；〜 90 °C，时间均为 0.05〜10.0小时；压强均为 0-4MPa，具体为 0.5-3.5MPa，所述压强不为 0; 或， The method according to claim 6, wherein in the step 1), the temperature of the slurry polymerization reaction and the bulk polymerization reaction are both 301; ～90 ° C, and the time is 0.05 to 10.0 hours. ; pressure is 0-4MPa, specifically 0.5-3.5MPa, the pressure is not 0; or,

所述步骤 2) 中，所述淤浆聚合反应和聚合反应的温度均为 60°C〜120°C，时间均为 0.1~10.0小时，压强均为 0-4MPa，具体为 0.5-3.5MPa, 所述压强不为 0。 In the step 2), the temperature of the slurry polymerization reaction and the polymerization reaction are both 60 ° C to 120 ° C, the time is 0.1 to 10.0 hours, and the pressure is 0-4 MPa, specifically 0.5-3.5 MPa. The pressure is not zero.

1 1、根据权利要求 7所述的方法，其特征在于：所述步骤 1 ) 中，所述淤桨聚合反应和本体聚合反应的温度均为 30°C〜90°C，时间均为 0.05〜10.0小时；压强均为 0-4MPa，具体为 0.5-3.5MPa，所述压强不为 0; 或， 1 1 . The method according to claim 7, wherein: in the step 1), the temperature of the slurry polymerization reaction and the bulk polymerization reaction are both 30° C. and 90° C., and the time is 0.05°. 10.0 hours; pressure is 0-4MPa, specifically 0.5-3.5MPa, the pressure is not 0; or,

所述步骤 2 ) 中，所述淤浆聚合反应和聚合反应的温度均为 60°C〜12(TC，时间均为 0.1~10.0小时，压强均为 0-4MPa，具体为 0.5-3.5MPa，所述压强不为 0。 In the step 2), the temperature of the slurry polymerization reaction and the polymerization reaction are both 60 ° C to 12 (TC, the time is 0.1 to 10.0 hours, the pressure is 0-4 MPa, specifically 0.5-3.5 MPa, The pressure is not zero.

12、根据权利要求 8所述的方法，其特征在于：所述步骤 1 ) 中，所述淤浆聚合反应和本体聚合反应的温度均为 30°C〜90°C , 时间均为 0.05〜10.0小时；压强均为 0-4MPa，具体为 0.5-3.5MPa，所述压强不为 0; 或， 12. The method according to claim 8, wherein: in the step 1), the temperature of the slurry polymerization reaction and the bulk polymerization reaction are both 30 ° C to 90 ° C, and the time is 0.05 to 10.0. Hours; pressure is 0-4MPa, specifically 0.5-3.5MPa, the pressure is not 0; or,

所述步骤 2) 中，所述淤浆聚合反应和聚合反应的温度均为 60Ό〜120Ό，时间均为 0.1~10.0小时，压强均为 0-4MPa，具体为 0.5-3.5MPa，所述压强不为 0。 In the step 2), the temperature of the slurry polymerization reaction and the polymerization reaction are both 60 Ό to 120 Ό, the time is 0.1 to 10.0 hours, the pressure is 0-4 MPa, specifically 0.5-3.5 MPa, and the pressure is not Is 0.

13、根据权利要求 4或 5所述的方法，其特征在于：所述方法还包括如下步骤：在所述步骤 1 ) 淤浆聚合反应或本体聚合反应之前，向反应体系中通入氢气；或，氢气的加入量为丙烯单体质量的 0.001%-0.5%，具体为 0.005-0.08%，且所述氢气的加入量不为 0。 The method according to claim 4 or 5, wherein the method further comprises the steps of: introducing hydrogen into the reaction system before the step 1) slurry polymerization or bulk polymerization; or The amount of hydrogen added is 0.001%-0.5%, specifically 0.005-0.08%, of the mass of the propylene monomer, and the amount of the hydrogen added is not 0.

14、根据权利要求 6所述的方法，其特征在于：所述方法还包括如下步骤：在所述步骤 1 ) 淤浆聚合反应或本体聚合反应之前，向反应体系中通入氢气；或，氢气的加入量为丙烯单体质量的 0.001%-0.5%，具体为 0.005-0.08%，且所述氢气的加入量不为 0。 14. The method according to claim 6, wherein: the method further comprises the steps of: introducing hydrogen into the reaction system before the step 1) slurry polymerization or bulk polymerization; or, hydrogen The amount added is 0.001% to 0.5% by mass of the propylene monomer, specifically 0.005 to 0.08%, and the amount of hydrogen added is not 0.

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15、根据权利要求 7所述的方法，其特征在于：所述方法还包括如下步骤：在所述步骤 1 ) 淤浆聚合反应或本体聚合反应之前，向反应体系中通入氢气；或，氢气的加入量为丙烯单体质量的 0.001%-0.5%，具体为 0.005-0.08%，且所述氢气的加入量不为 0。 15. The method according to claim 7, wherein: the method further comprises the steps of: introducing hydrogen into the reaction system before the step 1) slurry polymerization or bulk polymerization; or, hydrogen The amount added is 0.001% to 0.5% by mass of the propylene monomer, specifically 0.005 to 0.08%, and the amount of hydrogen added is not 0.

16、根据权利要求 8所述的方法，其特征在于：所述方法还包括如下步骤：在所述步骤 1 ) 淤浆聚合反应或本体聚合反应之前，向反应体系中通入氢气；或，氢气的加入量为丙烯单体质量的 0.001%-0.5%，具体为 0.005-0.08%，且所述氢气的加入量不为 0。 16. The method according to claim 8, wherein: the method further comprises the steps of: introducing hydrogen into the reaction system before the step 1) slurry polymerization or bulk polymerization; or, hydrogen The amount added is 0.001% to 0.5% by mass of the propylene monomer, specifically 0.005 to 0.08%, and the amount of hydrogen added is not 0.

17、根据权利要求 9-12任一所述的方法，其特征在于：所述方法还包括如下步骤：在所述步骤 1 )淤浆聚合反应或本体聚合反应之前，向反应体系中通入氢气；或， 17. A method according to any one of claims 9-12, characterized in that the method further comprises the step of introducing hydrogen into the reaction system prior to the step 1) slurry polymerization or bulk polymerization. ; or,

氢气的加入量为丙烯单体质量的 0.001%-0.5%，具体为 0.005-0.08%，且所述氢气的加入量不为 0。 The amount of hydrogen added is 0.001% to 0.5% by mass of the propylene monomer, specifically 0.005 to 0.08%, and the amount of hydrogen added is not 0.

18、根据权利要求 4或 5所述的方法，其特征在于：所述方法还包括如下步骤：在所述步骤 2) 淤浆聚合反应或聚合反应之前，向反应体系中通入氢气；或，氢气的加入量为乙烯和 α-烯烃单体总重的 0-5.0%，具体为 0.01-0.07%，且所述氢气的加入量不为 0。 The method according to claim 4 or 5, wherein the method further comprises the steps of: introducing hydrogen into the reaction system before the step 2) slurry polymerization or polymerization; or The amount of hydrogen added is from 0 to 5.0%, specifically from 0.01 to 0.07%, based on the total weight of the ethylene and the α-olefin monomer, and the amount of the hydrogen added is not zero.

19、根据权利要求 6所述的方法，其特征在于：所述方法还包括如下步骤：在所述步骤 2) 淤浆聚合反应或聚合反应之前，向反应体系中通入氢气；或， 19. The method according to claim 6, wherein: the method further comprises the steps of: introducing hydrogen into the reaction system before the step 2) slurry polymerization or polymerization; or

氢气的加入量为乙烯和 α-烯烃单体总重的 0-5.0%，具体为 0.01-0.07%，且所述氢气的加入量不为 0。 The amount of hydrogen added is 0-5.0%, specifically 0.01-0.07%, based on the total weight of the ethylene and the ?-olefin monomer, and the amount of hydrogen added is not 0.

20、根据权利要求 7所述的方法，其特征在于：所述方法还包括如下步骤：在所述步骤 2) 淤浆聚合反应或聚合反应之前，向反应体系中通入氢气；或， 20. The method according to claim 7, wherein: the method further comprises the steps of: introducing hydrogen into the reaction system before the step 2) slurry polymerization or polymerization; or

21、根据权利要求 8所述的方法，其特征在于：所述方法还包括如下步骤：在所述步骤 2) 淤浆聚合反应或聚合反应之前，向反应体系中通入氢气；或， 21. The method according to claim 8, wherein: the method further comprises the steps of: introducing hydrogen into the reaction system before the step 2) slurry polymerization or polymerization; or

22、根据权利要求 9-17任一所述的方法，其特征在于：所述方法还包括如下步骤：在所述步骤 2)淤浆聚合反应或聚合反应之前，向反应体系中通入氢气；或，氢气的加入量为乙烯和 α-烯烃单体总重的 0-5.0%，具体为 0.01-0.07%，且所述氢气的加入量不为 0。 The method according to any one of claims 9-17, wherein the method further comprises the step of: introducing hydrogen into the reaction system before the step 2) slurry polymerization or polymerization; Or, the amount of hydrogen added is 0-5.0%, specifically 0.01-0.07%, based on the total weight of the ethylene and the α-olefin monomer, and the hydrogen is added in an amount of not 0.

23、根据权利要求 4或 5所述的方法，其特征在于：所述方法还包括如下步骤：在所述步骤 1 )淤浆聚合反应或本体聚合反应之前，向反应体系中加入结构通式为 R4__nSi(OR')_n的给电子体； The method according to claim 4 or 5, wherein the method further comprises the step of: adding a structural formula to the reaction system before the step 1) slurry polymerization or bulk polymerization An electron donor of R4_ _n Si(OR') _n ;

所述 R4_-nSi(OR')_n中， n为 1-3的整数， R与 R'均选自 C1-C8的垸基、 C5-C10 的环烷基和 C6-C10的芳基中的至少一种，具体选自二苯基二甲基硅烷、二环己基 In the R4 - _n Si(OR') _n , n is an integer of 1-3, and R and R' are each selected from a C1-C8 fluorenyl group, a C5-C10 cycloalkyl group, and a C6-C10 aryl group. At least one selected from the group consisting of diphenyldimethylsilane and dicyclohexyl

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替换页（细则第 26条）二甲基硅烷和苯基三甲基硅烷中的至少一种；或， Replacement page (Article 26) At least one of dimethylsilane and phenyltrimethylsilane; or

所述给电子体与所述助催化剂中垸基铝的摩尔比为 0.01-1.0: 1，具体为 0.1-1.0: The molar ratio of the electron donor to the bismuth aluminum in the cocatalyst is 0.01-1.0:1, specifically 0.1-1.0:

24、根据权利要求 6所述的方法，其特征在于：所述方法还包括如下步骤：在所述步骤 1 )淤浆聚合反应或本体聚合反应之前，向反应体系中加入结构通式为 R4._nSi(OR%的给电子体； 24. The method according to claim 6, wherein the method further comprises the step of: adding a structural formula of R4 to the reaction system before the step 1) slurry polymerization or bulk polymerization. _n Si (OR% electron donor;

所述 R^Si OR';^中， n为 1-3的整数， R与 R'均选自 C1-C8的烷基、 C5-C10 的环烷基和 C6-C10的芳基中的至少一种，具体选自二苯基二甲基硅垸、二环己基二甲基硅烷和苯基三甲基硅烷中的至少一种；或， In the R^Si OR';, n is an integer of 1-3, and R and R' are each selected from the group consisting of a C1-C8 alkyl group, a C5-C10 cycloalkyl group, and a C6-C10 aryl group. a specific one selected from the group consisting of at least one of diphenyldimethylsilyl, dicyclohexyldimethylsilane, and phenyltrimethylsilane; or

所述给电子体与所述助催化剂中烷基铝的摩尔比为 0.01-1.0: 1，具体为 0.1-1.0: The molar ratio of the electron donor to the aluminum alkyl in the cocatalyst is 0.01-1.0:1, specifically 0.1-1.0:

25、根据权利要求 7所述的方法，其特征在于：所述方法还包括如下步骤：在所述步骤 1 )淤浆聚合反应或本体聚合反应之前，向反应体系中加入结构通式为 R4._nSi(OR')_n的给电子体； The method according to claim 7, wherein the method further comprises the step of: adding a structural formula of R4 to the reaction system before the step 1) slurry polymerization or bulk polymerization. An electron donor of _n Si(OR') _n ;

所述 R4-_nSi(OR')_n中， n为 1-3的整数， R与 R'均选自 C1-C8的烷基、 C5-C10 的环烷基和 C6-C10的芳基中的至少一种，具体选自二苯基二甲基硅烷、二环己基二甲基硅烷和苯基三甲基硅垸中的至少一种；或， In the R4- _n Si(OR') _n , n is an integer of 1-3, and R and R' are each selected from a C1-C8 alkyl group, a C5-C10 cycloalkyl group, and a C6-C10 aryl group. At least one selected from the group consisting of at least one of diphenyldimethylsilane, dicyclohexyldimethylsilane, and phenyltrimethylsilyl; or

所述给电子体与所述助催化剂中垸基铝的摩尔比为 0.01-1.0: 1，具体为 0.1-1.0: 26、根据权利要求 8-23任一所述的方法，其特征在于：所述方法还包括如下步骤- 在所述步骤 1 )淤浆聚合反应或本体聚合反应之前，向反应体系中加入结构通式为 R^_nSi(OR')_n的给电子体； The molar ratio of the electron donor to the ruthenium aluminum in the cocatalyst is from 0.01 to 1.0:1, specifically from 0.1 to 1.0:26, according to any one of claims 8 to 23, characterized in that: The method further comprises the steps of: adding an electron donor having the general formula R^ _n Si(OR') _n to the reaction system before the step 1) slurry polymerization or bulk polymerization;

所述 R4_-nSi(OR')_n中， n为 1-3的整数， R与 R'均选自 C1-C8的垸基、 C5-C10 的环垸基和 C6-C10的芳基中的至少一种，具体选自二苯基二甲基硅烷、二环己基二甲基硅烷和苯基三甲基硅烷中的至少一种；或， In the R4 - _n Si(OR') _n , n is an integer of 1-3, and R and R' are each selected from a C1-C8 fluorenyl group, a C5-C10 cyclodecyl group, and a C6-C10 aryl group. At least one selected from the group consisting of at least one of diphenyldimethylsilane, dicyclohexyldimethylsilane, and phenyltrimethylsilane; or

U U

27、根据权利要求 4-26任一所述的方法，其特征在于：所述有机溶剂选自 C5~C10的垸烃和 C6-C8的芳香烃中的至少一种，具体选自庚垸、己垸和甲苯中的至少一种。 The method according to any one of claims 4 to 26, wherein the organic solvent is at least one selected from the group consisting of a C5-C10 terpene hydrocarbon and a C6-C8 aromatic hydrocarbon, and is specifically selected from the group consisting of gadolinium, At least one of hexane and toluene.

28、权利要求 1-3任一所述含有碳纳米管的聚丙烯釜内合金在制备汽车用零部件、包装材料、阻隔材料、阻燃材料、电器材料和电导材料中至少一种的应用。 The use of a carbon nanotube-containing polypropylene in-wall alloy according to any one of claims 1 to 3 for the preparation of at least one of automotive parts, packaging materials, barrier materials, flame retardant materials, electrical materials and electrically conductive materials.

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