WO2014100923A1

WO2014100923A1 - Clay-enhanced polypropylene intra-autoclave alloy, preparation method for same, and applications thereof

Info

Publication number: WO2014100923A1
Application number: PCT/CN2012/001772
Authority: WO
Inventors: 董金勇; 秦亚伟; 王宁
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 clay-enhanced polypropylene intra-autoclave alloy, a preparation method for same, and applications thereof. The intra-autoclave alloy comprises a clay, a homopolymer polypropylene resin, and an olefin polymer. The preparation method is completed by utilizing a catalyst-polymer particle form-copying effect for in situ catalysis of a homopolymerization of propylene monomers and a polymerization reaction of one or two or more types of olefin monomers on a clay-loaded transitional metal catalyst that is spherical in terms of particle superficial form. The nanometer clay-enhanced polypropylene and copolymer resin prepared with the method are spherical in terms of particle forms; this not only implements the goals that the polymer is non-stick to an autoclave, flows easily, and is easy to transport, but also allows clay platelets in an exfoliated form to be distributed evenly in a resin substrate. The clay-enhanced polypropylene intra-autoclave alloy resin provided in the present invention has broad application prospects in the fields of automobile spare parts, packaging materials, barrier materials, flame retardant materials, electrical materials, construction materials, and materials for daily use products.

Description

粘土增强的聚丙烯釜内合金及其制备方法与应用技术领域 Clay-reinforced polypropylene in-cylinder alloy and preparation method and application thereof

本发明涉及一种粘土增强的聚丙烯釜内合金及其制备方法与应用。 The invention relates to a clay reinforced polypropylene in-cylinder alloy and a preparation method and application thereof.

背景技术 Background technique

粘土是一类价廉易得、由纳米片层通过范德华力结合的天然矿物质，因其能够在较少添加量下（一般添加量为 3~5%) 即可显著地提高聚合物的刚性、耐热性能和阻隔性能而成为近年来聚合物纳米改性领域的研究热点之一。 Clay is a kind of natural mineral that is cheap and easy to obtain, and is combined by van der Waals force. It can significantly increase the rigidity of the polymer with less addition amount (3~5% in general). , heat resistance and barrier properties have become one of the research hotspots in the field of polymer nano-modification in recent years.

聚丙烯也是一类价格低廉、性价比突出的高分子材料。近年来，随着聚丙烯的应用领域不断拓宽，人们对其性能寄予了更高的要求，期望其能够兼具高刚和高韧的性能。将粘土为纳米改性剂与聚丙烯合金树脂复合，成为实现上述目标的最有效的途径之一。该方法即可利用粘土的刚性，也可充分发挥聚丙烯合金中橡胶相的韧性，最终制备刚韧平衡的聚丙烯合金树脂。其中，以共混法制备的聚丙烯 /蒙脱土纳米复合材料在汽车塑料中已显示出巨大的应用潜力。 Polypropylene is also a kind of low-cost, cost-effective polymer material. In recent years, as the application field of polypropylene has been broadened, people have placed higher demands on their performance, and they are expected to have both high-rigidity and high-toughness properties. The combination of clay as a nano-modifier and polypropylene alloy resin is one of the most effective ways to achieve the above objectives. The method can utilize the rigidity of the clay, and can fully exert the toughness of the rubber phase in the polypropylene alloy, and finally prepare a rigid-to-balanced polypropylene alloy resin. Among them, the polypropylene/montmorillonite nanocomposite prepared by the blending method has shown great application potential in automotive plastics.

原位聚合方法被认为是制备聚丙烯纳米复合材料的最行之有效的方法之一。该技术是通过富集于粘土片层之间的聚烯烃过渡催化剂的催化活性中心催化丙烯单体聚合反应，避免了由聚丙烯和蒙脱土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。（CN1824696A、 US6613711B2、 CN101235169A US646554313 K US5830820) 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，还可以通过在聚丙烯基体上引入可以导致与粘土片层形成强界面相互作用的功能性基团，从而对界面进行设计，有效体现纳米复合对聚丙烯性能改善的纳米效应（Huang Y J， Yang K F， Dong J Y. Macromol Rapid Commun, 2006, 27： 1278-1283 ) 。也有研究者从催化聚合和规模制备的角度出发，从制备具有球形形态的粘土负载聚烯烃催化剂入手，成功解决了聚丙烯纳米复合树脂的原位聚合制备过程中的颗粒形态差的问题，并将颗粒反应器技术引入到聚丙烯纳米复合树脂的制备过程，成功制备了纳米增强的聚丙烯釜内合金。（Qin Y W， Wang N, Zhou Y, Huang Y J, Niu H， Dong J Y. Macromol Rapid Commun2011,32: 1052-1059) In-situ polymerization is considered to be one of the most effective methods for preparing polypropylene nanocomposites. The technology catalyzes the polymerization of propylene monomer through the catalytically active center of the polyolefin transition catalyst enriched between the clay sheets, avoiding the demanding thermodynamic requirements caused by the difference in polarity between polypropylene and montmorillonite, and thus succeeds. A nano-reinforced polypropylene resin was prepared. (CN1824696A, US6613711B2, CN101235169A US646554313 K US5830820) At the same time, the in-situ polymerization technology allows molecular design of the polypropylene matrix during the compounding process, so that the polypropylene composition and structure can be flexibly adjusted by changing the polyolefin catalyst or copolymerization reaction. The nanocomposites with different matrix properties can expand the performance range, and can also design the interface by introducing a functional group which can form a strong interfacial interaction with the clay sheet on the polypropylene matrix, effectively embodying the nanocomposite pairing Nano-effects of improved propylene performance (Huang YJ, Yang KF, Dong J Y. Macromol Rapid Commun, 2006, 27: 1278-1283). Some researchers have begun to solve the problem of poor particle morphology during the in-situ polymerization of polypropylene nanocomposite resin from the perspective of catalytic polymerization and scale preparation, from the preparation of clay-supported polyolefin catalysts with spherical morphology. The particle reactor technology was introduced into the preparation process of polypropylene nanocomposite resin, and the nano-reinforced polypropylene in-cylinder alloy was successfully prepared. (Qin Y W, Wang N, Zhou Y, Huang Y J, Niu H, Dong J Y. Macromol Rapid Commun 2011, 32: 1052-1059)

使用粘土负载聚烯烃催化剂，分段催化丙烯均聚合反应和一种或两种以上烯烃单体聚合反应，未见报道。 The use of a clay-supported polyolefin catalyst, a stage-catalyzed homopolymerization of propylene and a polymerization of one or two or more olefin monomers has not been reported.

发明公开 Invention disclosure

本发明的目的是提供一种粘土增强聚丙烯釜内合金及其制备方法与应用。 The object of the present invention is to provide a clay-reinforced polypropylene in-cylinder alloy and a preparation method and application thereof.

本发明提供的粘土增强的聚丙烯釜内合金，包括粘土、均聚聚丙烯树脂和烯烃聚合物。 The present invention provides a clay-reinforced polypropylene in-caber alloy comprising clay, a homopolypropylene resin and an olefin polymer.

该粘土增强的聚丙烯釜内合金也可只由上述组分组成。 The clay-reinforced polypropylene in-cylinder alloy may also consist of only 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 200000-800000 g/mol; The homopolypropylene resin is selected from at least one of isotactic polypropylene, syndiotactic polypropylene, and random polypropylene resin. a homopolypropylene resin having a weight average molecular weight of 20,000 to 1,000,000 g/mol, specifically 200,000 to 800,000 g/mol;

所述烯烃聚合物是由 α-烯烃中的一种或两种单体发生聚合反应而得的聚合物，且所述烯烃聚合物不为均聚聚丙烯；其中，所述 α-烯烃为乙烯、丙烯、 1-丁烯、 1- 戊烯、 1-己烯、 1-辛烯、 1-壬烯或 1-癸烯；具体的，所述烯烃类聚合物为均聚等规聚 1-辛烯、乙烯 /1-辛烯无规共聚物、丙烯 /1-丁烯无规共聚物、丙烯 /1-丁烯无规共聚物、均聚等规聚 1-丁烯、均聚聚乙烯或乙烯 /丙烯无规共聚物； The olefin polymer is a polymer obtained by polymerizing one or two monomers of an α-olefin, and the olefin polymer is not a homopolypropylene; wherein the α-olefin is ethylene , propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-decene; specifically, the olefin polymer is homopolymeric isotactic 1- Octene, ethylene/1-octene random copolymer, propylene/1-butene random copolymer, propylene/1-butene random copolymer, homopolymeric isotactic 1-butene, homopolyethylene Or an ethylene/propylene random copolymer;

所述均聚聚丙烯树脂与所述烯烃聚合物的质量比为 40.0 99.0: 1.0-60.0, 具体为 60-95.5 : 4.5-40；更具体为 88.46: 10.2或 86.08: 13.1或 74.24: 25.2或 93.81 : 5.55或 86.83 : 5.55或 77.05 : 22.5或 92.98: 5.6或 95.5 : 2.5或 74.24-95.5 : 5.55-25.2 或 77.05-93.81 : 5.55-22.5； The mass ratio of the homopolypropylene resin to the olefin polymer is 40.0 99.0: 1.0-60.0, specifically 60-95.5: 4.5-40; more specifically 88.46: 10.2 or 86.08: 13.1 or 74.24: 25.2 or 93.81 : 5.55 or 86.83 : 5.55 or 77.05 : 22.5 or 92.98: 5.6 or 95.5 : 2.5 or 74.24-95.5 : 5.55-25.2 or 77.05-93.81 : 5.55-22.5;

所述粘土占所述粘土增强的聚丙烯釜内合金的质量百分含量为 0.01-25%，具体为 0.2-5%，更具体为 1.34%或 0.82%或 0.56%或 0.64%或 0.67%或 0.45%或 1.42% 或 2%或 0.45-2%或 0.56-1.42%或 0.64-1.34%。 The clay comprises 0.01 to 5% by mass of the alloy in the clay-reinforced polypropylene kettle, specifically 0.2 to 5%, more specifically 1.34% or 0.82% or 0.56% or 0.64% or 0.67% or 0.45% or 1.42% or 2% or 0.45-2% or 0.56-1.42% or 0.64-1.34%.

所述粘土增强的聚丙烯釜内合金的颗粒表观形态为球形，粒径为 10〜10000μιη，具体为 50-1000μιη，更具体为 50~200μιη或 50~500μιη; The particle shape of the clay-reinforced polypropylene in-cylinder alloy is spherical, and the particle diameter is 10~10000μηη, specifically 50-1000μηη, more specifically 50-200μιη or 50-500μιη;

所述粘土在所述聚丙烯釜内合金中以剥离的片层形式存在。 The clay is present in the polypropylene in-cylinder alloy as a peeled sheet.

上述粘土增强的聚丙烯釜内合金也可为按照下述方法制备而得的产物。 The above clay-reinforced polypropylene in-cylinder alloy may also be a product obtained by the following method.

本发明提供的制备上述粘土增强的聚丙烯釜内合金的方法，包括如下步骤： 1 ) 在惰性气氛中，将丙烯单体与粘土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，反应完毕得到含有粘土和均聚聚丙烯树脂的复合物；或者，将丙烯单体与粘土负载过渡金属催化剂、助催化剂进行本体聚合反应，反应完毕得到含有粘土和均聚聚丙烯树脂的复合物； The method for preparing the above clay-reinforced polypropylene in-cavity alloy provided by the present invention comprises the following steps: 1) slurry polymerization of a propylene monomer and a clay-supported transition metal catalyst and a cocatalyst in an organic solvent in an inert atmosphere The reaction is completed to obtain a composite containing clay and a homopolypropylene resin; or, the propylene monomer is bulk-polymerized with a clay-supported transition metal catalyst and a cocatalyst, and the reaction is completed to obtain a composite containing clay and a homopolypropylene resin. ;

2) 在惰性气氛中，向所述步骤 1 ) 所得含有粘土和均聚聚丙烯树脂的复合物中加入一种或两种 α-烯烃，于有机溶剂中进行淤浆聚合反应，反应完毕得到所述粘土增强的聚丙烯釜内合金； 2) adding one or two α-olefins to the composite containing the clay and the homopolypropylene resin obtained in the step 1) in an inert atmosphere, and performing slurry polymerization in an organic solvent, and the reaction is completed. a clay-reinforced polypropylene in-cavity alloy;

或者，向所述步骤 1 )所得含有粘土和均聚聚丙烯树脂的复合物中加入一种或两种 α-烯烃进行聚合反应，反应完毕得到粘土增强的聚丙烯釜内合金。 Alternatively, one or two α-olefins may be added to the composite containing the clay and the homopolypropylene resin obtained in the step 1) to carry out polymerization, and the reaction is completed to obtain a clay-reinforced 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；所述步骤 1 ) 和 2) 中，所述有机溶剂均选自 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；或， In the method, the promoter is at least one selected from the group consisting of a C1-C4 alkyl aluminum and a C1-C4 aluminum alkoxide, and is specifically selected from the group consisting of trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum. And at least one of methylaluminoxane; in the steps 1) and 2), the organic solvent is selected from at least one of a C5 C10 alkane and a C6-C8 aromatic hydrocarbon, specifically selected from the group consisting of At least one of an alkane, hexane, and toluene; or,

所述 α烯烃均为乙烯、丙烯、 1-丁烯、 1-戊烯、 1-己烯、 1-辛烯、 1-壬烯或 1- 癸烯。所述步骤 1 ) 中，助催化剂中的铝元素与粘土负载过渡金属催化剂中过渡金属元素的摩尔比为 1 5000: 1，具体为 10-2000: 1，更具体为 200: 1或 400: 1或 600: 1或 2000: 1或 200-2000: 1或 200-600: 1或 200-400: 1或 400-2000: 1或 400-600: 1 或 600-2000: 1或 400-600: 1； The alpha olefins are all ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-decene. In the step 1), the molar ratio of the aluminum element in the cocatalyst to the transition metal element in the clay-supported transition metal catalyst is 15000:1, specifically 10-2000: 1, more specifically 200:1 or 400:1 Or 600: 1 or 2000: 1 or 200-2000: 1 or 200-600: 1 or 200-400: 1 or 400-2000: 1 or 400-600: 1 or 600-2000: 1 or 400-600: 1 ;

所述粘土负载过渡金属催化剂的加入量为所述丙烯单体质量的 0.1-20%，具体为 0.4-10%, 更具体为 0.4%或 1.25%或 0.4%- 1.25%； The clay-supported transition metal catalyst is added in an amount of 0.1-20% by mass of the propylene monomer, specifically 0.4-10%, more specifically 0.4% or 1.25% or 0.4%-1.25%;

所述步骤 2)中，所述 α-烯烃的加入量为所述步骤 1所得含有粘土和均聚聚丙烯树脂的复合物质量的 0.5〜80.0%，具体为 1-80%，更具体为 33%或 77%或 38%或 20%或 56%或 60%或 63%或 42%或 31%或 20%-77%或 31%-63%或 33%-60%或 38%-42%或 20-56%; In the step 2), the α-olefin is added in an amount of 0.5 to 80.0%, specifically 1-80%, more specifically 33%, of the mass of the composite containing the clay and the homopolypropylene resin obtained in the step 1. % or 77% or 38% or 20% or 56% or 60% or 63% or 42% or 31% or 20%-77% or 31%-63% or 33%-60% or 38%-42% or 20-56%;

选用两种 α烯烃时，两种 α烯烃的加入比例为任意比例，具体为质量比为 5-20: 40-80的丙烯和 1-丁烯，或质量比为 5-20: 40-80的乙烯和丙烯，或摩尔比为 1 : 2 的乙烯和丙烯； When two alpha olefins are selected, the ratio of the two alpha olefins is any ratio, specifically propylene and 1-butene in a mass ratio of 5-20: 40-80, or a mass ratio of 5-20: 40-80. Ethylene and propylene, or ethylene and propylene in a molar ratio of 1:2;

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的外给电子体； The method further comprises the steps of: adding an external electron donor having the general formula R4_ _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的烷基、 C5-C10 的环烷基和 C6-C10的芳基中的至少一种，具体选自 C1-C5的烷基和苯基中的至少一种，更具体的， R为甲基， R'为苯基， n为 2 ; 所述外给电子体具体为二甲基二苯基硅烷；外给电子体与助催化剂中铝元素的摩尔比为 0.01-1.0: 1，具体 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，所述氢气的加入量为所述丙烯单体质量的 0-0.5%，具体为 0-0.1%, 更具体为 0.02%或 0.04%或 0.08%或 0.02-0.08%或 0.02-0.04%或 0.04-0.08%, 且所述氢气的加入量不为 0; 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 one, specifically selected from the group consisting of at least one of a C1-C5 alkyl group and a phenyl group, more specifically, R is a methyl group, R' is a phenyl group, and n is 2; the external electron donor is specifically Dimethyldiphenylsilane; the molar ratio of the external electron donor to the aluminum element in the cocatalyst is from 0.01 to 1.0:1, specifically from 0.1 to 1.0:1; the method further comprises the step of: silting in the step 1) Before the slurry polymerization reaction or the bulk polymerization reaction, hydrogen is introduced into the reaction system; wherein the hydrogen is added in an amount of 0-0.5%, specifically 0-0.1%, more specifically 0.02%, of the mass of the propylene monomer. Or 0.04% or 0.08% or 0.02-0.08% or 0.02-0.04% or 0.04-0.08%, and the amount of hydrogen added is not 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，所述氢气的加入量为所述 α烯烃总重的 0-5.0%，具体为 0-0.5%，更具体为 0.035%或 0.04%或 0.05%或或 0.0625%或或 0.067%或 0.07%或 0.1%或 0.15%或 0.04-0.15%或 0.05-0.1%或 0.04-0.07%或 0.04-0.067%或 0.035-0.07%，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 0-5.0 of the total weight of the alpha olefin. %, specifically 0-0.5%, more specifically 0.035% or 0.04% or 0.05% or 0.0625% or 0.067% or 0.07% or 0.1% or 0.15% or 0.04-0.15% or 0.05-0.1% or 0.04- 0.07% or 0.04-0.067% or 0.035-0.07%, and the amount of hydrogen added is not zero.

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，具体为 70°C或 75 °C或 70-75 °C，时间均为 0.05〜10.0小时，具体为 0.2小时或 0.5 小时或 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 0.70MPa或 3.10MPa或 3.00MPa或 3.2MPa或 0.70-3. lOMPa或 0.70-3. OOMPa 或 3.00-3. lOMPa或 0.7-3.2MPa; In the step 1), the temperature of the slurry polymerization reaction and the bulk polymerization reaction are both 30 ° C to 90 ° C, specifically 70 ° C or 75 ° C or 70-75 ° C, the time is 0.05~ 10.0 hours, specifically 0.2 hours or 0.5 hours or 0.2-0.5 hours, the pressure is 0-4MPa, specifically 0.5-3.5MPa, the pressure is not 0, more specifically 0.70MPa or 3.10MPa or 3.00MPa or 3.2 MPa or 0.70-3. lOMPa or 0.70-3. OOMPa or 3.00-3. lOMPa or 0.7-3.2MPa;

所述步骤 2) 中，所述淤浆聚合反应和聚合反应的温度均为 50°C〜120°C，具体为 50°C或 70°C或 90°C或 50-90°C或 70-90°C或 50-70°C，时间均为 0.1 10.0小时，具体为 0.2小时或 0.5小时或 1小时或 2小时或 0.2-2小时或 0.5-1小时或 0.2-0.5小时或 0.5-2小时或 0.2-1小时或 1-2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 0.50MPa或 l .OOMPa或 1.2MPa或 2.50MPa或 1.70MPa 或 0.50-2.50MPa或 1.00-1.70MPa或 0.50-1.70MPa或 0.50-1. OOMPa或 1.00-2.50MPa 或 1.70-2.50MPa; In the step 2), the temperature of the slurry polymerization reaction and the polymerization reaction are both 50 ° C to 120 ° C, specifically 50 ° C or 70 ° C or 90 ° C or 50-90 ° C or 70- 90 ° C or 50-70 ° C, the time is 0.1 10.0 hours, specifically 0.2 hours or 0.5 hours or 1 hour or 2 hours or 0.2-2 hours or 0.5-1 hours or 0.2-0.5 hours or 0.5-2 hours Or 0.2-1 hour or 1-2 hours; the pressure is 0-4MPa, specifically 0.5-3.5MPa, the pressure is not 0, more specifically 0.50MPa or 1.000MPa or 1.2MPa or 2.50MPa or 1.70MPa Or 0.50-2.50MPa or 1.00-1.70MPa or 0.50-1.70MPa or 0.50-1. OOMPa or 1.00-2.50MPa or 1.70-2.50MPa;

此外，上述方法中所用粘土负载过渡金属催化剂均为申请号为 200910235506.X 的中国发明专利申请中公开的粘土负载过渡金属催化剂。该粘土负载过渡金属催化剂由粘土催化剂载体、过渡金属化合物、金属化合物和内给电子体组成；其颗粒表观形态为球形，粒径为 5-100微米，比表面积为 5-500m²/g，平均孔径为 2-50纳米，孔容为 0.05-100cm³/g; Further, the clay-supported transition metal catalyst used in the above method is a clay-supported transition metal catalyst disclosed in Chinese Patent Application No. 200910235506.X. The clay-supported transition metal catalyst is composed of a clay catalyst carrier, a transition metal compound, a metal compound and an internal electron donor; The shape of the sphere is spherical, the particle diameter is 5-100 μm, the specific surface area is 5-500 m ² /g, the average pore diameter is 2-50 nm, and the pore volume is 0.05-100 cm ³ /g;

其中，所述粘土催化剂载体由粘土矿物质与反应性二氧化硅组成； Wherein the clay catalyst carrier consists of a clay mineral and a reactive silica;

所述反应性二氧化硅，是按照包含如下步骤的方法进行制备的：将硅酸酯或硅酸酯钠与带有反应性基团的含硅有机化合物以摩尔比 1 : 0.01— 0.5、反应温度为 0-80 V的条件下发生水解和缩合反应，反应 0.5〜20.0小时后得到所述反应性二氧化硅；或者，将硅酸酯与碱性反应介质混合，在反应温度为 0-80°C的条件下进行溶胶凝胶反应，反应 0.5〜20.0小时后得到所述反应性二氧化硅； The reactive silica is prepared according to a method comprising the steps of: reacting sodium silicate or sodium silicate with a silicon-containing organic compound having a reactive group in a molar ratio of 1:0.01 to 0.5. Hydrolysis and condensation reaction occurs at a temperature of 0-80 V, and the reactive silica is obtained after 0.5 to 20.0 hours of reaction; or, the silicate is mixed with an alkaline reaction medium at a reaction temperature of 0-80. The sol-gel reaction is carried out under the condition of ° C, and the reactive silica is obtained after reacting for 0.5 to 20.0 hours;

其中，所述硅酸酯的结构通式为 Si(OR)₄，R为主链和侧链的总碳原子数为 1~18 的直链或异构化烷烃； Wherein, the silicate has a structural formula of Si(OR) ₄ , and R is a linear or isomerized alkane having a total carbon number of 1 to 18 as a main chain and a side chain;

所述带有反应性基团的含硅有机化合物的结构通式为 R'_mSi(OR)_n， R'选自羟基、烷氧基、羧基、环氧基、双键、氨基、巯基、脲基、四硫基和卤素， l≤m≤3， l≤n<3 , R为主链和侧链的总碳原子数为 1~18 的直链或异构化烷烃。所述水解和缩合反应和溶胶凝胶反应是在 pH值为 8〜 11的反应介质中进行的，所述反应介质选自四氢呋喃、碳原子数为 2至 12的一元醇、丙酮和水中的至少一种。 The structural group of the silicon-containing organic compound having a reactive group is R' _m Si(OR) _n , and R' is selected from the group consisting of a hydroxyl group, an alkoxy group, a carboxyl group, an epoxy group, a double bond, an amino group, a thiol group, Urea, tetrathio and halogen, l ≤ m ≤ 3, l ≤ n < 3, R is a linear or isomerized alkane having 1 to 18 total carbon atoms in the main chain and the side chain. The hydrolysis and condensation reaction and the sol-gel reaction are carried out in a reaction medium having a pH of 8 to 11, and the reaction medium is selected from the group consisting of tetrahydrofuran, a monohydric alcohol having 2 to 12 carbon atoms, acetone, and at least One.

所述粘土催化剂载体中，所述粘土矿物质选自蒙脱土、云母、蛭石和经有机插层剂改性的粘土矿物质中的至少一种；其中，所述经有机插层剂改性的粘土矿物质中，所述有机插层剂选自带有双键、羟基、氨基或烷氧基的烷基季铵盐、咪唑鎗盐和烷基磷盐中的至少一种；所述带有双键、羟基、氨基或烷氧基的烷基季铵盐和烷基磷盐中，所述烷基的结构通式为 CH₃CCH₂)n -， 6≤n≤10000，具体为 12-18; In the clay catalyst carrier, the clay mineral is at least one selected from the group consisting of montmorillonite, mica, vermiculite, and an organic intercalation-modified clay mineral; wherein the organic intercalation agent is modified In the clay mineral, the organic intercalant is at least one selected from the group consisting of an alkyl quaternary ammonium salt having a double bond, a hydroxyl group, an amino group or an alkoxy group, an imidazole gun salt, and an alkyl phosphate salt; In the alkyl quaternary ammonium salt and alkyl phosphonium salt having a double bond, a hydroxyl group, an amino group or an alkoxy group, the structural formula of the alkyl group is CH ₃ CCH ₂ ) n -, 6 ≤ n ≤ 10000, specifically 12 -18;

所述经有机插层剂改性的粘土矿物质，是按照包括如下步骤的方法进行制备的: 将 0.01 0.1质量份的粘土矿物质分散于 1质量份的水或由体积比为 0.05~3: 1的醇与水组成的混合液中形成悬浮液，再加入摩尔用量为粘土矿物质 0.5-20倍的有机插层齐 U，于 20〜90°C下反应 4.0〜20.0小时后过滤，用水或醇和水的混合液洗涤，再于 60〜100°C下真空干燥 4.0 24.0小时，得到所述经有机插层剂改性的粘土矿物质；其中，所述醇选自甲醇、乙醇、正丙醇和异丙醇中的至少一种；所述粘土矿物质的摩尔数按阳离子交换容量计； The organic mineral modifier-modified clay mineral is prepared according to the method comprising the steps of: dispersing 0.01 0.1 part by mass of the clay mineral in 1 part by mass of water or from a volume ratio of 0.05 to 3: a suspension of a mixture of alcohol and water is formed, and an organic intercalation layer of 0.5-20 times the molar amount of the clay mineral is added, and the reaction is carried out at 20 to 90 ° C for 4.0 to 20.0 hours, followed by filtration, using water or The mixture of alcohol and water is washed and dried under vacuum at 60 to 100 ° C for 4.0 24.0 hours to obtain the organic intercalation agent-modified clay mineral; wherein the alcohol is selected from the group consisting of methanol, ethanol, n-propanol and At least one of isopropyl alcohol; the number of moles of the clay mineral is based on cation exchange capacity;

所述粘土矿物质与所述反应性二氧化硅的质量比为 80-99.5: 0.5-20；所述粘土矿物质中，阳离子交换容量为 80-120meq/100g，比表面积为 10-700m²/g，平均孔径为 5-50纳米，孔容为 0.05-500cm³/g，片层间距为 1.0-5.0纳米，所述粘土矿物质中吸附的阳离子为 Na⁺、 K⁺、 Ca²⁺、 H⁺或 Li⁺; The mass ratio of the clay mineral to the reactive silica is 80-99.5: 0.5-20; in the clay mineral, the cation exchange capacity is 80-120 meq/100 g, and the specific surface area is 10-700 m ² / g, an average pore diameter of 5 to 50 nm, a pore volume of 0.05 to 500 cm ³ /g, a sheet spacing of 1.0 to 5.0 nm, and cations adsorbed in the clay mineral are Na ⁺ , K ⁺ , Ca ²⁺ , H ⁺ or Li ⁺ ;

所述反应性二氧化硅的平均粒径为 5-100纳米； The reactive silica has an average particle diameter of 5-100 nm;

所述粘土催化剂载体的颗粒表观形态为球形，粒径大小 5-100微米，比表面积为 10-700m²/g，平均孔径为 5-50纳米，孔容为 0.05-500cm³/g; The particle size of the clay catalyst carrier is spherical, having a particle size of 5 to 100 μm, a specific surface area of 10 to 700 m ² /g, an average pore diameter of 5 to 50 nm, and a pore volume of 0.05 to 500 cm ³ /g;

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 transition metal compound is selected from at least one of a Ziegler-Natta catalyst, 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; Wherein, the titanium tetrahalide used in the Ziegler-Natta catalyst is TiCl ₄ , TiBr ₄ or Til _4;

所述茂金属催化剂如式 II结构通式所示， (Cp -B-Cp^MR^R b The metallocene catalyst is represented by the structural formula of formula II, (Cp -B-Cp^MR^R b

式 II Formula II

所述式 II中， M选自 Ti、 Zr、 Hf、 V、 Fe、 Y、 Sc和镧系金属中的至少一种； In the formula II, M is at least one selected from the group consisting of Ti, Zr, Hf, V, Fe, Y, Sc, and a lanthanide metal;

Cp¹和 Cpⁿ均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，取代基选自〜^的烷基、 C₃〜C₁₈的环烷基和 C₆〜C₁₈的芳香基中的至少一种； Cp ¹ and Cp ⁿ each represent a cyclopentadienyl group or a cyclopentadienyl group having a substituent; in the cyclopentadienyl group having a substituent, the substituent is selected from an alkyl group of ~^, C _{3 to} C _At least one of a cycloalkyl group of _{18 and} an aromatic group of C _{6 to} C ₁₈ ;

R¹和 R²为 H、卤原子、 C1〜C8的烷基、 C1〜C8的烷氧基、 C6〜C20的芳基、 C1〜C15 的烷基取代的 C6〜C20 的芳基、 C1〜C8 的酰氧基、烯丙基和 C1〜C15 的硅烷基中的至少一种； R ¹ and R ² are H, a halogen atom, a C1 to C8 alkyl group, a C1 to C8 alkoxy group, a C6 to C20 aryl group, a C1 to C15 alkyl group-substituted C6 to C20 aryl group, C1~ At least one of an acyloxy group, an allyl group, and a silane group of C1 to C15;

a和 b均为 0-2的整数，且 a+b=2; Both a and b are integers 0-2, and a+b=2;

所述 B代表烷基桥或硅烷基桥，具体为 -C(R³R⁴)-或 -Si(R³R⁴)-; 所述 -C(R³R⁴)- 或 -Si(R³R⁴)-中， R³和 R⁴均为 H、 C1-C4的烷基或 C6 C10的芳基； e为 1、 2或 3 ; 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 、 Me₂Si(2-Me-4-Naph-Ind)₂ZrCl₂或 Ph₂Si(Ind)₂ZrCl₂; 其中， Me为甲基， Ph为苯基， Cp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为萘基； The B represents an alkyl bridge or a silane bridge, specifically -C(R ³ R ⁴ )- or -Si(R ³ R ⁴ )-; the -C(R ³ R ⁴ )- or -Si(R ³ R ⁴ )-, R ³ and R ⁴ are each H, a C1-C4 alkyl group or a C6 C10 aryl group; e is 1, 2 or 3; 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 , Me ₂ Si(2-Me-4-Naph-Ind) ₂ ZrCl ₂ or Ph ₂ Si(Ind) ₂ ZrCl ₂ ; wherein Me is Methyl, Ph is phenyl, Cp is cyclopentadienyl, Ind is fluorenyl, H ₄ Ind is 4,5,6,7-tetrahydroanthracene, Flu is fluorenyl, Naph is naphthyl;

所述非茂金属催化剂如式 III结构通式所示， The non-metallocene catalyst is represented by the structural formula of Formula III,

尸 w Corpse w

、 n , n

式 III Formula III

所述式 III中， M选自 Zr、 Ti、 V和 Hf中的至少一种； In the formula III, M is at least one selected from the group consisting of Zr, Ti, V and Hf;

R R2和 R3均选自 H、卤原子、 C1〜C8的烷基、 C1〜C8的烷氧基、 C6〜C20 的芳基、 C1〜C6的烷基取代的 C6〜C20的芳基、 C3〜C18的环烷基取代的 C6〜 C20的芳基、 C6〜C18的芳香基取代的 C6〜C20的芳基、 C1〜C8的酰氧基、烯丙基和 C1〜C15的硅烷基中的至少一种； X为卤原子， Cl， Br, I或 F; n为 2; R R 2 and R 3 are each selected from the group consisting of H, a halogen atom, a C1 to C8 alkyl group, a C1 to C8 alkoxy group, a C6 to C20 aryl group, a C1 to C6 alkyl group-substituted C6 to C20 aryl group, and C3. ~C18 cycloalkyl substituted C6~C20 aryl, C6~C18 aryl substituted C6~C20 aryl, C1~C8 acyloxy, allyl and C1~C15 silane group At least one; X is a halogen atom, Cl, Br, I or F; n is 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) aniline]zirconium dichloride;

所述金属化合物为含镁化合物和 /或含铝化合物； The metal compound is a magnesium-containing compound and/or an aluminum-containing compound;

其中，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；所述 RMgX中， R为碳原子数为 1-10的烷基， X为氟、氯、溴或碘； Wherein, 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; wherein, in the MgX ₂ , X is a fluorine, chlorine, bromine or iodine element; and in the RMgX, R is An alkyl group having 1 to 10 carbon atoms, and X is fluorine, chlorine, bromine or iodine;

所述含铝化合物为 Al(OR')_nR₃__n，n为 0-3的整数， R和 R'均为 C2 C10的烷基；所述内给电子体选自邻苯二甲酸二异丁酯、芴二醚、苯甲酸甲酯和邻苯二甲酸二丁酯中的至少一种； The aluminum-containing compound is Al(OR') _n R ₃ _ _n , n is an integer of 0-3, and R and R' are both C2 C10 alkyl groups; the internal electron donor is selected from the group consisting of phthalic acid At least one of isobutyl ester, decane diether, methyl benzoate and dibutyl phthalate;

所述粘土催化剂载体在所述粘土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 75-90%; The mass percentage of the clay catalyst support in the clay-supported transition metal catalyst is 70.0-99.0%, specifically 75-90%;

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粘土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 1.0-10.0%； The sum of the metal element in the metal compound and the transition metal element in the transition metal compound is 1.0 to 30.0% by mass in the clay-supported transition metal catalyst, specifically 1.0 to 10.0%;

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粘土负载过渡金属催化剂中的质量百分含量为 0.5~5.0%； When the metal compound is a magnesium-containing compound, the mass percentage of the transition metal element in the transition metal compound in the clay-supported transition metal catalyst is 0.5 to 5.0%;

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粘土负载过渡金属催化剂中的质量百分含量为 0.05 2.0%; When the metal compound is an aluminum-containing compound, a mass percentage of the transition metal element in the transition metal compound in the clay-supported transition metal catalyst is 0.05% by weight;

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粘土负载过渡金属催化剂中的质量百分含量为 0.55-7.0%。 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 clay-supported transition metal catalyst is from 0.55 to 7.0%.

所述内给电子体在所述粘土负载过渡金属催化剂中的质量百分含量为 2.50-15.0%。 The internal electron donor has a mass percentage of 2.50-15.0% in the clay-supported transition metal catalyst.

另外，上述本发明提供的粘土增强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、建筑材料和日常生活用材料中的至少一种中的应用，也属于本发明的保护范围。 In addition, the above-mentioned clay-reinforced polypropylene in-cavity alloy provided by the present invention is used for preparing at least one of automotive parts, packaging materials, barrier materials, flame retardant materials, electrical materials, building materials, and materials for daily use. It also falls within the scope of protection of the present invention.

附图说明 DRAWINGS

图 1为实施例 1中含粘土片层的聚丙烯釜内合金树脂颗粒的表观形貌。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an apparent morphology of a polypropylene resin in-cylinder alloy resin particle containing a clay sheet layer in Example 1.

图 2为实施例 1中含粘土片层的聚丙烯釜内合金树脂的广角 X射线衍射图。图 3为实施例 1中含粘土片层的聚丙烯釜内合金树脂的透射电镜照片。 Fig. 2 is a wide-angle X-ray diffraction diagram of the alloy resin in the polypropylene kettle containing the clay sheet layer in Example 1. Fig. 3 is a transmission electron micrograph of a polypropylene resin in a cage containing a clay sheet in Example 1.

图 4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 4 is a graph showing the temperature-raising nuclear magnetic carbon spectrum of the homopolypropylene obtained in the step 1) of Example 1.

图 5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。 Fig. 5 is a graph showing the elevated nuclear magnetic carbon spectrum of the olefin polymer (ethylene propylene random copolymer) obtained in the step 2) of Example 1.

图 6实施例 1中粘土负载的过渡金属催化剂的表观形貌。 Figure 6. Apparent topography of a clay supported transition metal catalyst in Example 1.

图 7为实施例 1中粘土载体及粘土负载过渡金属催化剂的广角 X射线衍射图。图 8为实施例 2中含纳米硅酸盐片层的聚丙烯釜内合金树脂颗粒的表观形态。图 9为实施例 2中含纳米硅酸盐片层的聚丙烯釜内合金树脂加工后样品的透射电镜照片。 Figure 7 is a wide-angle X-ray diffraction pattern of the clay carrier and the clay-supported transition metal catalyst of Example 1. Fig. 8 is a view showing the appearance of the polypropylene resin in-cylinder alloy resin particles containing the nanosilicate plate layer in Example 2. Fig. 9 is a transmission electron micrograph of a sample of a polypropylene resin in an in-cylinder alloy resin containing a nanosilicate layer in Example 2.

图 10为实施例 2中粘土负载过渡金属催化剂的表观形貌。 Figure 10 is an apparent topography of the clay-supported transition metal catalyst of Example 2.

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

以下具体实施例就发明的粘土增强聚丙烯及共聚物树脂的制备方法做出详细的解释。但这些实施例并不本限制发明的范围，也不应理解为只有本发明提供的条件、参数或数值才能实施本发明。粘土负载过渡金属催化剂中钛元素和锆元素的含量均用紫外分光光度法测得，催化剂中镁元素和铝元素的含量均用滴定法测得。本发明着重于对粘土增强的聚丙烯釜内合金聚合物颗粒形态的控制，故对产物的表征主要通过两手段：扫描电镜测试（观察其形态）和广角 X射线衍射测试（测试粘土片层的剥离分散情况）。下述实施例中各反应均在惰性气氛中进行。 The following specific examples explain in detail the preparation methods of the inventive clay-reinforced polypropylene and copolymer resins. However, the examples are not intended to limit the scope of the invention, nor should they be construed as being limited to the scope of the invention. The content of titanium and zirconium in the clay-supported transition metal catalyst was measured by ultraviolet spectrophotometry, and the contents of magnesium and aluminum in the catalyst were measured by titration. The present invention focuses on the control of the morphology of the alloy polymer particles in the clay-reinforced polypropylene, so the product is characterized by two means: scanning electron microscopy (observation of its morphology) and wide-angle X-ray diffraction test (testing of clay sheets) Stripping the dispersion). Each of the reactions in the following examples was carried out under an inert atmosphere.

实施例 1 1 ) 真空状态下，将 8g丙烯单体充入反应釜土负载中，依次加入 50ml溶剂己烷、含 5.5mmol助催化剂三乙基铝的庚烷溶液 3.5ml及 0.1克粘土负载的过渡金属催化剂（助催化剂三乙基铝中铝元素与粘土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 200: 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，得到含有粘土和重均分子量为 365000g/mol的均聚等规聚丙烯的复合物 6.0g，然后，停止通入丙烯单体； Example 1 1) Under vacuum, 8g of propylene monomer is charged into the reactor soil load, and 50ml of solvent hexane, 3.5ml of heptane solution containing 5.5mmol of cocatalyst triethylaluminum and 0.1g of clay-supported transition metal catalyst are sequentially added. (The molar ratio of aluminum in the cocatalyst triethylaluminum to the transition metal element in the clay-supported transition metal catalyst is 200:1), the pressure in the autoclave is constant at 0.7 MPa, and the reaction temperature is 70 ° C. The slurry polymerization reaction was carried out for 0.5 hour to obtain 6.0 g of a composite containing clay and a homopolymeric isotactic polypropylene having a weight average molecular weight of 365,000 g/mol, and then, the passage of the propylene monomer was 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) 2g，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 6.7克粘土增强的聚丙烯釜内合金； 2) In step 1), a mixture of ethylene and propylene (in which the molar ratio of ethylene to propylene is 1:2) 2 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 6.7 g of a clay-reinforced polypropylene in-cylinder alloy;

该粘土增强的聚丙烯釜内合金由质量比为 1.34: 88.46： 10.2 的粘土、均聚等规聚丙烯树脂和乙烯 /丙烯无规共聚物组成。颗粒表观形态为球形，如图 1所示，颗粒粒径为 50~200μιη_; 广角 X射线（如图 2所示）和透射电镜照片（如图 3所示）均表明，粘土以剥离的纳米片层的形式存在。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 4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 5所示。 The clay-reinforced polypropylene in-cylinder alloy is composed of a clay having a mass ratio of 1.34: 88.46: 10.2, a homopolymeric isotactic polypropylene resin, and an ethylene/propylene random copolymer. The apparent morphology of the particles is spherical, as shown in Figure 1, the particle size is 50~200μιη _; wide-angle X-rays (as shown in Figure 2) and transmission electron micrographs (as shown in Figure 3) indicate that the clay is stripped of nano The form of the slice exists. 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. The molecular structure of the olefin polymer (ethylene/propylene random copolymer) obtained by the step 2) is determined by the temperature-raising nuclear magnetic carbon spectrum, as shown in FIG.

其中，所用粘土负载的过渡金属催化剂按照如下方法制备而得： Wherein, the clay-supported transition metal catalyst used is prepared as follows:

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 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； 1) 2.0 g of anhydrous magnesium chloride MgCl ₂ and 5.5 ml of isooctanol were dispersed in 50 ml of decane, heated to 130 ° C to form a transparent solution, and reacted at 130 ° C for 2.0 hours to obtain a magnesium chloride alcoholate;

将上述氯化镁醇合物滴加入 3.0g球形的粘土催化剂载体与 50ml癸烷的悬浮液中，于 60°C下恒温反应 4.0小时，然后滤除液体，滤出的固体用癸烷洗涤 3次，干燥后得到粘土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 a spherical clay catalyst carrier and 50 ml of decane, and reacted at 60 ° C for 4.0 hours under constant temperature, and then the liquid was filtered off, and the filtered solid was washed 3 times with decane. After drying, a magnesium composite of a clay catalyst carrier is obtained;

2) 向 -20°C的 100ml四氯化钛溶液中加入 5.0g步骤 1 )所得粘土催化剂载体的镁复合物，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，干燥后得到粘土负载的过渡金属催化剂。 2) To 100 ml of a titanium tetrachloride solution at -20 ° C, 5.0 g of the magnesium composite of the clay catalyst carrier obtained in the step 1) was added, and the mixture was reacted at -20 ° C for 1.0 hour under constant temperature. 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 clay-supported transition metal catalyst.

该粘土负载过渡金属催化剂为球形颗粒 (图 6)，由粘土催化剂载体、过渡金属化合物 Ti化合物（TiCl₄) 、内给电子体邻苯二甲酸二异丁酯和金属化合物镁化合物（氯化镁）组成；其中，钛元素、镁元素的含量分别为 1.34wt%、 2.15wt%, 邻苯二甲酸二异丁酯和粘土催化剂载体的含量分别为 5.9wt%、 75wt%。 The clay-supported transition metal catalyst is a spherical particle (Fig. 6) composed of a clay catalyst carrier, a transition metal compound Ti compound (TiCl ₄ ), an internal electron donor diisobutyl phthalate, and a metal compound magnesium compound (magnesium chloride). The content of the titanium element and the magnesium element is 1.34 wt% and 2.15 wt%, respectively, and the content of the diisobutyl phthalate and the clay catalyst carrier are 5.9 wt% and 75 wt%, respectively.

该粘土催化剂载体中粘土片层间距为 2.0nm，而在粘土负载过渡金属催化剂的广角 X射线衍射图（图 7)上，粘土片层的 (001)面特征峰向低角度移动，且该特征峰变宽，粘土负载过渡金属催化剂中粘土片层间距大于 2.0nm，这说明催化活性组分进入了粘土片层之间并均匀分布于粘土负载过渡金属催化剂颗粒的内外。氮气吸附测试结果可知，该粘土负载过渡金属催化剂的比表面积为 137.5m²/g，孔容为 0.36cm³/g, 平均孔径为 16.7nm。 The clay catalyst carrier has a clay sheet spacing of 2.0 nm, and on the wide-angle X-ray diffraction pattern of the clay-supported transition metal catalyst (Fig. 7), the (001) plane characteristic peak of the clay sheet moves to a low angle, and the feature The peak broadens and the clay sheet spacing in the clay-supported transition metal catalyst is greater than 2.0 nm, indicating that the catalytically active component enters between the clay sheets and is evenly distributed inside and outside the clay-supported transition metal catalyst particles. As a result of nitrogen adsorption test, the clay-supported transition metal catalyst had a specific surface area of 137.5 m ² /g, a pore volume of 0.36 cm ³ /g, and an average pore diameter of 16.7 nm.

其中，步骤 1 ) 所用粘土催化剂载体，是按照下述方法制备的： 1 )将 10克钠基蒙脱土分散于 500毫升水和 500毫升乙醇的混合溶液中形成悬浮液，向该悬浮液中加入 12克十六烷基三甲基氯化铵，于 80°C下反应 4.0小时后过滤，分别用 200毫升水和乙醇洗涤三次，再于 80°C下真空干燥 20.0小时，得到经十八烷基三甲基氯化铵改性的有机粘土。 Wherein, the clay catalyst carrier used in the step 1) is prepared according to the following method: 1) Dispersing 10 g of sodium montmorillonite in a mixed solution of 500 ml of water and 500 ml of ethanol to form a suspension, and adding 12 g of cetyltrimethylammonium chloride to the suspension at 80 ° C After the reaction for 4.0 hours, it was filtered, washed three times with 200 ml of water and ethanol, and then dried under vacuum at 80 ° C for 20.0 hours to obtain an octadecyltrimethylammonium chloride-modified organoclay.

2) 60°C下，向 100ml反应瓶中，依次加入 0.3578克浓氨水、 1.3694克去离子水和 22.7572克无水乙醇，磁力搅拌 0.5小时后，滴加入 1.0000克正硅酸乙酯。 60 °C下反应 4.0小时。然后除去溶剂，干燥后得到反应性二氧化硅纳米微粒，其平均粒径为 40nm。 2) In a 100 ml reaction flask, 0.3578 g of concentrated ammonia water, 1.3694 g of deionized water and 22.7572 g of absolute ethanol were successively added at 60 ° C, and magnetic stirring was carried out for 0.5 hour, and then 1.0000 g of tetraethyl orthosilicate was added dropwise. The reaction was carried out at 60 ° C for 4.0 hours. Then, the solvent was removed, and after drying, reactive silica nanoparticles having an average particle diameter of 40 nm were obtained.

3 )取 20克干燥的步骤 1 )所得经十八烷基三甲基氯化铵改性的有机粘土，经过超声作用分散于 400 毫升乙醇中（有机粘土在该悬浮液中的质量百分浓度为 6.2wt%) 。 60°C下，将 93.98克步骤 2) 所得反应性二氧化硅纳米微粒的乙醇悬浮液（其中，反应性二氧化硅纳米微粒的质量百分浓度为 1.12wt%; 反应性二氧化硅纳米微粒与有机粘土的质量比为 1 : 19) 滴加入已均匀分散的有机粘土悬浮液中。滴加完成后，反应 4.0小时，再加入 2.0克碳酸氢铵（碳酸氢铵与有机粘土的质量比例为 0.1 : 1 ) ，继续搅拌 0.5小时后，喷雾干燥成型得到粘土催化剂载体。 3) Take 20 g of the dried step 1) the obtained octadecyltrimethylammonium chloride-modified organoclay, which is ultrasonically dispersed in 400 ml of ethanol (mass concentration of organoclay in the suspension) 6.2wt%). At 60 ° C, 93.98 g of the ethanol suspension of the reactive silica nanoparticles obtained in the step 2) (wherein the mass concentration of the reactive silica nanoparticles is 1.12% by weight; reactive silica nanoparticles) The mass ratio to the organoclay is 1: 19) Dropped into the uniformly dispersed organoclay suspension. After the completion of the dropwise addition, the reaction was carried out for 4.0 hours, and then 2.0 g of ammonium hydrogencarbonate (the ratio of the mass ratio of ammonium hydrogencarbonate to the organoclay was 0.1 : 1 ) was added, and stirring was continued for 0.5 hour, followed by spray drying to obtain a clay catalyst carrier.

该粘土催化剂载体由质量比为 95: 5的经有机插层剂改性的粘土（由质量比为 20： 80的有机插层剂十八烷基二甲基羟乙基硝酸铵和钠基蒙脱土组成，钠基蒙脱土的性质如下：阳离子交换容量为 90meq/100g，比表面积为 17.89m²/g，平均孔径为 21.90nm, 孔容为 0.10cm³/g，片层间距为 l.Onm) 和平均粒径为 40nm的反应性二氧化硅组成，其颗粒形态为球形，其颗粒粒径为 10~30μιη，比表面积为 42.1m²/g，孔容为 0.18cm³/g，平均孔径为 13.4nm。粘土催化剂载体和有机粘土的广角 X射线衍射测试结果可知，衍射角在 1.5°~10°范围内均出现粘土的（001 )面特征峰，根据 Bragg方程 2dsine= 计算，其片层间距均为 2.0nm，这说明片层间距并未因反应性二氧化硅纳米微粒的加入而发生变化。 The clay catalyst carrier is composed of an organic intercalation agent-modified clay having a mass ratio of 95:5 (the organic intercalation agent octadecyldimethylhydroxyethyl ammonium nitrate and sodium-based monoxide having a mass ratio of 20:80) Desiccant composition, the properties of sodium-based montmorillonite are as follows: cation exchange capacity is 90meq/100g, specific surface area is 17.89m ² /g, average pore diameter is 21.90nm, pore volume is 0.10cm ³ /g, and sheet spacing is l .Onm) and a reactive silica having an average particle diameter of 40 nm, the particle shape is spherical, the particle size is 10 to 30 μm, the specific surface area is 42.1 m ² /g, and the pore volume is 0.18 cm ³ /g. The average pore diameter was 13.4 nm. The wide-angle X-ray diffraction test results of the clay catalyst carrier and the organoclay show that the (001) surface characteristic peak of the clay appears in the diffraction angle range of 1.5° to 10°, and the interlayer spacing is 2.0 according to the Bragg equation 2dsine= . Nm, which means that the interlamellar spacing is not altered by the addition of reactive silica nanoparticles.

实施例 2 Example 2

1 ) 将 250克液态丙烯加入至反应釜中， 30°C下依次加入含 0.25mol助催化剂三乙基铝， 0.05mol助催化剂甲基铝氧烷及 1.0克粘土负载过渡金属催化剂（三乙基铝中的铝元素与粘土负载过渡金属催化剂中过渡金属元素钛的摩尔比为 600: 1；甲基铝氧烷中的铝元素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，进行本体聚合反应 0.2小时，得到 104.28g含有粘土和重均分子量为 660000g/mol的均聚等规聚丙烯的复合物，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.25 mol of cocatalyst triethylaluminum, 0.05 mol of cocatalyst methylaluminoxane and 1.0 g of clay-supported transition metal catalyst (triethyl group) were sequentially added at 30 ° C The molar ratio of the aluminum element in the aluminum to the transition metal element titanium in the clay-supported transition metal catalyst is 600:1; the molar ratio of the aluminum element in the methylaluminoxane to the transition metal element zirconium in the catalyst is 2000: 1 ) and hydrogen 0.2 g, a pressure of 3.1 MPa, and the temperature was raised to 70 ° C, and bulk polymerization was carried out for 0.2 hours to obtain 104.28 g of a composite containing a clay and a homopolymerized isotactic polypropylene having a weight average molecular weight of 660000 g/mol, and directly proceeding 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 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，进行聚合反应 0.2小时，最终得到粘土增强的聚丙烯釜内合金 120.0g。 2) The propylene remaining in the reaction vessel in the above step 1) was vented and cooled to 50 ° 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 polymerization was carried out for 0.2 hours, and finally 120.0 g of a clay-reinforced polypropylene in-cylinder alloy was obtained.

该粘土增强的聚丙烯釜内合金由质量比为 0.82: 86.08： 13.1 的粘土、均聚等规聚丙烯树脂和乙烯 /丙烯无规共聚物组成。该粘土增强的聚丙烯合金颗粒表观形态为球形，如图 8所示，颗粒粒径为 50~200μιη_; 广角 X射线测试结果表明透射电镜照片（图 9) 均表明，纳米粘土以剥离的纳米片层的形式存在。其中，所用粘土负载过渡金属催化剂是按照下述方法进行制备的： The clay-reinforced polypropylene in-cylinder alloy was composed of a clay having a mass ratio of 0.82: 86.08: 13.1, a homopolymeric isotactic polypropylene resin, and an ethylene/propylene random copolymer. The apparent morphology of the clay-reinforced polypropylene alloy particles is spherical, as shown in Fig. 8, the particle size is 50~200μιη _{; the} wide-angle X-ray test results show that the transmission electron micrograph (Fig. 9) indicates that the nanoclay is stripped of nanometer. The form of the slice exists. Among them, the clay-supported transition metal catalyst used was prepared as follows:

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, and heated to 110 ° C to form a transparent solution, which was reacted at 110 ° C for 4.0 hours.

将上述氯化镁醇合物滴加入 3.0g球形粘土载体 /100ml癸烷的悬浮液中，于 90 °C下恒温反应 12.0小时，然后滤除液体，滤出的固体用癸烷洗涤 3次，干燥后得到粘土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 a spherical clay carrier/100 ml of decane, and the mixture was reacted at 90 ° C for 12.0 hours, and then the liquid was filtered off, and the filtered solid was washed 3 times with decane, dried. A magnesium composite of a clay catalyst support is obtained.

2) 向 -20°C的 100ml四氯化钛溶液中加入 lO.Og球形所述粘土催化剂载体的镁复合物，并于 -20°C下恒温反应 1.0小时。缓慢升温至 110°C，加入 0.3ml邻苯二甲酸二异丁酯，然后于 110°C下恒温反应 2.0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，干燥后得到粘土负载钛化合物。 2) To 100 ml of titanium tetrachloride solution at -20 ° C, 10 g of a magnesium composite of spherical clay 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 0.3 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 ° C. The reaction was carried out under constant temperature for 2.0 hours. Finally, it was washed 3 to 6 times with hexane, and after drying, a clay-supported titanium compound was obtained.

3 ) 取 5.0 克所述球形粘土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小时，然后用甲苯洗涤 5 次，干燥后得到活化的粘土催化剂。 3) Take 5.0 g of the spherical clay-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, then wash 5 times with toluene, and dry. The activated clay catalyst is then obtained.

4 ) 将 0.15 克过渡金属化合物 rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂加入至含有4) 0.15 g of transition metal compound rac-Me ₂ Si(2-Me-4-PhInd) ₂ ZrCl _{2 is} added to the

O. lOmol甲基铝氧烷的甲苯溶液 40ml中，于 0°C下反应 4.0小时，得到活化的催化剂溶液。 O. lOmol methylaluminoxane in 40 ml of a toluene solution was reacted at 0 ° 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 5.0克所述步骤 3 )制备所得活化的粘土催化剂的 50ml甲苯悬浮液中，于 90°C下反应 4.0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粘土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 clay 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 clay-supported transition metal catalyst provided by the present invention was obtained.

该粘土负载过渡金属催化剂为球形颗粒，如图 10所示。由粘土催化剂载体、过渡金属化合物钛化合物（TiCl₄) 、内给电子体邻苯二甲酸二异丁酯和锆化合物The clay-supported transition metal catalyst is a spherical particle as shown in FIG. Clay catalyst support, transition metal compound titanium compound (TiCl ₄ ), internal electron donor diisobutyl phthalate and zirconium compound

( rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂ )与镁化合物（MgCl₂)和铝化合物（甲基铝氧烷）组成，其中钛元素、镁元素、锆元素和铝元素的含量分别为 1.98wt%、 3.01wt%、 0.20wt%、 7.98wt%, 邻苯二甲酸二异丁酯的含量为 10.02wt%。粘土催化剂载体的质量百分含量为 72%。广角 X射线衍射测试结果，其中粘土片层间距大于 2.0nm，催化活性组分进入粘土片层间隙并均匀分布于粘土负载过渡金属催化剂颗粒内外。该催化剂的比表面积为 56.8m²/g，孔容为 0.16cm³/g，平均孔径为 14.4nm。 (rac-Me ₂ Si(2-Me-4-PhInd) ₂ ZrCl ₂ ) is composed of a magnesium compound (MgCl ₂ ) and an aluminum compound (methylaluminoxane), wherein titanium, magnesium, zirconium and aluminum The content was 1.98 wt%, 3.01 wt%, 0.20 wt%, 7.98 wt%, and the content of diisobutyl phthalate was 10.02 wt%. The clay catalyst carrier has a mass percentage of 72%. The results of the wide-angle X-ray diffraction test, wherein the clay sheet spacing is greater than 2.0 nm, the catalytically active component enters the clay sheet gap and is uniformly distributed inside and outside the clay-supported transition metal catalyst particles. The catalyst had a specific surface area of 56.8 m ² /g, a pore volume of 0.16 cm ³ /g, and an average pore diameter of 14.4 nm.

其中，所用粘土催化剂载体，是按照下述方法制备的： Among them, the clay catalyst carrier used was prepared as follows:

1 )经十八烷基三甲基氯化铵改性的有机粘土的制备：将 10克钠基蒙脱土分散于 500毫升水和 500毫升乙醇的混合溶液中形成悬浮液，向该悬浮液中加入 12克十六烷基三甲基氯化铵，于 80°C下反应 4.0小时后过滤，分别用 200毫升水和乙醇洗涤三次，再于 80°C下真空干燥 20.0小时，得到经十八烷基三甲基氯化铵改性的有机粘土。 1) Preparation of octadecyltrimethylammonium chloride-modified organoclay: Dispersing 10 g of sodium montmorillonite in a mixed solution of 500 ml of water and 500 ml of ethanol to form a suspension to the suspension 12 g of cetyltrimethylammonium chloride was added thereto, and the mixture was reacted at 80 ° C for 4.0 hours, filtered, washed three times with 200 ml of water and ethanol, and dried under vacuum at 80 ° C for 20.0 hours to obtain ten Octamethyltrimethylammonium chloride modified organoclay.

2) 反应性二氧化硅纳米粒子的制备： 60°C下，向 100ml反应瓶中，依次加入 2) Preparation of reactive silica nanoparticles: 60 ° C, into a 100 ml reaction bottle, sequentially added

0.3578克浓氨水、 1.3694克去离子水和 22.7572克无水乙醇，磁力搅拌 0.5小时后，滴加入 1.0000克正硅酸乙酯。 60°C下反应 4.0小时。然后除去溶剂，干燥后得到反应性二氧化硅纳米微粒，其平均粒径为 40nm。 3 )粘土催化剂载体的制备：取 20克干燥的所述经十八烷基三甲基氯化铵改性的有机粘土，经过超声作用分散于 400毫升乙醇中（有机粘土在该悬浮液中的质量百分浓度为 6.2wt%) 。 60°C下，将 93.98克反应性二氧化硅纳米微粒的乙醇悬浮液 (其中，反应性二氧化硅纳米微粒的质量百分浓度为 1.12wt%; 反应性二氧化硅纳米微粒与有机粘土的质量比为 1 : 19) 滴加入已均匀分散的有机粘土悬浮液中。滴加完成后，反应 4.0小时，再加入 2.0克碳酸氢铵（碳酸氢铵与有机粘土的质量比例为 0.1 : 1 ) ，继续搅拌 0.5小时后，喷雾干燥成型制备得到粘土催化剂载体。 0.3578 g of concentrated ammonia water, 1.3694 g of deionized water and 22.7572 g of absolute ethanol were added, and after magnetic stirring for 0.5 hour, 1.0000 g of tetraethyl orthosilicate was added dropwise. The reaction was carried out at 60 ° C for 4.0 hours. Then, the solvent was removed, and after drying, reactive silica nanoparticles were obtained, and the average particle diameter was 40 nm. 3) Preparation of clay catalyst carrier: 20 g of the dried octadecyltrimethylammonium chloride-modified organoclay was dispersed by ultrasonication in 400 ml of ethanol (organic clay in the suspension) The mass percent concentration is 6.2 wt%). An ethanol suspension of 93.98 g of reactive silica nanoparticles (wherein the mass concentration of reactive silica nanoparticles is 1.12% by weight; at 60 ° C; reactive silica nanoparticles and organoclay The mass ratio is 1: 19) Dropped into the uniformly dispersed organoclay suspension. After the completion of the dropwise addition, the reaction was carried out for 4.0 hours, and then 2.0 g of ammonium hydrogencarbonate (a mass ratio of ammonium hydrogencarbonate to organoclay was 0.1:1) was added thereto, and stirring was continued for 0.5 hours, followed by spray drying to prepare a clay catalyst carrier.

该粘土催化剂载体由质量比为 95: 5 的有机粘土（有机粘土由质量比为 20: 80的有机插层剂十八烷基二甲基羟乙基硝酸铵和钠基蒙脱土组成，钠基蒙脱土的性质如下：阳离子交换容量为 90meq/100g，比表面积为 17.89m²/g，平均孔径为 21.90nm，孔容为 0.10cm³/g，片层间距为 l.Onm)和平均粒径为 40nm的反应性二氧化硅组成，其颗粒形态为球形，其颗粒粒径大小为 10~30μιη，比表面积为 42.1m²/g，孔容为 0.18cm³/g, 平均孔径为 13.4nm。粘土催化剂载体和有机粘土的广角 X射线衍射测试结果可知，衍射角在 1.5°~10°范围内均出现粘土的（001 ) 面特征峰，根据 Bragg 方程 2dsine= 计算，其片层间距均为 2.0nm，这说明片层间距并未因反应性二氧化硅纳米微粒的加入而发生变化。 The clay catalyst carrier consists of an organoclay having a mass ratio of 95:5 (the organoclay is composed of an organic intercalant of octadecyldimethylhydroxyethylammonium nitrate and sodium montmorillonite having a mass ratio of 20:80, sodium The properties of montmorillonite are as follows: cation exchange capacity is 90 meq/100 g, specific surface area is 17.89 m ² /g, average pore diameter is 21.90 nm, pore volume is 0.10 cm ³ /g, sheet spacing is l. Onm) and average The composition of reactive silica having a particle diameter of 40 nm has a spherical shape of 10 to 30 μm, a specific surface area of 42.1 m ² /g, a pore volume of 0.18 cm ³ /g, and an average pore diameter of 13.4. Nm. The wide-angle X-ray diffraction test results of the clay catalyst carrier and the organoclay show that the (001) surface characteristic peak of the clay appears in the diffraction angle range of 1.5° to 10°, and the interlayer spacing is 2.0 according to the Bragg equation 2dsine= . Nm, which means that the interlamellar spacing is not altered by the addition of reactive silica nanoparticles.

实施例 3 Example 3

1 ) 将 250克液态丙烯加入至反应釜中， 30°C下依次加入 0.15mol助催化剂三乙基铝及 1.0克粘土负载过渡金属催化剂（三乙基铝中铝元素与粘土负载过渡金属催化剂中钛元素的摩尔比为 400: 1 ) ，升温至 70°C，压强为 3.1MPa，进行本体聚合反应 0.5小时，得到含有粘土和重均分子量为 785000g/mol的均聚等规聚丙烯的复合物 133g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.15 mol of promoter triethylaluminum and 1.0 g of clay-supported transition metal catalyst (triethylaluminum in aluminum element and clay-supported transition metal catalyst) were sequentially added at 30 °C. The molar ratio of titanium element is 400:1), the temperature is raised to 70 ° C, the pressure is 3.1 MPa, and bulk polymerization is carried out for 0.5 hour to obtain a complex containing clay and homopolymerized isotactic polypropylene having a weight average molecular weight of 785000 g/mol. 133g, proceed directly 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，再通入乙烯气 50克，通入氢气 0.05g，升温至 90°C，压强为 l.OMPa, 进行聚合反应 1小时，最终得到粘土增强聚丙烯釜内合金 180.0g。 2) The propylene remaining in the reaction vessel in the above step 1) is vented and cooled to 50 ° C, and then 50 g of ethylene gas is introduced, 0.05 g of hydrogen gas is introduced, and the temperature is raised to 90 ° C, and the pressure is 1.0 MPa. The polymerization was carried out for 1 hour, and finally 180.0 g of a clay-reinforced polypropylene in-cylinder alloy was obtained.

该粘土增强的聚丙烯釜内合金由质量比为 0.56: 74.24： 25.2 的粘土、均聚等规聚丙烯树脂和均聚聚乙烯组成。该粘土增强聚丙烯合金颗粒表观形态为球形，粒径为 50~500μιη_; 广角 X射线测试结果表明，粘土以剥离的纳米片层形式存在。 The clay-reinforced polypropylene in-cylinder alloy consists of a clay having a mass ratio of 0.56: 74.24: 25.2, a homopolymeric isotactic polypropylene resin, and a homopolyethylene. The apparent shape of the clay-reinforced polypropylene alloy particles is spherical and the particle size is 50-500 μm _{; the} wide-angle X-ray test results show that the clay exists in the form of exfoliated nanosheets.

其中，所用粘土负载过渡金属催化剂是按照下述方法进行制备的： Among them, the clay-supported transition metal catalyst used was prepared as follows:

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 1101) Disperse 2.0 g of anhydrous magnesium chloride MgCl ₂ and 5.5 ml of isooctanol in 20 ml of decane and heat to 110

°C，形成透明溶液，于 110°C下反应 4.0小时。 °C, a clear solution was formed and reacted at 110 ° C for 4.0 hours.

2) 向 -20°C的 100ml四氯化钛溶液中加入 lO.Og步骤 1 ) 所得球形粘土催化剂载体的镁复合物，并于 -20°C下恒温反应 1.0小时。缓慢升温至 80°C，加入 2.0克芴二醚然后于 110°C下恒温反应 2.0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，干燥后得到粘土负载的过渡金属催化剂。 2) To 100 ml of titanium tetrachloride solution at -20 ° C, 10 g of the magnesium complex of the spherical clay catalyst carrier obtained in the step 1) was added, and the reaction was carried out at -20 ° C for 1.0 hour under constant temperature. The temperature was slowly raised to 80 ° C, 2.0 g of decane diether was added, and the reaction was carried out at 110 ° C for 2.0 hours. After completion of the reaction, the liquid was filtered off, and 100 ml of a titanium tetrachloride solution was again added thereto, and the reaction was carried out at 120 ° C for 2.0 hours under constant temperature. Finally, wash with hexane for 3 to 6 times, after drying To the clay-supported transition metal catalyst.

该粘土负载过渡金属催化剂为球形颗粒，由粘土催化剂载体、过渡金属化合物钛化合物（TiCl₄) 与氯化镁以及内给电子体芴二醚组成，其中钛元素、镁元素的含量分别为 1.89wt°/^P 3.53wt%，芴二醚的含量为 13.72wt%。广角 X射线衍射测试结果，其中粘土片层间距大于 2.0nm，催化活性组分进入粘土片层间隙并均匀分布于粘土负载过渡金属催化剂颗粒内外。该粘土负载过渡金属催化剂的比表面积为 47.9m²/g，孔容为 0.15cm³/g，平均孔径为 12.7nm。 The clay-supported transition metal catalyst is a spherical particle composed of a clay catalyst carrier, a transition metal compound titanium compound (TiCl ₄ ) and magnesium chloride, and an internal electron donor decane, wherein the content of titanium element and magnesium element is 1.89 wt ° / ^P 3.53 wt%, the content of the decane diether was 13.72% by weight. The results of the wide-angle X-ray diffraction test, wherein the clay sheet spacing is greater than 2.0 nm, the catalytically active component enters the clay sheet gap and is uniformly distributed inside and outside the clay-supported transition metal catalyst particles. The clay-supported transition metal catalyst had a specific surface area of 47.9 m ² /g, a pore volume of 0.15 cm ³ /g, and an average pore diameter of 12.7 nm.

1 )经十八烷基三甲基氯化铵改性的有机粘土的制备：将 10克钠基蒙脱土分散于 500毫升水和 500毫升乙醇的混合溶液中形成悬浮液，向该悬浮液中加入 12克十六烷基三甲基氯化铵，于 80°C下反应 4.0小时后过滤，分别用 200毫升水和乙醇洗涤三次，再于 80°C下真空干燥 20.0小时，得到经十八烷基三甲基氯化铵改性的有机粘土。 1) Preparation of octadecyltrimethylammonium chloride-modified organoclay: 10 g of sodium montmorillonite is dispersed in a mixed solution of 500 ml of water and 500 ml of ethanol to form a suspension to the suspension 12 g of cetyltrimethylammonium chloride was added thereto, and the mixture was reacted at 80 ° C for 4.0 hours, filtered, washed three times with 200 ml of water and ethanol, and dried under vacuum at 80 ° C for 20.0 hours to obtain ten Octamethyltrimethylammonium chloride modified organoclay.

2 ) 反应性二氧化硅纳米粒子的制备： 60°C下，向 100ml反应瓶中，依次加入 0.3578克浓氨水、 1.3694克去离子水和 22.7572克无水乙醇，磁力搅拌 0.5小时后，滴加入 1.0000克正硅酸乙酯。 60°C下反应 4.0小时。然后除去溶剂，干燥后得到反应性二氧化硅纳米微粒，其平均粒径为 40nm。 2) Preparation of reactive silica nanoparticles: In a 100 ml reaction flask, 0.3578 g of concentrated ammonia water, 1.3694 g of deionized water and 22.7572 g of absolute ethanol were added in sequence at 60 ° C, magnetically stirred for 0.5 hours, and then added dropwise. 1.0000 g of tetraethyl orthosilicate. The reaction was carried out at 60 ° C for 4.0 hours. Then, the solvent was removed, and after drying, reactive silica nanoparticles were obtained, which had an average particle diameter of 40 nm.

3 )粘土催化剂载体的制备：取 20克干燥的所述经十八烷基三甲基氯化铵改性的有机粘土，经过超声作用分散于 400毫升乙醇中（有机粘土在该悬浮液中的质量百分浓度为 6.2wt% ) 。 60°C下，将 93.98克反应性二氧化硅纳米微粒的乙醇悬浮液 (其中，反应性二氧化硅纳米微粒的质量百分浓度为 1.12wt%; 反应性二氧化硅纳米微粒与有机粘土的质量比为 1 : 19 ) 滴加入已均匀分散的有机粘土悬浮液中。滴加完成后，反应 4.0小时，再加入 2.0克碳酸氢铵（碳酸氢铵与有机粘土的质量比例为 0.1 : 1 ) ，继续搅拌 0.5小时后，喷雾干燥成型得到粘土催化剂载体。 3) Preparation of clay catalyst carrier: 20 g of the dried octadecyltrimethylammonium chloride-modified organoclay was dispersed by ultrasonication in 400 ml of ethanol (organic clay in the suspension) The mass percent concentration is 6.2 wt%). An ethanol suspension of 93.98 g of reactive silica nanoparticles (wherein the mass concentration of reactive silica nanoparticles is 1.12% by weight; at 60 ° C; reactive silica nanoparticles and organoclay The mass ratio was 1:19) and added dropwise to the uniformly dispersed organoclay suspension. After completion of the dropwise addition, the reaction was carried out for 4.0 hours, and then 2.0 g of ammonium hydrogencarbonate (the mass ratio of ammonium hydrogencarbonate to the organoclay was 0.1 : 1 ) was further added, and stirring was continued for 0.5 hour, followed by spray drying to obtain a clay catalyst carrier.

该粘土催化剂载体由质量比为 90: 10的有机粘土（有机粘土由质量比为 15 : The clay catalyst carrier is composed of an organoclay having a mass ratio of 90:10 (the organic clay is composed of a mass ratio of 15:

85的有机插层剂十八烷基二甲基羟乙基硝酸铵和钠基蒙脱土组成，钠基蒙脱土的性质如下：阳离子交换容量为 90meq/100g，比表面积为 17.89m²/g，平均孔径为 21.90nm，孔容为 0.10cm³/g，片层间距为 l .Onm)和平均粒径为 40nm的反应性二氧化硅组成，其颗粒形态为球形，其颗粒粒径为 10~30μιη，比表面积为 44.78m²/g，孔容为 0.22cm³/g, 平均孔径为 1 1.6nm。粘土催化剂载体和有机粘土的广角 X射线衍射测试结果可知，衍射角在 1.5°~10°范围内均出现粘土的（001 ) 面特征峰，根据 Bragg 方程 2dsine= 计算，其片层间距均为 2.0nm，这说明片层间距并未因反应性二氧化硅纳米微粒的加入而发生变化。 The organic intercalant of 85 is composed of octadecyldimethylhydroxyethyl ammonium nitrate and sodium montmorillonite. The properties of the sodium montmorillonite are as follows: the cation exchange capacity is 90 meq/100 g, and the specific surface area is 17.89 m ² / g, an average pore diameter of 21.90 nm, a pore volume of 0.10 cm ³ /g, a sheet spacing of l. Onm) and a reactive silica having an average particle diameter of 40 nm, the particle morphology of which is spherical, and the particle size thereof is 10 to 30 μm, a specific surface area of 44.78 m ² /g, a pore volume of 0.22 cm ³ /g, and an average pore diameter of 1 1.6 nm. The wide-angle X-ray diffraction test results of the clay catalyst carrier and the organoclay show that the (001) surface characteristic peak of the clay appears in the diffraction angle range of 1.5° to 10°, and the interlayer spacing is 2.0 according to the Bragg equation 2dsine= . Nm, which means that the interlamellar spacing is not altered by the addition of reactive silica nanoparticles.

实施例 4 Example 4

1 )将 250克液态丙烯加入至反应釜中， 30°C下依次加入 0.2mol助催化剂三乙基铝、 0.02mol外给电子体二甲基二苯基硅烷以及 1.0 克粘土负载过渡金属催化剂 (三乙基铝中铝元素与粘土负载过渡金属催化剂中钛元素的摩尔比为 700: 1；外给电子体二甲基二苯基硅烷与粘土负载过渡金属催化剂中钛元素的摩尔比为 0.1 : 1 ) 以及氢气 0.2g，升温至 70°C，压强为 3.1MPa，进行本体聚合反应 0.2小时，得到含有粘土和重均分子量为 300000g/mol的均聚等规聚丙烯的复合物 104g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.2 mol of cocatalyst triethylaluminum, 0.02 mol of external electron donor dimethyldiphenylsilane, and 1.0 g of a clay-supported transition metal catalyst were sequentially added at 30 ° C ( The molar ratio of the aluminum element in the triethylaluminum to the titanium element in the clay-supported transition metal catalyst is 700:1; the molar ratio of the external electron donor dimethyldiphenylsilane to the titanium element in the clay-supported transition metal catalyst is 0.1: 1 ) And 0.2 g of hydrogen, the temperature was raised to 70 ° C, the pressure was 3.1 MPa, and bulk polymerization was carried out for 0.2 hours to obtain 104 g of a composite containing clay and a homopolyisotactic polypropylene having a weight average molecular weight of 300,000 g/mol, and proceeding directly to the next step. 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 20gl- 丁烯，通入氢气 0.03g，升温至 50°C，压强为 2.5MPa，进行聚合反应 0.5小时，最终得到粘土增强聚丙烯釜内合金 110.0g。 2) The propylene remaining in the reaction vessel in the above step 1) was vented and cooled to 50 ° C, then 20 g of butene was introduced, 0.03 g of hydrogen was introduced, the temperature was raised to 50 ° C, and the pressure was 2.5 MPa. After reacting for 0.5 hour, 110.0 g of a clay-reinforced polypropylene in-cylinder alloy was finally obtained.

该粘土增强的聚丙烯釜内合金由质量比为 0.64: 93.81： 5.55 的粘土、均聚等规聚丙烯树脂和均聚等规聚 1-丁烯组成。颗粒表观形态为球形，颗粒粒径为 50~500μιη; 广角 X射线测试结果表明，粘土以剥离的纳米片层的形式存在。 The clay-reinforced polypropylene in-cylinder alloy consists of a clay having a mass ratio of 0.64: 93.81: 5.55, a homopolymeric polypropylene resin, and a homopolymeric isotactic polybutene. The apparent morphology of the particles is spherical, and the particle size is 50~500μιη; the wide-angle X-ray test results show that the clay exists in the form of exfoliated nanosheets.

2) 向 -20°C的 100ml四氯化钛溶液中加入 lO.Og球形所述粘土催化剂载体的镁复合物，并于 -20°C下恒温反应 1.0小时。缓慢升温至 80°C，加入 0.3ml 邻苯二甲酸二异丁酯，然后于 110°C下恒温反应 2.0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，干燥后得到粘土负载钛化合物。 2) To 100 ml of titanium tetrachloride solution at -20 ° C, 10 g of a magnesium composite of spherical clay 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 0.3 ml of diisobutyl phthalate, and then 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 clay-supported titanium compound.

3 ) 取 5.0 克所述球形粘土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小时，然后用甲苯洗涤 5 次，干燥后得到活化的粘土催化剂。 3) Take 5.0 g of the spherical clay-supported titanium compound and disperse it in 100 ml of toluene, then add 30 ml of a toluene solution containing 0.1 mol of methylaluminoxane, react at 110 ° C for 4.0 hours, and then wash 5 times with toluene. An activated clay catalyst is obtained after drying.

4) 将 0.20克过渡金属化合物 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.

该粘土负载过渡金属催化剂为球形颗粒，由粘土催化剂载体、过渡金属化合物钛化合物（TiCl₄) 和锆化合物（Et(Ind)₂ZrCl₂ ) 与金属化合物镁化合物（氯化镁）和铝化合物（甲基铝氧烷）以及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 1.34wt%、 2.89wt% 0.30\¥1%和 14.68wt%，邻苯二甲酸二异丁酯和粘土催化剂载体的含量为分别为 9.78^%和 70wt%。广角 X 射线衍射测试结果，其中粘土片层间距大于 2.0nm，催化活性组分进入粘土片层间隙并均匀分布于粘土负载过渡金属催化剂颗粒内外。该催化剂的比表面积为 47.9m²/g，孔容为 0.15cm³/g，平均孔径为 12.7nm。 The clay-supported transition metal catalyst is a spherical particle composed of a clay catalyst carrier, a transition metal compound titanium compound (TiCl ₄ ), and a zirconium compound (Et(Ind) ₂ ZrCl ₂ ) and a metal compound magnesium compound (magnesium chloride) and an aluminum compound (methyl group). Aluminoxane) and an internal electron donor diisobutyl phthalate, wherein the contents of titanium, magnesium, zirconium, and aluminum are 1.34 wt%, 2.89 wt%, 0.30, and 1%, respectively. The content of %, diisobutyl phthalate and clay catalyst carrier was 9.78% and 70% by weight, respectively. The results of wide-angle X-ray diffraction test, in which the clay sheet spacing is greater than 2.0 nm, the catalytically active component enters the clay sheet gap and is uniformly distributed inside and outside the clay-supported transition metal catalyst particles. The catalyst had a specific surface area of 47.9 m ² /g, a pore volume of 0.15 cm ³ /g, and an average pore diameter of 12.7 nm.

1 )经十八烷基三甲基氯化铵改性的有机粘土的制备：将 10克钠基蒙脱土分散于 500毫升水和 500毫升乙醇的混合溶液中形成悬浮液，向该悬浮液中加入 12克十六烷基三甲基氯化铵，于 80°C下反应 4.0小时后过滤，分别用 200毫升水和乙醇洗涤三次，再于 80°C下真空干燥 20.0小时，得到经十八烷基三甲基氯化铵改性的有机粘土。 1) Preparation of octadecyltrimethylammonium chloride modified organoclay: Disperse 10 g of sodium montmorillonite A suspension was formed in a mixed solution of 500 ml of water and 500 ml of ethanol, and 12 g of cetyltrimethylammonium chloride was added to the suspension, which was reacted at 80 ° C for 4.0 hours, and then filtered, respectively, using 200 ml. The water and ethanol were washed three times and then dried under vacuum at 80 ° C for 20.0 hours to obtain an octadecyltrimethylammonium chloride-modified organoclay.

0.3578克浓氨水、 1.3694克去离子水和 22.7572克无水乙醇，磁力搅拌 0.5小时后，滴加入 1.0000克正硅酸乙酯。 60°C下反应 4.0小时。然后除去溶剂，干燥后得到反应性二氧化硅纳米微粒，其平均粒径为 40nm。 0.3578 g of concentrated ammonia water, 1.3694 g of deionized water and 22.7572 g of absolute ethanol were magnetically stirred for 0.5 hour, and then 1.0000 g of tetraethyl orthosilicate was added dropwise. The reaction was carried out at 60 ° C for 4.0 hours. Then, the solvent was removed, and after drying, reactive silica nanoparticles were obtained, which had an average particle diameter of 40 nm.

3 )粘土催化剂载体的制备：取 20克干燥的所述经十八烷基三甲基氯化铵改性的有机粘土，经过超声作用分散于 400毫升乙醇中（有机粘土在该悬浮液中的质量百分浓度为 6.2wt%) 。 60°C下，将 93.98克反应性二氧化硅纳米微粒的乙醇悬浮液 (其中，反应性二氧化硅纳米微粒的质量百分浓度为 1.12wt%; 反应性二氧化硅纳米微粒与有机粘土的质量比为 1 : 19) 滴加入已均匀分散的有机粘土悬浮液中。滴加完成后，反应 4.0小时，再加入 2.0克碳酸氢铵（碳酸氢铵与有机粘土的质量比例为 0.1 : 1 ) ，继续搅拌 0.5小时后，喷雾干燥成型制备得到粘土催化剂载体。 3) Preparation of clay catalyst carrier: 20 g of the dried octadecyltrimethylammonium chloride-modified organoclay was dispersed by ultrasonication in 400 ml of ethanol (organic clay in the suspension) The mass percent concentration is 6.2 wt%). An ethanol suspension of 93.98 g of reactive silica nanoparticles (wherein the mass concentration of reactive silica nanoparticles is 1.12% by weight; at 60 ° C; reactive silica nanoparticles and organoclay The mass ratio is 1: 19) Dropped into the uniformly dispersed organoclay suspension. After the completion of the dropwise addition, the reaction was carried out for 4.0 hours, and then 2.0 g of ammonium hydrogencarbonate (the mass ratio of ammonium hydrogencarbonate to the organoclay was 0.1 : 1 ) was added thereto, and stirring was continued for 0.5 hour, followed by spray drying to prepare a clay catalyst carrier.

该粘土催化剂载体由质量比为 95 : 5 的有机粘土（有机粘土由质量比为 20: 80的有机插层剂十八烷基二甲基羟乙基硝酸铵和钠基蒙脱土组成，钠基蒙脱土的性质如下：阳离子交换容量为 90meq/100g，比表面积为 17.89m²/g，平均孔径为 21.90nm，孔容为 0.10cm³/g，片层间距为 l .Onm)和平均粒径为 40nm的反应性二氧化硅组成，其颗粒形态为球形，其颗粒粒径为 10~30μιη，比表面积为 42.1m²/g，孔容为 0.18cm³/g，平均孔径为 13.4nm。粘土催化剂载体和有机粘土的广角 X射线衍射测试结果可知，衍射角在 1.5°~10°范围内均出现粘土的（001 )面特征峰，根据 Bragg方程

计算，其片层间距均为 2.0nm，这说明片层间距并未因反应性二氧化硅纳米微粒的加入而发生变化。 The clay catalyst carrier consists of an organoclay having a mass ratio of 95:5 (the organoclay consists of an organic intercalant of octadecyldimethylhydroxyethylammonium nitrate and sodium montmorillonite having a mass ratio of 20:80, sodium The properties of montmorillonite are as follows: cation exchange capacity is 90 meq/100 g, specific surface area is 17.89 m ² /g, average pore diameter is 21.90 nm, pore volume is 0.10 cm ³ /g, sheet spacing is l. Onm) and average The composition of reactive silica having a particle diameter of 40 nm has a spherical shape of 10 to 30 μm, a specific surface area of 42.1 m ² /g, a pore volume of 0.18 cm ³ /g, and an average pore diameter of 13.4 nm. . The wide-angle X-ray diffraction test results of the clay catalyst carrier and the organoclay show that the (001) surface characteristic peak of the clay appears in the diffraction angle in the range of 1.5° to 10°, according to the Bragg equation.

Calculated, the interlayer spacing was 2.0 nm, which indicates that the interlayer spacing was not changed by the addition of reactive silica nanoparticles.

实施例 5 Example 5

1 ) 将 250克液态丙烯加入至反应釜中， 30°C下依次加入 0.25mol助催化剂三异丁基铝及 1.0克粘土负载过渡金属催化剂（三异丁基铝中铝元素与粘土负载过渡金属催化剂中钛元素的摩尔比为 460: 1 )以及氢气 0.2g，升温至 70°C，压强为 3.2MPa，进行本体聚合反应 0.2小时，得到含有粘土和重均分子量为 400000g/mol的均聚等规聚丙烯的复合物 108g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.25 mol of cocatalyst triisobutylaluminum and 1.0 g of clay-supported transition metal catalyst (aluminum element and clay-loaded transition metal in triisobutylaluminum) were sequentially added at 30 °C. The molar ratio of titanium in the catalyst was 460:1) and 0.2 g of hydrogen, the temperature was raised to 70 ° C, the pressure was 3.2 MPa, and bulk polymerization was carried out for 0.2 hours to obtain a homopolymer containing clay and a weight average molecular weight of 400,000 g/mol. 108 g of the compound of the polypropylene 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 20g 丙烯和 40gl-丁烯的混合气，通入氢气 0.03g，升温至 90°C，压强为 1.2 MPa，进行聚合反应 0.2小时，最终得到粘土增强聚丙烯釜内合金 125.0g。 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 20 g of propylene and 40 g of butene was introduced, and 0.03 g of hydrogen was introduced thereto, and the temperature was raised to 90 ° C. At 1.2 MPa, the polymerization was carried out for 0.2 hours, and finally 125.0 g of a clay-reinforced polypropylene in-cylinder alloy was obtained.

该粘土增强的聚丙烯釜内合金由质量比为 0.67: 86.83： 5.55 的粘土、均聚等规聚丙烯树脂和丙烯 /1-丁烯无规共聚物组成。颗粒表观形态为球形，颗粒粒径为 50~500μιη; 广角 X射线测试结果表明，粘土以剥离的纳米片层的形式存在。 The clay-reinforced polypropylene in-cylinder alloy was composed of a clay having a mass ratio of 0.67: 86.83: 5.55, a homopolymeric polypropylene resin, and a propylene/1-butene random copolymer. The apparent morphology of the particles is spherical, and the particle size is 50~500μιη; the wide-angle X-ray test results show that the clay exists in the form of exfoliated nanosheets.

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 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；将上述氯化镁醇合物滴加入 3.0g球形粘土载体与 50ml癸烷的悬浮液中，于 60 °C下恒温反应 4.0小时，然后滤除液体，滤出的固体用癸烷洗涤 3次，干燥后得到粘土催化剂载体的镁复合物； 1) 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, a transparent solution is formed, and reacted at 130 ° C for 2.0 hours to obtain a magnesium chloride alcoholate; the above magnesium chloride alcoholate is added dropwise to a suspension of 3.0 g of a spherical clay carrier and 50 ml of decane, and the reaction is kept at a constant temperature at 60 ° C. After 4.0 hours, the liquid was filtered off, and the filtered solid was washed 3 times with decane, and dried to obtain a magnesium composite of a clay catalyst carrier;

2) 向 -20°C的 100ml四氯化钛溶液中加入 5.0g所述粘土催化剂载体的镁复合物，并于 -20°C下恒温反应 1.0小时。缓慢升温至 120°C，加入 0.5克芴二醚，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，干燥后得到本发明提供的粘土负载的过渡金属催化剂。 2) To 100 ml of a titanium tetrachloride solution at -20 ° C, 5.0 g of the magnesium catalyst of the clay catalyst carrier was added and reacted at -20 ° C for 1.0 hour under constant temperature. Slowly raise the temperature to 120 ° C, add 0.5 g of decyl ether, and then react at a constant temperature of 120 ° C for 1.5 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 for 2.0 hours. . Finally, it was washed 3 to 6 times with hexane, and dried to obtain a clay-supported transition metal catalyst provided by the present invention.

该粘土负载过渡金属催化剂为球形颗粒中，由粘土催化剂载体、过渡金属化合物 TiCl₄、 MgCl₂和内给电子体芴二醚组成；其中钛元素、镁元素的含量分别为 2.56wt% 2.15wt%, 芴二醚和粘土催化剂载体的含量分别为 10.5 wt°/^P 65wt%。广角 X射线衍射测试结果中，粘土片层间距大于 2.0nm，催化活性组分进入粘土片层间隙并均匀分布于粘土负载过渡金属催化剂颗粒内外。该催化剂的比表面积为 42.1m²/g，孔容为 0.18cm³/g，平均孔径为 13.4nm。 The clay-supported transition metal catalyst is a spherical particle composed of a clay catalyst carrier, a transition metal compound TiCl ₄ , MgCl ₂ and an internal electron donor sebacon; wherein the content of titanium element and magnesium element is 2.56 wt% 2.15 wt%, respectively. The content of the decane diether and clay catalyst carrier was 10.5 wt / / P 65 wt%, respectively. In the wide-angle X-ray diffraction test results, the clay sheet spacing is greater than 2.0 nm, and the catalytically active component enters the clay sheet gap and is uniformly distributed inside and outside the clay-supported transition metal catalyst particles. The catalyst had a specific surface area of 42.1 m ² /g, a pore volume of 0.18 cm ³ /g, and an average pore diameter of 13.4 nm.

2) 反应性二氧化硅纳米粒子的制备： 60°C下，向 100ml反应瓶中，依次加入 0.3578克浓氨水、 1.3694克去离子水和 22.7572克无水乙醇，磁力搅拌 0.5小时后，滴加入 1.0000克正硅酸乙酯。 60°C下反应 4.0小时。然后除去溶剂，干燥后得到反应性二氧化硅纳米微粒，其平均粒径为 40nm。 2) Preparation of reactive silica nanoparticles: In a 100 ml reaction flask, 0.3578 g of concentrated ammonia water, 1.3694 g of deionized water and 22.7572 g of absolute ethanol were added in sequence at 60 ° C, magnetically stirred for 0.5 hours, and then added dropwise. 1.0000 g of tetraethyl orthosilicate. The reaction was carried out at 60 ° C for 4.0 hours. Then, the solvent was removed, and after drying, reactive silica nanoparticles were obtained, which had an average particle diameter of 40 nm.

3 )粘土催化剂载体的制备：取 20克干燥的所述经十八烷基三甲基氯化铵改性的有机粘土，经过超声作用分散于 400毫升乙醇中（有机粘土在该悬浮液中的质量百分浓度为 6.2wt%) 。 60°C下，将 93.98克反应性二氧化硅纳米微粒的乙醇悬浮液 3) Preparation of clay catalyst carrier: 20 g of the dried octadecyltrimethylammonium chloride-modified organoclay was dispersed by ultrasonication in 400 ml of ethanol (organic clay in the suspension) The mass percent concentration is 6.2 wt%). 93.98 grams of ethanol suspension of reactive silica nanoparticles at 60 ° C

(其中，反应性二氧化硅纳米微粒的质量百分浓度为 1.12wt%; 反应性二氧化硅纳米微粒与有机粘土的质量比为 1 : 19) 滴加入已均匀分散的有机粘土悬浮液中。滴加完成后，反应 4.0小时，再加入 2.0克碳酸氢铵（碳酸氢铵与有机粘土的质量比例为 0.1 : 1 ) ，继续搅拌 0.5小时后，喷雾干燥成型制备得到粘土催化剂载体。 (wherein the mass percentage of the reactive silica nanoparticles is 1.12% by weight; the mass ratio of the reactive silica nanoparticles to the organoclay is 1:19) is added dropwise to the uniformly dispersed organoclay suspension. After the completion of the dropwise addition, the reaction was carried out for 4.0 hours, and then 2.0 g of ammonium hydrogencarbonate (the mass ratio of ammonium hydrogencarbonate to the organoclay was 0.1 : 1 ) was added thereto, and stirring was continued for 0.5 hour, followed by spray drying to prepare a clay catalyst carrier.

该粘土催化剂载体由质量比为 95 : 5 的有机粘土（有机粘土由质量比为 20: 80的有机插层剂十八烷基二甲基羟乙基硝酸铵和钠基蒙脱土组成，钠基蒙脱土的性质如下：阳离子交换容量为 90meq/100g，比表面积为 17.89m²/g，平均孔径为 21.90nm，孔容为 0.10cm³/g，片层间距为 l .Onm)和平均粒径为 40nm的反应性二氧化硅组成，其颗粒形态为球形，其颗粒粒径为 10~30μιη，比表面积为 42.1m²/g，孔容为 0.18cm³/g，平均孔径为 13.4nm。广角 X射线衍射测试结果可知，由此方法制备的粘土催化剂载体和有机粘土的衍射图上显示，衍射角在 1.5°~10°范围内均出现粘土的（001 )面特征峰，根据 Bragg方程 2( ηθ=λ计算，其片层间距均为 2.0nm，这说明片层间距并未因反应性二氧化硅纳米微粒的加入而发生变化。 The clay catalyst carrier consists of an organoclay having a mass ratio of 95:5 (the organoclay consists of an organic intercalant of octadecyldimethylhydroxyethylammonium nitrate and sodium montmorillonite having a mass ratio of 20:80, sodium The properties of montmorillonite are as follows: cation exchange capacity is 90 meq/100 g, specific surface area is 17.89 m ² /g, average pore diameter is 21.90 nm, pore volume is 0.10 cm ³ /g, sheet spacing is l. Onm) and average The composition of reactive silica having a particle diameter of 40 nm has a spherical shape of 10 to 30 μm, a specific surface area of 42.1 m ² /g, a pore volume of 0.18 cm ³ /g, and an average pore diameter of 13.4 nm. . The wide-angle X-ray diffraction test results show that the clay catalyst prepared by this method The diffractograms of the carrier and the organoclay show that the (001) surface characteristic peak of the clay appears in the diffraction angle in the range of 1.5° to 10°, and the interlayer spacing is 2.0 nm according to the Bragg equation 2 (ηθ=λ). This indicates that the interlayer spacing is not altered by the addition of reactive silica nanoparticles.

实施例 6 Example 6

1 ) 将 250克液态丙烯加入至反应釜中， 30°C下依次加入 0.25mol助催化剂三乙基铝及 1.0克粘土负载过渡金属催化剂（三乙基铝中铝元素与粘土负载过渡金属催化剂中钛元素之间摩尔比为 460: 1 )以及氢气 O. lg，升温至 75 °C，压强为 3.1MPa，进行本体聚合反应 0.2小时，得到含有粘土和重均分子量为 560000g/mol的均聚等规聚丙烯的复合物 134.8g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.25 mol of cocatalyst triethylaluminum and 1.0 g of clay-supported transition metal catalyst (aluminum element in triethylaluminum and clay-supported transition metal catalyst) were sequentially added at 30 °C. The molar ratio between titanium elements is 460: 1 ) and hydrogen O. lg, the temperature is raised to 75 ° C, the pressure is 3.1 MPa, and bulk polymerization is carried out for 0.2 hours to obtain a homopolymer containing clay and a weight average molecular weight of 560000 g/mol. The compound of the polypropylene was 134.8 g, 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 5g 丙烯和 80gl-丁烯的混合气，通入氢气 0.03g，升温至 90°C，压强为 l .OMPa, 进行聚合反应 1.0小时，最终得到粘土增强的聚丙烯釜内合金 175.0g。 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 5 g of propylene and 80 g of butene was introduced, and 0.03 g of hydrogen was introduced thereto, and the temperature was raised to 90 ° C. The polymerization was carried out for 1.0 hour at 1.0 MPa, and finally 175.0 g of a clay-reinforced polypropylene in-cylinder alloy was obtained.

该粘土增强的聚丙烯釜内合金由质量比为 0.45: 77.05： 22.5 的粘土、均聚等规聚丙烯树脂和丙烯 /1-丁烯无规共聚物组成。颗粒表观形态为球形，颗粒粒径大小为 50~500μιη_; 广角 X射线测试结果表明，粘土以剥离的纳米片层的形式存在。 The clay-reinforced polypropylene in-cavity alloy consists of a clay having a mass ratio of 0.45: 77.05: 22.5, a homopolymeric isotactic polypropylene resin, and a propylene/1-butene random copolymer. The apparent morphology of the particles is spherical, and the particle size is 50~500μιη _{. The} wide-angle X-ray test results show that the clay exists in the form of exfoliated nanosheets.

将上述氯化镁醇合物滴加入 3.0g球形粘土载体与 50ml癸烷的悬浮液中，于 60 °C下恒温反应 4.0小时，然后滤除液体，滤出的固体用癸烷洗涤 3次，干燥后得到粘土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 a spherical clay carrier and 50 ml of decane, and reacted at 60 ° C for 4.0 hours under constant temperature, and then the liquid was filtered off, and the filtered solid was washed 3 times with decane, and dried. Obtaining a magnesium composite of a clay catalyst support;

该粘土负载过渡金属催化剂为球形颗粒，由粘土催化剂载体、过渡金属化合物 TiCl₄、 MgCl₂和内给电子体芴二醚组成；其中钛元素、镁元素的含量分别为 2.56wt% 和 2.15wt%，芴二醚和粘土催化剂载体的含量分别为 10.5 wt°/^P 65wt%。广角 X射线衍射测试结果，与图 7相同，不再重复，其中粘土片层间距大于 2.0nm，催化活性组分进入粘土片层间隙并均匀分布于粘土负载过渡金属催化剂颗粒内外。该催化剂的比表面积为 42.1m²/g，孔容为 0.18cm³/g，平均孔径为 13.4nm。 The clay-supported transition metal catalyst is a spherical particle composed of a clay catalyst carrier, a transition metal compound TiCl ₄ , MgCl ₂ and an internal electron donor sebacon; wherein the content of titanium element and magnesium element is 2.56 wt% and 2.15 wt%, respectively. The content of the decane diether and clay catalyst carrier was 10.5 wt / / P 65 wt%, respectively. The results of the wide-angle X-ray diffraction test are the same as those of Fig. 7, and are not repeated, wherein the clay sheet spacing is greater than 2.0 nm, and the catalytically active component enters the clay sheet gap and is uniformly distributed inside and outside the clay-supported transition metal catalyst particles. The catalyst had a specific surface area of 42.1 m ² /g, a pore volume of 0.18 cm ³ /g, and an average pore diameter of 13.4 nm.

1 )经十八烷基三甲基氯化铵改性的有机粘土的制备：将 10克钠基蒙脱土分散于 500毫升水和 500毫升乙醇的混合溶液中形成悬浮液，向该悬浮液中加入 12克十六烷基三甲基氯化铵，于 80°C下反应 4.0小时后过滤，分别用 200毫升水和乙醇洗涤三次，再于 80°C下真空干燥 20.0小时，得到经十八烷基三甲基氯化铵改性的有机粘土。 2) 反应性二氧化硅纳米粒子的制备： 60°C下，向 100ml反应瓶中，依次加入 0.3578克浓氨水、 1.3694克去离子水和 22.7572克无水乙醇，磁力搅拌 0.5小时后，滴加入 1.0000克正硅酸乙酯。 60°C下反应 4.0小时。然后除去溶剂，干燥后得到反应性二氧化硅纳米微粒，其平均粒径为 40nm。 1) Preparation of octadecyltrimethylammonium chloride-modified organoclay: Dispersing 10 g of sodium montmorillonite in a mixed solution of 500 ml of water and 500 ml of ethanol to form a suspension to the suspension 12 g of cetyltrimethylammonium chloride was added thereto, and the mixture was reacted at 80 ° C for 4.0 hours, filtered, washed three times with 200 ml of water and ethanol, and dried under vacuum at 80 ° C for 20.0 hours to obtain ten Octamethyltrimethylammonium chloride modified organoclay. 2) Preparation of reactive silica nanoparticles: In a 100 ml reaction flask, 0.3578 g of concentrated ammonia water, 1.3694 g of deionized water and 22.7572 g of absolute ethanol were added in sequence at 60 ° C, magnetically stirred for 0.5 hours, and then added dropwise. 1.0000 g of tetraethyl orthosilicate. The reaction was carried out at 60 ° C for 4.0 hours. Then, the solvent was removed, and after drying, reactive silica nanoparticles were obtained, and the average particle diameter was 40 nm.

3 )粘土催化剂载体的制备：取 20克干燥的所述经十八烷基三甲基氯化铵改性的有机粘土，经过超声作用分散于 400毫升乙醇中（有机粘土在该悬浮液中的浓度为 6.2wt%) 。 60°C下，将 93.98克反应性二氧化硅纳米微粒的乙醇悬浮液（其中，反应性二氧化硅纳米微粒的质量百分浓度为 1.12wt%; 反应性二氧化硅纳米微粒与有机粘土的质量比为 1 : 19)滴加入已均匀分散的有机粘土悬浮液中。滴加完成后，反应 4.0小时，再加入 2.0克碳酸氢铵（碳酸氢铵与有机粘土的质量比为 0.1 : 1 ) ，继续搅拌 0.5小时后，喷雾干燥成型制备得到粘土催化剂载体。 3) Preparation of clay catalyst carrier: 20 g of the dried octadecyltrimethylammonium chloride-modified organoclay was dispersed by ultrasonication in 400 ml of ethanol (organic clay in the suspension) The concentration is 6.2 wt%). An ethanol suspension of 93.98 g of reactive silica nanoparticles (wherein the mass concentration of reactive silica nanoparticles is 1.12% by weight; at 60 ° C; reactive silica nanoparticles and organoclay The mass ratio of 1: 19) was added dropwise to the uniformly dispersed organoclay suspension. After completion of the dropwise addition, the reaction was carried out for 4.0 hours, and then 2.0 g of ammonium hydrogencarbonate (the mass ratio of ammonium hydrogencarbonate to the organoclay was 0.1:1) was added, and stirring was continued for 0.5 hours, followed by spray drying to prepare a clay catalyst carrier.

该粘土催化剂载体由质量比为 95 : 5 的有机粘土（有机粘土由质量比为 20: 80的有机插层剂十八烷基二甲基羟乙基硝酸铵和钠基蒙脱土组成，钠基蒙脱土的性质如下：阳离子交换容量为 90meq/100g，比表面积为 17.89m²/g，平均孔径为 21.90nm，孔容为 0.10cm³/g，片层间距为 l .Onm)和平均粒径为 40nm的反应性二氧化硅组成，其颗粒形态为球形，其颗粒粒径为 10~30μιη，比表面积为 42.1m²/g，孔容为 0.18cm³/g，平均孔径为 13.4nm。广角 X射线衍射测试结果可知，由此方法制备的粘土催化剂载体和有机粘土的衍射图上显示，衍射角在 1.5°~10°范围内均出现粘土的（001 )面特征峰，根据 Bragg方程 2( ηθ=λ计算，其片层间距均为 2.0nm，这说明片层间距并未因反应性二氧化硅纳米微粒的加入而发生变化。 The clay catalyst carrier consists of an organoclay having a mass ratio of 95:5 (the organoclay consists of an organic intercalant of octadecyldimethylhydroxyethylammonium nitrate and sodium montmorillonite having a mass ratio of 20:80, sodium The properties of montmorillonite are as follows: cation exchange capacity is 90 meq/100 g, specific surface area is 17.89 m ² /g, average pore diameter is 21.90 nm, pore volume is 0.10 cm ³ /g, sheet spacing is l. Onm) and average The composition of reactive silica having a particle diameter of 40 nm has a spherical shape of 10 to 30 μm, a specific surface area of 42.1 m ² /g, a pore volume of 0.18 cm ³ /g, and an average pore diameter of 13.4 nm. . The wide-angle X-ray diffraction test results show that the diffraction pattern of the clay catalyst carrier and the organoclay prepared by the method shows that the (001) surface characteristic peak of the clay appears in the diffraction angle in the range of 1.5° to 10°, according to the Bragg equation 2 ( η θ = λ, the sheet spacing is 2.0 nm, which means that the sheet spacing is not changed by the addition of reactive silica nanoparticles.

实施例 7 Example 7

1 ) 将 250克液态丙烯加入至反应釜中， 30°C下依次加入 0.25mol助催化剂三乙基铝及 1.0克粘土负载过渡金属催化剂（三乙基铝中铝元素与粘土负载过渡金属催化剂中钛元素之间的摩尔比为 460: 1 )以及氢气 0.05g，升温至 75 °C，压强为 3.0MPa，进行本体聚合反应 0.2小时，得到含有粘土和重均分子量为 620000g/mol的均聚等规聚丙烯的复合物 107g，直接进行下一步反应。 1) 250 g of liquid propylene was added to the reaction vessel, and 0.25 mol of cocatalyst triethylaluminum and 1.0 g of clay-supported transition metal catalyst (aluminum element in triethylaluminum and clay-supported transition metal catalyst) were sequentially added at 30 °C. The molar ratio between the titanium elements was 460:1) and the hydrogen gas was 0.05 g, the temperature was raised to 75 ° C, the pressure was 3.0 MPa, and bulk polymerization was carried out for 0.2 hours to obtain a homopolymer containing clay and a weight average molecular weight of 620,000 g/mol. 107 g of the complex of the polypropylene 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 40g 乙烯和 5gl-辛烯，通入氢气 0.03g，升温至 90°C，压强为 1.7 MPa, 进行聚合反应 1.0小时，最终得到粘土增强聚丙烯釜内合金 115.0g。 2) The propylene remaining in the reaction vessel in the above step 1) was vented and cooled to 50 ° C, and then 40 g of ethylene and 5 g of octene were introduced, and 0.03 g of hydrogen was introduced thereto, and the temperature was raised to 90 ° C, and the pressure was 1.7 MPa. The polymerization reaction was carried out for 1.0 hour to finally obtain 115.0 g of a clay-reinforced polypropylene in-cylinder alloy.

该粘土增强的聚丙烯釜内合金由质量比为 1.42: 92.98： 5.6的粘土、均聚等规聚丙烯树脂和乙烯 /1-辛烯无规共聚物组成。颗粒表观形态为球形，颗粒粒径大小为 50~500μιη; 广角 X射线测试结果表明，粘土以剥离的纳米片层的形式存在。 The clay-reinforced polypropylene in-cylinder alloy was composed of a clay having a mass ratio of 1.42: 92.98: 5.6, a homopolymerized isotactic polypropylene resin, and an ethylene/1-octene random copolymer. The apparent morphology of the particles is spherical, and the particle size is 50~500μιη; the wide-angle X-ray test results show that the clay exists in the form of exfoliated nanosheets.

将上述氯化镁醇合物滴加入 3.0g球形粘土载体与 50ml癸烷的悬浮液中，于 60 °C下恒温反应 4.0小时，然后滤除液体，滤出的固体用癸烷洗涤 3次，干燥后得到粘土催化剂载体的镁复合物； 2) 向 -20°C的 100ml四氯化钛溶液中加入 5.0g所述粘土催化剂载体的镁复合物，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，干燥后得到本发明提供的粘土负载的过渡金属催化剂。 The above magnesium chloride alcoholate was added dropwise to a suspension of 3.0 g of a spherical clay carrier and 50 ml of decane, and reacted at 60 ° C for 4.0 hours under constant temperature, and then the liquid was filtered off, and the filtered solid was washed 3 times with decane, and dried. Obtaining a magnesium composite of a clay catalyst support; 2) To 100 ml of a titanium tetrachloride solution at -20 ° C, 5.0 g of the magnesium composite of the clay catalyst carrier was added, and the mixture was reacted at -20 ° C for 1.0 hour under constant temperature. Slowly raise the temperature to 120 ° C, add 0.2 ml of diisobutyl phthalate, and then react at a constant temperature of 120 ° C for 1.5 hours. After the reaction is completed, the liquid is filtered off, and 100 ml of titanium tetrachloride solution is added again 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 clay-supported transition metal catalyst provided by the present invention.

该粘土负载过渡金属催化剂为球形颗粒，由粘土催化剂载体、过渡金属化合物 TiCl₄、MgCl₂和内给电子体芴二醚组成；其中钛元素、镁元素的含量分别为 2.56wt%、 2.15wt%, 芴二醚和粘土催化剂载体的含量分别为 10.5wt%、 65wt%。该催化剂的广角 X射线衍射测试结果与图 7相同，不再重复，其中粘土片层间距大于 2.0nm，催化活性组分进入粘土片层间隙并均匀分布于粘土负载过渡金属催化剂颗粒内外。该催化剂的比表面积为 42.1m²/g，孔容为 0.18cm³/g，平均孔径为 13.4nm。 The clay-supported transition metal catalyst is a spherical particle composed of a clay catalyst carrier, a transition metal compound TiCl ₄ , MgCl ₂ and an internal electron donor sediment; wherein the content of titanium element and magnesium element is 2.56 wt% and 2.15 wt%, respectively. The content of the decane diether and clay catalyst carrier was 10.5 wt% and 65 wt%, respectively. The wide-angle X-ray diffraction test results of the catalyst are the same as those in Fig. 7, and are not repeated, wherein the clay sheet spacing is greater than 2.0 nm, and the catalytically active component enters the clay sheet gap and is uniformly distributed inside and outside the clay-supported transition metal catalyst particles. The catalyst had a specific surface area of 42.1 m ² /g, a pore volume of 0.18 cm ³ /g, and an average pore diameter of 13.4 nm.

3 )粘土催化剂载体的制备：取 20克干燥的所述经十八烷基三甲基氯化铵改性的有机粘土，经过超声作用分散于 400毫升乙醇中（有机粘土在该悬浮液中的质量百分浓度为 6.2wt%) 。 60°C下，将 93.98克反应性二氧化硅纳米微粒的乙醇悬浮液 (其中，反应性二氧化硅纳米微粒的质量百分浓度为 1.12wt%; 反应性二氧化硅纳米微粒与有机粘土的质量比为 1 : 19) 滴加入已均匀分散的有机粘土悬浮液中。滴加完成后，反应 4.0小时，再加入 2.0克碳酸氢铵（碳酸氢铵与有机粘土的质量比例为 0.1 : 1 ) ，继续搅拌 0.5小时后，喷雾干燥成型得到粘土催化剂载体。 3) Preparation of clay catalyst carrier: 20 g of the dried octadecyltrimethylammonium chloride-modified organoclay was dispersed by ultrasonication in 400 ml of ethanol (organic clay in the suspension) The mass percent concentration is 6.2 wt%). An ethanol suspension of 93.98 g of reactive silica nanoparticles (wherein the mass concentration of reactive silica nanoparticles is 1.12% by weight; at 60 ° C; reactive silica nanoparticles and organoclay The mass ratio is 1: 19) Dropped into the uniformly dispersed organoclay suspension. After completion of the dropwise addition, the reaction was carried out for 4.0 hours, and then 2.0 g of ammonium hydrogencarbonate (the mass ratio of ammonium hydrogencarbonate to the organoclay was 0.1 : 1 ) was further added, and stirring was continued for 0.5 hour, followed by spray drying to obtain a clay catalyst carrier.

实施例 8 1 ) 将 250克液态丙烯加入至反应釜中， 30°C下依次加入 0.25mol助催化剂三乙基铝及 1.0克粘土负载过渡金属催化剂以及氢气 0.2g，三乙基铝中铝元素与粘土负载过渡金属催化剂中钛元素之间的摩尔比为 460: 1，升温至 70°C，压强为 3.1MPa，进行本体聚合反应 0.5小时，得到含有粘土和重均分子量为 320000g/mol的均聚等规聚丙烯的复合物 97.14g，直接进行下一步反应。 Example 8 1) 250 g of liquid propylene was added to the reaction vessel, and 0.25 mol of cocatalyst triethylaluminum and 1.0 g of clay-supported transition metal catalyst and 0.2 g of hydrogen were sequentially added at 30 ° C, and aluminum and clay were loaded in triethyl aluminum. The molar ratio between the titanium elements in the transition metal catalyst was 460:1, the temperature was raised to 70 ° C, the pressure was 3.1 MPa, and bulk polymerization was carried out for 0.5 hour to obtain a homopolymer having a clay and a weight average molecular weight of 320,000 g/mol. A composite of 97.14 g of polypropylene 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 30gl- 辛烯，通入氢气 0.03g，升温至 60°C，压强为 l .OMPa, 进行聚合反应 2小时，最终得到粘土增强的聚丙烯釜内合金 102.0g。 2) The propylene remaining in the reaction vessel in the above step 1) was vented and cooled to 50 ° C, then 30 g of octene was introduced, 0.03 g of hydrogen was introduced, the temperature was raised to 60 ° C, and the pressure was 1.0 MPa. The polymerization was carried out for 2 hours, and finally 102.0 g of a clay-reinforced polypropylene in-cylinder alloy was obtained.

该粘土增强的聚丙烯釜内合金由质量比为 2.0: 95.5： 2.5的粘土、均聚等规聚丙烯树脂和均聚等规聚 1-辛烯组成。颗粒表观形态为球形，颗粒粒径为 50~500μιη_; 广角 X射线测试结果表明，粘土以剥离的纳米片层的形式存在。 The clay-reinforced polypropylene in-cavity alloy consists of a clay having a mass ratio of 2.0:95.5:2.5, a homopolymeric isotactic polypropylene resin, and homopolymeric isotactic poly(1-octene). The apparent morphology of the particles is spherical, and the particle size is 50~500μιη _{. The} wide-angle X-ray test results show that the clay exists in the form of exfoliated nanosheets.

将上述氯化镁醇合物滴加入 3.0g球形粘土载体与 50ml癸烷的悬浮液中，于 60 The above magnesium chloride alcoholate was added dropwise to a suspension of 3.0 g of a spherical clay carrier and 50 ml of decane at 60

°C下恒温反应 4.0小时，然后滤除液体，滤出的固体用癸烷洗涤 3次，干燥后得到粘土催化剂载体的镁复合物； The reaction was heated at ° C for 4.0 hours, then the liquid was filtered off, and the filtered solid was washed three times with decane, and dried to obtain a magnesium composite of a clay catalyst carrier;

2) 向 -20°C的 100ml四氯化钛溶液中加入 5.0g所述粘土催化剂载体的镁复合物，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，干燥后得到本发明提供的粘土负载的过渡金属催化剂。 2) To 100 ml of a titanium tetrachloride solution at -20 ° C, 5.0 g of the magnesium catalyst of the clay catalyst carrier was added and reacted at -20 ° C for 1.0 hour under constant temperature. Slowly raise the temperature to 120 ° C, add 0.2 ml of diisobutyl phthalate, and then react at a constant temperature of 120 ° C for 1.5 hours. After the reaction is completed, the liquid is filtered off, and 100 ml of titanium tetrachloride solution is added again at 120 ° C. The reaction was carried out under constant temperature for 2.0 hours. Finally, it is washed 3 to 6 times with hexane, and after drying, the clay-supported transition metal catalyst provided by the present invention is obtained.

该粘土负载过渡金属催化剂为球形颗粒，由粘土催化剂载体、过渡金属化合物 TiCl₄、MgCl₂和内给电子体芴二醚组成；其中钛元素、镁元素的含量分别为 2.56wt%、 2.15wt%, 芴二醚和粘土催化剂载体的含量分别为 10.5wt%、 65wt%。广角 X射线衍射测试结果，与图 7相同，不再重复，其中粘土片层间距大于 2.0nm，催化活性组分进入粘土片层间隙并均匀分布于催化剂颗粒内外。该催化剂的比表面积为 42.1m²/g, 孔容为 0.18cm³/g，平均孔径为 13.4nm。 The clay-supported transition metal catalyst is a spherical particle composed of a clay catalyst carrier, a transition metal compound TiCl ₄ , MgCl ₂ and an internal electron donor sediment; wherein the content of titanium element and magnesium element is 2.56 wt% and 2.15 wt%, respectively. The content of the decane diether and clay catalyst carrier was 10.5 wt% and 65 wt%, respectively. The results of the wide-angle X-ray diffraction test are the same as those of Fig. 7, and are not repeated, wherein the clay sheet layer spacing is greater than 2.0 nm, and the catalytically active component enters the clay sheet gap and is uniformly distributed inside and outside the catalyst particles. The catalyst had a specific surface area of 42.1 m ² /g, a pore volume of 0.18 cm ³ /g, and an average pore diameter of 13.4 nm.

0.3578克浓氨水、 1.3694克去离子水和 22.7572克无水乙醇，磁力搅拌 0.5小时后，滴加入 1.0000克正硅酸乙酯。 60°C下反应 4.0小时。然后除去溶剂，干燥后得到反应性二氧化硅纳米微粒，其平均粒径为 40nm。 3 )粘土催化剂载体的制备：取 20克干燥的所述经十八烷基三甲基氯化铵改性的有机粘土，经过超声作用分散于 400毫升乙醇中（有机粘土在该悬浮液中的质量百分浓度为 6.2wt%) 。 60°C下，将 93.98克反应性二氧化硅纳米微粒的乙醇悬浮液 (其中，反应性二氧化硅纳米微粒的质量百分浓度为 1.12wt%; 反应性二氧化硅纳米微粒与有机粘土的质量比为 1 : 19) 滴加入已均匀分散的有机粘土悬浮液中。滴加完成后，反应 4.0小时，再加入 2.0克碳酸氢铵（碳酸氢铵与有机粘土的质量比例为 0.1 : 1 ) ，继续搅拌 0.5小时后，喷雾干燥成型得到粘土催化剂载体。 0.3578 g of concentrated ammonia water, 1.3694 g of deionized water and 22.7572 g of absolute ethanol were added, and after magnetic stirring for 0.5 hour, 1.0000 g of tetraethyl orthosilicate was added dropwise. The reaction was carried out at 60 ° C for 4.0 hours. Then, the solvent was removed, and after drying, reactive silica nanoparticles were obtained, and the average particle diameter was 40 nm. 3) Preparation of clay catalyst carrier: 20 g of the dried octadecyltrimethylammonium chloride-modified organoclay was dispersed by ultrasonication in 400 ml of ethanol (organic clay in the suspension) The mass percent concentration is 6.2 wt%). An ethanol suspension of 93.98 g of reactive silica nanoparticles (wherein the mass concentration of reactive silica nanoparticles is 1.12% by weight; at 60 ° C; reactive silica nanoparticles and organoclay The mass ratio is 1: 19) Dropped into the uniformly dispersed organoclay suspension. After completion of the dropwise addition, the reaction was carried out for 4.0 hours, and then 2.0 g of ammonium hydrogencarbonate (a mass ratio of ammonium hydrogencarbonate to organoclay was 0.1:1) was added thereto, and stirring was continued for 0.5 hour, followed by spray drying to obtain a clay catalyst carrier.

该粘土催化剂载体由质量比为 95: 5 的有机粘土（有机粘土由质量比为 20: 80的有机插层剂十八烷基二甲基羟乙基硝酸铵和钠基蒙脱土组成，钠基蒙脱土的性质如下：阳离子交换容量为 90meq/100g，比表面积为 17.89m²/g，平均孔径为 21.90nm，孔容为 0.10cm³/g，片层间距为 l.Onm)和平均粒径为 40nm的反应性二氧化硅组成，其颗粒形态为球形，其颗粒粒径为 10~30μιη，比表面积为 42.1m²/g，孔容为 0.18cm³/g，平均孔径为 13.4nm。粘土催化剂载体和有机粘土的广角 X射线衍射测试结果可知，衍射角在 1.5°~10°范围内均出现粘土的（001 )面特征峰，根据 Bragg方程

计算，其片层间距均为 2.0nm，这说明片层间距并未因反应性二氧化硅纳米微粒的加入而发生变化。 The clay catalyst carrier consists of an organoclay having a mass ratio of 95:5 (the organoclay is composed of an organic intercalant of octadecyldimethylhydroxyethylammonium nitrate and sodium montmorillonite having a mass ratio of 20:80, sodium The properties of montmorillonite are as follows: cation exchange capacity is 90 meq/100 g, specific surface area is 17.89 m ² /g, average pore diameter is 21.90 nm, pore volume is 0.10 cm ³ /g, sheet spacing is l. Onm) and average The composition of reactive silica having a particle diameter of 40 nm has a spherical shape of 10 to 30 μm, a specific surface area of 42.1 m ² /g, a pore volume of 0.18 cm ³ /g, and an average pore diameter of 13.4 nm. . The wide-angle X-ray diffraction test results of the clay catalyst carrier and the organoclay show that the (001) surface characteristic peak of the clay appears in the diffraction angle in the range of 1.5° to 10°, according to the Bragg equation.

实施例 9 Example 9

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）制样并测试实施例 1、 2和 5所得粘土增强的聚丙烯釜内合金的力学性能，测试结果如表 1所示。 The clay-reinforced polypropylene kettles obtained in Examples 1, 2 and 5 were prepared and tested according to the standards IS0527-2-5A (tensile test), ASTM 638-V (bend test) and ASTM D256-02 (impact performance test). The mechanical properties of the alloy, the test results are shown in Table 1.

表 1、粘土增强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 clay-reinforced polypropylene in-cavity alloy

该对比样品的制备方法如下： The preparation method of the comparative sample is as follows:

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 1) Under vacuum, 20 g of propylene monomer was charged into the reaction vessel, and 50 ml of solvent hexane, 3.5 ml of a heptane solution containing 1.5 mmol of a promoter of triethylaluminum, and 0.02 g of a magnesium chloride-supported transition metal catalyst were sequentially added.

(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，得到重均分子量为 420000g/mol的均聚聚丙烯 15.0g，然后，停止通入丙烯单体； (The molar ratio between the aluminum element in the promoter of triethylaluminum and the transition metal catalyst supported by magnesium chloride is 150: 1), the pressure in the autoclave is constant at 0.7 MPa, the reaction temperature is 70 ° C, and the reaction is carried out. The slurry polymerization reaction was carried out for 0.5 hour to obtain 15.0 g of a homopolypropylene having a weight average molecular weight of 420,000 g/mol, and then, the passage of the propylene monomer was 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； 2) To the step 1), a mixture of ethylene and propylene (in which the molar ratio of ethylene to propylene) is introduced into the reactor For 1 : 2) 5g, continue the reaction 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, and washed with deionized water and ethanol at 60 ° C. Drying in a vacuum to obtain 17.0 g of an alloy in a polypropylene kettle;

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。 The polypropylene in-cylinder alloy was composed of a homopolypropylene resin and an ethylene/propylene random copolymer having a mass ratio of 88.24% and 11.76%.

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:

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。 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.

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%。 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%.

由上可知，本发明提供的粘土增强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。与不含粘土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。 It can be seen from the above that the clay-reinforced polypropylene in-cylinder alloy provided by the present invention has high modulus and impact toughness, thereby achieving the goals of high modulus and high toughness at the same time, and obtaining an in-cabin alloy excellent in performance. Compared with the non-clay polypropylene inner cylinder alloy, its mechanical properties are improved to varying degrees.

其余实施例所得粘土增强的聚丙烯釜内合金的力学性能检测结果与上无实质性差别，此处不再赘述。 The results of the mechanical properties test of the clay-reinforced polypropylene in-cylinder alloy obtained in the remaining examples are not substantially different from those in the above, and will not be described herein.

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的粘土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粘土增强的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 a clay-supported transition metal catalyst with an apparent morphology of the particles to obtain a clay-reinforced polypropylene in-cavity alloy. Resin. The invention has the following advantages:

1、本发明着重于对粘土增强的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聚丙烯釜内合金的方法。由于聚丙烯产物的球形形态，从而具有较大的堆密度，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，如果聚丙烯产物是无定形状态，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 is directed to controlling the particle morphology of a clay-reinforced polypropylene in-cylinder alloy, and provides a method for preparing a polypropylene in-caber alloy having an apparent morphology of spherical particles. Due to the spherical shape of the polypropylene product, it has a large bulk density, and does not cause the polymer to adhere to the wall of the kettle during the polymerization process, so that it is easy to flow and transport; otherwise, if the polypropylene product is in an amorphous state , its bulk density is small, easy to adhere to the wall of the kettle, thus affecting the transmission of the polymer, thereby limiting its subsequent application prospects.

2、本发明提供的粘土增强的聚丙烯釜内合金中，粘土以片层剥离的形式均匀分散于树脂基体中，可知本发明通过原位聚合方法成功制备得到了粘土增强的聚丙烯釜内合金树脂。 2. In the clay-reinforced polypropylene in-cylinder alloy provided by the present invention, the clay is uniformly dispersed in the resin matrix in the form of exfoliation, and it is understood that the clay-reinforced polypropylene in-cylinder alloy is successfully prepared by the in-situ polymerization method. Resin.

3、本发明提供的粘土增强的聚丙烯釜内合金中，通过第二段聚合引入的均聚聚 α烯烃或烯烃共聚物，为聚丙烯釜内合金的性能多样性和高性能化提供了一新的途径，进一步丰富了聚丙烯树脂的种类，从而为聚丙烯提供了更加宽广的应用空间。 3. In the clay-reinforced polypropylene in-cylinder alloy provided by the present invention, the homopolymerized poly-α-olefin or olefin copolymer introduced by the second-stage polymerization provides a performance diversity and high performance for the alloy in the polypropylene kettle. The new approach further enriches the variety of polypropylene resins, providing a broader application space for polypropylene.

该粘土增强的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、建筑材料以及日常生活用材料等领域，均具有广泛的应用前景。 The clay-reinforced polypropylene in-cylinder alloy resin has broad application prospects in automotive parts, packaging materials, barrier materials, flame retardant materials, electrical materials, building materials, and materials for daily use.

Claims

权利要求 Rights request

1、粘土增强的聚丙烯釜内合金，包括粘土、均聚聚丙烯树脂和烯烃聚合物。 1. Clay-reinforced polypropylene kettle alloy, including clay, homopolymer polypropylene resin and olefin polymer.

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， 2. The polypropylene kettle alloy according to claim 1, characterized in that: the homopolymer polypropylene resin is selected from at least one of isotactic polypropylene, syndiotactic polypropylene and atactic polypropylene resin,

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 homopolymer polypropylene resin is 20000-1000000g/mol, specifically:

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

所述烯烃聚合物是由 α-烯烃中的一种或两种单体发生聚合反应而得的聚合物；其中，所述 α-烯烃为乙烯、丙烯、 1-丁烯、 1-戊烯、 1-己烯、 1-辛烯、 1-壬烯或 1- 癸烯；或， The olefin polymer is a polymer obtained by the polymerization reaction of one or two monomers in α-olefins; wherein the α-olefins are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene or 1-decene; or,

所述均聚聚丙烯树脂与所述烯烃聚合物的质量比为 40.0 99.0: 1.0-60.0, 具体为 60-95 : 5-40； The mass ratio of the homopolymer polypropylene resin to the olefin polymer is 40.0-99.0: 1.0-60.0, specifically 60-95: 5-40;

所述粘土占所述粘土增强的聚丙烯釜内合金的质量百分含量为 0.01-25%，具体为 0.2-5%。 The mass percentage of the clay in the alloy in the clay-reinforced polypropylene kettle is 0.01-25%, specifically 0.2-5%.

3、根据权利要求 1或 2任一所述的聚丙烯釜内合金，其特征在于：所述粘土增强的聚丙烯釜内合金的颗粒表观形态为球形，粒径为 10〜10000μιη，具体为 3. The polypropylene kettle alloy according to claim 1 or 2, characterized in that: the apparent morphology of the particles of the clay-reinforced polypropylene kettle alloy is spherical, and the particle size is 10~10000 μm, specifically:

50-1000μηΐ; 或， 50-1000μnΐ; or,

所述粘土在所述聚丙烯釜内合金中以剥离的片层形式存在。 The clay is present in the polypropylene autoclave alloy as exfoliated flakes.

4、一种制备权利要求 1-3任一所述粘土增强的聚丙烯釜内合金的方法，包括如下步骤： 4. A method for preparing the clay-reinforced polypropylene autoclave alloy of any one of claims 1-3, including the following steps:

1 ) 在惰性气氛中，将丙烯单体与粘土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，反应完毕得到含有粘土和均聚聚丙烯树脂的复合物；或者，将丙烯单体与粘土负载过渡金属催化剂、助催化剂进行本体聚合反应，反应完毕得到含有粘土和均聚聚丙烯的复合物； 1) In an inert atmosphere, perform a slurry polymerization reaction of propylene monomer with a clay-supported transition metal catalyst and cocatalyst in an organic solvent. After the reaction is completed, a composite containing clay and homopolymer polypropylene resin is obtained; or, propylene monomer is The bulk polymerization reaction is carried out with the clay-supported transition metal catalyst and cocatalyst, and after the reaction is completed, a composite containing clay and homopolypropylene is obtained;

2) 在惰性气氛中，向所述步骤 1 ) 所得含有粘土和均聚聚丙烯树脂的复合物中加入一种或两种 α-烯烃，于有机溶剂中进行淤浆聚合反应，反应完毕得到所述粘土增强的聚丙烯釜内合金； 2) In an inert atmosphere, add one or two α-olefins to the composite containing clay and homopolymer polypropylene resin obtained in step 1), and perform a slurry polymerization reaction in an organic solvent. After the reaction is completed, the obtained The clay-reinforced polypropylene kettle alloy;

或者，向所述步骤 1 )所得含有粘土和均聚聚丙烯树脂的复合物中加入一种或两种 α-烯烃进行聚合反应，反应完毕得到粘土增强的聚丙烯釜内合金。 Alternatively, one or two α-olefins are added to the composite containing clay and homopolymer polypropylene resin obtained in step 1) to perform a polymerization reaction, and upon completion of the reaction, a clay-reinforced polypropylene kettle alloy is obtained.

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的烷基铝和 C1-C4的烷氧基铝中的至少一种，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；或， 5. The method according to claim 4, characterized in that: the cocatalyst is selected from at least one of C1-C4 aluminum alkyls and C1-C4 aluminum alkoxides, specifically selected from trimethylaluminum , at least one of triethylaluminum, triisobutylaluminum and methylaluminoxane; or,

所述 α烯烃为乙烯、丙烯、 1-丁烯、 1-戊烯、 1-己烯、 1-辛烯、 1-壬烯或 1-癸烯。 The α-olefin is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene or 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，助催化剂中的铝元素与粘土负载过渡金属催化剂中过渡金属元素的摩尔比为 1 5000: 1，具体为 10-2000： 1；或， 6. The method according to claim 4 or 5, characterized in that: in step 1), the molar ratio of the aluminum element in the cocatalyst to the transition metal element in the clay-loaded transition metal catalyst is 15000:1, specifically for 10-2000: 1; or,

所述粘土负载过渡金属催化剂的加入量为所述丙烯单体质量的 0.1-20%，具体为 0.4-10%。 The added amount of the clay-supported transition metal catalyst is 0.1-20% of the mass of the propylene monomer, specifically 0.4-10%.

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，所述 α- 烯烃的加入量为所述步骤 1所得含有粘土和均聚聚丙烯树脂的复合物质量的 0.5〜 80.0%, 具体为 1-80%。 7. The method according to claim 4 or 5, characterized in that: in step 2), the amount of α-olefin added is the mass of the composite containing clay and homopolymer polypropylene resin obtained in step 1. 0.5~80.0%, specifically 1-80%.

8、根据权利要求 6所述的方法，其特征在于：所述步骤 2 ) 中，所述 α-烯烃的加入量为所述步骤 1所得含有粘土和均聚聚丙烯树脂的复合物质量的 0.5〜80.0%，具体为 1-80%。 8. The method according to claim 6, characterized in that: in step 2), the addition amount of the α-olefin is 0.5 of the mass of the composite containing clay and homopolymer polypropylene resin obtained in step 1. ~80.0%, specifically 1-80%.

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， 9. The method according to claim 4 or 5, characterized in that: in the step 1), the temperature of the slurry polymerization reaction and the bulk polymerization reaction are both 30°C~90°C, and the time is 0.05 ~10.0 hours, the 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 50°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 50°C~120°C, the time is 0.1-10.0 hours, and the pressure is 0-4MPa, specifically 0.5-3.5MPa, so The pressure is not 0.

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， 10. The method according to claim 6, characterized in that: in the step 1), the temperature of the slurry polymerization reaction and the bulk polymerization reaction are both 30°C~90°C, and the time is 0.05~10.0 hours, the pressure is 0-4MPa, specifically 0.5-3.5MPa, and the pressure is not 0; or,

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， 1 1. The method according to claim 7, characterized in that: in the step 1), the temperature of the slurry polymerization reaction and the bulk polymerization reaction are both 30°C~90°C, and the time is 0.05~ 10.0 hours, the pressure is 0-4MPa, specifically 0.5-3.5MPa, the pressure is not 0; or,

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, characterized in that: in the step 1), the temperature of the slurry polymerization reaction and the bulk polymerization reaction are both 30°C~90°C, and the time is 0.05~10.0 hours, the pressure is 0-4MPa, specifically 0.5-3.5MPa, and the pressure is not 0; or,

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，所述氢气的加入量为所述丙烯单体质量的 0-0.5%，具体为 0-0.2%，且所述氢气的加入量不为 0; 或， 13. The method according to claim 4 or 5, characterized in that: the method further includes the following steps: before step 1) slurry polymerization or bulk polymerization, introducing hydrogen into the reaction system; or , the added amount of hydrogen is 0-0.5% of the mass of the propylene monomer, specifically 0-0.2%, and the added amount of hydrogen is not 0; or,

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， The method also includes the following steps: before step 2) slurry polymerization or polymerization, introducing hydrogen into the reaction system; or,

所述氢气的加入量为所述 a烯烃总重的 0-5.0%，具体为 0-0.5%，且所述氢气的加入量不为 0。 The added amount of hydrogen is 0-5.0% of the total weight of the a-olefin, specifically 0-0.5%, and the added amount of hydrogen 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，所述氢气的加入量为所述丙烯单体质量的 0-0.5%，具体为 0-0.2%，且所述氢气的加入量不为 0; 或，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， 14. The method according to claim 6, characterized in that: the method further includes the following steps: before step 1) slurry polymerization or bulk polymerization, introducing hydrogen into the reaction system; or, The added amount of hydrogen is 0-0.5% of the mass of the propylene monomer, specifically 0-0.2%, and the added amount of hydrogen is not 0; or, The method further includes the following steps: before step 2) slurry polymerization or polymerization, introducing hydrogen into the reaction system; or,

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，所述氢气的加入量为所述丙烯单体质量的 0-0.5%，具体为 0-0.2%，且所述氢气的加入量不为 0; 或， 15. The method according to claim 7, characterized in that: the method further includes the following steps: before step 1) slurry polymerization or bulk polymerization, introducing hydrogen into the reaction system; or, The added amount of hydrogen is 0-0.5% of the mass of the propylene monomer, specifically 0-0.2%, and the added amount of hydrogen is not 0; or,

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，所述氢气的加入量为所述丙烯单体质量的 0-0.5%，具体为 0-0.2%，且所述氢气的加入量不为 0; 或， 16. The method according to claim 8, characterized in that: the method further includes the following steps: before step 1) slurry polymerization or bulk polymerization, introducing hydrogen into the reaction system; or, The added amount of hydrogen is 0-0.5% of the mass of the propylene monomer, specifically 0-0.2%, and the added amount of hydrogen is not 0; or,

17、根据权利要求 9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，所述氢气的加入量为所述丙烯单体质量的 0-0.5%，具体为 0-0.2%，且所述氢气的加入量不为 0; 或， 17. The method according to claim 9, characterized in that: the method further includes the following steps: before step 1) slurry polymerization or bulk polymerization, introducing hydrogen into the reaction system; or, The added amount of hydrogen is 0-0.5% of the mass of the propylene monomer, specifically 0-0.2%, and the added amount of hydrogen is not 0; or,

18、根据权利要求 10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，所述氢气的加入量为所述丙烯单体质量的 0-0.5%，具体为 0-0.2%，且所述氢气的加入量不为 0; 或， 18. The method according to claim 10, characterized in that: the method further includes the following steps: before step 1) slurry polymerization or bulk polymerization, introducing hydrogen into the reaction system; or, The added amount of hydrogen is 0-0.5% of the mass of the propylene monomer, specifically 0-0.2%, and the added amount of hydrogen is not 0; or,

所述氢气的加入量为所述 α烯烃总重的 0-5.0%，具体为 0-0.5%，且所述氢气的加入量不为 0。 The added amount of hydrogen is 0-5.0% of the total weight of the α-olefin, specifically 0-0.5%, and the added amount of hydrogen is not 0.

19、根据权利要求 1 1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，所述氢气的加入量为所述丙烯单体质量的 0-0.5%，具体为 0-0.2%，且所述氢气的加入量不为 0; 或， 19. The method according to claim 11, characterized in that: the method further includes the following steps: before step 1) slurry polymerization or bulk polymerization, introducing hydrogen into the reaction system; or, The added amount of hydrogen is 0-0.5% of the mass of the propylene monomer, specifically 0-0.2%, and the added amount of hydrogen is not 0; or,

20、根据权利要求 12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，所述氢气的加入量为所述丙烯单体质量的 0-0.5%，具体为 0-0.2%，且所述氢气的加入量不为 0; 或， 20. The method according to claim 12, characterized in that: the method further includes the following steps: before step 1) slurry polymerization or bulk polymerization, introducing hydrogen into the reaction system; or, The added amount of hydrogen is 0-0.5% of the mass of the propylene monomer, specifically 0-0.2%, and the added amount of hydrogen is not 0; or,

21、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的外给电子体；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；或， 21. The method according to claim 4 or 5, characterized in that: the method further includes the following steps: before step 1) slurry polymerization or bulk polymerization, adding a structural general formula of: _R4.n Si(OR';) _n is an external electron donor; in the _R4.n Si(OR';) _n , n is an integer of 1-3, and R and R' are both selected from C1-C8 alkane. At least one of a C5-C10 cycloalkyl group and a C6-C10 aryl group; or,

所述外给电子体与所述助催化剂中铝元素的摩尔比为 0.01-1.0 : 1，具体为 0.1-1.0： 1。 The molar ratio of the external electron donor to the aluminum element in the cocatalyst is 0.01-1.0:1, specifically 0.1-1.0:1.

22、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';)_n的外给电子体；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；或， 22. The method according to claim 6, characterized in that: the method further includes the following steps: before step 1) slurry polymerization or bulk polymerization, adding a structural formula of R4 to the reaction system. _n Si(OR';) _n is an external electron donor; in the R4. _n Si(OR';) _n , n is an integer of 1-3, and R and R' are both selected from C1-C8 alkyl groups, At least one of C5-C10 cycloalkyl and C6-C10 aryl; or,

所述外给电子体与所述助催化剂中铝元素的摩尔比为 0.01-1.0 : 1，具体为 The molar ratio of the external electron donor to the aluminum element in the cocatalyst is 0.01-1.0:1, specifically:

0.1-1.0： 1。 0.1-1.0: 1.

23、根据权利要求 7-20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^SiCOR')^^外给电子体；所述 R4._nSiCOR')_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；或， 23. The method according to any one of claims 7 to 20, characterized in that: the method further includes the following steps: before step 1) slurry polymerization or bulk polymerization, adding structural fluid to the reaction system The formula is R^SiCOR')^^ external electron donor; in the R4. _n SiCOR') _n , n is an integer of 1-3, R and R' are both selected from C1-C8 alkyl, C5-C10 At least one of cycloalkyl and C6-C10 aryl; or,

24、根据权利要求 4-23任一所述的方法，其特征在于：所述步骤 1 )和 2 )中，所述有机溶剂均选自 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。 24. The method according to any one of claims 4 to 23, characterized in that in steps 1) and 2), the organic solvents are selected from at least one of C5 C10 alkanes and C6-C8 aromatic hydrocarbons. One, specifically at least one selected from the group consisting of heptane, hexane and toluene.

25、权利要求 1-3任一所述粘土增强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、建筑材料和日常生活用材料中至少一种中的应用。 25. The clay-reinforced polypropylene kettle alloy of any one of claims 1 to 3 is used to prepare at least one of automotive parts, packaging materials, barrier materials, flame retardant materials, electrical materials, building materials and daily life materials. applications in.