CN102964479A - Supported non-metallocene catalyst, preparation method and application - Google Patents

Supported non-metallocene catalyst, preparation method and application Download PDF

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CN102964479A
CN102964479A CN 201110259299 CN201110259299A CN102964479A CN 102964479 A CN102964479 A CN 102964479A CN 201110259299 CN201110259299 CN 201110259299 CN 201110259299 A CN201110259299 A CN 201110259299A CN 102964479 A CN102964479 A CN 102964479A
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non
metallocene
supported
catalyst
method
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CN102964479B (en )
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任鸿平
李传峰
左胜武
阚林
郭峰
梅利
柏基业
陈韶辉
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中国石油化工股份有限公司
中国石化扬子石油化工有限公司
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Abstract

The invention relates to a supported non-metallocene catalyst and a preparation method. The supported non-metallocene catalyst is prepared by the steps of directly drying a magnesium compound slurry containing a non-metallocene ligand and a porous carrier, and reacting with an IVB group chemical treating agent. The preparation method is simple and feasible, and the load capacity of the non-metallocene ligand is adjustable. The invention also relates to the application of the supported non-metallocene catalyst in olefin homopolymerisation/copolymerization. Compared with the prior art, the supported non-metallocene catalyst has the characteristics of less usage of a cocatalyst for catalyzing polymerization of alkene, high polymerization activity, substantial copolymerization effect, high bulk density of polymer, narrow molecular weight distribution, and high and adjustable viscosity average molecular weight of the prepared ultrahigh molecular weight polyethylene.

Description

负载型非茂金属催化剂、其制备方法及其应用 Supported non-metallocene catalysts, their preparation and their use

[0001] 本申请基于《国家十一五支撑计划课题》在研项目。 [0001] This application is based on the "National Eleventh Five Pillar Program" in the research project. 该项目得到了国家科技部的高度重视和大力支持,其目标是形成具有自主知识产权的新一代聚烯烃催化剂技术,并改善国内相关产品同质化现象,提高我国聚烯烃品种档次,促进其向多样化、系列化、专用化、高性能化的方向发展。 The project by the State Ministry of Science and attaches great importance to and vigorously support, its goal is to form a new generation of polyolefin catalyst technology with independent intellectual property rights, and improving domestic product homogeneity, to improve the grade of polyolefin varieties, to promote their diversity, series, dedicated, high performance development direction.

技术领域 FIELD

[0002] 本发明涉及一种非茂金属催化剂。 [0002] The present invention relates to a non-metallocene catalyst. 具体而言,本发明涉及一种负载型非茂金属催化剂、其制备方法及其在烯烃均聚/共聚中的应用。 In particular, the present invention relates to a supported non-metallocene catalysts, their preparation and homopolymerization / copolymerization of olefins in the application.

背景技术 Background technique

[0003] 二十世纪九十年代中后期出现的非茂金属催化剂,又称茂后催化剂,主催化剂的中心原子包括了几乎所有的过渡金属元素,在某些性能方面已经达到,甚至超过茂金属催化剂,成为继Ziegler、Ziegler-Natta和茂金属催化剂之后的第四代烯烃聚合催化剂。 [0003] 1990 non-metallocene catalyst of the late, after the central atom, also known as metallocene catalysts, the main catalysts include almost all of the transition metal elements, in some aspects of performance has been achieved and even exceeded metallocene the catalyst, after becoming Ziegler, Ziegler-Natta catalysts and metallocene olefin polymerization catalyst of the fourth generation. 根据主催化剂的中心原子的不同,进一步又可区分为非茂前过渡金属(IIIB族、IVB族、VB族、VIB族、VIIB族)催化剂和非茂后过渡金属(VIII族)催化剂。 Depending on the central atom of the main catalyst, but also to further differentiate the transition metal (IIIB group, IVB group, VB group, VIB group, VIIB group) metallocene catalyst and a non late transition metal (VIII group) non-metallocene pre-catalyst. 由该类催化剂所制造的聚烯烃产品的性能优良,而且制造成本低。 Excellent properties of the polyolefin products produced by such catalysts, and low manufacturing cost. 非茂金属催化剂配位原子为氧、氮、硫和磷,不含有环戊二烯基团或其衍生基团,如茚基和芴基等,其特征是中心离子具有较强的亲电性,且具有顺式烷基或卤素金属中心结构,容易进行烯烃插入和σ-键转移,中心金属容易烷基化,有利于阳离子活性中心的生成;形成的配合物具有限定的几何构型,立体选择性、电负性及手性可调节性,另外,所形成的金属-碳键容易极化,更有利于烯烃的聚合和共聚合。 Non-metallocene catalyst ligand are oxygen, nitrogen, sulfur and phosphorus, does not contain a cyclopentadienyl group or a group derived therefrom, such as indenyl and fluorenyl, wherein the central ion has a strong electrophilicity and having the cis configuration alkyl or halogen metal center, easy insertion and σ- olefin chain transfer, the central metal readily alkylated facilitate generating a cationic active center; complex formed has a defined geometry, perspective selectivity, electronegativity chiral adjustability, additionally, the formed metal - carbon bond is easily polarized, more conducive to polymerization and copolymerization of olefins. 因此,即使在较高的聚合反应温度下也能获得较高分子量的烯烃聚合物。 Thus, even at high polymerization temperatures can be obtained an olefin polymer of higher molecular weight.

[0004] 但均相催化剂在烯烃聚合反应中已被证实其具有活性持续时间短、容易粘釜、高的甲基铝氧烷用量,以及得到聚合物分子量太低或太高等不足之处,仅能用于溶液聚合工艺或高压聚合工艺,严重限制了其工业应用范围。 [0004] However, the heterogeneous catalyst in the polymerization of olefins which has been shown to have a short duration of activity, easy to stick kettle, high amounts of methyl aluminoxane, and the like to give the polymer molecular weight is too low or too high shortcomings, only can be used in a high pressure polymerization process or the solution polymerization process, severely limits its industrial application.

[0005]专利 ZL 01126323. 7、ZL 02151294. 9ZL 02110844. 7 和WO 03/010207 公开了一种烯烃均聚/共聚催化剂或催化体系,具有广泛的烯烃均聚/共聚性能,但在该专利所公开的催化剂或催化体系在烯烃聚合时需要较高的助催化剂用量,才能获得合适的烯烃聚合活性,而且聚合过程中存在着活性持续时间短,聚合物粘釜等现象。 [0005] Patent No. ZL 01126323. 7, ZL 02151294. 9ZL 02110844. 7 and WO 03/010207 discloses an olefin homopolymerization / copolymerization catalyst or catalyst system, having a wide range of olefin homopolymerization / copolymerization performance, but in this patent catalysts or catalyst systems disclosed in the polymerization of olefins require a high amount of cocatalyst, in order to obtain a suitable olefin polymerization activity and the polymerization process there are active for a short time, and so the polymer sticky kettle.

[0006] 通常的做法是将非茂金属催化剂通过一定的负载化技术,制成负载型催化剂,从而改善烯烃的聚合性能和所得聚合物的颗粒形态。 [0006] It is common practice by some non-metallocene catalyst loading technique, made of a supported catalyst, thereby improving the particle morphology of the olefin polymerization and the resulting properties of the polymer. 其表现为在一定程度上适当降低了催化剂的初始活性,延长催化剂的聚合活性寿命,减少甚至避免了聚合过程中的结块或暴聚现象,改善聚合物的形态,提高聚合物的表观密度,可以使其满足更多的聚合工艺过程,如气相聚合或淤浆聚合等。 Its performance is appropriate to reduce to some extent the initial activity of the catalyst, extend the life of the polymerization activity of the catalyst, reducing or even avoiding the agglomeration of the polymerization or during polymerization violent phenomenon, improved polymer morphology, and increase the apparent density of the polymer , so that it can meet more polymerization process, such as gas phase polymerization or slurry polymerization.

[0007] 已有的烯烃聚合催化剂专利大多基于茂金属催化剂,如US 480856UUS 5240894、CN 1344749Α、CN 1126480Α、ZL94101358. 8、CN 1307594Α、CN 1103069Α、CN1363537A、US6444604、ΕΡ0685494、US4871705和ΕΡ0206794等,但是这些专利也都涉及将含有过渡金属的茂金属催化剂负载于处理后的载体之上。 [0007] The olefin polymerization catalyst has been mostly based Patent metallocene catalyst, such as US 480856UUS 5240894, CN 1344749Α, CN 1126480Α, ZL94101358. 8, CN 1307594Α, CN 1103069Α, CN1363537A, US6444604, ΕΡ0685494, US4871705 ΕΡ0206794 and the like, but these the patent also relates to a metallocene catalyst comprising a transition metal supported on the carrier after the treatment.

[0008]针对专利 ZL 01126323. 7、ZL02151294. 9ZL 02110844. 7 和W003/010207 所公开的非茂金属催化剂,专利CN 1539855A、CN 1539856A、CN 1789291A、CN 1789292A、CN1789290A、W0/2006/063501、专利ZL200510119401. x等提供了多种方式进行负载以得到负 [0008] for Patent ZL 01126323. 7, ZL02151294. 9ZL 02110844. 7 and W003 / 010207 non-metallocene catalysts disclosed in the patent CN 1539855A, CN 1539856A, CN 1789291A, CN 1789292A, CN1789290A, W0 / 2006/063501, Pat. ZL200510119401. x provide a variety of ways to obtain a negative load

载型非茂金属催化剂,但这些专利均涉及将含有过渡金属的非茂金属有机化合物负载于处理后的载体之上。 Type non-metallocene catalyst carrier, these patents are directed to the carrier on the non-metallocene transition metal-containing organic compound to the processed load.

[0009] 中国专利CN200910180602. 9公开了一种负载型非茂金属催化剂的制备方法,其是使镁化合物和非茂金属配合物溶解于溶剂中,干燥后得到负载型非茂金属催化剂。 [0009] Chinese patent CN200910180602. 9 discloses a method for preparing a supported non-metallocene catalyst, which is a magnesium compound and non-metallocene complex was dissolved in a solvent, to give a supported non-metallocene catalyst was dried. 专利200910180605. 2公开了一种负载型非茂金属催化剂的制备方法,其是使镁化合物和非茂金属配合物溶解于溶剂中,加入沉淀剂沉淀,过滤洗涤干燥后得到负载型非茂金属催化剂。 Patent No. 200910180605.2 discloses a method for preparing a supported non-metallocene catalyst, which is a magnesium compound and non-metallocene complex was dissolved in a solvent, precipitating agent is added precipitate was filtered to give a supported non-metallocene catalyst was washed and dried . 这两种方法采用的是镁化合物载体,催化剂的颗粒形态难以控制,限制了由此聚合得到的聚合物颗粒形态。 Both methods used is a magnesium compound carrier, the morphology of the catalyst particles is difficult to control, thus limiting the morphology of the polymer particles obtained by polymerization.

[0010]中国专利 CN200910180603. 3、CN200910180604. 8、CN200910210989. 8、CN200910210986. 4、CN200910210985. X、CN200910210990. O 公开的负载型非茂金属催化剂 [0010] Chinese patent CN200910180603. 3, CN200910180604. 8, CN200910210989. 8, CN200910210986. 4, CN200910210985. X, CN200910210990. Non-supported metallocene catalyst disclosed O

制备方法与上述专利类似,均使用的是镁化合物作为载体,依然存在催化剂的颗粒形态难以控制,限制了由此聚合得到的聚合物颗粒形态。 Prepared similar to the above patents, the magnesium compound are used as a carrier, it remains difficult to control the morphology of the catalyst particles, thereby limiting the morphology of the polymer particles obtained by polymerization.

[0011] 以无水氯化镁为载体的催化剂在烯烃聚合过程中显示出较高的催化活性,但此类催化剂非常脆,在聚合反应器中容易破碎,从而导致聚合物形态不好。 [0011] In anhydrous magnesium chloride supported catalysts exhibit high catalytic activity in the olefin polymerization process, but such a catalyst is very brittle and easily broken polymerization reactor, leading to poor polymer morphology. 二氧化硅负载的催化剂具有很好的流动性,可用于气相流化床聚合,但二氧化硅负载茂金属和非茂金属催化剂则表现出较低的催化活性。 Silica supported catalysts have good mobility, may be employed in gas phase fluidized bed polymerization, the silica-supported metallocene and non-metallocene catalyst showed a lower catalytic activity. 因此如果将氯化镁和二氧化硅进行很好的有机结合,就可能制备出具有高催化活性,粒度大小可控及良好耐磨损强度的催化剂。 Therefore, if the magnesium chloride and a good combination of silicon dioxide, it is possible to prepare a catalyst having high catalytic activity, controlled particle size and good abrasion strength.

[0012] 比如CN1539856A公开了一种复合载体负载的非茂金属催化剂的负载化方法,其是按照如下步骤:(I)将作为载体的多孔载体在100-100(TC、惰性气氛或减压条件下,干燥或焙烧I〜24h进行热活化;(2)将镁化合物溶解于四氢呋喃-醇混合体系中形成溶液,再将热活化过的多孔固体加入到此溶液中,在O〜60°C搅拌条件下充分反应形成透明体系;经过过滤洗涤、干燥和抽干后制得复合载体;或者将此透明溶液加入非极性有机溶液使之沉淀充分析出,然后过滤洗涤、干燥抽干制得复合载体;(3)将非茂金属烯烃聚合催化剂溶解于溶剂中,然后与复合载体或修饰复合载体接触12〜72小时后过滤洗涤、干燥抽干成负载型非茂金属催化剂。这种方法需要先制备复合载体,再与催化剂溶液接触。 [0012] For example, CN1539856A discloses a method of non-supported metallocene catalyst is a composite load support, which is in accordance with the following steps: (I) a porous support to support at 100-100 (TC, an inert atmosphere or under reduced pressure , the drying or calcining I~24h thermally activated; (2) a magnesium compound is dissolved in tetrahydrofuran - alcohol mixed system to form a solution, and then through a heat activated porous solids added to this solution, stirred at O~60 ° C under conditions sufficient to form a transparent system; after filtration and washing, drained and dried to obtain a composite carrier; or this clear solution was added a non-polar organic solution was left to precipitate sufficiently precipitate, then filtered and washed, drained and dried to obtain composite carrier ; (3) a non-metallocene olefin polymerization catalyst dissolved in a solvent and then mixed with a carrier, or a composite modified composite carrier was filtered and washed after contacting 12~72 hours, drained and dried to a non-supported metallocene catalyst prepared in this way need to. composite carrier, and then contacted with the catalyst solution.

[0013] CN1789290A公开了一种负载型非茂金属催化剂的高活性负载方法,其包括如下步骤:将载体与化学活化剂作用,得到修饰载体;将镁化合物溶解于四氢呋喃-醇混合体系中形成溶液,再将修饰载体加入到此溶液中进行反应,经过滤洗涤、干燥和抽干制得复合载体;将非茂金属烯烃聚合催化剂溶解于溶剂中,然后与复合载体反应后洗涤过滤、干燥抽干,制得负载型非茂金属催化剂。 [0013] CN1789290A discloses a method for loading a high activity supported non-metallocene catalyst, comprising the steps of: a carrier and a chemical activating agent to obtain a modified carrier; dissolving a magnesium compound in tetrahydrofuran - alcohol mixed system to form a solution , then the modified carrier is added to this reaction solution, it was filtered, washed, drained and dried to obtain a composite carrier; non-metallocene olefin polymerization catalyst dissolved in a solvent, the reaction was then filtered and washed with a composite carrier, drained and dried to prepare the supported non-metallocene catalyst. 这种方法是先制备出修饰载体,再与镁化合物反应得到混合载体,再与催化剂溶液接触。 This method is to prepare a modified support, a magnesium compound and then reacted with the carrier mixture and then contacted with the catalyst solution.

[0014] 专利CN101423574A公开了一种负载化非茂单中心催化剂组分及其制备方法,该方法包括:(I)氯化镁/硅胶载体的制备;(2)烷基铝氧烷/氯化镁/硅胶载体的制备和(3)负载化非茂单活性中心催化剂组分的制备。 [0014] Patent CN101423574A discloses a supported non-metallocene single-site based catalyst component and its preparation, the method comprising: preparing (I) chloride / silica gel support; and (2) an alkyl aluminoxane / magnesium / silica support preparation and (3) preparing a non-metallocene single-site catalyst component of the load. 这种方法也是先制备出复合载体,再与烷基铝氧烷反应,最后与催化剂溶液接触。 This method is to prepare a composite carrier, and then reacted with an alkyl aluminoxane, and finally contacted with the catalyst solution. [0015] EP260130提出将负载型茂金属或非茂过渡金属化合物负载于甲基铝氧烷处理的二氧化硅载体之上,这里的非茂过渡金属仅仅是指ZrCl4、TiCl4或者VOCl3,该专利认为最优的是载体表面经有机镁或镁化合物与烷基铝的混合物,但是这个过程比较复杂,需要经过许多制备步骤。 [0015] EP260130 proposes a supported metallocene or non-metallocene transition metal compound supported on a silica support methylaluminoxane treated, where the non-metallocene transition metal refers only ZrCl4, TiCl4 or VOCl3, this patent that optimal the support surface by a mixture of an organomagnesium compound with an alkyl magnesium or aluminum, but the process is complex, many steps are required after preparation.

[0016] 专利CN200610026765. 8公开了一类单活性中心齐格勒-纳塔烯烃聚合催化剂。 . [0016] Patent CN200610026765 8 discloses a class of single site Ziegler - Natta olefin polymerization catalyst. 该催化剂以含有配位基团的水杨醛亚胺或取代的水杨醛亚胺衍生物作为给电子体,是通过向镁化合物(如氯化镁)/四氢呋喃溶液中加入经过预处理的载体(如硅胶)、金属化合物(如四氯化钛)及该给电子体进行处理后而得到的。 The catalyst containing salicylaldehyde imine derivative salicylaldimine ligand group or substituted as electron donor, the magnesium compound is obtained by (e.g., magnesium chloride) / tetrahydrofuran was added through the support pretreated (e.g., silica), metal compound (e.g., titanium tetrachloride) and post-processing the electron donor is obtained.

[0017] 专利CN200610026766. 2与之相类似,公开了一类含杂原子的有机化合物及其在齐格勒-纳塔催化剂中的应用。 [0017] Patent CN200610026766 2 with a similar, discloses a class of heteroatom-containing organic compound and a Ziegler - Natta catalyst.

[0018] 专利CN200910210988. 3和CN200910210984. 5公开了在没有醇存在下,将非茂金属配体溶解于镁化合物溶液中,接着加入多孔载体,直接干燥或过滤洗涤干燥后经IVB族化学处理剂处理,从而得到负载型非茂金属催化剂的制备方法及聚合用途,虽然非茂金属配体均匀的存在于载体之中,但由于孔道效应,含有非茂金属配体的镁化合物溶液中非茂金属配体和镁化合物在多孔载体孔道内的分布大于孔道之外,因此在后续与IVB族化学处理剂接触时,非茂金属配体和镁化合物接触机会均等,由于镁化合物的存在,限制了IVB族化学处理剂与非茂金属配体的充分接触,从而降低了催化烯烃聚合的协同作用机会,因而在实施例中催化乙烯聚合活性较低。 [0018] Patent No. CN200910210988. 3 and CN200910210984. 5 discloses the presence of an alcohol in the absence of the nonmetallocene ligand was dissolved in a solution of a magnesium compound, followed by addition of a porous support, directly after the drying or dried filtered and washed Group IVB chemical treatments process, whereby preparing a supported non-metallocene catalyst and a polymerization use, although non-homogeneous metallocene ligand present in the carrier, but the tunnel effect, a magnesium compound containing non-metallocene ligand metallocene solution Africa distribution ligand and the magnesium compound in the porous carrier is larger than the bore outside the tunnel, so when subsequent contact with the chemical treatment group IVB, the non-uniformly metallocene ligand and the chance of contact of the magnesium compound, the presence of a magnesium compound, limiting IVB group full contact with the chemical treatment of non-metallocene ligands, thereby reducing the chance synergistic effect catalytic polymerization of olefins, and thus lower the catalytic activity in the polymerization of ethylene embodiment.

[0019] 专利CN200910180100. 6和CN200910180607. I公开了在没有醇存在下,将非茂金 [0019] Patent No. CN200910180100. 6 and CN200910180607. I is not disclosed in the presence of an alcohol, a non-metallocene

属配合物溶解于镁化合物溶液中,接着加入多孔载体,直接干燥或过滤洗涤干燥后经IVB族化学处理剂处理,从而得到负载型非茂金属催化剂的制备方法及聚合用途,其非茂金属配合物均匀的存在于载体之中,但在实施例中催化乙烯聚合活性较低,而与之类似的是专利CN200910180601. 4和CN200910180606. 7公开的负载型非茂金属催化剂制备方法及聚合用途,其主要差别在于不经过IVB族化学处理剂处理,因而导致催化剂聚合活性较低。 Metal complexes dissolved in the magnesium compound solution, followed by addition of a porous support, dried or filtered directly after washing dried Group IVB chemical treating agent, whereby preparing a supported non-metallocene catalyst and a polymerization purposes, non-metallocene complex It is uniformly present in the carrier, but lower activity in the ethylene polymerization catalyst embodiments, and is similar thereto patent CN200910180601. 4 and CN200910180606. 7 discloses the preparation of a supported non-metallocene catalyst and a polymerization method of use thereof The main difference is that the group IVB without the chemical treatment process, resulting in lower polymerization activity of the catalyst.

[0020] 专利CN200710162666. 7公开了负载型催化剂、负载型非茂金属催化剂及其制备方法,其是在有醇存在下,将镁化合物溶解于四氢呋喃溶剂中,加入多孔载体,直接干燥后与四氯化钛反应,最后再负载非茂金属配合物,催化剂活性较高,并且由此聚合得到的聚合物具有高的堆密度,但制备过程较为复杂,化学处理剂与载体反应会破坏已成型的载体结构,继而在聚合过程中产生聚合物细粉。 [0020] Patent No. CN200710162666. 7 discloses a supported catalyst, a supported non-metallocene catalyst and a preparation method, which is an alcohol in the presence of a magnesium compound is dissolved in tetrahydrofuran solvent, adding a porous support, dried and four direct titanium chlorination reaction, and finally the load non-metallocene complex, higher catalyst activity, and thus obtained a polymer having a high polymerization bulk density, but the manufacturing process is complex, the chemical treatment reaction with the carrier will destroy an already formed support structure, and then produce a polymer fines during polymerization.

[0021] 虽然如此,现有技术中存在的负载型非茂金属催化剂普遍存在的问题是,负载化过程复杂,一般需要进行载体的多步处理之后再负载非茂金属配合物,烯烃聚合活性低且难以调节,并且为了提高其聚合活性,在进行烯烃聚合时必须辅助较高的助催化剂用量。 [0021] Nevertheless, the non-supported metallocene catalysts common problem present in the prior art, the load of the process is complex, then the load after the non-metallocene complex generally require multi-step treatment of the support, the olefin polymerization activity is low and difficult to adjust, and in order to improve the polymerization activity, it must be assisted high amount of cocatalyst during the polymerization of olefins.

[0022] 因此,仍旧需要一种负载型非茂金属催化剂,其制备方法简单,适合工业化生产,并且可以克服以制备现有技术负载型非茂金属催化剂过程中存在的那些问题。 [0022] Accordingly, still a need for a non-supported metallocene catalysts, their preparation method is simple and suitable for industrial production, and can overcome the problems with the prior art process of preparing a supported non-metallocene present in the catalyst.

发明内容 SUMMARY

[0023] 本发明人在现有技术的基础上经过刻苦的研究发现,通过使用一种特定的制备方法来制造所述负载型非茂金属催化剂,就可以解决前述问题,并由此完成了本发明。 [0023] The present invention found through assiduous studies on the basis of the prior art, by using a specific method of preparing the supported non-producing metallocene catalyst can solve the aforementioned problems, and thus completed the present invention.

[0024] 在本发明的负载型非茂金属催化剂的制备方法中,不添加质子授体(比如本领域常规使用的那些)。 [0024] In the production method of the present invention is a supported non-metallocene catalyst, without adding a proton donor (such as those conventionally used in the art). 另外,在本发明的负载型非茂金属催化剂的制备方法中,不添加给电子体(比如本领域中为此而常规使用的单酯类、双酯类、二醚类、二酮类和二醇酯类等化合物)。 Further, in the method of the present invention, the supported nonmetallocene catalyst, was not added to the electron donor (such as in the art for this purpose and conventionally used monoesters, diesters, diethers, diketones and bis an alcohol-based compound, etc.). 再者,在本发明的负载型非茂金属催化剂的制备方法中,也无须苛刻的反应要求和反应条件。 Further, in the production method of the present invention, a supported non-metallocene catalyst, there is no need severe reaction requirements and reaction conditions. 因此,该负载型催化剂的制备方法简单,并且非常适合于工业化生产。 Thus, the preparation method of the supported catalyst is simple and is very suitable for industrial production.

[0025] 具体而言,本发明涉及以下方面的内容: [0025] In particular, the present invention relates to the following aspects:

[0026] I. 一种负载型非茂金属催化剂的制备方法,包括以下步骤: Preparation [0026] I. Methods a supported non-metallocene catalyst, comprising the steps of:

[0027] 使镁化合物溶解于溶剂中,获得镁化合物溶液的步骤; [0028] 使任选经过热活化处理的多孔载体与所述镁化合物溶液接触,获得第一混合浆液的步骤; [0027] The magnesium compound dissolved in a solvent, a step to obtain a magnesium compound solution; [0028] that the porous support optionally through heat activation of the magnesium compound solution is contacted with the step of obtaining a first mixed slurry;

[0029] 使非茂金属配体与所述第一混合浆液接触,获得第二混合浆液的步骤; [0029] of the non-metallocene ligand in contact with the first mixed slurry to obtain a mixed slurry of the second step;

[0030] 直接干燥所述第二混合浆液,获得修饰复合载体的步骤,和 [0030] Direct drying the second slurry mixing step of obtaining a modified composite carrier, and

[0031] 使选自IVB族金属化合物的化学处理剂与所述修饰复合载体反应,获得所述负载型非茂金属催化剂的步骤。 [0031] so that the chemical treatment is selected from Group IVB metal compound to react with the modified composite carrier, the step of obtaining the supported non-metallocene catalyst.

[0032] 2.按照前述任一方面所述的制备方法,其特征在于,所述多孔载体选自烯烃均聚物或共聚物、聚乙烯醇或其共聚物、环糊精、聚酯或共聚酯、聚酰胺或共聚酰胺、氯乙烯均聚物或共聚物、丙烯酸酯均聚物或共聚物、甲基丙烯酸酯均聚物或共聚物、苯乙烯均聚物或共聚物、这些均聚物或共聚物的部分交联形式、元素周期表IIA、IIIA、IVA或IVB族金属的难熔氧化物或难熔复合氧化物、粘土、分子筛、云母、蒙脱土、膨润土和硅藻土中的一种或多种,优选选自部分交联的苯乙烯聚合物、二氧化硅、氧化铝、氧化镁、氧化硅铝、氧化镁铝、二氧化钛、分子筛和蒙脱土中的一种或多种,更优选选自二氧化硅。 [0032] 2. The production method according to any preceding aspect, wherein the porous support is selected from an olefin homopolymer or copolymer, a polyvinyl alcohol or a copolymer thereof, a cyclodextrin, or co-polyesters polyesters, polyamides or copolyamides, or copolymers of vinyl chloride homopolymer, an acrylate homopolymer or copolymer, a methacrylate homopolymer or copolymer, a styrene homopolymer or copolymer, such homo- partially crosslinked form or copolymer Periodic Table IIA, IIIA, IVA or group IVB metal refractory oxide or refractory composite oxide, clay, zeolite, mica, montmorillonite, bentonite, and diatomaceous earth the one or more, preferably styrene polymer selected from partially crosslinked, silica, alumina, magnesia, silica alumina, magnesium aluminum oxide, titanium dioxide, molecular sieves and one or more of montmorillonite species, and more preferably selected from silica.

[0033] 3.按照前述任一方面所述的制备方法,其特征在于,所述镁化合物选自卤化镁、烷氧基卤化镁、烷氧基镁、烷基镁、烷基卤化镁和烷基烷氧基镁中的一种或多种,优选选自卤化镁中的一种或多种,更优选氯化镁。 [0033] 3. The production method according to any preceding aspect, wherein the magnesium compound selected from magnesium halide, alkoxy magnesium halide, alkoxy magnesium, alkyl magnesium, alkyl magnesium halide and alkyl alkoxy group of one or more of magnesium, a magnesium halide is preferably selected from one or more, and more preferably magnesium chloride.

[0034] 4.按照前述任一方面所述的制备方法,其特征在于,所述溶剂选自C6_12芳香烃、卤代(;_12芳香烃、酯和醚中的一种或多种,优选选自(:6_12芳香烃和四氢呋喃中的一种或多种,最优选四氢呋喃。 [0034] 4. The production method according to any preceding aspect, wherein the aromatic hydrocarbon solvent is selected from C6_12, halo (; _12 aromatic hydrocarbon, one or more esters and ethers, preferably selected by (: 6_12 aromatic and one or more of tetrahydrofuran, most preferably tetrahydrofuran.

[0035] 5.按照前述任一方面所述的制备方法,其特征在于,所述非茂金属配体选自具有 [0035] 5. The production method according to any preceding aspect, wherein the nonmetallocene ligand is selected from

如下化学结构式的化合物中的一种或多种: The following compound of formula in one or more of:

[0036] [0036]

Figure CN102964479AD00111

[0037] 优选选自具有如下化学结构式的化合物(A)和化合物⑶中的一种或多种: [0037] preferably selected from compounds (A) has the following chemical structure formula and a compound of one or more ⑶:

[0038] [0038]

Figure CN102964479AD00121

[0039] 更优选选自具有如下化学结构式的化合物(AI)至化合物(A-4)和化合物(BI)至化合物(B-4)中的一种或多种: [0039] The compounds of the following chemical structure formula (AI) is more preferably selected to have a compound (A-4) and Compound (BI) to one or more compounds (B-4) of:

[0040] [0040]

Figure CN102964479AD00131
Figure CN102964479AD00141

[0042] 在以上所有的化学结构式中, [0042] In all of the above chemical structural formula,

[0043] q 为0 或I ; [0043] q is 0 or I;

[0044] d 为0 或I ; [0044] d is 0 or I;

[0045] A 选自氧原子、硫原子、硒原子、 [0045] A is selected from oxygen atom, a sulfur atom, a selenium atom,

Figure CN102964479AD00142

R3ciOR31、砜基、亚砜基或-Se(O)R39,其中N、O、S、Se和P各自为配位用原子; R3ciOR31, a sulfone group, a sulfoxide group or -Se (O) R39, wherein N, O, S, Se and P are each coordinated with atom;

[0046] B选自氮原子、含氮基团、含磷基团或C1-C3tl烃基; [0046] B is selected from a nitrogen atom, a nitrogen group, a phosphorus-containing hydrocarbyl group or a C1-C3tl;

[0047] D选自氮原子、氧原子、硫原子、硒原子、磷原子、含氮基团、含磷基团、C1-C3tl烃基、砜基、亚砜基^ [0047] D is selected from a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a nitrogen-containing group, phosphorus-containing groups, C1-C3tl hydrocarbon group, a sulfone group, a sulfoxide group ^

Figure CN102964479AD00151

或-P(0)R32(OR33),其中N、O、S、Se 和P 各自为配位用原子; Or -P (0) R32 (OR33), wherein N, O, S, Se and P are each coordinated with atom;

[0048] E选自含氮基团、含氧基团、含硫基团、含硒基团、含磷基团或氰基,其中N、0、S、Se和P各自为配位用原子; [0048] E is selected from nitrogen-containing group, oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group or a cyano group, wherein N, 0, S, Se and P are each used as ligand atoms ;

[0049] F选自氮原子、含氮基团、含氧基团、含硫基团、含硒基团或含磷基团,其中N、O、S、Se和P各自为配位用原子; [0049] F is selected from a nitrogen atom, a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group or a phosphorus-containing group, wherein N, O, S, Se and P are each used as ligand atoms ;

[0050] G选自C1-C3tl烃基、取代的C1-C3tl烃基或惰性功能性基团; [0050] G is selected from C1-C3tl hydrocarbyl, substituted C1-C3tl hydrocarbyl or an inert functional group;

[0051] Y选自含氮基团、含氧基团、含硫基团、含硒基团或含磷基团,其中N、O、S、Se和P各自为配位用原子; [0051] Y is selected from nitrogen-containing group, oxygen-containing group, a sulfur-containing group, a selenium-containing group or a phosphorus-containing group, wherein N, O, S, Se and P are each coordinated with atom;

[0052] Z选自含氮基团、含氧基团、含硫基团、含硒基团、含磷基团或氰基,其中N、0、S、Se和P各自为配位用原子; [0052] Z is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group or a cyano group, wherein N, 0, S, Se and P are each coordinated with an atomic ;

[0053]—代表单键或双键; [0053] - represents a single or a double bond;

[0054]-代表共价键或离子键; [0054] - represents a covalent bond or an ionic bond;

[0055] R1至R4、R6至R36、R38和R39各自独立地选自氢、C「C3(I烃基、取代的C1-C3tl烃基或惰性功能性基团,上述基团彼此间可以相同也可以不同,其中相邻基团可以彼此结合在一起成键或成环,优选形成芳香族环;并且 [0055] R1 to R4, R6 to R36, R38 and R39 are each independently selected from hydrogen, C "C3 (I hydrocarbyl, substituted C1-C3tl hydrocarbyl or an inert functional group, the above groups may be identical to each other different, wherein the adjacent groups may be bonded to each other to form a ring or a bond, preferably form an aromatic ring;

[0056] R5选自氮上孤对电子、氢、C1-C30烃基、取代的C1-C3tl烃基、含氧基团、含硫基团、含氮基团、含硒基团或含磷基团;当R5为含氧基团、含硫基团、含氮基团、含硒基团或含磷基团时,R5中的N、O、S、P和Se可以作为配位用原子与所述中心IVB族金属原子进行配位, [0056] R5 is selected from the nitrogen lone pair of electrons, hydrogen, C1-C30 hydrocarbyl, substituted C1-C3tl hydrocarbon, oxygen-containing group, a sulfur group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group ; when R5 is oxygen-containing group, a sulfur group, a nitrogen-containing group, a selenium-containing group, or when the phosphorus-containing groups, R5 is N, O, S, P and Se atoms may be used as the ligand said central metal atom of group IVB be coordinated,

[0057] 所述惰性功能性基团选自卤素、含氧基团、含氮基团、含硅基团、含锗基团、含硫基团、含锡基团、C1-Cltl酯基和硝基, [0057] The inert functional group selected from halogen, oxygen-containing group, a nitrogen-containing group, a silicon-containing group, a germanium-containing group, a sulfur-containing group, a tin-containing group, C1-Cltl ester group, and nitro,

[0058] 所述非茂金属配体进一步优选选自具有如下化学结构式的化合物中的一种或多种: [0058] The nonmetallocene ligand is more preferably one or more compounds selected from the chemical structure of the formula:

[0059] [0059]

Figure CN102964479AD00152

[0060] [0060]

Figure CN102964479AD00161

[0061] 所述非茂金属配体最优选选自具有如下化学结构式的化合物中的一种或多种: [0061] The nonmetallocene ligand is most preferably selected from one or more compounds having the following chemical structure of formula:

[0062] [0062]

Figure CN102964479AD00162

[0063] 6.按照前述任一方面所述的制备方法,其特征在于, [0063] 6. A production method according to any preceding aspect, wherein,

[0064] 所述卤素选自F、Cl、Br或I ; [0064] The halogen is selected from F, Cl, Br or I;

Figure CN102964479AD00163

[0065]所述含氮基团选自 [0065] The nitrogen-containing groups selected from

Figure CN102964479AD00164

'R22 -NR23R24、-T-NR23R24 或-N (0) R25R26 ; 'R22 -NR23R24, -T-NR23R24 or -N (0) R25R26;

[0066]所述含磷基团选自、JR27 -PR28R29、-P (0) R30R31 或-P (0) R32 (0R33); [0066] The phosphorus-containing group is selected, JR27 -PR28R29, -P (0) R30R31, or -P (0) R32 (0R33);

[0067] 所述含氧基团选自羟基、-OR34和-T-OR34 ; [0067] The oxygen-containing group selected from hydroxyl, -OR34 and -T-OR34;

[0068]所述含硫基团选自-SR35、-T-SR35、-S (0) R36 或-T-SO2R37 ; [0068] The sulfur-containing group is selected from -SR35, -T-SR35, -S (0) R36 or -T-SO2R37;

[0069]所述含硒基团选自-SeR38、-T-SeR38, -Se (0) R39 或-T-Se (0) R39 ; [0069] The selenium-containing group is selected from -SeR38, -T-SeR38, -Se (0) R39 or -T-Se (0) R39;

[0070] 所述基团T选自C1-C3tl烃基、取代的C1-C3tl烃基或所述惰性功能性基团; [0070] T is selected from the group C1-C3tl hydrocarbyl, substituted hydrocarbyl or C1-C3tl the inert functional group;

[0071] 所述R37选自氢、C1-C3tl烃基、取代的C1-C3tl烃基或所述惰性功能性基团; [0071], wherein R37 is selected from hydrogen, C1-C3tl hydrocarbyl, substituted hydrocarbyl or C1-C3tl the inert functional group;

[0072] 所述C1-C3tl烃基选自C1-C3tl烷基、C7-C5tl烷芳基、C7-C5tl芳烷基、C3-C3tl环状烷基、C2-C30烯基、C2-C3tl炔基、C6-C3tl芳基、C8-C3tl稠环基或C4-C3tl杂环基,其中所述杂环基含有1-3个选自氮原子、氧原子或硫原子的杂原子; [0072] The hydrocarbon group is selected from C1-C3tl C1-C3tl alkyl, C7-C5tl alkylaryl, C7-C5tl aralkyl, C3-C3tl cyclic alkyl, C2-C30 alkenyl, C2-C3tl alkynyl , C6-C3tl aryl, C8-C3tl fused ring group or a C4-C3tl heterocyclyl, wherein the heterocyclyl contains 1-3 heteroatoms selected from nitrogen atom, an oxygen atom or a sulfur atom;

[0073] 所述取代的C1-C3tl烃基选自带有一个或多个所述齒素和/或所述C1-C3tl烷基作为取代基的所述C1-C3tl烃基; [0073] The substituted hydrocarbon group is selected from C1-C3tl with one or more teeth of said element and / or the alkyl group as the C1-C3tl C1-C3tl hydrocarbyl substituent;

[0074] 所述含硅基团选自-SiR42R43R44或-T-SiR45 ; [0074] The silicon-containing group selected -SiR42R43R44 or -T-SiR45;

[0075] 所述含锗基团选自-GeR46R47R48或-T-GeR49 ; [0075] The germanium-containing group selected -GeR46R47R48 or -T-GeR49;

[0076]所述含锡基团选自-SnR5°R51R52、-T-SnR53 或-T-Sn (0) R54 ; [0076] The tin-containing group selected -SnR5 ° R51R52, -T-SnR53 or -T-Sn (0) R54;

[0077] 所述R42至R54各自独立地选自氢、所述C1-C3tl烃基、所述取代的C1-C3tl烃基或所述惰性功能性基团,上述基团彼此间可以相同也可以不同,其中相邻基团可以彼此结合在一起成键或成环,并且 [0077], wherein R42 to R54 are each independently selected from hydrogen, a C1-C3tl hydrocarbyl, the substituted C1-C3tl hydrocarbyl or an inert functional group, among the above groups may be the same or different from each other, wherein adjacent groups may be bonded to each other to form a ring or a bond, and

[0078] 所述基团T同前述任一方面定义。 [0078] The group T as defined in any preceding aspect.

[0079] 7.按照前述任一方面所述的制备方法,其特征在于,所述IVB族金属化合物选自IVB族金属齒化物、IVB族金属烷基化合物、IVB族金属烷氧基化合物、IVB族金属烷基卤化物和IVB族金属烷氧基卤化物中的一种或多种,优选选自IVB族金属卤化物中的一种或多种,更优选选自TiCl4、TiBr4、ZrCl4、ZrBr4、HfCljP HfBr4中的一种或多种,最优选选自TiCl4和ZrCl4中的一种或多种。 [0079] 7. A production method according to any of the foregoing, wherein said compound is selected from Group IVB metal compound of Group IVB metal teeth, Group IVB metal alkyl compound, a Group IVB metal alkoxy compound, IVB metal alkyl halides and alkoxy halides of group IVB metal of one or more, preferably group IVB metal halide is one or more, more preferably selected from TiCl4, TiBr4, ZrCl4, ZrBr4 , one or more of HfCljP HfBr4, and most preferably TiCl4 and ZrCl4 in the selected one or more.

[0080] 8.按照前述任一方面所述的制备方法,其特征在于,以Mg元素计的所述镁化合物与所述非茂金属配体的摩尔比为I : 0.0001-1,优选I : 0.0002-0. 4,更优选I : 0.0008-0. 2,进一步优选I : 0.001-0. 1,所述镁化合物与所述溶剂的比例为Imol : 75 〜400ml,优选Imol : 150 〜300ml,更优选Imol : 200 〜250ml,以Mg 元素计的所述镁化合物与以IVB族金属元素计的所述化学处理剂的摩尔比为I : 0.01-1,优选I : 0.01-0. 50,更优选I : 0. 10-0. 30,并且以镁化合物固体计的所述镁化合物与所述多孔载体的质量比为I : 0.1-20,优选I : 0.5-10,更优选I : 1-5。 [0080] 8. The production method according to any preceding aspect, wherein the molar ratio of Mg in the magnesium compound on an elemental basis of the nonmetallocene ligand is I: 0.0001 to 1, preferably I: . 0.0002-0 4, more preferably I:. 0.0008-0 2, more preferably I:. 0.001-0 1, the ratio of said magnesium compound and said solvent is Imol: 75 ~400ml, preferably Imol: 150 ~300ml, more preferably Imol: 200 ~250ml, the molar ratio of Mg in the magnesium compound calculated as elemental chemical treatment with the group IVB metal element in terms of I: 0.01-1, preferably I:. 0.01-0 50, more preferably I:. 0. 10-0 30, and the mass of the magnesium compound to the magnesium compound with the porous solids support ratio of I: 0.1-20, preferably I: 0.5-10, more preferably I: 1- 5.

[0081] 9. 一种负载型非茂金属催化剂,它是由按照前述任一方面所述的制备方法制造的。 [0081] A supported nonmetallocene catalyst, which is produced by the production method according to any preceding aspect of.

[0082] 10. 一种烯烃均聚/共聚方法,其特征在于,以按照方面9所述的负载型非茂金属催化剂为主催化剂,以选自招氧烧、烧基招、齒代烧基招、砸氣烧、烧基砸和烧基砸按盐中的一种或多种为助催化剂,使烯烃均聚或共聚。 [0082] 10. An olefin homopolymerization / copolymerization process, wherein, according to a supported non-metallocene-based catalyst is a catalyst according to aspect 9, selected from oxygen firing strokes, strokes burn group, the teeth of burning yl move, hit the gas burn, burn and burn-yl group drop to drop one of its salts according to one or more cocatalyst, olefin homopolymerization or copolymerization.

[0083] 11. 一种烯烃均聚/共聚方法,其特征在于,包括以下步骤: [0083] A process for olefin homopolymerization / copolymerization process, characterized by comprising the steps of:

[0084] 按照前述任一方面所述的制备方法制造负载型非茂金属催化剂,和 [0084] producing a supported non-metallocene catalyst prepared according to the method of any of the foregoing, and

[0085] 以所述负载型非茂金属催化剂为主催化剂,以选自铝氧烷、烷基铝、卤代烷基铝、硼氟烷、烷基硼和烷基硼铵盐中的一种或多种为助催化剂,使烯烃均聚或共聚。 [0085] In the supported non-metallocene catalyst-based catalyst, selected from an alumoxane, an alkyl aluminum, halogenated alkyl aluminum, boron, fluoroalkyl, alkyl and one boron or boron alkyl ammonium salt species cocatalyst, olefin homopolymerization or copolymerization.

[0086] 技术效果 [0086] A technical effect

[0087] 本发明的负载型非茂金属催化剂的制备方法属于非茂金属配合物的原位负载化方法,工艺简单可行。 [0087] In situ preparation of a supported non-metallocene catalyst of the present invention is a non-metallocene complex loading method is simple and feasible. 由于含有非茂金属配体、多孔载体的镁化合物浆液是通过直接干燥方法得到的,非茂金属配体的负载量可控可调,由此可充分发挥其在催化烯烃聚合得到聚烯烃产物的性能。 Since the metallocene ligand containing a non-porous support slurry of the magnesium compound is obtained by a direct drying method, load non-metallocene ligand controllable adjustable, whereby its full polyolefin product obtained in the catalytic polymerization olefins performance.

[0088] 另外,通过采用不同的非茂金属配体用量,进而与化学处理剂反应原位生成具有烯烃聚合活性的非茂金属配合物,可以获得不同催化烯烃聚合活性的负载型非茂金属催化齐U,并且所得到的聚合物颗粒形态较好,堆密度较高,聚合物分子量分布较窄,制备超高分子量聚乙烯时聚合物粘均分子量较高,由此适应不同的烯烃聚合要求和聚烯烃的产品应用。 [0088] Further, by using different amounts of non-metallocene ligands, and further reacted with a chemical treatment agent is generated in situ olefin polymerization activity having a non-metallocene complex, olefin polymerization catalyst to obtain a different type of non-supported catalytically active metallocene Qi U, and the obtained polymer particle morphology is better, higher bulk density, narrow molecular weight distribution, the polymer viscosity average molecular weight higher preparing ultrahigh molecular weight polyethylene, thereby accommodating different olefin polymerization requirements and polyolefin product applications.

[0089] 本发明发现,采用本发明所获得的负载型非茂金属催化剂与助催化剂构成催化体系时,仅需要比较少的助催化剂(比如甲基铝氧烷或三乙基铝)用量,就可以获得高的烯烃聚合活性,共聚时表现出显著的共聚单体效应,即在相对同等的条件下,共聚活性高于均聚活性,而且通过催化烯烃均聚或共聚所得到的聚乙烯等聚合物具有优良的聚合物形态和高的聚合物堆积密度。 [0089] The present inventors have found that using the supported non-metallocene catalyst with a cocatalyst obtained by the present invention, when the catalytic system configuration, requires only a relatively small cocatalyst (such as methyl aluminoxane or triethyl aluminum) amount to possible to achieve high olefin polymerization activity, show a significant effect of the copolymerization of the comonomers, i.e. at relatively the same conditions, the copolymerization activity is higher than the activity of homopolymerization, and olefin by catalytic homopolymerization or copolymerization of the resulting polyethylene, the polymerization polymers having excellent morphology and high polymer bulk density.

[0090] 同时也发现,相比于镁化合物溶液中有醇的存在所得到的负载型非茂金属催化齐U,本发明催化剂制备过程镁化合物溶液中没有醇的存在所得到的负载型非茂金属催化齐U,具有更高的催化烯烃聚合活性、聚合物堆密度,以及窄的聚合物分子量分布,并且所得到的超高分子量聚乙烯粘均分子量。 [0090] also found that, compared to the magnesium compound solution with a supported non-metallocene catalyzed presence of an alcohol of the obtained homogeneous U, magnesium compound solution during preparation of the catalyst of the present invention without the presence of the supported non-metallocene of the resulting alcohol metal-catalyzed homogeneous U, having higher catalytic activity for olefin polymerization, a polymer bulk density and narrow molecular weight distribution, and the resulting ultrahigh molecular weight polyethylene having a viscosity average molecular weight. [0091] 本发明发现,相比于非茂金属配体先于镁化合物共同溶解于溶剂中,加入多孔载体直接干燥后,再与IVB族化学处理剂反应后过滤洗涤干燥所制备的负载型非茂金属催化齐U,本发明所提供的镁化合物溶解于溶剂中,加入多孔载体后再加入非茂金属体,直接干燥后再与IVB族化学处理剂反应后过滤洗涤干燥所制备的负载型非茂金属催化剂,由于孔道效应,镁化合物优先进入多孔载体中,非茂金属配体分布于镁化合物之上,因此能够充分与IVB族化学处理剂反应,发挥两者催化烯烃的协同作用,因此催化剂活性和聚合物堆密度较高,并且制备的超高分子量聚乙烯粘均分子量也较高。 [0091] The present inventors have found that, compared to the nonmetallocene ligand to the magnesium compound is first dissolved in a solvent together, directly after addition of a porous support and dried, then filtered washing and drying the supported non prepared after chemical treatment agent to Group IVB supported metallocene-catalyzed homogeneous non-U, the present invention provides a magnesium compound is dissolved in a solvent, and then added to a porous support member join nonmetallocene, filtered and washed and dried and then dried directly after the chemical treatment group IVB prepared by reacting metallocene catalyst, since the tunnel effect, a magnesium compound preferentially into the porous carrier, the nonmetallocene ligand is distributed over magnesium compound, it is possible to sufficiently react with the group IVB chemical treatment, both the synergy olefins, thus the catalyst activity and higher polymer bulk density and ultrahigh molecular weight polyethylene prepared by viscosity average molecular weight higher.

[0092] 同时也发现,采用本发明所获得的负载型非茂金属催化剂与助催化剂构成催化体系时,仅需要比较少的助催化剂(比如甲基铝氧烷或三乙基铝)用量,就可以获得高的烯烃聚合活性,聚合物分子量分布窄、共聚时表现出显著的共聚单体效应,即在相对同等的条件下,共聚活性高于均聚活性,而且通过催化烯烃均聚或共聚所得到的聚乙烯等聚合物具有优良的聚合物形态和高的聚合物堆积密度。 [0092] also found that use of a supported non-metallocene catalyst with a cocatalyst obtained by the present invention when catalytic system configuration, requires only a relatively small cocatalyst (such as methyl aluminoxane or triethyl aluminum) amount to possible to achieve high olefin polymerization activity and a narrow molecular weight distribution, exhibit a remarkable effect of the copolymerization of comonomers, i.e. at relatively the same conditions, the copolymerization activity is higher than the activity of homopolymerization, and olefin catalyzed by the homopolymerization or copolymerization of the resulting polyethylene polymer having excellent polymer morphology and high polymer bulk density.

具体实施方式 detailed description

[0093] 下面对本发明的具体实施方式进行详细说明,但是需要指出的是,本发明的保护范围并不受这些具体实施方式的限制,而是由附录的权利要求书来确定。 [0093] The following specific embodiments of the present invention will be described in detail, it should be noted that the scope of the present invention is not limited to these specific embodiments, but rather defined by the appended claims appendix.

[0094] 在本发明的上下文中,除非另有明确定义,或者该含义超出了本领域技术人员的理解范围,3个碳原子以上的烃或烃衍生物基团(比如丙基、丙氧基、丁基、丁烷、丁烯、丁烯基、己烷等)在未冠以词头“正”时均具有与冠以词头“正”时相同的含义。 [0094] In the context of the present invention, unless otherwise explicitly defined, the meaning or outside the purview of the skilled artisan, three or more carbon atoms in the hydrocarbon or hydrocarbon derivative group (for example propyl, propoxy , butyl, butane, butene, butenyl, hexane, etc.) is not preceded by the prefix has the same meaning as when preceded by the prefix "n" to "n." 比如,丙基一般理解为正丙基,而丁基一般理解为正丁基。 For example, as is generally understood propyl n-propyl and n-butyl generally understood.

[0095] 本发明涉及一种负载型非茂金属催化剂的制备方法,包括以下步骤:使镁化合物溶解于溶剂中,获得镁化合物溶液的步骤;使任选经过热活化处理的多孔载体与所述镁化合物溶液接触,获得第一混合浆液的步骤;使非茂金属配体与所述第一混合浆液接触,获得第二混合浆液的步骤;直接干燥所述第二混合浆液,获得修饰复合载体的步骤,和使选自IVB族金属化合物的化学处理剂与所述修饰复合载体反应,获得所述负载型非茂金属催化剂的步骤。 [0095] The present invention relates to a method for preparing a supported non-metallocene catalyst, comprising the steps of: dissolving a magnesium compound in a solvent in the step of obtaining a magnesium compound solution; that the thermally activated porous carrier, optionally after treatment with the contacting the magnesium compound solution, a first step of obtaining a mixed slurry; non metallocene ligand mixing contact with the first slurry, the second step of obtaining a mixed slurry; mixing directly drying the second slurry to obtain a modified composite carrier step, and that the metal compound is selected from group IVB of the chemical treatment step of the modified composite carrier reaction, the supported non-metallocene catalyst.

[0096] 以下对所述镁化合物进行具体的说明。 [0096] Here will be specifically described the magnesium compound.

[0097] 根据本发明,术语“镁化合物”使用本领域通常的概念,指的是作为负载型烯烃聚合催化剂的载体常规使用的有机或无机固体无水含镁化合物。 [0097] According to the present invention, the term "magnesium compound" concept is usually used in the art, refers to a supported olefin polymerization catalyst carriers conventionally used organic or inorganic solid anhydrous magnesium containing compound.

[0098] 根据本发明,作为所述镁化合物,比如可以举出卤化镁、烷氧基卤化镁、烷氧基镁、 [0098] According to the present invention, as the magnesium compound include magnesium halides such as, alkoxy magnesium halide, alkoxy magnesium,

烷基镁、烷基齒化镁和烷基烷氧基镁。 Magnesium, alkyl magnesium teeth and alkyl alkoxy magnesium.

[0099] 具体而言,作为所述卤化镁,比如可以举出氯化镁(MgCl2)、溴化镁(MgBr2)、碘化镁(MgI2)和氟化镁(MgF2)等,其中优选氯化镁。 [0099] Specifically, the magnesium halide, such as magnesium chloride include (MgCI2), magnesium bromide (MgBr2), magnesium iodide (MgI2) and magnesium fluoride (MgF2) and the like, wherein the magnesium chloride is preferred.

[0100] 作为所述烷氧基卤化镁,比如可以举出甲氧基氯化镁(Mg (OCH3) Cl)、乙氧基氯化镁(Mg(OC2H5)Cl)、丙氧基氯化镁(Mg(OC3H7)Cl)、正丁氧基氯化镁(Mg (OC4H9) Cl)、异丁氧基氯化镁(Mg(i-0C4H9)C1)、甲氧基溴化镁(Mg(OCH3)Br)、乙氧基溴化镁(Mg (OC2H5) Br)、丙氧基溴化镁(Mg(OC3H7)Br)、正丁氧基溴化镁(Mg(OC4H9)Br)、异丁氧基溴化镁(Mg(i_0C4H9)Br)、甲氧基碘化镁(Mg (OCH3) I)、乙氧基碘化镁(Mg (OC2H5) I)、丙氧基碘化镁(Mg (OC3H7) I)、正丁氧基碘化镁(Mg(OC4H9)I)和异丁氧基碘化镁(Mg(i-0C4H9)I)等,其中优选甲氧基氯化镁、乙氧基氯化镁和异丁氧基氯化镁。 [0100] Examples of the alkoxy magnesium halide such as magnesium chloride include methoxy (Mg (OCH3) Cl), ethoxy magnesium (Mg (OC2H5) Cl), propoxy magnesium chloride (Mg (OC3H7) Cl ), n-butoxy magnesium chloride (Mg (OC4H9) Cl), isobutoxy magnesium (Mg (i-0C4H9) C1), methoxy magnesium bromide (Mg (OCH3) Br), ethoxy magnesium bromide (Mg (OC2H5) Br), propoxy magnesium bromide (Mg (OC3H7) Br), n-butoxy magnesium bromide (Mg (OC4H9) Br), isobutoxy magnesium bromide (Mg (i_0C4H9) Br ), magnesium methoxide (Mg (OCH3) I) iodide, ethoxy magnesium (Mg (OC2H5) I) iodide, propoxy magnesium iodide (Mg (OC3H7) I), n-butoxy iodide magnesium (Mg (OC4H9) I) and isobutoxy magnesium iodide (Mg (i-0C4H9) I) and the like, wherein preferably methoxy magnesium chloride, ethoxy magnesium chloride and isobutoxy magnesium chloride.

[0101] 作为所述烷氧基镁,比如可以举出甲氧基镁(Mg(OCH3)2)、乙氧基镁(Mg(OC2H5)2)、丙氧基镁(Mg(OC3H7)2)、丁氧基镁(Mg(OC4H9)2)、异丁氧基镁(Mg(i-0C4H9)2)和2-乙基己氧基镁(Mg(OCH2CH(C2H5)C4H)2)等,其中优选乙氧基镁和异丁氧基镁。 [0101] Examples of the alkoxy magnesium such as magnesium include methoxy (Mg (OCH3) 2), ethoxy magnesium (Mg (OC2H5) 2), propoxy magnesium (Mg (OC3H7) 2) , butoxy magnesium (Mg (OC4H9) 2), isobutoxy magnesium (Mg (i-0C4H9) 2) and 2-ethyl hexyloxy magnesium (Mg (OCH2CH (C2H5) C4H) 2), etc., wherein preferably ethoxy magnesium and isobutoxy magnesium.

[0102] 作为所述烷基镁,比如可以举出甲基镁(Mg(CH3)2)、乙基镁(Mg(C2H5)2)、丙基镁(Mg(C3H7)2)、正丁基镁(Mg(C4H9)2)和异丁基镁(Mg(i-C4H9)2)等,其中优选乙基镁和正丁基镁。 [0102] Examples of the alkyl magnesium, may include for example methyl magnesium (Mg (CH3) 2), ethyl magnesium (Mg (C2H5) 2), propyl magnesium (Mg (C3H7) 2), n-butyl magnesium (Mg (C4H9) 2) and isobutyl magnesium (Mg (i-C4H9) 2) and the like, wherein preferably ethyl magnesium and n-butyl magnesium.

[0103] 作为所述烷基卤化镁,比如可以举出甲基氯化镁(Mg(CH3)Cl)、乙基氯化镁(Mg (C2H5) Cl)、丙基氯化镁(Mg (C3H7) Cl)、正丁基氯化镁(Mg (C4H9) Cl)、异丁基氯化镁(Mg (I-C4H9) Cl)、甲基溴化镁(Mg (CH3) Br)、乙基溴化镁(Mg (C2H5) Br)、丙基溴化镁(Mg (C3H7)Br)、正丁基溴化镁(Mg(C4H9)Br)、异丁基溴化镁(Mg (i_C4H9) Br)、甲基碘化镁(Mg (CH3) I)、乙基碘化镁(Mg(C2H5) I)、丙基碘化镁(Mg (C3H7) I)、正丁基碘化镁(Mg(C4H9)I)和异丁基碘化镁(Mg(i-C4H9)I)等,其中优选甲基氯化镁、乙基氯化镁和异丁基氯化镁。 [0103] Examples of the alkyl magnesium halide include methyl chloride such as (Mg (CH3) Cl), ethyl magnesium chloride (Mg (C2H5) Cl), propyl magnesium chloride (Mg (C3H7) Cl), n-butyl magnesium chloride (Mg (C4H9) Cl), isobutyl magnesium chloride (Mg (I-C4H9) Cl), methyl magnesium bromide (Mg (CH3) Br), ethyl magnesium bromide (Mg (C2H5) Br), propyl magnesium bromide (Mg (C3H7) Br), n-butyl magnesium bromide (Mg (C4H9) Br), isobutyl magnesium bromide (Mg (i_C4H9) Br), methyl magnesium iodide (Mg (CH3 ) the I), ethyl magnesium (Mg (C2H5) I) iodide, propyl magnesium (Mg (C3H7) I) iodide, n-butyl magnesium iodide (Mg (C4H9) I) and isobutyl magnesium iodide (Mg (i-C4H9) I) and the like, wherein preferably methyl magnesium chloride, ethyl magnesium chloride and isobutyl magnesium chloride.

[0104] 作为所述烷基烷氧基镁,比如可以举出甲基甲氧基镁(Mg(OCH3) (CH3))、甲基乙氧基镁(Mg(OC2H5) (CH3))、甲基丙氧基镁(Mg(OC3H7) (CH3))、甲基正丁氧基镁(Mg(OC4H9)(CH3))、甲基异丁氧基镁(Mg(i-0C4H9) (CH3))、乙基甲氧基镁(Mg(OCH3) (C2H5))、乙基乙氧基镁(Mg (OC2H5) (C2H5))、乙基丙氧基镁(Mg (OC3H7) (C2H5))、乙基正丁氧基镁(Mg (OC4H9)(C2H5))、乙基异丁氧基镁(Mg (I-OC4H9) (C2H5))、丙基甲氧基镁(Mg (OCH3) (C3H7))、丙基乙氧基镁(Mg(OC2H5) (C3H7))、丙基丙氧基镁(Mg(OC3H7) (C3H7))、丙基正丁氧基镁(Mg(OC4H9)(C3H7))、丙基异丁氧基镁(Mg (I-OC4H9) (C3H7))、正丁基甲氧基镁(Mg (OCH3) (C4H9))、正丁基乙氧基镁(Mg(OC2H5) (C4H9))、正丁基丙氧基镁(Mg(OC3H7) (C4H9))、正丁基正丁氧基镁(Mg (OC4H9) (C4H9))、正丁基异丁氧基镁(Mg (I-OC4H9) (C4H9))、异丁基甲氧基镁(Mg (OCH3)Q-C4H9))、异丁基乙氧基镁(Mg(OC2H5) Q-C4H9)) [0104] Examples of the alkyl alkoxy magnesium such groups include methyl methoxy magnesium (Mg (OCH3) (CH3)), methyl ethoxy magnesium (Mg (OC2H5) (CH3)), A yl-propoxy magnesium (Mg (OC3H7) (CH3)), methyl n-butoxy magnesium (Mg (OC4H9) (CH3)), methyl isobutoxy magnesium (Mg (i-0C4H9) (CH3)) , ethyl methoxy magnesium (Mg (OCH3) (C2H5)), ethyl ethoxy magnesium (Mg (OC2H5) (C2H5)), ethyl propoxy magnesium (Mg (OC3H7) (C2H5)), ethyl -n-butoxy magnesium (Mg (OC4H9) (C2H5)), ethyl isobutoxy magnesium (Mg (I-OC4H9) (C2H5)), propyl methoxy magnesium (Mg (OCH3) (C3H7)) , propyl ethoxy magnesium (Mg (OC2H5) (C3H7)), propyl propoxy magnesium (Mg (OC3H7) (C3H7)), propyl n-butoxy magnesium (Mg (OC4H9) (C3H7)), propyl isobutoxy magnesium (Mg (I-OC4H9) (C3H7)), n-butyl methoxy magnesium (Mg (OCH3) (C4H9)), n-butyl ethoxy magnesium (Mg (OC2H5) (C4H9)) , n-propoxy magnesium (Mg (OC3H7) (C4H9)), n-butyl n-butoxy magnesium (Mg (OC4H9) (C4H9)), n-butyl isobutoxy magnesium (Mg (I-OC4H9) ( C4H9)), isobutyl methoxy magnesium (Mg (OCH3) Q-C4H9)), isobutyl ethoxy magnesium (Mg (OC2H5) Q-C4H9)) 异丁基丙氧基镁(Mg(OC3H7) (i_C4H9))、异丁基正丁氧基镁(Mg(OC4H9) (I-C4H9))和异丁基异丁氧基镁(Mg(i-0C4H9) (I-C4H9))等,其中优选丁基乙氧基镁。 Isobutyl propoxy magnesium (Mg (OC3H7) (i_C4H9)), isobutyl n-butoxy magnesium (Mg (OC4H9) (I-C4H9)) and isobutyl isobutoxy magnesium (Mg (i-0C4H9) (I-C4H9)) and the like, wherein preferably butyl ethoxy magnesium.

[0105] 这些镁化合物可以单独使用一种,也可以多种混合使用,并没有特别的限制。 [0105] These magnesium compounds may be used alone, may be used a variety of mixing is not particularly limited.

[0106] 在以多种混合的形式使用时,所述镁化合物混合物中的两种镁化合物之间的摩尔比比如为0.25〜4 : 1,优选0.5〜3 : 1,更优选I〜2 : I。 [0106] When used in a variety of forms of mixing the magnesium molar ratio between the two compounds in the mixture of the magnesium compound such as 0.25~4: 1, preferably 0.5~3: 1, more preferably I~2: I.

[0107] 根据本发明,使镁化合物溶解于溶剂(不包括醇类溶剂)中,获得镁化合物溶液。 [0107] According to the present invention, the magnesium compound is dissolved in a solvent (alcoholic solvent is not included), the obtained magnesium compound solution.

[0108] 以下对获得所述镁化合物溶液的步骤进行具体的说明。 [0108] Hereinafter, the step of obtaining the magnesium compound solution will be specifically described.

[0109] 具体而言,使所述镁化合物(固体)溶解于适当的溶剂(以下有时称为用于溶解所述镁化合物的溶剂)中,从而获得所述镁化合物溶液。 [0109] Specifically, the magnesium compound (solid) was dissolved in an appropriate solvent (hereinafter sometimes referred to as the solvent for dissolving the magnesium compound), to thereby obtain a magnesium compound solution.

[0110] 作为所述溶剂,比如可以举出c6_12芳香烃、卤代c6_12芳香烃、酯和醚等溶剂。 [0110] Examples of the solvent include c6_12 such aromatic hydrocarbons, halogenated aromatic hydrocarbons c6_12, ester and ether solvents.

[0111] 作为所述(:6_12芳香烃,比如可以举出甲苯、二甲苯、三甲苯、乙苯、二乙苯。 [0111] Examples of the (: 6_12 aromatic hydrocarbons, such as include toluene, xylene, mesitylene, ethylbenzene, diethylbenzene.

[0112] 作为所述卤代C6_12芳香烃,比如可以举出氯代甲苯、氯代乙苯、溴代甲苯、溴代乙苯等。 [0112] As the halogenated C6_12 aromatic hydrocarbon, such as may include chlorinated toluene, chlorinated ethyl benzene, brominated toluene, ethylbenzene bromo.

[0113] 作为所述酯,比如可以举出甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸丁酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酸甲酯、丙酸乙酯、丙酸丁酯、丁酸丁酯等。 [0113] Examples of the ester, include for example methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl butyrate.

[0114] 作为所述醚,比如可以举出乙醚、甲乙醚、四氢呋喃等。 [0114] Examples of the ethers include for example diethyl ether, methyl ethyl ether, tetrahydrofuran and the like. [0115] 其中,优选C6_12芳香烃和四氢呋喃,最优选四氢呋喃。 [0115] Among these, aromatic hydrocarbons and C6_12 tetrahydrofuran, most preferably tetrahydrofuran.

[0116] 根据本发明一个优选的实施方式,所述溶剂优选可以同时溶解所述镁化合物(固体)和下文所述的非茂金属配体。 [0116] According to a preferred embodiment of the invention, the solvent capable of dissolving the magnesium compound simultaneously (solid) and non-metallocene ligands described below. 此时,作为所述溶剂,比如可以举出所述C6_12芳香烃、所述卤代C6_12芳香烃以及四氢呋喃等。 In this case, as the solvent, there may be mentioned for example the C6_12 aromatic hydrocarbons, aromatic hydrocarbons and the halogenated C6_12 tetrahydrofuran.

[0117] 需要指出的是,本发明在制备所述负载型非茂金属催化剂时,在任何步骤中均不使用醇类(比如乙醇等脂肪族醇、苯甲醇等芳香族醇等)。 [0117] It should be noted that the present invention is in the preparation of the supported non-metallocene catalyst, not using alcohol (such as ethanol, aliphatic alcohols, aromatic alcohols such as benzyl alcohol, etc.) in any step.

[0118] 这些溶剂可以单独使用一种,也可以以任意的比例多种混合使用。 [0118] These solvents may be used alone or more in combination at any ratio.

[0119] 为了制备所述镁化合物溶液,将所述镁化合物计量添加到所述溶剂中进行溶解即可。 [0119] To prepare a solution of said magnesium compound, the magnesium compound added to the solvent in the metering dissolved. [0120] 对所述镁化合物溶液的制备时间(即所述镁化合物的溶解时间)没有特别的限定,但一般为0. 5〜24h,优选4〜24h。 [0120] (i.e., the dissolution time of the magnesium compound) is not particularly limited to the time of preparation of the magnesium compound solution, but is typically 0. 5~24h, preferably 4~24h. 在该制备过程中,可以利用搅拌来促进所述镁化合物的溶解。 In this manufacturing process, can facilitate dissolution of the magnesium compound by stirring. 该搅拌可采用任何的形式,比如搅拌桨(转速一般为10〜1000转/分钟)等。 The stirring may take any form, such as a stirring blade (rotation speed typically of 10~1000 rpm / min) and the like. 根据需要,有时可以通过适当的加热(但最高温度必须低于所述溶剂的沸点)来促进溶解。 If necessary, to promote dissolution may sometimes be appropriate by heating (maximum temperature, but must be below the boiling point of the solvent).

[0121] 以下对所述多孔载体进行具体的说明。 [0121] Hereinafter, the porous support will be specifically described.

[0122] 根据本发明,作为所述多孔载体,比如可以举出本领域在制造负载型烯烃聚合催化剂时作为载体而常规使用的那些有机或无机多孔固体。 [0122] According to the present invention, as the porous support, such as the present art include the manufacture of a supported olefin as those conventionally used carrier and an organic or inorganic porous solid polymerization catalyst.

[0123] 具体而言,作为所述有机多孔固体,比如可以举出烯烃均聚物或共聚物、聚乙烯醇或其共聚物、环糊精、(共)聚酯、(共)聚酰胺、氯乙烯均聚物或共聚物、丙烯酸酯均聚物或共聚物、甲基丙烯酸酯均聚物或共聚物,以及苯乙烯均聚物或共聚物等,以及这些均聚物或共聚物的部分交联形式,其中优选部分交联(比如交联度至少为2%但小于100% )的苯乙烯聚合物。 [0123] Specific examples of the organic porous solid, may include for example olefin homo- or copolymers, polyvinyl alcohol or a copolymer thereof, a cyclodextrin, (co) polyesters, (co) polyamide, part of vinyl chloride homopolymers or copolymers, acrylic homopolymers or copolymers, methacrylic ester homopolymers or copolymers, and styrene homopolymer or copolymer, etc., and these homopolymers or copolymers crosslinked form, wherein preferably partially crosslinked (such as the degree of crosslinking of at least 2% but less than 100%) of a styrene polymer.

[0124] 根据本发明一个优选的实施方案,优选在所述有机多孔固体的表面上带有比如选自羟基、伯氨基、仲氨基、磺酸基、羧基、酰胺基、N-单取代的酰胺基、磺酰胺基、N-单取代的磺酰胺基、巯基、酰亚氨基和酰肼基中的任意一种或多种的活性官能团,其中优选羧基和羟基中的至少一种。 [0124] According to a preferred embodiment of the invention, preferably with such selected from hydroxyl, primary amino, secondary amino group, a sulfonic acid group, a carboxyl group, an amide group, N- mono-substituted amides at the surface of the organic porous solid group, a sulfonamide group, N- mono-substituted sulfonamide group, a mercapto group, an imido group and hydrazide any one or more reactive functional groups, wherein at least one carboxyl group and preferably hydroxyl group.

[0125] 根据本发明一个实施方案,在使用前对所述有机多孔固体进行热活化处理。 [0125] According to an embodiment of the present invention, a thermal activation treatment of the organic porous solids before use. 该热活化处理可以按照通常的方式进行,比如在减压条件下或惰性气氛下对所述有机多孔固体进行加热处理。 The thermal activation treatment may be carried out in the usual way, such as heat treatment of the organic porous solid under reduced pressure or under an inert atmosphere. 这里所说的惰性气氛是指气体中仅含有极其微量或者不含有可与所述有机多孔固体反应的组分。 Mentioned here refers to an inert gas atmosphere containing only a very small amount or not containing component reactive with said organic porous solid. 作为所述惰性气氛,比如可以举出氮气或稀有气体气氛,优选氮气气氛。 Examples of the inert atmosphere, such as nitrogen or may include a rare gas atmosphere, preferably nitrogen atmosphere. 由于有机多孔固体的耐热性差,因此该热活化过程以不破坏所述有机多孔固体本身的结构和基本组成为前提。 Since the heat resistant porous solid organic difference, so that the thermal activation process so as not to destroy the structure of the organic porous solid consisting essentially premised itself. 一般地,该热活化的温度为50〜400°C,优选100〜250°C,而热活化时间为I〜24h,优选2〜12h。 Generally, the thermal activation temperature of 50~400 ° C, preferably 100~250 ° C, and the heat activation time is I~24h, preferably 2~12h. 热活化处理后,所述有机多孔固体需要在惰性气氛下正压保存备用。 After thermal activation, the pressure required organic porous solid were stored under an inert atmosphere.

[0126] 作为所述无机多孔固体,比如可以举出元素周期表II A、IIIA、IVA或IVB族金属的难熔氧化物(比如二氧化硅(又称为氧化硅或硅胶)、氧化铝、氧化镁、氧化钛、氧化锆或氧化钍等),或者这些金属的任意难熔复合氧化物(比如氧化硅铝、氧化镁铝、氧化钛硅、氧化钛镁和氧化钛铝等),以及粘土、分子筛(比如ZSM-5和MCM-41)、云母、蒙脱土、膨润土和硅藻土等。 [0126] Examples of the porous inorganic solid, such as may include the periodic table II A, IIIA, IVA, or IVB metal refractory oxide (such as silica (also called silica or silica gel), alumina, any), or the metals magnesium, titanium oxide, zirconium oxide, thorium oxide, or a refractory composite oxide (such as silica alumina, magnesium aluminum oxide, silicon oxide, magnesium oxide and aluminum oxide, etc.), and clay , molecular sieves (such as ZSM-5 and MCM-41), mica, montmorillonite, bentonite, and diatomaceous earth. 作为所述无机多孔固体,还可以举出由气态金属卤化物或气态硅化合物通过高温水解而生成的氧化物,比如由四氯化硅高温水解得到的硅胶,或者由三氯化铝高温水解得到的氧化铝等。 Examples of the porous inorganic solid, gaseous oxides may include a metal halide or a gaseous silicon compound is generated by pyrohydrolysis, such as obtained by high-temperature hydrolysis of silicon tetrachloride, silica gel, or obtained by the flame hydrolysis of aluminum trichloride the alumina.

[0127] 作为所述无机多孔固体,优选二氧化硅、氧化铝、氧化镁、氧化硅铝、氧化镁铝、氧化钛娃、二氧化钛、分子筛和蒙脱土等,特别优选二氧化娃。 [0127] Examples of the porous inorganic solid, preferably silica, alumina, magnesia, silica alumina, magnesia aluminum, titanium baby, titania, zeolite and montmorillonite, and particularly preferably baby dioxide.

[0128] 根据本发明,适宜的二氧化硅可以通过常规方法制造,或者可以是任意的可购买的商业产品,比如可以举出Grace公司的Grace 955、Grace 948、Grace SP9-351、GraceSP9-485、Grace SP9-10046、Davsion Syloid 245 和Aerosil812,Ineos 公司的ES70、ES70X、ES70Y、ES70W、ES757、EPlOX 和EPlI,以及PQ 公司的CS-2133 和MS-3040„ [0128] According to the present invention, a suitable silica can be produced by a conventional method, or may be any available commercial products, such companies include Grace Grace 955, Grace 948, Grace SP9-351, GraceSP9-485 , Grace SP9-10046, Davsion Syloid 245 and Aerosil812, Ineos company ES70, ES70X, ES70Y, ES70W, ES757, EPlOX and EPlI, and PQ Corporation's CS-2133 and MS-3040 "

[0129] 根据本发明一个优选的实施方案,优选在所述无机多孔固体的表面上带有羟基等活性官能团。 [0129] According to a preferred embodiment of the invention, preferred reactive with hydroxyl functional groups on the surface of the inorganic porous solid.

[0130] 根据本发明,在一个实施方案中,在使用前对所述无机多孔固体进行热活化处理。 [0130] According to the present invention, in one embodiment, a thermal activation treatment of the inorganic porous solids before use. 该热活化处理可以按照通常的方式进行,比如在减压条件下或惰性气氛下对所述无机多孔固体进行加热处理。 The thermal activation treatment may be carried out in the usual way, such as by heating the treated inorganic porous solid under reduced pressure or under an inert atmosphere. 这里所说的惰性气氛是指气体中仅含有极其微量或者不含有可与所述无机多孔固体反应的组分。 Mentioned here refers to an inert gas atmosphere containing only a very small amount or not containing component reactive with the inorganic porous solids. 作为所述惰性气氛,比如可以举出氮气或稀有气体气氛,优选氮气气氛。 Examples of the inert atmosphere, such as nitrogen or may include a rare gas atmosphere, preferably nitrogen atmosphere. 一般地,该热活化的温度为200-800°C,优选400〜700°C,最优选400〜650°C,加热时间比如为0. 5〜24h,优选2〜12h,最优选4〜8h。 Generally, the heat activation temperature of 200-800 ° C, preferably 400~700 ° C, most preferably 400~650 ° C, the heating time such as 0. 5~24h, preferably 2~12h, most preferably 4~8h . 热活化处理后,所述无机多孔固体需要在惰性气氛下正压保存备用。 After thermal activation, said inorganic porous solids requires a positive pressure under an inert atmosphere for use.

[0131] 根据本发明,对所述多孔载体的表面积没有特别的限定,但一般为10〜IOOOm2/g (BET法测定),优选100〜600m2/g ;该多孔载体的孔容积(氮吸附法测定)一般为0. I〜4cm3/g,优选0. 2〜2cm3/g,而其平均粒径(激光粒度仪测定)优选I〜500 um,更优选I〜100 u m0 [0131] According to the present invention is not particularly limited surface area of ​​the porous support, but is generally 10~IOOOm2 (BET method) / g, preferably 100~600m2 / g; pore volume of the porous support (nitrogen adsorption method assay) is generally 0. I~4cm3 / g, preferably 0. 2~2cm3 / g, and the average particle diameter (laser particle sizer) which is preferably I~500 um, more preferably I~100 u m0

[0132] 根据本发明,所述多孔载体可以是任意的形态,比如微粉末、粒状、球状、聚集体或其它形式。 [0132] According to the invention, the porous support may be any shape, such as a fine powder, pellets, spheres, aggregates or other form.

[0133] 通过使所述任选经过热活化的多孔载体与所述镁化合物溶液接触(混合),由此 [0133] optionally by passing through the porous support and the heat-activated magnesium compound solution is contacted (mixed), thereby

获得第一混合衆液。 Obtaining a first mixing all the liquid.

[0134] 根据本发明,所述多孔载体与所述镁化合物溶液的混合过程可以采用通常的方法进行,没有特别的限定。 [0134] According to the invention, the porous support with the magnesium compound solution mixing method can be employed generally carried out is not particularly limited. 比如可以举出,在常温至所述镁化合物溶液的制备温度下,向所述镁化合物溶液中计量加入所述多孔载体,或者向所述多孔载体中计量加入所述镁化合物溶液,混合0. I〜8h,优选0. 5〜4h,最优I〜2h(必要时借助搅拌)即可。 For example there may be mentioned, was prepared at room temperature to the lower temperature of the magnesium compound solution, the porous support is added to the magnesium compound solution metered or metered to the porous carrier was added a solution of the compound, the magnesium mixing 0. I~8h, preferably 0. 5~4h, optimal I~2h (stirring means, if necessary) to.

[0135] 根据本发明,作为所述多孔载体的用量,使得所述镁化合物(以所述镁化合物溶液中含有的镁化合物固体计)与所述多孔载体的质量比达到I : 0.1-20,优选I : 0.5-10,更优选I : 1-5。 [0135] According to the present invention, as an amount of the porous support, such that said magnesium compound (magnesium compound to the magnesium compound solids contained in the solution) and the mass ratio of the porous support I: 0.1-20, preferred I: 0.5-10, more preferably I: 1-5.

[0136] 此时,所获得的第一混合浆液是一种浆状的体系。 [0136] At this time, the first mixed slurry obtained is a slurry system. 虽然并不必需,但为了确保体系的均勻性,该混合衆液在制备后优选进行一定时间(2〜48h,优选4〜24h,最优选6〜18h)的密闭静置。 While not essential, but in order to ensure homogeneity of the system, all of the mixed solution for a certain time (2~48h, preferably 4~24h, most preferably 6~18h) preferably sealed after preparation was allowed to stand.

[0137] 根据本发明,术语“非茂金属配合物”是一种相对于茂金属催化剂而言的单中心烯烃聚合催化剂,结构中不含有茂环、芴环或茚环等环戊二烯基或其衍生物,并且在与助催化剂(比如下文所述的那些)组合时能够显示出烯烃聚合催化活性的金属有机化合物(因此所述非茂金属配合物有时也被称为非茂金属烯烃聚合性配合物)。 [0137] According to the present invention, the term "non-metallocene complex" with respect to a single site metallocene catalyst in terms of olefin polymerization catalyst structure containing no cyclopentadienyl ring, fluorene ring or indenyl cyclopentadienyl ring or a derivative thereof, and is sometimes called non-metallocene with a cocatalyst in the polymerization of olefins (such as those described hereinafter) combination can exhibit catalytic activity for olefin polymerization organometallic compound (and therefore the non-metallocene complex of the complex). 该化合物包含中心金属原子和至少一个与所述中心金属原子以配位键结合的多齿配体(优选三齿配体或更多齿配体),而术语“非茂金属配体”即为前述的多齿配体。 The compound comprises a central metal atom and at least one coordination bond with the central metal atom polydentate ligand (preferably more tridentate ligand or a polydentate ligand), while the term "non-metallocene ligand" shall the multidentate ligand.

[0138] 根据本发明,所述非茂金属配体选自具有如下化学结构式的化合物: [0138] According to the invention, the nonmetallocene ligand is a compound of the following chemical structural formula selected from:

[0139] [0139]

Figure CN102964479AD00221

[0140] 根据本发明,该化合物中的基团A、D和E (配位用基团)通过其所含的配位用原子(比如N、O、S、Se和P等杂原子)与本发明中作为化学处理剂使用的IVB族金属化合物所含的IVB族金属原子发生配位反应而形成配位键,由此形成以该IVB族金属原子为中心金属原子的配合物(即本发明所述的非茂金属配合物)。 [0140] According to the invention, in the compound group A, D and E (with a ligand group) through which contain atoms with a ligand (such as N, O, S, Se and P heteroatom) and to form a coordination bond complexing reaction of the present invention as a group IVB metal atom of group IVB metal compound contained in the treatment agent used, to thereby form the group IVB metal atom as a central metal atom of the complex (i.e., of the present invention the non-metallocene complex).

[0141] 在一个更为具体的实施方案中,所述非茂金属配体选自具有如下化学结构式的化合物(A)和化合物⑶: [0141] In a more specific embodiment, the nonmetallocene ligand is selected from compounds of the following chemical structure formula (A) and compound ⑶:

[0142] [0142]

Figure CN102964479AD00222

[0143] 在一个更为具体的实施方案中,所述非茂金属配体选自具有如下化学结构式的化合物(AI)至化合物(A-4)和化合物(BI)至化合物(B-4): [0143] In a more specific embodiment, the nonmetallocene ligand is selected from compounds of the following chemical structure formula (AI) to the compound to a compound having a (A-4) and Compound (BI) (B-4) :

[0144] [0144]

Figure CN102964479AD00231

[0145](A [0145] (A

Figure CN102964479AD00241
Figure CN102964479AD00242

[0146] 在以上所有化学结构式中, [0146] In all the above chemical structural formula,

[0147] q为0或I; [0147] q is 0 or I;

[0148] d为0或I; [0148] d is 0 or I;

[0149] A 选自氧原子、硫原子、硒原子、、R22 -NR23R24, -N(O)R25R26,VPR27 -PR28R29、-P(0) [0149] A is selected from oxygen atom, a sulfur atom, a selenium atom ,, R22 -NR23R24, -N (O) R25R26, VPR27 -PR28R29, -P (0)

R3ciOR31、砜基、亚砜基或-Se(O)R39,其中N、O、S、Se和P各自为配位用原子; R3ciOR31, a sulfone group, a sulfoxide group or -Se (O) R39, wherein N, O, S, Se and P are each coordinated with atom;

[0150] B选自氮原子、含氮基团、含磷基团或C1-C3tl烃基; [0150] B is selected from a nitrogen atom, a nitrogen group, a phosphorus-containing hydrocarbyl group or a C1-C3tl;

[0151] D选自氮原子、氧原子、硫原子、硒原子、磷原子、含氮基团、含磷基团、C1-C3tl烃基、砜基、亚砜基 [0151] D is selected from a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a nitrogen-containing group, phosphorus-containing groups, C1-C3tl hydrocarbon group, a sulfone group, a sulfoxide group

Figure CN102964479AD00251

或-P(0)R32(OR33),其中N、O、S、Se 和P 各自为配位用原子; Or -P (0) R32 (OR33), wherein N, O, S, Se and P are each coordinated with atom;

[0152] E选自含氮基团、含氧基团、含硫基团、含硒基团、含磷基团或氰基(-CN),其中N、O、S、Se和P各自为配位用原子; [0152] E is selected from nitrogen-containing group, oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group or a cyano (-CN), where N, O, S, Se and P are each coordinating with the atom;

[0153] F选自氮原子、含氮基团、含氧基团、含硫基团、含硒基团或含磷基团,其中N、O、S、Se和P各自为配位用原子; [0153] F is selected from a nitrogen atom, a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group or a phosphorus-containing group, wherein N, O, S, Se and P are each used as ligand atoms ;

[0154] G选自C1-C3tl烃基、取代的C1-C3tl烃基或惰性功能性基团; [0154] G is selected from C1-C3tl hydrocarbyl, substituted C1-C3tl hydrocarbyl or an inert functional group;

[0155] Y选自含氮基团、含氧基团、含硫基团、含硒基团或含磷基团,其中N、O、S、Se和P 各自为配位用原子; [0155] Y is selected from nitrogen-containing group, oxygen-containing group, a sulfur-containing group, a selenium-containing group or a phosphorus-containing group, wherein N, O, S, Se and P are each coordinated with atom;

[0156] Z选自含氮基团、含氧基团、含硫基团、含硒基团、含磷基团或氰基(-CN),比如可以举出-NR23R24' -N(O)R25R26, -PR28R29' -P(O)R30R31' -0R34、-SR35、-S (0)R36、-SeR38 或-Se (0)R39,其中N、O、S、Se和P各自为配位用原子; [0156] Z is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group or a cyano (-CN), for example may include -NR23R24 '-N (O) R25R26, -PR28R29 '-P (O) R30R31' -0R34, -SR35, -S (0) R36, -SeR38 or -Se (0) R39, wherein N, O, S, Se and P are each coordinated with atom;

[0157]—代表单键或双键; [0157] - represents a single or a double bond;

[0158]-代表共价键或离子键。 [0158] - represents a covalent bond or an ionic bond.

[0159] R1至R4、R6至R36、R38和R39各自独立地选自氢、C1-C3tl烃基、取代的C1-C3tl烃基(其中优选齒代烃基,比如-CH2Cl和-CH2CH2Cl)或惰性功能性基团。 [0159] R1 to R4, R6 to R36, R38 and R39 are each independently selected from hydrogen, C1-C3tl hydrocarbyl, substituted C1-C3tl hydrocarbon group (preferably wherein the teeth hydrocarbon group, such as -CH2Cl and -CH2CH2Cl) or an inert functional group. 上述基团彼此间可以相同也可以不同,其中相邻基团比如R1与R2,R6与R7,R7与R8,R8与R9,R13与R14, R14与R15, R15与R16, R18与R19,R19与R20,R20与R21, R23与R24,或者R25与R26等可以彼此结合在一起成键或成环,优选形成芳香族环,比如未取代的苯环或被1-4 AC1-C3tl烃基、取代的C1-C3tl烃基(其中优选齒代烃基,比如-CH2Cl和-CH2CH2Cl)或惰性功能性基团取代的苯环。 Among the above groups may be the same or different, such as where adjacent radicals R1 and R2, R6 and R7, R7 and R8, R8 and R9, R13 and R14, R14 and R15, R15 and R16, R18 and R19, R19 and R20, R20 and R21, R23 and R24, or R25 may be bonded together to form a ring or a bond, preferably form an aromatic ring, such an unsubstituted benzene ring or a hydrocarbon group with 1-4 AC1-C3tl R26 equal to each other, substituted the C1-C3tl hydrocarbon group (preferably wherein the teeth hydrocarbon group, such as -CH2Cl and -CH2CH2Cl) or an inert functional group-substituted benzene ring.

[0160] R5选自氮上孤对电子、氢、C1-C3tl烃基、取代的C1-C3tl烃基、含氧基团、含硫基团、含氮基团、含硒基团或含磷基团。 [0160] R5 is selected from the nitrogen lone pair of electrons, hydrogen, C1-C3tl hydrocarbyl, substituted C1-C3tl hydrocarbon, oxygen-containing group, a sulfur group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group . 当R5为含氧基团、含硫基团、含氮基团、含硒基团或含磷基团时,R5中的N、O、S、P和Se可以作为配位用原子与所述中心IVB族金属原子进行配位。 When R5 is an oxygen-containing group, a sulfur group, a nitrogen-containing group, a selenium-containing group, or when the phosphorus-containing groups, R5 is N, O, S, P and Se atoms may be used as the ligand Center group IVB metal atom is coordinated.

[0161] 根据本发明,在前述所有的化学结构式中,根据具体情况,任何相邻的两个或多个基团,比如R21与基团Z,或者R13与基团Y,可以彼此结合在一起成环,优选形成包含来自于所述基团Z或Y的杂原子的C6-C3tl芳香族杂环,比如吡啶环等,其中所述芳香族杂环任选被I个或多个选自C1-C3tl烃基、取代的C1-C3tl烃基和惰性功能性基团的取代基取代。 [0161] According to the present invention, in all of the preceding chemical formulas, depending on the circumstances, any adjacent two or more groups, such as R21 and the group Z, a group or R13 and Y, can be combined with each other form a ring, preferably an aromatic C6-C3tl formed from a heterocycle comprising hetero atoms in the group Z or Y, such as pyridine ring, wherein the aromatic heterocyclic ring is optionally one or more substituents selected from C1 I -C3tl hydrocarbyl, substituted C1-C3tl substituted hydrocarbyl and an inert functional group.

[0162] 在本发明的上下文中, [0162] In the context of the present invention,

[0163] 所述卤素选自F、Cl、Br或I。 [0163] The halogen is selected from F, Cl, Br or I. 所述含氮基团选自 The nitrogen-containing groups selected from

Figure CN102964479AD00252

-NR23R24、-T-NR23R24或-N (0) -NR23R24, -T-NR23R24 or -N (0)

R25R26。 R25R26. 所述含磷基团选自 The phosphorus-containing group is selected from

Figure CN102964479AD00253

-PR28R29、-P (0) R30R31或-P (0) R32 (0R33)。 -PR28R29, -P (0) R30R31, or -P (0) R32 (0R33). 所述含氧基团选自 The oxygen-containing groups selected from

羟基、-OR34和-T-OR34。 Hydroxy, -OR34 and -T-OR34. 所述含硫基团选自-SR35、-T-SR35、-S (0) R36或-T-SO2R'所述含硒基团选自-SeR38、-T-SeR38, -Se (0) R39或-T-Se (0) R390所述基团T选自C1-C3tl烃基、取代的C1-C30烃基或惰性功能性基团。 The sulfur-containing group is selected from -SR35, -T-SR35, -S (0) R36 or -T-SO2R 'is selected from the group selenium -SeR38, -T-SeR38, -Se (0) R39 or -T-Se (0) T is selected from the group R390 C1-C3tl hydrocarbyl, substituted C1-C30 hydrocarbyl or an inert functional group. 所述R37选自氢、C1-C3tl烃基、取代的C1-C3tl烃基或惰性功能性基团。 The R37 is selected from hydrogen, C1-C3tl hydrocarbyl, substituted C1-C3tl hydrocarbyl or an inert functional group.

[0164] 在本发明的上下文中,所述C1-C3tl烃基选自C1-C3tl烷基(优选C1-C6烷基,比如异丁基)X7-C5tl烷芳基(比如甲苯基、二甲苯基、二异丁基苯基等)X7-C5tl芳烷基(比如苄基)、C3-C30环状烷基、C2-C30烯基、C2-C3tl炔基、C6-C3tl芳基(比如苯基、萘基、蒽基等)、C8-C3tl稠环基或C4-C3tl杂环基,其中所述杂环基含有1-3个选自氮原子、氧原子或硫原子的杂原子,比如吡啶基、吡咯基、呋喃基或噻吩基等。 [0164] In the context of the present invention, the C1-C3tl hydrocarbon group selected from C1-C3tl alkyl (preferably C1-C6 alkyl, such as isobutyl) X7-C5tl alkaryl (such as tolyl, xylyl , diisobutyl phenyl) X7-C5tl aralkyl (such as benzyl), C3-C30 cyclic alkyl, C2-C30 alkenyl, C2-C3tl alkynyl, C6-C3tl aryl group (such as phenyl , naphthyl, anthryl, etc.), C8-C3tl fused ring group or a C4-C3tl heterocyclyl, wherein the heterocyclyl contains 1-3 heteroatoms selected from nitrogen atom, oxygen atom or sulfur atom, such as pyridine group, pyrrolyl group, furyl group or thienyl group.

[0165] 根据本发明,在本发明的上下文中,根据与其所结合的相关基团的具体情况,所述C1-C30烃基有时指的是C1-C3tl烃二基(二价基团,或者称为C1-C3tl亚烃基)或C1-C3tl烃三基(三价基团),这对于本领域技术人员而言是显然的。 [0165] According to the present invention, in the context of the present invention, depending on the individual group to which it is bound, the C1-C30 hydrocarbon group is sometimes referred to two C1-C3tl hydrocarbon group (a divalent group, or said is C1-C3tl alkylene) or C1-C3tl hydrocarbon group three (trivalent group), it will be apparent to those skilled in the art.

[0166] 在本发明的上下文中,所述取代的C1-C3tl烃基指的是带有一个或多个惰性取代基的前述C1-C3tl烃基。 [0166] In the context of the present invention, the substituted C1-C3tl hydrocarbon group means a hydrocarbon group having the C1-C3tl one or more inert substituents. 所谓惰性取代基,指的是这些取代基对前述配位用基团(指的是前述基团A、D、E、F、Y和Z,或者还任选包括R5)与中心金属原子(前述IVB族金属原子)的配位过程没有实质性的干扰;换句话说,受本发明配体的化学结构所限,这些取代基没有能力或没有机会(比如受到位阻等的影响)与所述IVB族金属原子发生配位反应而形成配位键。 The so-called inert substituents, means that these substituents on the ligand with a group (refer to the group A, D, E, F, Y and Z, or optionally further comprising R5) with a central metal atom (the group IVB metal atom) coordination processes without substantial interference; in other words, by the chemical structure of the ligand according to the present invention is limited, the substituent is not capable of or opportunity (such as affected by steric hindrance or the like) and the to form a bond with the group IVB metal atom is coordinated reaction. 一般而言,所述惰性取代基选自前述的齒素或C1-C3tl烷基(优选C1-C6烷基,比如异丁基)。 Generally, the inert substituents selected from the teeth biotin or C1-C3tl alkyl (preferably C1-C6 alkyl, such as isobutyl).

[0167] 在本发明的上下文中,所述惰性功能性基团不包括前述的C1-C3tl烃基和前述的取代的C1-C3tl烃基。 [0167] In the context of this invention, the inert functional group substituted hydrocarbon group of C1-C3tl of the hydrocarbon group and the C1-C3tl is not included. 作为所述惰性功能性基团,比如可以举出选自前述卤素、前述含氧基团、前述含氮基团、含硅基团、含锗基团、前述含硫基团、含锡基团、C1-Cltl酯基和硝基(-NO2)的至少一种等。 Examples of the inert functional group, such as an element selected from the halo, the oxygen-containing group, the nitrogen-containing group, a silicon-containing group, a germanium-containing group, the sulfur-containing group, a tin-containing group , C1-Cltl ester group and a nitro group (-NO2) at least one other.

[0168] 在本发明的上下文中,受本发明配体的化学结构所限,所述惰性功能性基团具有以下特点: [0168] In the context of the present invention, by the chemical structure of the ligand according to the present invention is limited, the inert functional group has the following characteristics:

[0169] (I)不干扰所述基团A、D、E、F、Y或Z与所述IVB族金属原子的配位过程,和 [0169] (I) do not interfere with the groups A, ligand D, E, F, Y or Z of the Group IVB metal atom process, and

[0170] (2)与所述IVB族金属原子的配位能力低于所述A、D、E、F、Y和Z基团,并且不置换这些基团与所述IVB族金属原子的已有配位。 [0170] (2) and the coordinating ability of the Group IVB metal atoms is less than the A, D, E, F, Y and Z groups, and these groups are not substituted with the Group IVB metal atom there coordinated.

[0171] 在本发明的上下文中,所述含硅基团选自-SiR42R43R44或-T-SiR45 ;所述含锗基团选自-GeR46R47R48 或-T-GeR49 ;所述含锡基团选自-SnR5°R51R52、-T-SnR53 或-T-Sn (0) R54 ;并且所述R42至R54各自独立地选自氢、前述的C1-C3tl烃基、前述的取代的C1-C3tl烃基或前述的惰性功能性基团,上述基团彼此间可以相同也可以不同,其中相邻基团可以彼此结合在一起成键或成环。 [0171] In the context of the present invention, the silicon-containing group selected -SiR42R43R44 or -T-SiR45; the germanium-containing group selected -GeR46R47R48 or -T-GeR49; tin-containing group selected from -SnR5 ° R51R52, -T-SnR53 or -T-Sn (0) R54; and wherein R42 to R54 are each independently selected from hydrogen, C1-C3tl aforementioned hydrocarbon group, the substituted hydrocarbyl or C1-C3tl foregoing an inert functional group, among the above groups may be the same or different from each other, wherein the adjacent groups may be bonded to each other to form a ring or a bond. 其中基团T的定义同前。 Wherein the group T is defined as before.

[0172] 作为所述非茂金属配体,比如可以举出如下化合物: [0172] As the nonmetallocene ligand, for example the following compounds may be mentioned:

[0173] [0173]

[0174] [0174]

Figure CN102964479AD00261
Figure CN102964479AD00271
Figure CN102964479AD00281

[0176] [0176]

Figure CN102964479AD00291

[0177] 所述非茂金属配体优选选自如下化合物: [0177] The nonmetallocene ligand is preferably selected from the following compounds:

Figure CN102964479AD00292
Figure CN102964479AD00301

[0180] 所述非茂金属配体进一步优选选自如下化合物: [0180] The nonmetallocene ligand is more preferably selected from the following compounds:

[0181] [0181]

Figure CN102964479AD00302

[0182] [0182]

Figure CN102964479AD00311

[0183] 所述非茂金属配体更优选选自如下化合物: [0183] The nonmetallocene ligand is more preferably selected from the following compounds:

[0184] [0184]

Figure CN102964479AD00312

[0185] 这些非茂金属配体可以单独使用一种,或者以任意的比例组合使用多种。 [0185] These non-metallocene ligands may be used alone or in any combination using a variety of proportions.

[0186] 根据本发明,所述非茂金属配体并不是本领域中作为电子给体化合物通常使用的二醚化合物。 [0186] According to the invention, the nonmetallocene ligand is not present art diether compound as the electron donor compound is generally used.

[0187] 所述非茂金属配体可以按照本领域技术人员已知的任何方法进行制造。 The [0187] nonmetallocene ligands may be produced according to any method known to the skilled person. 关于其制造方法的具体内容,比如可参见W003/010207以及中国专利ZL01126323. 7和ZL02110844. 7等,本说明书就此引入这些文献的全文作为参考。 Specific details about the manufacturing process, such as can be found in W003 / 010207 and the like China Patent ZL01126323. 7 and ZL02110844. 7, the full text of the specification of these documents thus incorporated by reference.

[0188] 根据本发明,为了计量和操作方便,所述非茂金属配体在必要时以溶液的形式使用的。 [0188] According to the present invention, to measure and easy to operate, the nonmetallocene ligand is used when necessary in the form of a solution.

[0189] 在制备所述非茂金属配体的溶液时,对此时所用的溶剂没有特别的限定,只要可以溶解所述非茂金属配体即可。 [0189] When the non-metallocene ligand solution prepared is not particularly limited, the solvent used in this case, as long as can dissolve the nonmetallocene ligand to. 作为所述溶剂,比如可以与所述用于溶解所述镁化合物的溶剂相同的溶剂等。 Examples of the solvent, the same solvents and the like such as the magnesium compound may be dissolved for the. 其中,优选C6_12芳香烃和四氢呋喃。 Wherein, preferably tetrahydrofuran, and aromatic hydrocarbons C6_12.

[0190] 这些溶剂可以单独使用一种,或者以任意的比例组合使用多种。 [0190] These solvents may be used alone or in any combination using a variety of proportions.

[0191] 在溶解所述非茂金属配体时,可以根据需要使用搅拌(该搅拌的转速一般为10〜500转/分钟)。 [0191] In dissolving the nonmetallocene ligand may stirring (the stirring speed is generally 10~500 revolutions / min) used as necessary.

[0192] 根据本发明,所述非茂金属配体相对于所述溶剂的比例一般为0. 02〜0. 30克/晕升,优选0. 05〜0. 15克/晕升,但有时并不限于此。 [0192] According to the present invention, the ratio of the nonmetallocene ligand to the solvent is generally 0. 02~0. 30 g / liter halo, preferably 0. 05~0. 15 g / l Halo, but sometimes It is not limited to this.

[0193] 根据本发明,使所述非茂金属配体(或其溶液)与所述第一混合浆液接触,即可获得第二混合浆液。 [0193] According to the present invention, the nonmetallocene ligand (or a solution) in contact with said first mixing a slurry, mixing the slurry to obtain a second.

[0194] 在制造所述第二混合浆液时,对所述第一混合浆液与所述非茂金属配体的接触方式没有特别的限定,比如可以举出向所述第一混合浆液中直接计量添加所述非茂金属配体的方式,或者将所述非茂金属配体按照前述预先配制成溶液,然后向所述第一混合浆液中计量添加该配体溶液的方式等。 [0194] In the manufacture of the second slurry mixing is not particularly limited to the first embodiment in contact with the non-metallocene slurry mixing ligands, include such metering directly to the first mixed slurry adding the non-metallocene ligand manner, or the nonmetallocene ligand according to the pre-formulated as a solution, and then added to the ligand solution manner to the first mixing slurry metering.

[0195] 另外,为了制造所述第二混合浆液,比如可以在常温至低于所使用的任何溶剂的沸点的温度下,使所述第一混合浆液与所述非茂金属配体的接触反应进行0. I〜8h,优选0. 5〜4h,最优I〜2h(必要时借助搅拌)即可。 At a temperature of the boiling point [0195] Further, in order to manufacture the second mixing slurry such as to be below any solvent used at normal temperature, contacting the reaction mixture of the first slurry with the nonmetallocene ligand for 0. I~8h, preferably 0. 5~4h, optimal I~2h (stirring means, if necessary) to.

[0196] 此时,所获得的混合浆液是一种浆状的体系。 [0196] In this case, the obtained mixed slurry is a slurry system. 虽然并不必需,但为了确保体系的均勻性,该混合衆液在制备后优选进行一定时间(2〜48h,优选4〜24h,最优选6〜18h)的 While not essential, but in order to ensure homogeneity of the system, which after mixing all liquid is preferably prepared in a predetermined time (2~48h, preferably 4~24h, most preferably 6~18h) of

密闭静置。 Closed standing.

[0197] 通过对所述第二混合浆液直接干燥,可以获得一种流动性良好的固体产物,即修饰复合载体。 [0197] achieved by a good flowability of the second solid product is directly mixed slurry was dried, can be obtained, i.e., a modified composite carrier.

[0198] 此时,所述直接干燥可以采用常规方法进行,比如惰性气体气氛下干燥、真空气氛下干燥或者真空气氛下加热干燥等,其中优选真空气氛下加热干燥。 [0198] In this case, the direct drying may be carried out by conventional methods, such as drying under an inert gas atmosphere, a vacuum atmosphere drying or drying by heating under a vacuum atmosphere, preferably under a vacuum atmosphere wherein the heat drying. 干燥温度一般为30〜160°C,优选60〜130°C,干燥时间一般为2〜24h,但有时并不限于此。 The drying temperature is generally 30~160 ° C, preferably 60~130 ° C, the drying time is generally 2~24h, but sometimes is not limited thereto.

[0199] 以下对所述化学处理剂进行具体的说明。 [0199] Here will be specifically described for the chemical treatment agent. · ·

[0200] 根据本发明,以IVB族金属化合物作为所述化学处理剂。 [0200] According to the present invention, the Group IVB metal compound is used as the chemical treatment agent.

[0201] 作为所述IVB族金属化合物,比如可以举出选自IVB族金属卤化物、IVB族金属烷基化合物、IVB族金属烷氧基化合物、IVB族金属烷基齒化物和IVB族金属烷氧基齒化物的至少一种。 [0201] Examples of the Group IVB metal compound, such as an element selected from Group IVB metal halide, a Group IVB metal alkyl compound, a Group IVB metal alkoxy compound, a Group IVB metal alkyl compound and teeth IVB metal alkoxy alkoxy compound of at least one tooth.

[0202] 作为所述IVB族金属卤化物、所述IVB族金属烷基化合物、所述IVB族金属烷氧基化合物、所述IVB族金属烷基卤化物和所述IVB族金属烷氧基卤化物,比如可以举出如下通式(IV)结构的化合物: [0202] Examples of the Group IVB metal halide, a Group IVB metal alkyl compound, a Group IVB metal alkoxy compound, a Group IVB metal alkyl halide and the Group IVB metal alkoxy halide thereof, may include for example compounds of the following formula (IV):

[0203] M(OR1)mXnR24-^n (IV) [0203] M (OR1) mXnR24- ^ n (IV)

[0204]其中: [0204] wherein:

[0205] m 为0、1、2、3 或4; [0205] m is 3 or 4;

[0206] n 为0、1、2、3 或4; [0206] n is 0,1,2,3 or 4;

[0207] M为元素周期表中IVB族金属,比如钛、锆和铪等; [0207] M is a Group IVB metal in the periodic table, such as titanium, zirconium and hafnium;

[0208] X为卤素,比如F、Cl、Br和I等;并且 [0208] X is halogen, such as F, Cl, Br and I and the like; and

[0209] R1和R2各自独立地选自C1,烧基,比如甲基、乙基、丙基、正丁基、异丁基等,R1和R2可以相同,也可以不同。 [0209] R1 and R2 are each independently selected from C1, burn group, such as methyl, ethyl, propyl, n-butyl, isobutyl, R1, and R2 may be the same or different.

[0210] 具体而言,作为所述IVB族金属卤化物,比如可以举出四氟化钛(TiF4)、四氯化钛(TiCl4)、四溴化钛(TiBr4)、四碘化钛(TiI4); [0210] Specifically, as the Group IVB metal halide, such as may include titanium tetrafluoride (TiF4), titanium (of TiCl4) tetrachloride, titanium tetrabromide (TiBr4), of titanium iodide (TiI4 );

[0211] 四氟化锆(ZrF4)、四氯化锆(ZrCl4)、四溴化锆(ZrBr4)、四碘化锆(ZrI4); [0211] zirconium tetrafluoride (ZrF4), zirconium tetrachloride (ZrCl4), zirconium tetrabromide (ZrBr4), zirconium tetraiodide (ZrI4);

[0212] 四氟化铪(HfF4)、四氯化铪(HfCl4)、四溴化铪(HfBr4)、四碘化铪(HfI4)。 [0212] hafnium tetrafluoride (HfF4), hafnium (HfCl4) tetrachloride, hafnium bromide (HfBr4), hafnium tetraiodide (HfI4).

[0213] 作为所述IVB族金属烷基化合物,比如可以举出四甲基钛(Ti (CH3)4)、四乙基钛(Ti (CH3CH2) 4)、四异丁基钛(Ti(i-C4H9)4)、四正丁基钛(Ti (C4H9)4)、三乙基甲基钛(Ti (CH3)(CH3CH2) 3)、二乙基二甲基钛(Ti (CH3) 2 (CH3CH2) 2)、三甲基乙基钛(Ti (CH3) 3 (CH3CH2))、三异丁基甲基钛(Ti(CH3) (i_C4H9)3)、二异丁基二甲基钛(Ti (CH3)2 (i-C4H9)2)、三甲基异丁基钛(Ti (CH3)3(I-C4H9))、三异丁基乙基钛(Ti (CH3CH2) (I-C4H9)3)、二异丁基二乙基钛(Ti (CH3CH2)2(I-C4H9)2)、三乙基异丁基钛(Ti (CH3CH2)3Q-C4H9))、三正丁基甲基钛(Ti (CH3)(C4H9) 3)、二正丁基二甲基钛(Ti (CH3) 2 (C4H9) 2)、三甲基正丁基钛(Ti (CH3) 3 (C4H9))、三正丁基甲基钛(Ti(CH3CH2) (C4H9)3)、二正丁基二乙基钛(Ti (CH3CH2)2(C4H9)2)'三乙基正丁基钛(Ti(CH3CH2)3(C4H9))等; [0213] Examples of the Group IVB metal alkyl compounds, such as tetramethyl include titanium (Ti (CH3) 4), tetraethyl titanium (Ti (CH3CH2) 4), tetraisobutyl titanium (Ti (i -C4H9) 4), tetra-n-butyl titanium (Ti (C4H9) 4), triethylmethyl titanium (Ti (CH3) (CH3CH2) 3), diethyl methyl titanium (Ti (CH3) 2 ( CH3CH2) 2), trimethylethyl titanium (Ti (CH3) 3 (CH3CH2)), triisobutyl methyl titanium (Ti (CH3) (i_C4H9) 3), di-iso-butyl-dimethyl titanium (Ti (CH3 ) 2 (i-C4H9) 2), trimethyl butyl titanium (Ti (CH3) 3 (I-C4H9)), ethyl triisobutyl titanium (Ti (CH3CH2) (I-C4H9) 3), diisobutyl diethyl titanium (Ti (CH3CH2) 2 (I-C4H9) 2), triethyl-butyl titanium (Ti (CH3CH2) 3Q-C4H9)), tri-n-butylmethyl titanium (Ti (CH3) (C4H9) 3), di-n-butyldimethyl titanium (Ti (CH3) 2 (C4H9) 2), trimethyl n-butyl titanium (Ti (CH3) 3 (C4H9)), tri-n-butylmethyl titanium ( Ti (CH3CH2) (C4H9) 3), di-n-diethyl titanium (Ti (CH3CH2) 2 (C4H9) 2) 'triethyl n-butyl titanium (Ti (CH3CH2) 3 (C4H9)) and the like;

[0214]四甲基锆(Zr (CH3) 4)、四乙基锆(Zr (CH3CH2) 4)、四异丁基锆(Zr (I-C4H9) 4)、四正丁基锆(Zr (C4H9) 4)、 三乙基甲基锆(Zr (CH3) (CH3CH2) 3)、二乙基二甲基锆(Zr (CH3) 2 (CH3CH2) 2)、三甲基乙基错(Zr (CH3) 3 (CH3CH2))、三异丁基甲基错(Zr (CH3) (I-C4H9) 3)、二异丁基二甲基错(Zr (CH3) 2 (I-C4H9) 2)、三甲基异丁基锆(Zr (CH3) 3 (I-C4H9))、三异丁基乙基锆(Zr(CH3CH2) (I-C4H9) 3)、二异丁基二乙基锆(Zr(CH3CH2)2Q-C4H9)2)、三乙基异丁基锆(Zr (CH3CH2) 3 (i-C4H9))、三正丁基甲基锆(Zr (CH3) (C4H9) 3)、二正丁基二甲基锆(Zr (CH3) 2 (C4H9) 2)、三甲基正丁基错(Zr (CH3) 3 (C4H9))、三正丁基甲基锆(Zr (CH3CH2)(C4H9) 3)、二正丁基二乙基锆(Zr (CH3CH2)2 (C4H9) 2)、三乙基正丁基锆(Zr (CH3CH2) 3 (C4H9))等; [0214] tetramethyl zirconium (Zr (CH3) 4), tetraethyl zirconium (Zr (CH3CH2) 4), tetraisobutyl zirconium (Zr (I-C4H9) 4), tetra-n-butyl zirconium (Zr ( C4H9) 4), triethylmethyl zirconium (Zr (CH3) (CH3CH2) 3), diethyl methyl zirconium (Zr (CH3) 2 (CH3CH2) 2), trimethylethyl wrong (Zr ( CH3) 3 (CH3CH2)), triisobutyl methyl wrong (Zr (CH3) (I-C4H9) 3), di-iso-butyl-dimethyl-wrong (Zr (CH3) 2 (I-C4H9) 2), three isobutyl zirconium (Zr (CH3) 3 (I-C4H9)), tri-iso-butyl ethyl zirconium (Zr (CH3CH2) (I-C4H9) 3), diisobutyl ethyl zirconium (Zr (CH3CH2 ) 2Q-C4H9) 2), triethyl-butyl zirconium (Zr (CH3CH2) 3 (i-C4H9)), tri-n-butylmethyl zirconium (Zr (CH3) (C4H9) 3), di-n-dimethoxy yl zirconium (Zr (CH3) 2 (C4H9) 2), trimethyl n-butyl wrong (Zr (CH3) 3 (C4H9)), tri-n-butylmethyl zirconium (Zr (CH3CH2) (C4H9) 3), di-n diethyl butyl zirconium (Zr (CH3CH2) 2 (C4H9) 2), triethyl n-butyl zirconium (Zr (CH3CH2) 3 (C4H9)) and the like;

[0215]四甲基铪(Hf (CH3) 4)、四乙基铪(Hf (CH3CH2) 4)、四异丁基铪(Hf (I-C4H9) 4)、四正丁基铪(Hf(C4H9)4)、三乙基甲基铪(Hf(CH3) (CH3CH2)3)、二乙基二甲基铪(Hf (CH3) 2 (CH3CH2) 2)、三甲基乙基铪(Hf (CH3) 3 (CH3CH2))、三异丁基甲基铪(Hf (CH3) (I-C4H9) 3)、二异丁基二甲基铪(Hf (CH3) 2 (I-C4H9) 2)、三甲基异丁基铪(Hf (CH3) 3 (I-C4H9))、三异丁基乙基铪(Hf(CH3CH2) (I-C4H9) 3)、二异丁基二乙基铪(Hf (CH3CH2)2 (I-C4H9)2)、三乙基异丁基铪(Hf (CH3CH2) 3 (i-C4H9))、三正丁基甲基铪(Hf (CH3) (C4H9) 3)、二正丁基二甲基铪(Hf (CH3) 2 (C4H9) 2)、三甲基正丁基铪(Hf (CH3) 3 (C4H9))、三正丁基甲基铪(Hf (CH3CH2)(C4H9)3)、二正丁基二乙基铪(Hf (CH3CH2)2(C4H9)2)、三乙基正丁基铪(Hf(CH3CH2)3(C4H9))等。 [0215] tetramethyl hafnium (Hf (CH3) 4), tetraethyl hafnium (Hf (CH3CH2) 4), tetraisobutyl hafnium (Hf (I-C4H9) 4), tetra-n-butyl hafnium (Hf ( C4H9) 4), triethylmethyl hafnium (Hf (CH3) (CH3CH2) 3), diethyl methyl hafnium (Hf (CH3) 2 (CH3CH2) 2), trimethylethyl hafnium (Hf ( CH3) 3 (CH3CH2)), triisobutyl methyl hafnium (Hf (CH3) (I-C4H9) 3), di-iso-butyl-dimethyl hafnium (Hf (CH3) 2 (I-C4H9) 2), three isobutyl hafnium (Hf (CH3) 3 (I-C4H9)), tri-iso-butyl ethyl hafnium (Hf (CH3CH2) (I-C4H9) 3), diisobutyl diethyl hafnium (Hf (CH3CH2 ) 2 (I-C4H9) 2), triethyl-butyl hafnium (Hf (CH3CH2) 3 (i-C4H9)), tri-n-butylmethyl hafnium (Hf (CH3) (C4H9) 3), di-n-butyl dimethyl hafnium (Hf (CH3) 2 (C4H9) 2), trimethyl n-butyl hafnium (Hf (CH3) 3 (C4H9)), tri-n-butylmethyl hafnium (Hf (CH3CH2) (C4H9) 3), diethyl-n-butyl hafnium (Hf (CH3CH2) 2 (C4H9) 2), triethyl n-butyl hafnium (Hf (CH3CH2) 3 (C4H9)) and the like.

[0216] 作为所述IVB族金属烷氧基化合物,比如可以举出四甲氧基钛(Ti (OCH3)4)、四乙氧基钛(Ti (OCH3CH2)4)、四异丁氧基钛(Ti Q-OC4H9) 4)、四正丁氧基钛(Ti (OC4H9) 4)、三乙氧基甲氧基钛(Ti(OCH3) (OCH3CH2)3)、二乙氧基二甲氧基钛(Ti (OCH3)2(OCH3CH2)2)、三甲氧基乙氧基钛(Ti (OCH3) 3 (OCH3CH2))、三异丁氧基甲氧基钛(Ti(OCH3) (i-OC4H9) 3)、二异丁氧基二甲氧基钛(Ti (OCH3) 2 (I-OC4H9) 2)、三甲氧基异丁氧基钛(Ti (OCH3) 3 (I-OC4H9))、三异丁氧基乙氧基钛(Ti(OCH3CH2) Q-OC4H9) 3)、二异丁氧基二乙氧基钛(Ti (OCH3CH2) 2 Q-OC4H9) 2)、三乙氧基异丁氧基钛(Ti (OCH3CH2)3Q-OC4H9))、三正丁氧基甲氧基钛(Ti(OCH3) (OC4H9)3)、二正丁氧基二甲氧基钛(Ti (OCH3)2 (OC4H9) 2)、三甲氧基正丁氧基钛(Ti (OCH3)3(OC4H9))、三正丁氧基甲氧基钛(Ti(OCH3CH2) (OC4H9)3)、二正丁氧基二乙氧基钛(Ti (OCH3CH2)2(OC4H9)2)、三乙氧基正丁 [0216] Examples of the Group IVB metal alkoxide, for example can include tetramethoxy titanium (Ti (OCH3) 4), titanium tetraethoxide (Ti (OCH3CH2) 4), titanium tetraisobutoxide (Ti Q-OC4H9) 4), tetra-n-butoxy titanium (Ti (OC4H9) 4), methoxy triethoxy titanium (Ti (OCH3) (OCH3CH2) 3), dimethoxy diethoxy titanium (Ti (OCH3) 2 (OCH3CH2) 2), trimethoxy titanium ethoxide (Ti (OCH3) 3 (OCH3CH2)), three-methoxy-isobutoxy titanium (Ti (OCH3) (i-OC4H9) 3), di-dimethoxy isobutoxy titanium (Ti (OCH3) 2 (I-OC4H9) 2), trimethoxy isobutoxy titanium (Ti (OCH3) 3 (I-OC4H9)), tri-iso butoxyethoxy titanium (Ti (OCH3CH2) Q-OC4H9) 3), diisobutyl diethoxy titanium (Ti (OCH3CH2) 2 Q-OC4H9) 2), triethoxy isobutoxy titanium (Ti (OCH3CH2) 3Q-OC4H9)), tri-n-butoxymethoxy titanium (Ti (OCH3) (OC4H9) 3), di-n-butoxy-dimethoxy titanium (Ti (OCH3) 2 (OC4H9 ) 2), trimethoxy n-butoxy titanium (Ti (OCH3) 3 (OC4H9)), tri-n-butoxymethoxy titanium (Ti (OCH3CH2) (OC4H9) 3), diethyl di-n-butoxy alkoxy titanium (Ti (OCH3CH2) 2 (OC4H9) 2), triethoxy n-butoxy 基钦(Ti (OCH3CH2) 3 (OC4H9))等; Kitchin (Ti (OCH3CH2) 3 (OC4H9)) and the like;

[0217] 四甲氧基锆(Zr(OCH3)4)、四乙氧基锆(Zr(OCH3CH2)4)、四异丁氧基锆(Zr Q-OC4H9) 4)、四正丁氧基锆(Zr(OC4H9)4)、三乙氧基甲氧基锆(Zr(OCH3) (OCH3CH2) 3)、二乙氧基二甲氧基锆(Zr (OCH3) 2 (OCH3CH2) 2)、三甲氧基乙氧基锆(Zr (OCH3) 3 (OCH3CH2))、三异丁氧基甲氧基锆(Zr(OCH3) Q-OC4H9) 3)、二异丁氧基二甲氧基锆(Zr (OCH3)2 (i_0C4H9)2)、三甲氧基异丁氧基锆(Zr (OCH3) 3 (i-C4H9))、三异丁氧基乙氧基锆(Zr(OCH3CH2)(I-OC4H9)3)、二异丁氧基二乙氧基锆(Zr(OCH3CH2)2(I-OC4H9)2)、三乙氧基异丁氧基锆(Zr(OCH3CH2)3(i-OC4H9))、三正丁氧基甲氧基锆(Zr(OCH3) (OC4H9)3)、二正丁氧基二甲氧基锆(Zr (OCH3) 2 (OC4H9) 2)、三甲氧基正丁氧基锆(Zr (OCH3) 3 (OC4H9))、三正丁氧基甲氧基锆(Zr (OCH3CH2) (OC4H9) 3)、二正丁氧基二乙氧基锆(Zr (OCH3CH2) 2 (OC4H9) 2)、三乙氧基正丁氧基锆(Zr (OCH3CH2) 3 (OC4H9))等; [0217] tetramethoxy zirconium (Zr (OCH3) 4), tetraethoxy zirconium (Zr (OCH3CH2) 4), tetraisobutoxy zirconium (Zr Q-OC4H9) 4), tetra-n-butoxide, zirconium (Zr (OC4H9) 4), three ethoxymethoxy zirconium (Zr (OCH3) (OCH3CH2) 3), dimethoxy diethoxy zirconium (Zr (OCH3) 2 (OCH3CH2) 2), three-methoxy ethoxy zirconium (Zr (OCH3) 3 (OCH3CH2)), triisobutyl methoxymethoxy zirconium (Zr (OCH3) Q-OC4H9) 3), dimethoxy diisobutoxybenzene zirconium (Zr ( OCH3) 2 (i_0C4H9) 2), trimethoxy isobutoxy zirconium (Zr (OCH3) 3 (i-C4H9)), three-isobutoxy-ethoxy zirconium (Zr (OCH3CH2) (I-OC4H9) 3 ), diisobutyl diethoxy zirconium (Zr (OCH3CH2) 2 (I-OC4H9) 2), triethoxy isobutoxy, zirconium (Zr (OCH3CH2) 3 (i-OC4H9)), tri-n butoxymethoxy zirconium (Zr (OCH3) (OC4H9) 3), di-n-butoxy-dimethoxy zirconium (Zr (OCH3) 2 (OC4H9) 2), trimethoxy n-butoxy zirconium (Zr (OCH3) 3 (OC4H9)), tri-n-butoxymethoxy zirconium (Zr (OCH3CH2) (OC4H9) 3), di-n-diethoxy zirconium (Zr (OCH3CH2) 2 (OC4H9) 2) , triethoxy n-butoxy zirconium (Zr (OCH3CH2) 3 (OC4H9)) and the like;

[0218] 四甲氧基铪(Hf(OCH3)4)、四乙氧基铪(Hf(OCH3CH2)4)、四异丁氧基铪(Hf(i-0C4H9)4)、四正丁氧基铪(Hf(OC4H9)4)、三乙氧基甲氧基铪(Hf(OCH3) (OCH3CH2) 3)、二乙氧基二甲氧基铪(Hf (OCH3) 2 (OCH3CH2) 2)、三甲氧基乙氧基铪(Hf (OCH3) 3 (OCH3CH2))、三异丁氧基甲氧基铪(Hf(OCH3) Q-OC4H9) 3)、二异丁氧基二甲氧基铪(Hf (OCH3)2 Q-OC4H9)2)、三甲氧基异丁氧基铪(Hf (OCH3) 3 (I-OC4H9))、三异丁氧基乙氧基铪(Hf (OCH3CH2)(I-OC4H9)3)、二异丁氧基二乙氧基铪(Hf (OCH3CH2)2(I-OC4H9)2)、三乙氧基异丁氧基铪(Hf (OCH3CH2) 3 (i-C4H9))、三正丁氧基甲氧基铪(Hf(OCH3) (OC4H9) 3)、二正丁氧基二甲氧基铪(Hf (OCH3) 2 (OC4H9) 2)、三甲氧基正丁氧基铪(Hf (OCH3) 3 (OC4H9))、三正丁氧基甲氧基铪(Hf (OCH3CH2) (OC4H9) 3)、二正丁氧基二乙氧基铪(Hf (OCH3CH2) 2 (OC4H9) 2)、三乙氧基正丁氧基铪(Hf(OCH3CH2)3(OC4H9))等。 [0218] tetramethoxy hafnium (Hf (OCH3) 4), tetraethoxy hafnium (Hf (OCH3CH2) 4), tetraisobutoxy hafnium (Hf (i-0C4H9) 4), tetra-n-butoxy hafnium (Hf (OC4H9) 4), three ethoxymethoxy hafnium (Hf (OCH3) (OCH3CH2) 3), dimethoxy diethoxy hafnium (Hf (OCH3) 2 (OCH3CH2) 2), three butoxyethoxy hafnium (Hf (OCH3) 3 (OCH3CH2)), triisobutyl methoxymethoxy hafnium (Hf (OCH3) Q-OC4H9) 3), dimethoxy diisobutoxybenzene hafnium (Hf (OCH3) 2 Q-OC4H9) 2), trimethoxy isobutoxy, hafnium (Hf (OCH3) 3 (I-OC4H9)), three-isobutoxy-ethoxy hafnium (Hf (OCH3CH2) (I-OC4H9 ) 3), di-iso-diethoxy hafnium (Hf (OCH3CH2) 2 (I-OC4H9) 2), triethoxy isobutoxy, hafnium (Hf (OCH3CH2) 3 (i-C4H9)), tri-n-butoxymethoxy hafnium (Hf (OCH3) (OC4H9) 3), di-n-butoxy-dimethoxy hafnium (Hf (OCH3) 2 (OC4H9) 2), trimethoxy n-butoxy hafnium (Hf (OCH3) 3 (OC4H9)), tri-n-butoxymethoxy hafnium (Hf (OCH3CH2) (OC4H9) 3), di-n-diethoxy hafnium (Hf (OCH3CH2) 2 (OC4H9) 2), triethoxy n-butoxy hafnium (Hf (OCH3CH2) 3 (OC4H9)) and the like.

[0219] 作为所述IVB族金属烷基卤化物,比如可以举出三甲基氯化钛(TiCl(CH3)3)、三乙基氯化钛(TiCl (CH3CH2) 3)、三异丁基氯化钛(TiCl (I-C4H9) 3)、三正丁基氯化钛(TiCl (C4H9)3)、二甲基二氯化钛(TiCl2(CH3)2)、二乙基二氯化钛(TiCl2(CH3CH2)2)、二异丁基二氯化钛(TiCl2 (i-C4H9)2)、三正丁基氯化钛(TiCl (C4H9)3)、甲基三氯化钛(Ti (CH3)Cl3)、乙基三氯化钛(Ti (CH3CH2) Cl3)、异丁基三氯化钛(Ti (I-C4H9) Cl3)、正丁基三氯化钛(Ti (C4H9)Cl3); [0219] Examples of the Group IVB metal alkyl halides, such as trimethyl include titanium (TiCl (CH3) 3) chloride, titanium chloride triethylaluminum (TiCl (CH3CH2) 3), triisobutyl titanium chloride (TiCl (I-C4H9) 3), tri-n-butyl titanium chloride (TiCl (C4H9) 3), dimethyl titanium (TiCl2 (CH3) 2) titanium tetrachloride, diethyl dichloride (TiCl2 (CH3CH2) 2), diisobutyl titanium dichloride (TiCl2 (i-C4H9) 2), tri-n-butyl titanium (TiCl (C4H9) 3) titanium chloride, methyl trichloride (of Ti ( CH3) Cl3), ethyl titanium trichloride (Ti (CH3CH2) Cl3), isobutyl triethoxy titanium chloride (Ti (I-C4H9) Cl3), n-butyl titanium trichloride (Ti (C4H9) Cl3) ;

[0220] 三甲基溴化钛(TiBr (CH3) 3)、三乙基溴化钛(TiBr (CH3CH2) 3)、三异丁基溴化钛(TiBr (I-C4H9) 3)、三正丁基溴化钛(TiBr (C4H9) 3)、二甲基二溴化钛(TiBr2 (CH3) 2)、二乙基二溴化钛(TiBr2 (CH3CH2)2)、二异丁基二溴化钛(TiBr2 (i_C4H9)2)、三正丁基溴化钛(TiBr (C4H9) 3)、甲基三溴化钛(Ti (CH3) Br3)、乙基三溴化钛(Ti (CH3CH2) Br3)、异丁基三溴化钛(Ti(i-C4H9)fc3)、正丁基三溴化钛(Ti(C4H9)Br3); [0220] titanium bromide (TiBr (CH3) 3), triethyl titanium tetrabromide (TiBr (CH3CH2) 3), triisobutyl titanium tetrabromide (TiBr (I-C4H9) 3), tri-n butyl titanium tetrabromide (TiBr (C4H9) 3), titanium bromide dimethyl (TiBr2 (CH3) 2), titanium bromide diethyl (TiBr2 (CH3CH2) 2), diisobutyl dibromide titanium (TiBr2 (i_C4H9) 2), tri-n-butyl titanium tetrabromide (TiBr (C4H9) 3), titanium tetrabromide methyltris (Ti (CH3) Br3), ethyltriphenylphosphonium bromide, titanium (Ti (CH3CH2) Br3 ), isobutyl triethoxy titanium tetrabromide (Ti (i-C4H9) fc3), n-butyl titanium tribromide (Ti (C4H9) Br3);

[0221 ] 三甲基氯化锆(ZrCl (CH3) 3)、三乙基氯化锆(ZrCl (CH3CH2) 3)、三异丁基氯化锆(ZrCl (I-C4H9) 3)、三正丁基氯化锆(ZrCl (C4H9) 3)、二甲基二氯化锆(ZrCl2 (CH3) 2)、二乙基二氯化锆(ZrCl2(CH3CH2)2)、二异丁基二氯化锆(ZrCl2Q-C4H9)2)、三正丁基氯化锆(ZrCl (C4H9) 3)、甲基三氯化锆(Zr (CH3) Cl3)、乙基三氯化锆(Zr (CH3CH2) Cl3)、异丁基三氯化锆(Zr (I-C4H9) Cl3)、正丁基三氯化锆(Zr (C4H9) Cl3); [0221] trimethyl zirconium chloride (ZrCl (CH3) 3), triethyl zirconium chloride (ZrCl (CH3CH2) 3), triisobutyl zirconium chloride (ZrCl (I-C4H9) 3), tri-n butyl zirconium chloride (ZrCl (C4H9) 3), dimethyl zirconium dichloride (ZrCl2 (CH3) 2), diethyl zirconium (ZrCl2 (CH3CH2) 2) chloride, diisobutyl dichloride zirconium (ZrCl2Q-C4H9) 2), tri-n-butyl zirconium (ZrCl (C4H9) zirconium dichloride (Zr (CH3) Cl3) 3), methyl trichloride, ethyl zirconium trichloride (Zr (CH3CH2) Cl3 ), isobutyl three zirconium (Zr (I-C4H9) Cl3) chloride, n-butyl zirconium (Zr (C4H9) Cl3 trichloride);

[0222] 三甲基溴化锆(Zrfc (CH3) 3)、三乙基溴化锆(Zrfc (CH3CH2) 3)、三异丁基溴化锆(ZrBr (i-C4H9) 3)、三正丁基溴化锆(ZrBr (C4H9) 3)、二甲基二溴化锆(ZrBr2 (CH3) 2)、二乙基二溴化锆(ZrBr2 (CH3CH2) 2)、二异丁基二溴化锆(ZrBr2 (i-C4H9) 2)、三正丁基溴化锆(ZrBr (C4H9) 3)、甲基三溴化锆(Zr (CH3) Br3)、乙基三溴化锆(Zr (CH3CH2) Br3)、异丁基三溴化锆(ZHi-C4H9) Br3)、正丁基三溴化锆(Zr(C4H9Wr3); [0222] zirconium bromide (Zrfc (CH3) 3), triethyl zirconium bromide (Zrfc (CH3CH2) 3), triisobutyl zirconium bromide (ZrBr (i-C4H9) 3), tri-n butyl bromide, zirconium (ZrBr (C4H9) 3), zirconium bromide dimethyl (ZrBr2 (CH3) 2), zirconium bromide diethyl (ZrBr2 (CH3CH2) 2), diisobutyl dibromide zirconium (ZrBr2 (i-C4H9) 2), tri-n-butyl bromide, zirconium (ZrBr (C4H9) 3), zirconium bromide methyltris (Zr (CH3) Br3), ethyltriphenylphosphonium bromide, zirconium (Zr (CH3CH2 ) Br3), isobutyl triethoxy zirconium bromide (ZHi-C4H9) Br3), n-butyl bromide three zirconium (Zr (C4H9Wr3);

[0223] 三甲基氯化铪(HfCl (CH3) 3)、三乙基氯化铪(HfCl (CH3CH2) 3)、三异丁基氯化铪(HfCl (I-C4H9) 3)、三正丁基氯化铪(HfCl (C4H9) 3)、二甲基二氯化铪(HfCl2 (CH3) 2)、二乙基二氯化铪(HfCl2(CH3CH2)2)、二异丁基二氯化铪(HfCl2Q-C4H9)2)、三正丁基氯化铪(HfCl (C4H9)3)、甲基三氯化铪(Hf(CH3)Cl3)、乙基三氯化铪(Hf(CH3CH2)Cl3)、异丁基三氯化铪(Hf(i-C4H9) Cl3)、正丁基三氯化铪(Hf(C4H9)Cl3); [0223] trimethyl-hafnium (HfCl (CH3) 3) chloride, triethylsilyl chloride, hafnium (HfCl (CH3CH2) 3), triisobutyl hafnium chloride (HfCl (I-C4H9) 3), tri-n butyl hafnium chloride (HfCl (C4H9) 3), dimethyl hafnium (HfCl2 (CH3) 2) hafnium dichloride (HfCl2 (CH3CH2) 2), diethyl dichloride, diisobutyl dichloride hafnium (HfCl2Q-C4H9) 2), tri-n-butyl hafnium chloride (HfCl (C4H9) 3), methyl hafnium (Hf (CH3) Cl3) chloride, ethyl chloride, hafnium (Hf (CH3CH2) Cl3 ), iso-butyl hafnium trichloride (Hf (i-C4H9) Cl3), n-butyl chloride, hafnium (Hf (C4H9) Cl3);

[0224] 三甲基溴化铪(HfBr (CH3) 3)、三乙基溴化铪(HfBr (CH3CH2) 3)、三异丁基溴化铪(HfBr (i-C4H9) 3)、三正丁基溴化铪(HfBr (C4H9) 3)、二甲基二溴化铪(HfBr2 (CH3) 2)、二乙基二溴化铪(HfBr2 (CH3CH2) 2)、二异丁基二溴化铪(HfBr2 (i-C4H9) 2)、三正丁基溴化铪(HfBr (C4H9) 3)、甲基三溴化铪(Hf (CH3) Br3)、乙基三溴化铪(Hf (CH3CH2) Br3)、异丁基三溴化铪(Hf (I-C4H9) Br3)、正丁基三溴化铪(Hf (C4H9) Br3)。 [0224] trimethylammonium bromide, hafnium (HfBr (CH3) 3), triethylammonium bromide, hafnium (HfBr (CH3CH2) 3), triisobutyl bromide, hafnium (HfBr (i-C4H9) 3), tri-n butyl bromide, hafnium (HfBr (C4H9) 3), hafnium dimethyl bromide (HfBr2 (CH3) 2), diethyl hafnium bromide (HfBr2 (CH3CH2) 2), diisobutyl dibromide hafnium (HfBr2 (i-C4H9) 2), tri-n-butyl bromide, hafnium (HfBr (C4H9) 3), methyl tribromide hafnium (Hf (CH3) Br3) hafnium ethyl tribromide (Hf (CH3CH2 ) Br3), isobutyl tribromide hafnium (Hf (I-C4H9) Br3), n-butyl tribromide hafnium (Hf (C4H9) Br3).

[0225] 作为所述IVB族金属烷氧基卤化物,比如可以举出三甲氧基氯化钛(TiCl (OCH3) 3)、三乙氧基氯化钛(TiCl (OCH3CH2) 3)、三异丁氧基氯化钛(TiCl (I-OC4H9) 3)、三正丁氧基氯化钛(TiCl (OC4H9)3)、二甲氧基二氯化钛(TiCl2(OCH3)2)、二乙氧基二氯化钛(TiCl2 (OCH3CH2) 2)、二异丁氧基二氯化钛(TiCl2 (I-OC4H9) 2)、三正丁氧基氯化钛(TiCl (OC4H9) 3)、甲氧基三氯化钛(Ti (OCH3)Cl3)、乙氧基三氯化钛(Ti (OCH3CH2)Cl3)、异丁氧基三氯化钛(Ti(i-C4H9) Cl3)、正丁氧基三氯化钛(Ti(OC4H9)Cl3); [0225] Examples of the Group IVB metal alkoxy halide, such can include trimethoxy titanium (TiCl (OCH3) 3) chloride, triethoxy titanium chloride (TiCl (OCH3CH2) 3), triisobutyl butoxy titanium chloride (TiCl (I-OC4H9) 3), tri-n-butoxy titanium chloride (TiCl (OC4H9) 3), dimethoxy titanium dichloride (TiCl2 (OCH3) 2), diethyl alkoxy titanium dichloride (TiCl2 (OCH3CH2) 2), two isobutoxy titanium dichloride (TiCl2 (I-OC4H9) 2), tri-n-butoxy titanium chloride (TiCl (OC4H9) 3), A alkoxy titanium (Ti (OCH3) Cl3) trichloride, ethoxy titanium (Ti (OCH3CH2) Cl3) trichloride, isobutoxy titanium trichloride (Ti (i-C4H9) Cl3), n-butoxy group titanium trichloride (Ti (OC4H9) Cl3);

[0226] 三甲氧基溴化钛(TiBr (OCH3) 3)、三乙氧基溴化钛(TiBr (OCH3CH2) 3)、三异丁氧基溴化钛(TiBr (I-OC4H9) 3)、三正丁氧基溴化钛(TiBr (OC4H9) 3)、二甲氧基二溴化钛(TiBr2 (OCH3) 2)、二乙氧基二溴化钛(TiBr2 (OCH3CH2) 2)、二异丁氧基二溴化钛(TiBr2(I-OC4H9)2)、三正丁氧基溴化钛(TiBr(OC4H9)3)、甲氧基三溴化钛(Ti (OCH3)Br3)、乙氧基三溴化钛(Ti (OCH3CH2) Br3)、异丁氧基三溴化钛(Ti (I-C4H9) Br3)、正丁氧基三溴化钛(Ti(OC4H9)Br3); [0226] trimethoxy titanium tetrabromide (TiBr (OCH3) 3), triethoxy titanium tetrabromide (TiBr (OCH3CH2) 3), three isobutoxy titanium tetrabromide (TiBr (I-OC4H9) 3), tri-n-butoxy titanium tetrabromide (TiBr (OC4H9) 3), dimethoxy titanium dibromide (TiBr2 (OCH3) 2), diethoxy titanium dibromide (TiBr2 (OCH3CH2) 2), diisobutyl butoxy titanium dibromide (TiBr2 (I-OC4H9) 2), tri-n-butoxy titanium tetrabromide (TiBr (OC4H9) 3), methoxy triethylene titanium tetrabromide (Ti (OCH3) Br3), ethoxy tris titanium tetrabromide (Ti (OCH3CH2) Br3), isobutoxy titanium tribromide (Ti (I-C4H9) Br3), n-butoxy titanium tribromide (Ti (OC4H9) Br3);

[0227] 三甲氧基氯化锆(ZrCl (OCH3) 3)、三乙氧基氯化锆(ZrCl (OCH3CH2) 3)、三异丁氧基氯化锆(ZrCl (I-OC4H9) 3)、三正丁氧基氯化锆(ZrCl (OC4H9) 3)、二甲氧基二氯化锆(ZrCl2 (OCH3) 2)、二乙氧基二氯化锆(ZrCl2 (OCH3CH2) 2)、二异丁氧基二氯化锆(ZrCl2(I-OC4H9)2)、三正丁氧基氯化锆(ZrCl (OC4H9) 3)、甲氧基三氯化锆(Zr(OCH3)Cl3)、乙氧基三氯化锆(Zr(OCH3CH2)Cl3)、异丁氧基三氯化锆(Zr (i_C4H9) Cl3)、正丁氧基三氯化锆·(Zr(OC4H9)Cl3); [0227] trimethoxy zirconium chloride (ZrCl (OCH3) 3), triethoxy zirconium chloride (ZrCl (OCH3CH2) 3), triisobutyl group zirconium chloride (ZrCl (I-OC4H9) 3), tri-n-butoxy zirconium chloride (ZrCl (OC4H9) 3), dimethoxy zirconium dichloride (ZrCl2 (OCH3) 2), diethoxy zirconium (ZrCl2 (OCH3CH2) 2) chloride, diisobutyl butoxy zirconium dichloride (ZrCl2 (I-OC4H9) 2), tri-n-butoxide, zirconium chloride (ZrCl (OC4H9) 3), methoxy trichloride zirconium (Zr (OCH3) Cl3), ethoxyethyl tris zirconium (Zr (OCH3CH2) Cl3) chloride, iso-butoxy zirconium (Zr (i_C4H9) Cl3) trichloride, n-butoxy zirconium chloride · (Zr (OC4H9) Cl3);

[0228] 三甲氧基溴化锆(Zrfc (OCH3) 3)、三乙氧基溴化锆(Zrfc (OCH3CH2) 3)、三异丁氧基溴化锆(ZrBr (I-OC4H9) 3)、三正丁氧基溴化锆(ZrBr (OC4H9) 3)、二甲氧基二溴化锆(ZrBr2 (OCH3) 2)、二乙氧基二溴化锆(ZrBr2 (OCH3CH2) 2)、二异丁氧基二溴化锆(ZrBr2 (I-OC4H9) 2)、三正丁氧基溴化锆(ZrBr (OC4H9) 3)、甲氧基三溴化锆(Zr (OCH3) Br3)、乙氧基三溴化锆(Zr (OCH3CH2)Br3)、异丁氧基三溴化锆(Zr (I-C4H9)Br3)、正丁氧基三溴化锆(Zr(OC4H9)Br3); [0228] trimethoxy zirconium bromide (Zrfc (OCH3) 3), triethoxy zirconium bromide (Zrfc (OCH3CH2) 3), triisobutyl group zirconium bromide (ZrBr (I-OC4H9) 3), bromide, tri-n-butoxide, zirconium (ZrBr (OC4H9) 3), dimethoxy zirconium bromide (ZrBr2 (OCH3) 2), diethoxy zirconium bromide (ZrBr2 (OCH3CH2) 2), diisobutyl bromide butoxy zirconium (ZrBr2 (I-OC4H9) 2), tri-n-butoxide, zirconium bromide (ZrBr (OC4H9) 3), methoxy triethylene zirconium bromide (Zr (OCH3) Br3), ethoxy tris zirconium bromide (Zr (OCH3CH2) Br3), isobutoxy three zirconium bromide (Zr (I-C4H9) Br3), n-butoxy triglycol zirconium bromide (Zr (OC4H9) Br3);

[0229] 三甲氧基氯化铪(HfCl (OCH3) 3)、三乙氧基氯化铪(HfCl (OCH3CH2) 3)、三异丁氧基氯化铪(HfCl (I-OC4H9) 3)、三正丁氧基氯化铪(HfCl (OC4H9) 3)、二甲氧基二氯化铪(HfCl2 (OCH3) 2)、二乙氧基二氯化铪(HfCl2 (OCH3CH2) 2)、二异丁氧基二氯化铪(HfCl2(I-OC4H9)2)、三正丁氧基氯化铪(HfCl (OC4H9) 3)、甲氧基三氯化铪(Hf(OCH3)Cl3)、乙氧基三氯化铪(Hf(OCH3CH2)Cl3)、异丁氧基三氯化铪(Hf(i-C4H9)C13)、正丁氧基三氯化铪(Hf(OC4H9)Cl3); [0229] trimethoxy hafnium chloride (HfCl (OCH3) 3), triethoxy hafnium chloride (HfCl (OCH3CH2) 3), triisobutyl group, hafnium chloride (HfCl (I-OC4H9) 3), tri-n-butoxy hafnium chloride (HfCl (OC4H9) 3), dimethoxy hafnium (HfCl2 (OCH3) 2) hafnium dichloride, diethoxy dichloride (HfCl2 (OCH3CH2) 2), diisobutyl butoxy hafnium dichloride (HfCl2 (I-OC4H9) 2), tri-n-butoxy hafnium (HfCl (OC4H9) 3) chloride, methoxy hafnium trichloride (Hf (OCH3) Cl3), ethoxyethyl yl hafnium trichloride (Hf (OCH3CH2) Cl3), iso-butoxy hafnium (Hf (i-C4H9) C13) trichloride, trichloride, n-butoxy hafnium (Hf (OC4H9) Cl3);

[0230] 三甲氧基溴化铪(HfBr (OCH3) 3)、三乙氧基溴化铪(HfBr (OCH3CH2) 3)、三异丁氧基溴化铪(HfBr (I-OC4H9) 3)、三正丁氧基溴化铪(HfBr (OC4H9) 3)、二甲氧基二溴化铪(HfBr2 (OCH3) 2)、二乙氧基二溴化铪(HfBr2 (OCH3CH2) 2)、二异丁氧基二溴化铪(HfBr2 (I-OC4H9) 2)、三正丁氧基溴化铪(HfBr (OC4H9) 3)、甲氧基三溴化铪(Hf (OCH3) Br3)、乙氧基三溴化铪(Hf (OCH3CH2)Br3)、异丁氧基三溴化铪(Hf (I-C4H9)Br3)、正丁氧基三溴化铪(Hf(OC4H9)Br3)。 [0230] trimethoxyphenyl bromide, hafnium (HfBr (OCH3) 3), triethoxy tribromide hafnium (HfBr (OCH3CH2) 3), triisobutyl group, hafnium bromide (HfBr (I-OC4H9) 3), bromide, tri-n-butoxy hafnium (HfBr (OC4H9) 3), dimethoxy hafnium bromide (HfBr2 (OCH3) 2), diethoxy hafnium bromide (HfBr2 (OCH3CH2) 2), diisobutyl butoxy hafnium dibromide (HfBr2 (I-OC4H9) 2), tri-n-butoxy hafnium bromide (HfBr (OC4H9) 3), methoxy tribromide hafnium (Hf (OCH3) Br3), ethoxy yl tribromide hafnium (Hf (OCH3CH2) Br3), isobutoxy tribromide, hafnium (Hf (I-C4H9) Br3), n-butoxy tribromide, hafnium (Hf (OC4H9) Br3).

[0231] 作为所述IVB族金属化合物,优选所述IVB族金属卤化物,更优选TiCl4、TiBr4,ZrCl4, ZrBr4, HfCl4 和HfBr4,最优选TiCl4 和ZrCl40 [0231] Examples of the Group IVB metal compound, preferably a Group IVB metal halide, more preferably TiCl4, TiBr4, ZrCl4, ZrBr4, HfCl4 and HfBr4, and most preferably TiCl4 ZrCl40

[0232] 这些IVB族金属化合物可以单独使用一种,或者以任意的比例组合使用多种。 [0232] These IVB metal compound may be used singly or in any combination using a variety of proportions.

[0233] 当所述化学处理剂在常温下为液态时,可以通过向有待利用该化学处理剂处理的反应对象(比如前述的修饰复合载体)中直接滴加预定量的所述化学处理剂的方式使用所述化学处理剂。 [0233] When the chemical treatment agent is a liquid at normal temperature, can be (such as the modified composite carrier) directly using the reaction was added dropwise a predetermined amount of the target chemical treatment to be treated by the chemical treatment manner using the chemical conversion treatment agent.

[0234] 当所述化学处理剂在常温下为固态时,为了计量和操作方便起见,优选以溶液的形式使用所述化学处理剂。 [0234] When the chemical treatment agent is in the solid state, and operating convenience for measurement, preferably used in the form of a solution at room temperature, the chemical treatment agent. 当然,当所述化学处理剂在常温下为液态时,有时根据需要也可以以溶液的形式使用所述化学处理剂,并没有特别的限定。 Of course, when the chemical treatment agent is liquid at room temperature, may be sometimes necessary to use chemical treatments in the form of a solution is not particularly limited.

[0235] 在制备所述化学处理剂的溶液时,对此时所使用的溶剂没有特别的限定,只要其可以溶解该化学处理剂即可。 [0235] When preparing the chemical conversion treatment agent solution is not particularly limited, the solvent used in this case, as long as it can dissolve the chemical treatment can be.

[0236] 具体而言,可以举出C5_12烷烃、C5_12环烷烃、卤代C5_12烷烃、卤代C5_12环烷烃、C6_12芳烃或卤代C6_12芳烃等,比如可以举出戊烷、己烷、庚烷、辛烷、壬烷、癸烷、十一烷、十二烷、环戊烷、环己烷、环庚烷、环辛烷、甲苯、乙苯、二甲苯、氯代戊烷、氯代己烷、氯代庚烷、氯代辛烷、氯代壬烷、氯代癸烷、氯代i^一烷、氯代十二烷、氯代环己烷、氯代甲苯、氯代乙苯和氯代二甲苯等,其中优选戊烷、己烷、癸烷、环己烷和甲苯,最优选己烷和甲苯。 [0236] Specific examples thereof include C5_12 alkanes, cycloalkanes C5_12, C5_12 halogenated alkanes, halogenated cycloalkanes C5_12, C6_12 C6_12 aromatic or halogenated aromatics, such as may include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, toluene, ethylbenzene, xylene, chlorinated pentane, chlorinated hexane , chlorinated heptane, chlorinated octane, chlorinated nonane, chlorinated decane, chlorinated a i ^ alkoxy, chloro-dodecane, chloro-cyclohexane, chloro-toluene, chloro-ethylbenzene, chloro and substituting xylene and the like, wherein preferably pentane, hexane, decane, cyclohexane, and toluene, most preferably hexane and toluene.

[0237] 这些溶剂可以单独使用一种,或者以任意的比例组合使用多种。 [0237] These solvents may be used alone or in any combination using a variety of proportions.

[0238] 另外,对所述化学处理剂在其溶液中的浓度没有特别的限定,可以根据需要适当选择,只要其能够实现以预定量的所述化学处理剂来实施所述化学处理即可。 [0238] Further, not particularly limited, concentration of the chemical treatment agent in its solution, may be suitably selected according to need, as long as it can be realized in a predetermined amount of the chemical treating agent to the chemical treatment can be implemented. 如前所述,如果化学处理剂是液态的,可以直接使用化学处理剂来进行所述处理,但也可以将其调制成化学处理剂溶液后使用。 As described above, if the chemical conversion treatment agent is a liquid, a chemical treatment agent may be directly used to perform the processing, it may be post-treated to prepare a chemical solution.

[0239] 方便的是,所述化学处理剂在其溶液中的摩尔浓度一般设定为0. 01〜I. OmoI/L,但并不限于此。 [0239] Conveniently, the molar concentration of the chemical treatment agent in its solution is generally set to 0. 01~I. OmoI / L, but is not limited thereto.

[0240] 根据本发明,使所述化学处理剂与所述修饰复合载体反应,导致所述化学处理剂与该修饰复合载体上所含的前述非茂金属配体发生配位反应,从而在该修饰复合载体上原位生成以该IVB族金属原子为中心金属原子的非茂金属配合物(原位负载化反应),这是本发明的一大特征。 [0240] According to the present invention, the chemical treatment reaction to the modified composite carrier, causes the chemical treating agent to the nonmetallocene ligand of the modified contained on the composite support complexing reaction occurs, so that the modified composite carrier situ to the group IVB metal atom as a central metal atom of the non-metallocene complex (in-situ reaction load), which is a feature of the present invention.

[0241] 作为进行所述化学处理的方法,比如可以举出,在化学处理剂为固态(比如四氯化锆)的情况下,首先制备所述化学处理剂的溶液,然后向待处理的反应对象(比如前述的修饰复合载体)中加入(优选滴加)含有预定量的所述化学处理剂的所述溶液,以进行化学处理反应。 The [0241] As a method for the chemical treatment, there may be mentioned for example, in the chemical conversion treatment agent in a solid state (such as zirconium tetrachloride), the first chemical treatment solution was prepared, and then the reaction to be treated objects (such as the modified composite carrier) was added to the solution (preferably dropwise) a predetermined amount of the chemical treatment agent for chemical treatment reaction. 在化学处理剂为液态(比如四氯化钛)的情况下,可以直接将预定量的所述化学处理剂加入(优选滴加)待处理的反应对象(比如前述的修饰复合载体)中,以进行化学处理反应,或者在将该化学处理剂制备成溶液之后,向待处理的反应对象(比如前述的修饰复合载体)中加入(优选滴加)含有预定量的所述化学处理剂的所述溶液,以进行化学处理反应。 In the case of the chemical treatment agent is a liquid (like titanium tetrachloride) may be directly a predetermined amount of said chemical treating agent is added (preferably dropwise) reaction of objects to be treated (such as the modified composite carrier) to the chemical treatment chemical reaction process, or after the chemical treatment was prepared as a solution, the object to be treated reaction (such as the modified composite carrier) is added (preferably dropwise) a predetermined amount solution for chemical treatment reaction.

[0242] 一般而言,在-30〜60°C (优选-20〜30°C )的反应温度下使化学处理反应(必要时借助搅拌)进行0. 5〜24小时,优选I〜8小时,更优选2〜6小时即可。 [0242] Generally the chemical treatment reacted at -30~60 ° C (preferably -20~30 ° C) reaction temperature (if necessary with stirring) for 0.5 hours 5~24, preferably I~8 hours , and more preferably 2 ~ 6 hours.

[0243] 化学处理反应结束之后,通过过滤、洗涤和干燥,即可获得经过化学处理的产物,即本发明的负载型非茂金属催化剂。 After the [0243] Chemical treatment of the reaction by filtration, washed and dried to obtain a chemically treated product, i.e., non-supported metallocene catalysts of the present invention.

[0244] 根据本发明,所述过滤、洗涤和干燥可以采用常规方法进行,其中洗涤用溶剂可以采用与溶解所述化学处理剂时所用相同的溶剂。 [0244] According to the invention, the filtration, washing and drying can be carried out by a conventional method, washed with a solvent which may be employed when the same solvent is dissolved with the chemical treatment agent. 根据需要,该洗涤一般进行I〜8次,优选2〜6次,最优选2〜4次。 If necessary, the washing is generally performed I~8 times, preferably 2 ~ 6 times, most preferably 2 ~ 4 times.

[0245] 所述干燥可以采用常规方法进行,比如惰性气体干燥法、真空干燥法或者真空下加热干燥法,优选惰性气体干燥法或真空下加热干燥法,最优选真空下加热干燥法。 [0245] The drying may be carried out using conventional methods, an inert gas such as drying, vacuum drying or vacuum drying under heating, preferably under an inert gas heated drying or drying by heating under vacuum, most preferably a vacuum drying process. 所述干燥的温度范围一般为常温至140°C,干燥时间一般为2-20小时,但并不限于此。 The drying temperature range is generally room temperature to 140 ° C, the drying time is generally 2-20 hours, but is not limited thereto.

[0246] 根据本发明,作为所述非茂金属配体的用量,使得以Mg元素计的所述镁化合物(固体)与所述非茂金属配体的摩尔比达到I : 0.0001-1,优选I : 0.0002-0. 4,更优选I : 0. 0008-0. 2,进一步优选I : 0.001-0.1。 [0246] According to the present invention, as the amount of non-metallocene ligands, such that said magnesium compound (a solid) in a molar ratio of Mg with elemental basis of the nonmetallocene ligand to I: 0.0001-1, preferably I:. 0.0002-0 4, more preferably I:. 0. 0008-0 2, more preferably I: 0.001-0.1.

[0247] 根据本发明,作为所述用于溶解所述镁化合物的溶剂的用量,使得所述镁化合物(固体)与所述溶剂的比例达到Imol : 75〜400ml,优选Imol : 150〜300ml,更优选Imol : 200 〜250ml。 [0247] According to the present invention, as the amount of the solvent for dissolving the magnesium compound, such that said magnesium compound (a solid) and the ratio of the solvent to achieve Imol: 75~400ml, preferably Imol: 150~300ml, more preferably Imol: 200 ~250ml.

[0248] 根据本发明,作为所述多孔载体的用量,使得以镁化合物固体计的所述镁化合物与所述多孔载体的质量比达到I : 0.1-20,优选I : 0.5-10,更优选I : 1-5。 [0248] According to the present invention, as the amount of the porous support, so that the quality of the magnesium compound to the magnesium compound with the porous solids support ratio of I: 0.1-20, preferably I: 0.5-10, and more preferably I: 1-5.

[0249] 根据本发明,作为所述化学处理剂的用量,使得以Mg元素计的所述镁化合物(固体)与以IVB族金属(比如Ti)元素计的所述化学处理剂的摩尔比达到I : 0.01-1,优选I : 0.01-0. 50,更优选I : 0.10-0.30。 [0249] According to the present invention, as the chemical treatment agent is used in an amount such that the magnesium compound (a solid) in terms of the Mg element to the Group IVB metal (such as Ti) molar ratio on an elemental basis of the chemical treatment to I: 0.01-1, preferably I:. 0.01-0 50, more preferably I: 0.10-0.30. · ·

[0250] 根据本发明提供的非茂金属配体与化学处理剂的原位反应生成具有烯烃聚合活性的非茂金属配合物,其非茂金属配体摩尔加入量应不高于化学处理剂摩尔加入量。 [0250] The non-metallocene ligands of the invention provides a reaction in situ chemical treatment having olefin polymerization activity and generate a non-metallocene complex, non-metallocene ligand is not higher than the molar amount mol chemical treatments amount.

[0251] 本领域的技术人员已知的是,前述所有的方法步骤均优选在基本上无水无氧的条件下进行。 [0251] known to those skilled in the art that all of the aforementioned process steps are preferably carried out under substantially anhydrous oxygen-free conditions. 这里所说的基本上无水无氧指的是体系中水和氧的含量持续小于lOOppm。 Mentioned here refers to a substantially anhydrous oxygen-free system and oxygen content of water for less than lOOppm. 而且,本发明的负载型非茂金属催化剂在制备后通常需要在密闭条件下微正压惰性气体(比如氮气、氩气、氦气等)存在下保存备用。 Further, non-supported metallocene catalysts of the present invention after preparation under sealed conditions typically require slightly positive pressure of inert gas (such as nitrogen, argon, helium, etc.) in the presence for use.

[0252] 在一个实施方案中,本发明还涉及由前述的负载型非茂金属催化剂的制备方法制造的负载型非茂金属催化剂(有时也称为负载型非茂金属烯烃聚合催化剂)。 [0252] In one embodiment, the present invention also relates to a supported non-metallocene catalyst prepared by the method of the supported non-metallocene catalyst (sometimes also referred to as non-supported metallocene olefin polymerization catalyst).

[0253] 在一个进一步的实施方案中,本发明涉及一种烯烃均聚/共聚方法,其中以本发明的负载型非茂金属催化剂作为烯烃聚合用催化剂,使烯烃均聚或共聚。 [0253] In a further embodiment, the present invention relates to an olefin homopolymerization / copolymerization process, wherein in the supported non-metallocene catalyst of the invention as an olefin polymerization catalyst, homopolymerization or copolymerization of olefins.

[0254] 就本发明所涉及的该烯烃均聚/共聚方法而言,除了以下特别指出的内容以外,其他未言明的内容(比如聚合用反应器、烯烃用量、催化剂和烯烃的添加方式等),可以直接适用本领域常规已知的那些,并没有特别的限制,在此省略其说明。 [0254] For the present invention relates to olefin homopolymerization / copolymerization process terms, except for the following particularly pointed out in the contents, the contents other unspoken (such as polymerization reactor, the amount of olefin added embodiment, the catalyst and olefin, etc.) , it can be directly applied to those conventionally known in the art, and is not particularly limited, and description thereof is omitted here.

[0255] 根据本发明的均聚/共聚方法,以本发明的负载型非茂金属催化剂为主催化剂,以选自招氧烧、烧基招、齒代烧基招、砸氣烧、烧基砸和烧基砸按盐中的一种或多种为助催化剂,使烯烃均聚或共聚。 [0255] The present invention homopolymerization / copolymerization process, to the supported metallocene catalysts of the present invention the non-main catalyst selected from oxygen firing strokes, strokes burn group, the teeth of burning yl move, hit the gas burn, burn according to group drop by drop and burning one salt group or more cocatalyst, olefin homopolymerization or copolymerization.

[0256] 主催化剂和助催化剂向聚合反应体系中的加入方式可以是先加主催化剂,然后再加入助催化剂,或者先加入助催化剂,然后再加入主催化剂,或者是两者先接触混合后一起加入,或者分别同时加入。 [0256] The procatalyst and the cocatalyst to the polymerization reaction system may be added in a manner to add the procatalyst, cocatalyst and then added or first the cocatalyst is added, and then added to the main catalyst, or both the first contact and mix with the was added, simultaneously or separately added. 将主催化剂和助催化剂分别加入时既可以在同一加料管路中依次加入,也可以在多路加料管路中依次加入,而两者分别同时加入时应选择多路加料管路。 May be added sequentially during the procatalyst and cocatalyst are added in the same feed line, may be added sequentially in a multi feed line, and when both are simultaneously added to the feed line selecting multiplexer. 对于连续式聚合反应来说,优选多路加料管路同时连续加入,而对于间歇式聚合反应来说,优选两者先混合后在同一加料管路中一起加入,或者在同一加料管路中先加入助催化剂,然后再加入主催化剂。 For continuous polymerization, the preferred multiple pipe while continuously introducing feed, and for batch polymerization reactions, both preferably added after the first mixed together in the same feed line, or in addition to the same line promoter is added, and then added to the main catalyst.

[0257] 根据本发明,对所述烯烃均聚/共聚方法的反应方式没有特别的限定,可以采用本领域公知的那些,比如可以举出淤浆法、本体法和气相法等,其中优选淤浆法和气相法。 [0257] According to the present invention, the olefin homopolymerization / copolymerization reaction mode is not particularly limited, and may be employed are those known in the art, for example can include slurry, bulk and gas-phase method and the like, preferably wherein the slurry slurry and gas phase.

[0258] 根据本发明,作为所述烯烃,比如可以举出C2〜Cltl单烯烃、双烯烃、环状烯烃和其他烯键式不饱和化合物。 [0258] According to the present invention, as the olefin, such as C2~Cltl include monoolefins, diolefins, cyclic olefins and other ethylenically unsaturated compound. [0259] 具体而言,作为所述C2〜C12单烯烃,比如可以举出乙烯、丙烯、I-丁烯、I-己烯、I-庚烯、4-甲基-I-戍烯、I-辛烯、I-癸烯、I-十一烯、I-十二烯和苯乙烯等;作为所述环状烯烃,比如可以举出I-环戊烯和降冰片烯等;作为所述双烯烃,比如可以举出1,4_ 丁二烯、2,5_戊二烯、1,6_己二烯、降冰片二烯和1,7_辛二烯等;并且作为所述其他烯键式不饱和化合物,比如可以举出醋酸乙烯酯和(甲基)丙烯酸酯等。 [0259] Specifically, as the C2~C12 monoolefin, for example include ethylene, propylene, I- butene, I- hexene, I- heptene, 4-methyl pentene -I-, the I - octene, I- decene, undecene I-, I- dodecene and styrene; examples of the cyclic olefin such as cyclopentene and I- may include norbornene and the like; as the diolefins, such as butadiene include 1,4_, 2,5_-pentadiene, hexadiene 1,6_, 1,7_ norbornadiene octadiene and the like; and, as the other ethylenically unsaturated compounds such as vinyl acetate, and may include (meth) acrylate. 其中,优选乙烯的均聚,或者乙烯与丙烯、I-丁烯或I-己烯的共聚。 Wherein, preferably ethylene homopolymerization and ethylene or propylene, I- I- butene or hexene copolymer.

[0260] 根据本发明,均聚指的是仅一种所述烯烃的聚合,而共聚指的是两种以上所述烯烃之间的聚合。 [0260] According to the present invention, homopolymerization means that only the polymerization of an olefin, the copolymerization of two or more refers to the polymerization of olefins between.

[0261] 根据本发明,所述助催化剂选自铝氧烷、烷基铝、卤代烷基铝、硼氟烷、烷基硼和烷基砸按盐,其中优选招氧烧和烧基招。 [0261] According to the invention, the cocatalyst is selected from alumoxane, aluminum alkyl, halogenated aluminum alkyl, fluoroalkyl, boron, boron alkyl and alkyl hit by salt thereof, wherein preferably burned and burning the oxygen-yl strokes strokes.

[0262] 作为所述铝氧烷,比如可以举出下述通式(II)所示的线型铝氧烷=(R)(R)Al-(Al(R)-O)nO-Al(R) (R),以及下述通式(II-I)所不的环状招氧烧:-(Al (R)-O-)n+2-。 [0262] Examples of the aluminoxane, for example include the following general formula (II) is linear alumoxanes = (R) (R) Al- (Al (R) -O) nO-Al ( R) (R), and the following formula (II-I) do not move oxygen to burn cyclic :-( Al (R) -O-) n + 2-.

[0263] [0263]

Figure CN102964479AD00381

[0264] 在前述通式中,基团R彼此相同或不同(优选相同),各自独立地选自C1-C8烷基,优选甲基、乙基和异丁基,最优选甲基。 [0264] In the aforementioned formula, the group R is the same or different from each other (preferably the same), each independently selected from C1-C8 alkyl, preferably methyl, ethyl and isobutyl, most preferably methyl. n为1-50范围内的任意整数,优选10〜30范围内的任意整数。 n is any integer in the range of 1 to 50, preferably any integer within the range of 10~30.

[0265] 作为所述招氧烧,优选甲基招氧烧、乙基招氧烧、异丁基招氧烧和正丁基招氧烧,进一步优选甲基招氧烧和异丁基招氧烧,并且最优选甲基招氧烧。 [0265] As the firing strokes oxygen, preferably oxygen fired move methyl, ethyl move oxygen to burn, isobutyl and n-butyl firing strokes move oxygen to burn oxygen, more preferably a methyl isobutyl strokes and strokes of oxygen to burn the oxygen burn , and most preferably methyl move oxygen to burn.

[0266] 这些铝氧烷可以单独使用一种,或者以任意的比例组合使用多种。 [0266] These aluminoxanes may be used singly or in any combination using a variety of proportions.

[0267] 作为所述烷基铝,比如可以举出如下通式(III)所示的化合物: [0267] Examples of the alkyl aluminum, for example include compounds of the formula (III) shown below:

[0268] Al (R) 3 (III) [0268] Al (R) 3 (III)

[0269] 其中,基团R彼此相同或不同(优选相同),并且各自独立地选自C1-C8烷基,优选甲基、乙基和异丁基,最优选甲基。 [0269] wherein the radicals R the same or different (preferably the same), and are each independently selected from C1-C8 alkyl, preferably methyl, ethyl and isobutyl, most preferably methyl.

[0270] 具体而言,作为所述烷基铝,比如可以举出三甲基铝(Al (CH3)3)、三乙基铝(Al (CH3CH2) 3)、三正丙基铝(Al (C3H7) 3)、三异丁基铝(Al (I-C4H9) 3)、三正丁基铝(Al (C4H9)3)、三异戊基铝(Al (I-C5H11)3)、三正戊基铝(Al (C5H11)3)、三正己基铝(Al (C6H13)3)、三异己基铝(Al Q-C6H13)3)、二乙基甲基铝(Al(CH3) (CH3CH2)2)和二甲基乙基铝(Al(CH3CH2)(CH3) 2)等,其中优选二甲基招、二乙基招、二正丙基招和二异丁基招,进一步优选二乙基招和三异丁基铝,并且最优选三乙基铝。 [0270] Specifically, as the aluminum alkyls, such as may include trimethylaluminum (Al (CH3) 3), triethyl aluminum (Al (CH3CH2) 3), tri-n-propyl aluminum (Al ( C3H7) 3), triisobutyl aluminum (Al (I-C4H9) 3), tri-n-butyl aluminum (Al (C4H9) 3), tri-iso-pentyl aluminum (Al (I-C5H11) 3), tri-n amyl aluminum (Al (C5H11) 3), tri-n-hexyl aluminum (Al (C6H13) 3), three isohexyl aluminum (Al Q-C6H13) 3), diethyl methyl aluminum (Al (CH3) (CH3CH2) 2) and ethyl dimethyl aluminum (Al (CH3CH2) (CH3) 2) and the like, wherein preferably dimethyl strokes, strokes diethyl, di-n-propyl diisobutyl strokes and strokes, more preferably diethyl strokes and triisobutylaluminum, and most preferably triethyl aluminum.

[0271 ] 这些烷基铝可以单独使用一种,或者以任意的比例组合使用多种。 [0271] These alkyl aluminum may be used alone or in any combination using a variety of proportions.

[0272] 作为所述卤代烷基铝,比如可以举出如下通式(IV)所示的化合物: [0272] As the halogenated alkyl aluminum, for example include compounds of the formula (IV) shown below:

[0273] Al(R)nX3-n (IV) [0273] Al (R) nX3-n (IV)

[0274] 其中,基团R彼此相同或不同(优选相同),并且各自独立地选自C1-C8烷基,优选甲基、乙基和异丁基,最优选甲基。 [0274] wherein the radicals R the same or different (preferably the same), and are each independently selected from C1-C8 alkyl, preferably methyl, ethyl and isobutyl, most preferably methyl. 基团X为齒素,优选氣。 X is a group of teeth elements, preferably air. n为I或2。 n is I or 2.

[0275] 具体而言,作为所述卤代烷基铝,比如可以举出一氯二甲基铝(Al (CH3)2Cl)、二氯甲基铝(Al (CH3)Cl2))、一氯二乙基铝(Al (CH3CH2)2Cl)、二氯乙基铝(Al (CH3CH2) Cl2)、一氯二丙基铝(Al (C3H7)2Cl)、二氯丙基铝(Al (C3H7)Cl2))、一氯二正丁基铝(Al (C4H9) 2C1)、二氯正丁基铝(Al (C4H9)Cl2)、一氯二异丁基铝(Al(i-C4H9)2C1)、二氯异丁基铝(AKi-C4H9)Cl2)、一氯二正戊基铝(Al (C5Hn)2Cl)、二氯正戊基铝(Al (C5H11)Cl2)、一氯二异戊基铝(Al (I-C5H11)2Cl)、二氯异戊基铝(Al (I-C5H11)Cl2)、一氯二正己基铝(Al (C6H13)2Cl)、二氯正己基铝(Al (C6H13) Cl2)、一氯二异己基铝(Al (i-C6H13) 2C1)、二氯异己基铝(AKi-C6H13)Cl2), [0275] Specifically, as the halogenated alkyl aluminum, for example chloro can include a dimethyl aluminum (Al (CH3) 2Cl), dichloromethyl methyl aluminum (Al (CH3) Cl2)), diethyl monochloride group aluminum (Al (CH3CH2) 2Cl), ethyl aluminum dichloride (Al (CH3CH2) Cl2), a two-chloro-propyl aluminum (Al (C3H7) 2Cl), dichloropropyl aluminum (Al (C3H7) Cl2)) , di-n-butyl aluminum chloride (Al (C4H9) 2C1), dichloro-n-butyl aluminum (Al (C4H9) Cl2), diisobutylaluminum monochloride (Al (i-C4H9) 2C1), dichloroisocyanurate butylaluminum (aKi-C4H9) Cl2), a di-n-pentyl aluminum chloride (Al (C5Hn) 2Cl), dichloro-n-pentyl aluminum (Al (C5H11) Cl2), a chloro group diisoamyl aluminum (Al ( I-C5H11) 2Cl), dichloro-isopentyl aluminum (Al (I-C5H11) Cl2), a-chloro-di-n-hexyl aluminum (Al (C6H13) 2Cl), dichloro-n-hexyl aluminum (Al (C6H13) Cl2), chlorodifluoromethane hexyl aluminum (Al (i-C6H13) 2C1), dichloro isohexyl aluminum (aKi-C6H13) Cl2),

[0276] 一氯甲基乙基铝(Al(CH3) (CH3CH2) Cl)、一氯甲基丙基铝(Al(CH3) (C3H7)Cl)、一氯甲基正丁基铝(Al (CH3) (C4H9)Cl)、一氯甲基异丁基铝(Al (CH3) (i_C4H9)Cl)、一氯乙基丙基铝(Al(CH2CH3) (C3H7)Cl)、一氯乙基正丁基铝(AlCH2CH3) (C4H9) Cl)、一氯甲基异丁基铝(AlCH2CH3) (I-C4H9)Cl)等,其中优选一氯二乙基铝、二氯乙基铝、一氯二正丁基铝、二氯正丁基铝、一氯二异丁基铝、二氯异丁基铝、一氯二正己基铝、二氯正己基铝,进一步优选氯二乙基招、~■氣乙基招和一氣_■正己基招,并且最优选一氣_■乙基招。 [0276] methyl chloride, ethyl aluminum (Al (CH3) (CH3CH2) Cl), a chlorine-methylpropyl aluminum (Al (CH3) (C3H7) Cl), methyl n-butyl aluminum chloride (Al ( CH3) (C4H9) Cl), methyl isobutyl aluminum chloride (Al (CH3) (i_C4H9) Cl), a chloroethyl propyl aluminum (Al (CH2CH3) (C3H7) Cl), an n-chloroethyl butylaluminum (AlCH2CH3) (C4H9) Cl), methyl isobutyl aluminum chloride (AlCH2CH3) (I-C4H9) Cl) and the like, wherein a preferably diethyl aluminum chloride, ethyl aluminum dichloride, chlorodifluoromethyl n-butylaluminum dichloride, n-butylaluminum, diisobutylaluminum chloride, dichloro-isobutyl aluminum chloride, di-n-hexyl aluminum dichloride, n-hexyl aluminum, diethyl move more preferably chloro, ~ ■ move and stretch gas ethyl hexyl ■ _ strokes, and most preferably a stretch _ ■ ethyl strokes.

[0277] 这些卤代烷基铝可以单独使用一种,或者以任意的比例组合使用多种。 [0277] The halogenated alkyl aluminum may be used singly or in any combination using a variety of proportions.

[0278] 作为所述硼氟烷、所述烷基硼和所述烷基硼铵盐,可以直接使用本领域常规使用的那些,并没有特别的限制。 [0278] Examples of the fluoroalkyl boron, the boron alkyl and the alkyl boron salts, may be used as those conventionally used in the art, and is not particularly limited.

[0279] 另外,根据本发明,所述助催化剂可以单独使用一种,也可以根据需要以任意的比例组合使用多种前述的助催化剂,并没有特别的限制。 [0279] Further, according to the present invention, a cocatalyst may be used alone or in any combination of more of the foregoing ratio of cocatalyst necessary, and is not particularly limited.

[0280] 根据本发明,根据所述烯烃均聚/共聚方法的反应方式的不同(比如淤浆聚合),有时需要使用聚合用溶剂。 [0280] According to the invention, according to different (such as slurry polymerization) the olefin homopolymerization / copolymerization reaction method, sometimes necessary to use a solvent for polymerization.

[0281] 作为所述聚合用溶剂,可以使用本领域在进行烯烃均聚/共聚时常规使用的那些,并没有特别的限制。 [0281] with a solvent, this may be used as the olefin polymerization art performing homopolymerization / those not particularly limited and conventionally used in the copolymerization.

[0282] 作为所述聚合用溶剂,比如可以举出C4_1(l烷烃(比如丁烷、戊烷、己烷、庚烷、辛烷、壬烷或癸烷等)、卤代C1,烷烃(比如二氯甲烷)、c6_12环烷烃(环己烷、环庚烷、环辛烷、环壬烷或环癸烷)、c6_2(l芳香烃(比如甲苯和二甲苯)等。其中,优选使用戊烷、己烷、庚烷和环己烷作为所述聚合用溶剂,最优选己烷。 [0282] As the solvent for polymerization, such as may include C4_1 (l alkanes (such as butane, pentane, hexane, heptane, octane, nonane, decane, or the like), halogenated C1, alkanes (such as dichloromethane), c6_12 cycloalkanes (cyclohexane, cycloheptane, cyclooctane, nonane, decane or cyclic), c6_2 (l aromatic hydrocarbons (such as toluene and xylene), etc. among these, pentane , hexane, heptane and cyclohexane as the polymerization solvent, most preferably hexane.

[0283] 这些聚合用溶剂可以单独使用一种,或者以任意的比例组合使用多种。 [0283] These polymerization solvents may be used alone or in any combination using a variety of proportions.

[0284] 根据本发明,所述烯烃均聚/共聚方法的聚合反应压力一般为0. I〜lOMPa,优选0. I〜4MPa,更优选0.4〜3MPa,但有时并不限于此。 [0284] According to the present invention, the olefin homopolymerization / copolymerization polymerization pressure is generally 0. I~lOMPa, preferably 0. I~4MPa, more preferably 0.4~3MPa, but sometimes it is not limited thereto. 根据本发明,聚合反应温度一般为-40°C〜200°C,优选10°C〜100°C,更优选40°C〜95°C,但有时并不限于此。 According to the present invention, the polymerization temperature is usually -40 ° C~200 ° C, preferably 10 ° C~100 ° C, more preferably 40 ° C~95 ° C, but not always limited thereto.

[0285] 另外,根据本发明,所述烯烃均聚/共聚方法可以在有氢气存在的条件下进行,也可以在没有氢气存在的条件下进行。 [0285] Further, according to the present invention, the olefin homopolymerization / copolymerization process can be carried out in the presence of hydrogen, may be carried out under conditions without the presence of hydrogen. 在存在的情况下,氢气的分压可以是所述聚合反应压力的0. 01%〜99%,优选0. 01%〜50%,但有时并不限于此。 In the presence of a partial pressure of hydrogen in the polymerization can be 0.01% ~99% of the reaction pressure is preferably 0.01% ~ 50%, but sometimes it is not limited thereto.

[0286] 根据本发明,在进行所述烯烃均聚/共聚方法时,以铝或硼计的所述助催化剂与以所述中心金属原子计的所述负载型非茂金属催化剂的摩尔比一般为I〜1000 : 1,优选10〜500 : 1,更优选15〜300 : 1,但有时并不限于此。 When [0286] According to the present invention, performing the olefin homo- / copolymerization process, the molar ratio of aluminum or boron in the cocatalyst to the meter to the central metal atom of the supported non-metallocene catalyst is generally It is I~1000: 1, preferably 10~500: 1, more preferably 15~300: 1, but not always limited thereto.

[0287] 实施例 [0287] Example

[0288] 以下采用实施例进一步详细地说明本发明,但本发明并不限于这些实施例。 [0288] The following embodiment of the present invention using the embodiment described in more detail, but the present invention is not limited to these embodiments.

[0289] 聚合物堆密度(单位是g/cm3)的测定参照中国国家标准GB 1636-79进行。 Determination of [0289] a polymer bulk density (unit is g / cm3) reference for the Chinese national standard GB 1636-79.

[0290] 负载型非茂金属催化剂中IVB族金属(比如Ti)和Mg元素的含量采用ICP-AES法测定,非茂金属配体或配合物的含量采用元素分析法测定。 Content [0290] The supported non-metallocene catalyst Group IVB metals (such as Ti), and Mg elements were determined by ICP-AES, the content of the non-metallocene ligands or complexes was determined by elemental analysis. [0291] 催化剂的聚合活性按照以下方法计算:在聚合反应结束之后,将反应釜内的聚合产物过滤并干燥,然后称量该聚合产物的质量,以该聚合产物质量除以所用的负载型非茂金属催化剂的质量的比值来表示该催化剂的聚合活性(单位是kg聚合物/g催化剂或kg聚合物/gCat)。 [0291] Polymerization activity of the catalyst is calculated according to the following method: After the completion of the polymerization, the polymerization product in the reactor is filtered and dried, then weighed mass polymerization product, the polymerization supported to the quality of the product divided by the non-used mass ratio of metallocene catalyst to the polymerization activity of the catalyst is represented (in kg polymer / g catalyst or kg polymer / gCat).

[0292] 聚合物的分子量Mw、Mn和分子量分布(Mw/Mn)采用美国WATERS公司的GPC V2000型凝胶色谱分析仪进行测定,以1,2,4_三氯苯为溶剂,测定时的温度为150°C。 [0292] Mw of the polymer molecular weight, Mn and molecular weight distribution (Mw / Mn) by the United States company WATERS GPC V2000 gel chromatograph measured to 1,2,4_ trichlorobenzene as a solvent at the time of measurement temperature of 150 ° C.

[0293] 聚合物的粘均分子量按照以下方法计算:按照标准ASTM D4020-00,采用高温稀释型乌氏粘度计法(毛细管内径为0. 44_,恒温浴介质为300号硅油,稀释用溶剂为十氢萘,测定温度为135°C )测定所述聚合物的特性粘度,然后按照如下公式计算所述聚合物的粘均分子量Mv。 [0293] viscosity-average molecular weight calculated as follows: In accordance with Standard ASTM D4020-00, using an Ubbelohde type viscometer temperature dilution method (capillary diameter of 0. 44_, 300 constant temperature bath medium is a silicone oil diluted with a solvent is decalin, measurement temperature of 135 ° C) measured intrinsic viscosity of the polymer, the polymer is then calculated according to the following equation viscosity average molecular weight Mv.

[0294] Mv = 5. 37X IO4X [ n]L37 [0294] Mv = 5. 37X IO4X [n] L37

[0295] 其中,n为特性粘度。 [0295] where, n is the intrinsic viscosity.

[0296] 实施例I [0296] Example I

[0297] 镁化合物采用无水氯化镁,溶解镁化合物的溶剂采用四氢呋喃,多孔载体采用二氧化娃,即娃胶,型号为Ineos公司的ES757,在使用前将娃胶在600°C、氮气气氛下持续焙 [0297] use of anhydrous magnesium chloride, magnesium compound, magnesium compound is dissolved using tetrahydrofuran solvent, using a porous carrier dioxide baby, baby gum i.e., the model of the Ineos ES757, baby glue before use at 600 ° C, a nitrogen atmosphere continue baking

烧4h而热活化。 4h burning and thermal activation. 非茂金属配体采用结构 Using non-metallocene ligand structure

Figure CN102964479AD00401

为的化合物,IVB族金 It is a compound, IVB group metal

属化合物的化学处理剂采用四氯化钛,化学处理剂用溶剂采用己烷。 Genus chemical treatment using titanium tetrachloride compound, the chemical treatment using a solvent hexane.

[0298] 称取5g无水氯化镁,加入溶剂后常温下完全溶解,得到镁化合物溶液,然后加入经过热活化的硅胶,常温下搅拌2小时后形成第一混合浆液。 [0298] Weigh 5g of anhydrous magnesium chloride, the solvent is added after complete dissolution at room temperature, to obtain a magnesium compound solution, and then is thermally activated silica gel was added, and stirred at room temperature for 2 hours for the first slurry after mixing.

[0299] 接着向第一混合浆液中加入非茂金属配体,在常温下搅拌反应6小时,形成第二混合浆液,常温下抽真空干燥得到修饰复合载体。 [0299] nonmetallocene ligand mixture then added to the first slurry, the reaction was stirred at room temperature for 6 hours to form a second mixture slurry, evacuated and dried in vacuo at room temperature to obtain a modified composite carrier.

[0300] 将修饰复合载体加入到化学处理剂用溶剂己烷中,常温下30分钟内滴加入化学处理剂,然后在常温下反应6小时后,过滤,化学处理剂用溶剂洗涤3次,每次60ml,最后在常温下抽真空干燥,得到负载型非茂金属催化剂。 [0300] The modified composite carrier was added after the chemical treatment with a solvent of hexane at room temperature was added dropwise over 30 minutes a chemical treatment agent, followed by reaction at room temperature for 6 hours, filtered, washed three times with a chemical treatment agent with a solvent, each times 60ml, dried in vacuo and finally evacuated at room temperature to give a supported non-metallocene catalyst.

[0301] 其中配比为,镁化合物与溶解镁化合物的溶剂配比为Imol : 210ml ;镁化合物与非茂金属配体摩尔比为I : 0.08;镁化合物与多孔载体的质量比为I : 2;镁化合物与以IVB族金属元素计的化学处理剂摩尔比为I : 0.15。 [0301] wherein the ratio of the magnesium compound is dissolved with a solvent ratio of magnesium compound Imol: 210ml; molar ratio of magnesium compound with a nonmetallocene ligand I: 0.08; magnesium compound with the porous carrier mass ratio of I: 2 ; molar ratio of magnesium compound to chemical treatment group IVB metal element is I: 0.15.

[0302] 负载型非茂金属催化剂记为CAT-I。 [0302] The supported metallocene catalyst referred to as a non-CAT-I.

[0303] 实施例2 [0303] Example 2

[0304] 与实施例I基本相同,但有如下改变: [0304] substantially the same as Example I, but with the following changes:

[0305] 多孔载体改变为Grace公司的955,在400°C、氮气气氛下持续焙烧8h而热活化。 [0305] The porous support 955 is changed to Grace's for 8h calcination thermally activated at 400 ° C, a nitrogen atmosphere. [0306] 溶解镁化合物的溶剂改变为甲苯,非茂金属配体采用<ph [0306] changing the solvent is toluene, the magnesium compound is dissolved, using non-metallocene ligand <ph

Figure CN102964479AD00411

IVB族金属化合物的化学处理剂改变为四氯化锆(ZrCl4),化学处理剂用溶剂改变为环己烧。 The chemical treatment IVB metal compound was changed to zirconium tetrachloride (ZrCl4), the chemical treating agent was changed to a cyclohexyl burn with a solvent.

[0307] 其中配比为,镁化合物与溶剂配比为Imol : 150ml ;镁化合物与非茂金属配体摩尔比为I : 0.15;镁化合物与多孔载体的质量比为I : 4;镁化合物与以IVB族金属元素计的化学处理剂摩尔比为I : 0.20。 [0307] wherein the ratio of magnesium compound to solvent ratio of Imol: 150ml; molar ratio of magnesium compound with a nonmetallocene ligand I: 0.15; magnesium compound with the porous carrier mass ratio of I: 4; the magnesium compound and the molar ratio of the chemical treatment to group IVB metal element is I: 0.20.

[0308] 负载型非茂金属催化剂记为CAT-2。 [0308] The supported metallocene catalyst referred to as a non-CAT-2.

[0309] 实施例3 [0309] Example 3

[0310] 与实施例I基本相同,但有如下改变: [0310] substantially the same as Example I, but with the following changes:

[0311] 多孔载体采用三氧化二铝。 [0311] The porous aluminum oxide support employed. 将三氧化二铝在700°C、氮气气氛下持续焙烧6h。 The continuous aluminum oxide calcined 6h at 700 ° C, a nitrogen atmosphere.

[0312] 镁化合物改变为无水溴化镁(MgBr2),非茂金属配体采用 [0312] Anhydrous magnesium compound was changed to magnesium bromide (MgBr2), using a non-metallocene ligand

Figure CN102964479AD00412

剂改变为四溴化钛(TiBr4),化学处理剂用溶剂改变为庚烷。 Agent was changed to titanium tetrabromide (TiBr4), the chemical treating agent was changed to heptane solvent.

[0313] 其中配比为,镁化合物与溶剂配比为Imol : 250ml ;镁化合物与非茂金属配体摩尔比为I : 0.20;镁化合物与多孔载体的质量比为I : I ;镁化合物与以IVB族金属元素计的化学处理剂摩尔比为I : 0.30。 [0313] wherein the ratio of magnesium compound to solvent ratio of Imol: 250ml; molar ratio of magnesium compound with a nonmetallocene ligand I: 0.20; magnesium compound with the porous carrier mass ratio of I: I; the magnesium compound and the molar ratio of the chemical treatment to group IVB metal element is I: 0.30.

[0314] 负载型非茂金属催化剂记为CAT-3。 [0314] The supported metallocene catalyst referred to as a non-CAT-3.

[0315] 实施例4 [0315] Example 4

[0316] 与实施例I基本相同,但有如下改变: [0316] substantially the same as Example I, but with the following changes:

[0317] 多孔载体采用二氧化硅-氧化镁混合氧化物(质量比I : I)。 [0317] The porous support using silica - magnesia mixed oxide (mass ratio of I: I). 将二氧化硅-氧化镁混合氧化物在600°C、氩气气氛下持续焙烧4h。 Silica - magnesia continuously calcined mixed oxides 4h at 600 ° C, argon atmosphere.

[0318] 镁化合物改变为乙氧基氯化镁(MgCl (OC2H5)),非茂金属配体采用 [0318] The magnesium compound was changed to ethoxy magnesium chloride (MgCl (OC2H5)), using a non-metallocene ligand

Figure CN102964479AD00413

溶解镁化合物的溶剂改变为二甲苯,IVB族金属化合物的化学处理剂改变为四乙基钛(Ti (CH3CH2) 4),化学处理剂用溶剂改变为癸烷。 Solvent for dissolving the magnesium compound was changed to xylene, the chemical treatment IVB metal compound was changed to tetraethyl titanium (Ti (CH3CH2) 4), the chemical treating agent was changed to decane solvent used.

[0319] 其中配比为,镁化合物与溶剂配比为Imol : 300ml ;镁化合物与非茂金属配体摩尔比为I : 0.04;镁化合物与多孔载体的质量比为I : 3;镁化合物与以IVB族金属元素计的化学处理剂摩尔比为I : 0.05。 [0319] wherein the ratio of magnesium compound to solvent ratio of Imol: 300ml; molar ratio of magnesium compound with a nonmetallocene ligand I: 0.04; magnesium compound with the porous carrier mass ratio of I: 3; the magnesium compound and the molar ratio of the chemical treatment to group IVB metal element is I: 0.05.

[0320] 负载型非茂金属催化剂记为CAT-4。 [0320] The supported metallocene catalyst referred to as a non-CAT-4.

[0321] 实施例5 [0321] Example 5

[0322] 与实施例I基本相同,但有如下改变: [0322] substantially the same as Example I, but with the following changes:

[0323]多孔载体采用蒙脱土。 [0323] The porous support employed montmorillonite. 将蒙脱土在400°C、氮气气氛下持续焙烧8h。 8h continue montmorillonite calcined at 400 ° C, a nitrogen atmosphere. 镁化合物改 Modified magnesium compound

Figure CN102964479AD00421

物的溶剂改变为二乙苯,IVB族金属化合物的化学处理剂改变为四正丁基钛(Ti (C4H9)4),化学处理剂用溶剂改变为戊烷。 The solvent was changed to diethylbenzene, chemical treatment IVB metal compound was changed to tetra-n-butyl titanium (Ti (C4H9) 4), the chemical treating agent was changed to pentane solvent.

[0324] 其中配比为,镁化合物与溶剂配比为Imol : 400ml ;镁化合物与非茂金属配体摩尔比为I : 0. 30 ;镁化合物与多孔载体的质量比为I : 5 ;镁化合物与以IVB族金属元素计的化学处理剂摩尔比为I : 0.50。 [0324] wherein the ratio of magnesium compound to solvent ratio of Imol: 400ml; molar ratio of magnesium compound with a nonmetallocene ligand I: 0. 30; the magnesium compound with the porous carrier mass ratio is I: 5; Magnesium the molar ratio of compound of group IVB metal element to a chemical treatment agent I: 0.50.

[0325] 负载型非茂金属催化剂记为CAT-5。 [0325] The supported metallocene catalyst referred to as a non-CAT-5.

[0326] 实施例6 [0326] Example 6

[0327] 与实施例I基本相同,但有如下改变: [0327] substantially the same as Example I, but with the following changes:

[0328] 多孔载体采用部分交联(交联度为30% )的聚苯乙烯。 Partially cross-linked (cross-linking degree of 30%) polystyrene [0328] The porous support employed. 将该聚苯乙烯在100°C、氮气气氛下持续烘干12h。 The polystyrene continued drying 12h at 100 ° C, a nitrogen atmosphere.

[0329] 镁化合物改变为甲基氯化镁(Mg(CH3)Cl),非茂金属配体采用溶解镁化合物的溶剂改变为氯代甲苯。 [0329] The magnesium compound was changed to methyl magnesium chloride (Mg (CH3) Cl), the non-metallocene ligand with a solvent to dissolve the magnesium compound was changed to chloro toluene.

Figure CN102964479AD00422

[0330] 其中配比为,镁化合物与非茂金属配体摩尔比为I : 0. 10 ;镁化合物与多孔载体的质量比为I : 10;镁化合物与以IVB族金属元素计的化学处理剂摩尔比为I : 0.10。 [0330] wherein the ratio of the magnesium compound and the molar ratio of the non-metallocene ligand is I: 0. 10; the magnesium compound with the porous carrier mass ratio of I: 10; the magnesium compound and chemically treated to the Group IVB metal element molar ratio of agent I: 0.10.

[0331] 负载型非茂金属催化剂记为CAT-6。 [0331] The supported metallocene catalyst referred to as a non-CAT-6.

[0332] 实施例7 [0332] Example 7

[0333] 与实施例I基本相同,但有如下改变: [0333] substantially the same as Example I, but with the following changes:

[0334] 多孔载体采用硅藻土。 [0334] The porous support kieselguhr. 将硅藻土在500°C、氮气气氛下持续焙烧8h。 The calcined diatomaceous earth continue 8h at 500 ° C, a nitrogen atmosphere.

[0335] 镁化合物改变为乙基氯化镁(Mg (C2H5) Cl),溶解镁化合物的溶剂改变为溴代乙苯,非茂金属配体采用 [0335] The magnesium compound was changed to ethyl magnesium chloride (Mg (C2H5) Cl), changing the solvent to dissolve the magnesium compound is brominated ethyl benzene, using a non-metallocene ligand

Figure CN102964479AD00431

族金属化合物的化学处理剂改变为四乙氧基 The chemical treatment was changed to the metal compound tetraethyl

钛(Ti (OCH3CH2)4),化学处理剂用溶剂改变为环庚烷。 Titanium (Ti (OCH3CH2) 4), the chemical treating agent was changed to a ring-heptane solvent.

[0336] 其中配比为,镁化合物与多孔载体的质量比为I : 0.5;镁化合物与以IVB族金属元素计的化学处理剂摩尔比为I : I。 [0336] wherein the ratio is, the magnesium compound with the porous carrier mass ratio of I: 0.5; molar ratio of magnesium compound with metal element in Group IVB of the chemical treatment agent is I: I.

[0337] 负载型非茂金属催化剂记为CAT-7。 [0337] The supported metallocene catalyst referred to as a non-CAT-7.

[0338] 实施例8 [0338] Example 8

[0339] 与实施例I基本相同,但有如下改变: [0339] substantially the same as Example I, but with the following changes:

[0340] 多孔载体采用二氧化钛。 [0340] The porous support employed titania. 将二氧化钛在300°C、氮气气氛下持续焙烧 Continuously calcined titanium dioxide at 300 ° C, a nitrogen atmosphere

Figure CN102964479AD00432

.

IVB族金属化合物的化学处理剂改变为异丁基三氯化钛(Ti (I-C4H9) Cl3)。 The chemical treatment IVB metal compound was changed to isobutyl triethoxy titanium (Ti (I-C4H9) Cl3) chloride.

[0342] 负载型非茂金属催化剂记为CAT-8。 [0342] The supported metallocene catalyst referred to as a non-CAT-8.

[0343] 实施例9 [0343] Example 9

[0344] 与实施例I基本相同,但有如下改变: [0344] substantially the same as Example I, but with the following changes:

[0345] 镁化合物改变为甲基乙氧基镁(Mg (OC2H5) (CH3)),IVB族金属化合物的化学处理剂改变为三异丁氧基氯化钛(TiCl Q-OC4H9) 3),化学处理剂用溶剂改变为氯代环己烷。 [0345] methyl magnesium compound was changed to ethoxy magnesium (Mg (OC2H5) (CH3)), the chemical treatment IVB metal compound was changed to isobutoxy three titanium (TiCl Q-OC4H9) 3) chloride, The chemical treatment was changed to chloro cyclohexane solvent.

[0346] 负载型非茂金属催化剂记为CAT-9。 [0346] The supported metallocene catalyst referred to as a non-CAT-9.

[0347] 实施例10 [0347] Example 10

[0348] 与实施例I基本相同,但有如下改变: [0348] substantially the same as Example I, but with the following changes:

[0349] 镁化合物改变为丁基乙氧基镁(Mg(OC2H5) (C4H9)),IVB族金属化合物的化学处理剂改变为二甲氧基二氯化锆(ZrCl2(OCH3)2)。 [0349] The magnesium compound was changed to butyl ethoxy magnesium (Mg (OC2H5) (C4H9)), the chemical treatment IVB metal compound was changed to dimethoxyethane zirconium (ZrCl2 (OCH3) 2) chloride.

[0350] 负载型非茂金属催化剂记为CAT-10。 [0350] The supported metallocene catalyst referred to as a non-CAT-10.

[0351] 对比例A [0351] Comparative Example A

[0352] 与实施例I基本相同,但有如下改变: [0352] substantially the same as Example I, but with the following changes:

[0353] 镁化合物与非茂金属配体摩尔比改变为I : 0.16; [0353] The molar ratio of magnesium compound with a nonmetallocene ligand was changed to I: 0.16;

[0354] 催化剂记为CAT-A。 [0354] referred to as the catalyst CAT-A.

[0355] 对比例B [0355] Comparative Example B

[0356] 与实施例I基本相同,但有如下改变: [0356] substantially the same as Example I, but with the following changes:

[0357] 镁化合物与非茂金属配体摩尔比改变为I : 0.04;[0358] 催化剂记为CAT-B。 [0357] The molar ratio of magnesium compound with a nonmetallocene ligand was changed to I: 0.04; [0358] referred to as the catalyst CAT-B.

[0359] 对比例C [0359] Comparative Example C

[0360] 与实施例I基本相同,但有如下改变: [0361] 称取5g无水氯化镁,加入溶剂和丁醇后常温下完全溶解,得到镁化合物溶液。 [0360] substantially the same as Example I, but with the following modifications: [0361] Weigh 5g of anhydrous magnesium chloride was completely dissolved at room temperature after addition of the solvent and butanol, to obtain a magnesium compound solution.

[0362] 其中,镁化合物与丁醇摩尔比为I : 0.5; [0362] wherein the molar ratio of magnesium compound with alcohol to I: 0.5;

[0363] 催化剂记为CAT-C。 [0363] referred to as Catalyst CAT-C.

[0364] 对比例D [0364] Comparative Example D

[0365] 与实施例I基本相同,但有如下改变: [0365] substantially the same as Example I, but with the following changes:

[0366] 称取5g无水氯化镁以及非茂金属配体,加入溶剂后常温下完全溶解,然后加入经过热活化的硅胶,常温下搅拌2小时后形成混合浆液,常温下抽真空干燥得到修饰复合载体。 [0366] Weigh 5g of anhydrous magnesium chloride and the nonmetallocene ligand, the solvent is added after complete dissolution at room temperature, and is thermally activated silica gel was added to form mixed slurry was stirred at room temperature for 2 hours, and vacuum dried at room temperature to give MODIFIED carrier.

[0367] 催化剂记为CAT-D。 [0367] referred to as the catalyst CAT-D.

[0368] 实施例3 (应用实施例) [0368] Example 3 (Application Example)

[0369] 将本发明实施例中制得的催化剂CAT-I〜10、CAT-A〜D、分别在以下条件下按照以下方法进行乙烯的均聚、共聚和制备超高分子量聚乙烯。 [0369] The embodiment of the present invention, the catalyst CAT-I~10 prepared embodiment, CAT-A~D, ethylene respectively in the following manner under the following conditions homopolymerization, copolymerization and preparation of ultrahigh molecular weight polyethylene.

[0370] 均聚为:5升聚合高压釜,淤浆聚合工艺,2. 5升己烷溶剂,聚合总压0. 8MPa,聚合温度85°C,氢气分压0. 2MPa,反应时间2小时。 [0370] homo is: 5 l autoclave polymerization, slurry polymerization process, 25 liters of hexane solvent, the total polymerization pressure of 0. 8MPa, the polymerization temperature of 85 ° C, a hydrogen partial pressure of 0. 2MPa, a reaction time of 2 hours. . 首先将2. 5升己烷加入到聚合高压釜中,开启搅拌,然后加入50mg负载型非茂金属催化剂和助催化剂混合物,再加入氢气到0. 2MPa,最后持续通入乙烯使聚合总压恒定在0. 8MPa。 The first 2.5 liters of hexane was added to the polymerization autoclave, stirring open, non-metallocene catalyst and a cocatalyst mixture was then added 50mg supported, then hydrogen was added to 0. 2MPa, and finally continuing the polymerization ethylene was fed so the total pressure constant in 0. 8MPa. 反应结束后,将釜内气体放空,放出釜内聚合物,干燥后称量质量。 After completion of the reaction, the autoclave inside gas is vented, the autoclave discharged polymer mass weighed after drying. 该聚合反应的具体情况以及聚合评价结果如表I所示。 The details of this polymerization reaction and the polymerization evaluation results are shown in Table I below.

[0371] 共聚为:5升聚合高压釜,淤浆聚合工艺,2. 5升己烷溶剂,聚合总压0.8MPa,聚合温度85°C,氢气分压0. 2MPa,反应时间2小时。 [0371] copolymerization: 5 l autoclave polymerization, slurry polymerization process, 25 liters of hexane solvent, the total polymerization pressure of 0.8MPa, the polymerization temperature of 85 ° C, a hydrogen partial pressure of 0. 2MPa, a reaction time of 2 hours. 首先将2. 5升己烷加入到聚合高压釜中,开启搅拌,然后加入50mg负载型非茂金属催化剂和助催化剂混合物,一次性加入己烯-I共聚单体50g,再加入氢气到0. 2MPa,最后持续通入乙烯使聚合总压恒定在0. 8MPa。 The first 2.5 liters of hexane was added to the polymerization autoclave, stirring open, non-metallocene catalyst and a cocatalyst mixture was added 50mg supported then added in one -I hexene comonomer 50g, then hydrogen was added to 0. 2MPa, and finally continuing the polymerization ethylene was fed so the total pressure constant at 0. 8MPa. 反应结束后,将釜内气体放空,放出釜内聚合物,干燥后称量质量。 After completion of the reaction, the autoclave inside gas is vented, the autoclave discharged polymer mass weighed after drying. 该聚合反应的具体情况以及聚合评价结果如表I所示。 The details of this polymerization reaction and the polymerization evaluation results are shown in Table I below.

[0372] 制备超高分子量聚乙烯聚合为:5升聚合高压釜,淤浆聚合工艺,2. 5升己烷溶剂,聚合总压0. 5MPa,聚合温度70°C,反应时间2小时。 [0372] Preparation of ultrahigh molecular weight polyethylene polymerization: 5 liters autoclave polymerization, slurry polymerization process, 25 liters of hexane solvent, the total polymerization pressure of 0. 5MPa, a polymerization temperature of 70 ° C, a reaction time of 2 hours. 首先将2. 5升己烷加入到聚合高压釜中,开启搅拌,然后加入50mg负载型非茂金属催化剂和助催化剂混合物,助催化剂与催化剂活性金属摩尔比为100,最后持续通入乙烯使聚合总压恒定在0. 5MPa。 The first 2.5 liters of hexane was added to the polymerization autoclave, stirring open, non-metallocene catalyst and the cocatalyst was then added a mixture of 50mg supported, catalyst activity and the cocatalyst metal molar ratio is 100, the last continuously feeding ethylene polymerization the total pressure constant at 0. 5MPa. 反应结束后,将釜内气体放空,放出釜内聚合物,干燥后称量质量。 After completion of the reaction, the autoclave inside gas is vented, the autoclave discharged polymer mass weighed after drying. 该聚合反应的具体情况以及聚合评价结果如表2所示。 The details of this polymerization reaction and the polymerization evaluation results are shown in Table 2.

Figure CN102964479AD00451
Figure CN102964479AD00461

[0377] 通过对比表I中序号I和对比例序号14〜15的试验结果数据可知,催化剂中增加或减少非茂金属配体的加入量,其活性随之增加或降低,聚合物分子量分布有所变窄或变宽,超高分子量聚乙烯粘均分子量增加或降低,但聚合物堆密度有所降低。 [0377] Table I by comparing the number I and the test results of Comparative Example No. 14~15 data shows that the catalyst was added to increase or decrease the amount of non-metallocene ligand, increased or decreased activity, polymer molecular weight distribution the narrowed or widened, ultrahigh molecular weight polyethylene having a viscosity average molecular weight is increased or decreased, but the polymer bulk density decreased. 从而说明本发明提供的原位负载化方法,催化剂中非茂金属配体具有决定催化剂活性和聚合物性能的作用。 DESCRIPTION The present invention provides such a load-situ method, Africa metallocene catalyst ligand has a role in determining the catalyst activity and polymer properties.

[0378] 由表2可见,采用本发明所提供的催化剂,可以制备超高分子量聚乙烯,其堆密度均有所增加,而且对比序号I与2和3与4可见,采用甲基铝氧烷作为助催化剂能够增加聚合物的粘均分子量。 [0378] Table 2 shows that, using the catalysts of the present invention is provided, ultrahigh molecular weight polyethylene may be prepared, which have increased bulk density, and comparison with sequence number 2 and 3, and I 4 that the use of methyl aluminoxane as a co-catalyst capable of increasing viscosity average molecular weight of the polymer. 对比表2中序号I和对比例5〜6的试验结果数据可知,催化剂中增加或减少非茂金属配体,聚合物粘均分子量随之增加或减少。 Table 2 Comparison No. I data and test results can be seen in the ratio of 5 to 6, the catalyst to increase or decrease the non-metallocene ligands, polymer viscosity average molecular weight increased or decreased. 从而说明非茂金属配体还具有增加聚合物粘均分子量的作用。 Non-metallocene ligand thereby further increasing polymer having a viscosity-average molecular weight effect.

[0379] 通过对比表I中序号I和16,以及表2中序号I和7的试验结果可知,相比于镁化合物溶液中有醇的存在所得到的负载型非茂金属催化剂,本发明催化剂制备过程镁化合物溶液中没有醇的存在所得到的负载型非茂金属催化剂,具有更高的催化烯烃聚合活性、聚合物堆密度,以及窄的聚合物分子量分布,并且所得到的超高分子量聚乙烯粘均分子量较闻。 [0379] I I and 16 in number, and serial number in Table I and the test results can be seen by comparing the 27 meter, compared to the magnesium compound solution with a non-supported metallocene catalyst obtained in the presence of an alcohol, the catalyst of the present invention magnesium compound solution prepared in the process is not a supported non-metallocene catalyst in the presence of an alcohol obtained, having a higher catalytic activity for olefin polymerization, a polymer bulk density and narrow molecular weight distribution, and the resulting ultrahigh molecular weight polyethylene Wen viscosity average molecular weight than ethylene.

[0380] 对比表I中序号I和对比序号17,表2中I和8的试验结果可见,相比于非茂金属配体先于镁化合物共同溶解于溶剂中,加入多孔载体直接干燥后,再与IVB族化学处理剂反应后过滤洗涤干燥所制备的负载型非茂金属催化剂,本发明所提供的镁化合物溶解于溶剂中,加入多孔载体后再加入非茂金属配体,直接干燥后再与IVB族化学处理剂反应后过滤洗涤干燥所制备的负载型非茂金属催化剂,催化剂活性和聚合物堆密度较高,并且制备的超闻分子量聚乙烯粘均分子量也较闻。 [0380] Table I Comparative I and Comparative Reference number 17, the test results in Table I, and 8 2 is visible in the nonmetallocene ligand to the magnesium compound in the co-dissolved in a solvent as compared to the porous support after drying was added directly, supported non-metallocene catalyst by filtration and then washed and dried after the chemical treatment group IVB prepared by reacting a magnesium compound of the present invention is provided dissolved in a solvent, the porous support is added after the addition of a nonmetallocene ligand, directly after drying supported non-metallocene catalyst was filtered and washed and dried after the chemical treatment reaction of group IVB of the prepared catalyst activity and high bulk density of the polymer, and the super molecular weight polyethylene prepared smell viscosity average molecular weight are more audible.

[0381] 以上虽然已结合实施例对本发明的具体实施方式进行了详细的说明,但是需要指出的是,本发明的保护范围并不受这些具体实施方式的限制,而是由附录的权利要求书来确定。 [0381] Although the above embodiments in conjunction with the specific embodiments of the present invention has been described in detail, it should be noted that the scope of the present invention is not limited to these specific embodiments but by the appended claims appendices to make sure. 本领域技术人员可在不脱离本发明的技术思想和主旨的范围内对这些实施方式进行适当的变更,而这些变更后的实施方式显然也包括在本发明的保护范围之内。 Those skilled in the art can be appropriately changed in these embodiments without departing from the spirit and scope of the spirit of the present invention, the embodiment implemented these changes obviously be included within the scope of the present invention.

Claims (10)

  1. 1. 一种负载型非茂金属催化剂的制备方法,包括以下步骤: 使镁化合物溶解于溶剂中,获得镁化合物溶液的步骤; 使任选经过热活化处理的多孔载体与所述镁化合物溶液接触,获得第一混合浆液的步骤; 使非茂金属配体与所述第一混合浆液接触,获得第二混合浆液的步骤; 直接干燥所述第二混合浆液,获得修饰复合载体的步骤,和使选自IVB族金属化合物的化学处理剂与所述修饰复合载体反应,获得所述负载型非茂金属催化剂的步骤。 A method for preparing a supported non-metallocene catalyst, comprising the steps of: step a magnesium compound is dissolved in a solvent to obtain a magnesium compound solution; optionally after thermal activation process so that the porous support is contacted with the magnesium compound solution , a first step of obtaining a mixed slurry; non ligand metallocene mixed slurry into contact with the first, the second step the mixed slurry obtained; directly drying the second slurry mixing step of obtaining a modified composite carrier, and that the the chemical treatment is selected from group IVB metal compound to react with the modified composite carrier, the step of obtaining the supported non-metallocene catalyst.
  2. 2.按照权利要求I所述的制备方法,其特征在于,所述多孔载体选自烯烃均聚物或共聚物、聚乙烯醇或其共聚物、环糊精、聚酯或共聚酯、聚酰胺或共聚酰胺、氯乙烯均聚物或共聚物、丙烯酸酯均聚物或共聚物、甲基丙烯酸酯均聚物或共聚物、苯乙烯均聚物或共聚物、这些均聚物或共聚物的部分交联形式、元素周期表IIA、IIIA、IVA或IVB族金属的难熔氧化物或难熔复合氧化物、粘土、分子筛、云母、蒙脱土、膨润土和硅藻土中的一种或多种,优选选自部分交联的苯乙烯聚合物、二氧化硅、氧化铝、氧化镁、氧化硅铝、氧化镁铝、二氧化钛、分子筛和蒙脱土中的一种或多种,更优选选自二氧化硅。 2. The method of preparation according to claim I, wherein said porous support is selected from an olefin homopolymer or copolymer, a polyvinyl alcohol or a copolymer thereof, a cyclodextrin, polyester or copolyester, poly amide or copolyamides, or copolymers of vinyl chloride homopolymer, an acrylate homopolymer or copolymer, a methacrylate homopolymer or copolymer, a styrene homopolymer or copolymer, which homopolymer or copolymer partially crosslinked form, refractory oxide Periodic Table IIA, IIIA, IVA, or IVB metal compound or refractory oxide, clay, zeolite, mica, montmorillonite, bentonite, and diatomaceous earth of one or more, preferably styrene polymer selected from partially crosslinked, silica, alumina, magnesia, silica alumina, magnesium aluminum oxide, titanium oxide, zeolite and montmorillonite one or more, more preferably selected from silica.
  3. 3.按照权利要求I所述的制备方法,其特征在于,所述镁化合物选自卤化镁、烷氧基卤化镁、烷氧基镁、烷基镁、烷基卤化镁和烷基烷氧基镁中的一种或多种,优选选自卤化镁中的一种或多种,更优选氯化镁。 3. The production method according to claim I, wherein the magnesium is selected from magnesium halide, alkoxy magnesium halide, alkoxy magnesium compounds, alkyl magnesium, alkyl magnesium halide and alkyl alkoxy one or more of magnesium, a magnesium halide is preferably selected from one or more, and more preferably magnesium chloride.
  4. 4.按照权利要求I所述的制备方法,其特征在于,所述溶剂选自C6_12芳香烃、卤代C6_12芳香烃、酯和醚中的一种或多种,优选选自C6_12芳香烃和四氢呋喃中的一种或多种,最优选四氢呋喃。 4. The production method according to claim I, wherein said one or more solvents selected from C6_12 aromatic hydrocarbons, halogenated C6_12 aromatic hydrocarbons, esters and ethers, preferably tetrahydrofuran and an aromatic hydrocarbon selected from C6_12 one or more, most preferably tetrahydrofuran.
  5. 5.按照权利要求I所述的制备方法,其特征在于,所述非茂金属配体选自具有如下化学结构式的化合物中的一种或多种: The production method according to claim I, characterized in that said nonmetallocene ligand is selected from one or more compounds having the following chemical structure of formula:
    Figure CN102964479AC00021
    优选选自具有如下化学结构式的化合物(A)和化合物(B)中的一种或多种: Preferably selected from compounds of the following chemical structure formula (A) and compound (B) having one or more of:
    Figure CN102964479AC00031
    更优选选自具有如下化学结构式的化合物(AI)至化合物(A-4)和化合物(BI)至化合物(B-4)中的一种或多种: Compound (AI) is more preferably selected from the following chemical structure to the compound of formula (A-4) and Compound (BI) to one or more compounds (B-4) of:
    Figure CN102964479AC00032
    Figure CN102964479AC00041
    Figure CN102964479AC00051
    Figure CN102964479AC00052
    Figure CN102964479AC00053
    在以上所有的化学结构式中, q为O或I ; d为O或I ; A 选自氧原子、硫原子、硒原子、xNR22 -NR23R24、-N(O) R25R26、、R27 -PR28R29、-P (O)R3ciOR31、砜基、亚砜基或-Se(O)R39,其中N、O、S、Se和P各自为配位用原子; B选自氮原子、含氮基团、含磷基团或C1-C3tl烃基; D选自氮原子、氧原子、硫原子、硒原子、磷原子、含氮基团、含磷基团、C1-C3tl烃基、砜基、亚砜基、^J1r22 -N(O)R25R26、、ι^或-P(O)R32(OR33),其中N、O、S、Se 和P 各自为配位用原子; E选自含氮基团、含氧基团、含硫基团、含硒基团、含磷基团或氰基,其中N、0、S、Se和P各自为配位用原子; F选自氮原子、含氮基团、含氧基团、含硫基团、含硒基团或含磷基团,其中N、0、S、Se和P各自为配位用原子; G选自C1-C3tl烃基、取代的C1-C3tl烃基或惰性功能性基团; Y选自含氮基团、含氧基团、含硫基团、含硒基团或含磷基团 In all the above chemical structural formulas, q is O or I; d is O or I; A is selected from oxygen atom, a sulfur atom, a selenium atom, xNR22 -NR23R24, -N (O) R25R26,, R27 -PR28R29, -P (O) R3ciOR31, a sulfone group, a sulfoxide group or -Se (O) R39, wherein N, O, S, Se and P are each a ligand atom; B is selected from a nitrogen atom, a nitrogen group, a phosphorus group or C1-C3tl hydrocarbon group; D is selected from a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a nitrogen-containing group, phosphorus-containing groups, C1-C3tl hydrocarbon group, a sulfone group, a sulfoxide group, ^ J1r22 - N (O) R25R26,, ι ^, or -P (O) R32 (OR33), wherein N, O, S, Se and P are each of a coordination atom; E is selected from nitrogen-containing group, oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group or a cyano group, wherein N, 0, S, Se and P are each of a coordination atom; F. selected from nitrogen atom, a nitrogen-containing group, an oxygen-containing group , a sulfur-containing group, a selenium-containing group or a phosphorus-containing group, wherein N, 0, S, Se and P are each of a coordination atom; G is selected from C1-C3tl hydrocarbyl, substituted C1-C3tl hydrocarbyl or an inert functional of the group; Y is selected from nitrogen-containing group, oxygen-containing group, a sulfur-containing group, a selenium-containing group or a phosphorus-containing group 其中N、O、S、Se和P各自为配位用原子; Z选自含氮基团、含氧基团、含硫基团、含硒基团、含磷基团或氰基,其中N、0、S、Se和P各自为配位用原子; —代表单键或双键; -代表共价键或离子键; R1至R4、R6至R36、R38和R39各自独立地选自氢、C「C3(I烃基、取代的C1-C3tl烃基或惰性功能性基团,上述基团彼此间可以相同也可以不同,其中相邻基团可以彼此结合在一起成键或成环,优选形成芳香族环;并且R5选自氮上孤对电子、氢、C1-C3tl烃基、取代的C1-C3tl烃基、含氧基团、含硫基团、含氮基团、含硒基团或含磷基团;当R5为含氧基团、含硫基团、含氮基团、含硒基团或含磷基团时,R5中的N、O、S、P和Se可以作为配位用原子与所述中心IVB族金属原子进行配位, 所述惰性功能性基团选自卤素、含氧基团、含氮基团、含硅基团、含锗基团、含硫基团、含锡基团、C1- Wherein N, O, S, Se and P are each of a coordination atom; Z is selected from nitrogen-containing group, oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group or a cyano group, wherein N , 0, S, Se and P are each of a coordination atom; - represents a single or a double bond; - represents a covalent bond or an ionic bond; Rl to R4, R6 to R36, R38 and R39 are each independently selected from hydrogen, C "C3 (I hydrocarbyl, substituted C1-C3tl hydrocarbyl or an inert functional group, among the above groups may be the same or different from each other, wherein the adjacent groups may be bonded to each other to form a ring or a bond, preferably form an aromatic aromatic ring; and R5 is selected from a lone electron pair, hydrogen, C1-C3tl hydrocarbyl, substituted C1-C3tl hydrocarbon, oxygen-containing group, a sulfur group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group on the nitrogen group; R5 is when the oxygen-containing group, a sulfur group, a nitrogen-containing group, a selenium-containing group, or when the phosphorus-containing groups, R5 is N, O, S, P and Se atoms may be used as ligands with the central metal atom of group IVB coordinated to, the inert functional group selected from halogen, oxygen-containing group, a nitrogen-containing group, a silicon-containing group, a germanium-containing group, a sulfur-containing group, a tin-containing group group, C1- Cltl酯基和硝基, 所述非茂金属配体进一步优选选自具有如下化学结构式的化合物中的一种或多种: Cltl ester group and a nitro group, further the nonmetallocene ligand is preferably selected from one or more compounds having the following chemical structure of formula:
    Figure CN102964479AC00061
    所述非茂金属配体最优选选自具有如下化学结构式的化合物中的一种或多种: The nonmetallocene ligand is most preferably selected from one or more compounds having the following chemical structure of formula:
    Figure CN102964479AC00062
  6. 6.按照权利要求5所述的制备方法,其特征在于, 所述卤素选自F、Cl、Br或I ; 所述含氮基团选自 6. The production method according to claim 5, wherein said halogen is selected from F, Cl, Br or I; the nitrogen-containing groups selected from
    Figure CN102964479AC00063
    22 -NR23R24、-T-NR23R24 或-N(O) R25R26 ;所述含磷基团选自 22 -NR23R24, -T-NR23R24 or -N (O) R25R26; containing group selected from
    Figure CN102964479AC00071
    -PR28R29、-P (O) R30R31 或-P (O) R32 (OR33); 所述含氧基团选自羟基、-OR34和-T-OR34 ; 所述含硫基团选自-SR35、-T-SR35、-S (O) R36 或-T-SO2R37 ; 所述含硒基团选自-SeR38、-T-SeR38, -Se (O) R39 或-T-Se (O) R39 ; 所述基团T选自C1-C3tl烃基、取代的C1-C3tl烃基或所述惰性功能性基团; 所述R37选自氢、C1-C3tl烃基、取代的C1-C3tl烃基或所述惰性功能性基团; 所述C1-C3tl烃基选自C1-C3tl烷基、C7-C5tl烷芳基、C7-C5tl芳烷基、C3-C3tl环状烷基、C2-C30烯基、C2-C3tl炔基、C6-C3tl芳基、C8-C3tl稠环基或C4-C3tl杂环基,其中所述杂环基含有1-3个选自氮原子、氧原子或硫原子的杂原子; 所述取代的C1-C3tl烃基选自带有一个或多个所述卤素和/或所述C1-C3tl烷基作为取代基的所述C1-C3tl烃基; 所述含硅基团选自-SiR42R43R44或-T-SiR45 ; 所述含锗基团选自-GeR46R47R48或-T-GeR49 ; 所述含锡基团选自-SnRsiR51R52、-T-SnR53 或-T-Sn -PR28R29, -P (O) R30R31, or -P (O) R32 (OR33); oxygen-containing group selected from hydroxyl, -OR34 and -T-OR34; a sulfur-containing group is selected from -SR35, - T-SR35, -S (O) R36 or -T-SO2R37; selenium-containing group is selected from the -SeR38, -T-SeR38, -Se (O) R39 or -T-Se (O) R39; the T is selected from the group C1-C3tl hydrocarbyl, substituted hydrocarbyl or C1-C3tl the inert functional group; R37 is selected from a hydrogen, C1-C3tl hydrocarbyl, substituted hydrocarbyl or C1-C3tl the inert functional group group; the hydrocarbon group is selected from C1-C3tl C1-C3tl alkyl, C7-C5tl alkylaryl, C7-C5tl aralkyl, C3-C3tl cyclic alkyl, C2-C30 alkenyl, C2-C3tl alkynyl group, C6-C3tl aryl, C8-C3tl fused ring group or a C4-C3tl heterocyclyl, wherein the heterocyclyl contains 1-3 heteroatoms selected from nitrogen atom, an oxygen atom or a sulfur atom; said substituted C1 -C3tl hydrocarbon group having one or more selected from the halogen and / or C1-C3tl alkyl group as a substituent of the C1-C3tl hydrocarbon group; said silicon-containing group selected -SiR42R43R44 or -T-SiR45 ; selected -GeR46R47R48 containing germanium or a group -T-GeR49; tin-containing group selected -SnRsiR51R52, -T-SnR53 or -T-Sn (O) R54 ; 所述R42至R54各自独立地选自氢、所述C1-C3tl烃基、所述取代的C1-C3tl烃基或所述惰性功能性基团,上述基团彼此间可以相同也可以不同,其中相邻基团可以彼此结合在一起成键或成环,并且所述基团T同权利要求5定义。 (O) R54; R42 to R54 are each independently a selected from hydrogen, a C1-C3tl hydrocarbyl, the substituted C1-C3tl hydrocarbyl or an inert functional group, the above groups may be identical to each other different, wherein the adjacent groups may be bonded to each other to form a ring or a bond, and the group T 5 is defined in claims.
  7. 7.按照权利要求I所述的制备方法,其特征在于,所述IVB族金属化合物选自IVB族金属齒化物、IVB族金属烷基化合物、IVB族金属烷氧基化合物、IVB族金属烷基齒化物和IVB族金属烷氧基卤化物中的一种或多种,优选选自IVB族金属卤化物中的一种或多种,更优选选自TiCl4、TiBr4, ZrCl4, ZrBr4, HfCl4和HfBr4中的一种或多种,最优选选自TiCl4和ZrCl4中的一种或多种。 7. The production method according to claim I, wherein said compound is selected from Group IVB metal compound of Group IVB metal teeth, Group IVB metal alkyl compound, a Group IVB metal alkoxides, Group IVB metal alkyl one or more teeth thereof and a group IVB metal alkoxy halide, preferably group IVB metal halide is one or more, more preferably selected from TiCl4, TiBr4, ZrCl4, ZrBr4, HfCl4 and HfBr4 one or more, most preferably selected from TiCl4 and ZrCl4 of one or more.
  8. 8.按照权利要求I所述的制备方法,其特征在于,以Mg元素计的所述镁化合物与所述非茂金属配体的摩尔比为I : O. 0001-1,优选I : O. 0002-0. 4,更优选I : O. 0008-0. 2,进一步优选I : O. 001-0. 1,所述镁化合物与所述溶剂的比例为Imol : 75〜400ml,优选Imol : 150〜300ml,更优选Imol : 200〜250ml,以Mg元素计的所述镁化合物与以IVB族金属元素计的所述化学处理剂的摩尔比为I : 0.01-1,优选I : 0.01-0.50,更优选I : O. 10-0. 30,并且以镁化合物固体计的所述镁化合物与所述多孔载体的质量比为I : O. 1-20,优选I : O. 5-10,更优选I : 1-5。 8. The production method according to claim I, wherein the molar ratio of Mg in the magnesium compound on an elemental basis of the nonmetallocene ligand is I: O. 0001-1, preferably I: O. . 0002-04, and more preferably I: O. 0008-0 2, more preferably I:.. O. 001-0 1, the ratio of the magnesium compound and the solvent is Imol: 75~400ml, preferably Imol: 150~300ml, more preferably Imol: 200~250ml, the molar ratio of Mg in the magnesium compound calculated as elemental chemical treatment with the group IVB metal element in terms of I: 0.01-1, preferably I: 0.01-0.50 , more preferably I:. O. 10-0 30, and the mass of the magnesium compound to the magnesium compound with the porous solids support ratio of I: O. 1-20, preferably I: O. 5-10, more preferably I: 1-5.
  9. 9. 一种负载型非茂金属催化剂,它是由按照权利要求1-8任一项所述的制备方法制造的。 A supported nonmetallocene catalyst, which is produced by a production method according to claim any one of claims 1-8.
  10. 10. 一种烯烃均聚/共聚方法,其特征在于,以按照权利要求9所述的负载型非茂金属催化剂为主催化剂,以选自招氧烧、烧基招、齒代烧基招、砸氣烧、烧基砸和烧基砸按盐中的一种或多种为助催化剂,使烯烃均聚或共聚。 10. An olefin homopolymerization / copolymerization process, wherein, according to a supported non-metallocene-based catalyst The catalyst according to claim 9, selected from oxygen firing strokes, strokes burn group, the teeth of burning yl strokes, drop burning gas, burning and burning yl group drop to drop one of its salts according to one or more cocatalyst, olefin homopolymerization or copolymerization.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0260130A1 (en) * 1986-09-09 1988-03-16 Exxon Chemical Patents Inc. New supported polymerization catalyst
CN102059152A (en) * 2009-11-13 2011-05-18 中国石化扬子石油化工有限公司 Loaded non-metallocene catalyst and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0260130A1 (en) * 1986-09-09 1988-03-16 Exxon Chemical Patents Inc. New supported polymerization catalyst
CN102059152A (en) * 2009-11-13 2011-05-18 中国石化扬子石油化工有限公司 Loaded non-metallocene catalyst and preparation method and application thereof

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