CN117069771A - Metallocene-non-metallocene complex, preparation method thereof and application thereof in preparation of disentangled ultra-high molecular weight polyethylene - Google Patents

Metallocene-non-metallocene complex, preparation method thereof and application thereof in preparation of disentangled ultra-high molecular weight polyethylene Download PDF

Info

Publication number
CN117069771A
CN117069771A CN202311032500.9A CN202311032500A CN117069771A CN 117069771 A CN117069771 A CN 117069771A CN 202311032500 A CN202311032500 A CN 202311032500A CN 117069771 A CN117069771 A CN 117069771A
Authority
CN
China
Prior art keywords
complex
formula
substituted
unsubstituted
halogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311032500.9A
Other languages
Chinese (zh)
Inventor
王保力
曾玺文
崔冬梅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Institute of Applied Chemistry of CAS
Original Assignee
Changchun Institute of Applied Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CN202311032500.9A priority Critical patent/CN117069771A/en
Publication of CN117069771A publication Critical patent/CN117069771A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)

Abstract

The complex provided by the application has a structure of formula (I), formula (II) or formula (III), and consists of a ligand and a central metal, wherein the ligand is a hetero atom containing an aromatic group, the central metal is Ti, and can be used for catalyzing the synthesis of ultra-high molecular weight polyethylene, the viscosity average molecular weight of the prepared ultra-high molecular weight polyethylene is 100-800 ten thousand, the entanglement degree between molecular chains is lower, the melting point is 130-145 ℃, and the polymerization activity is higher than 10 6 . Moreover, the complex provided by the application is simple to synthesize, and the yield is high and can reach 50% -60%.

Description

茂-非茂金属配合物、其制备方法及在解缠结超高分子量聚乙 烯制备中的应用Metallocene-non-metallocene complex, preparation method thereof and application in preparation of disentangled ultrahigh molecular weight polyethylene

技术领域Technical Field

本发明涉及催化剂及其应用技术领域，具体是一种茂-非茂金属配合物、其制备方法及在解缠结超高分子量聚乙烯制备中的应用。The invention relates to the technical field of catalysts and their application, in particular to a metallocene-non-metallocene complex, a preparation method thereof and application thereof in the preparation of disentangled ultra-high molecular weight polyethylene.

背景技术Background Art

1975年荷兰利用十氢萘做溶剂发明了凝胶纺丝法(Gelspinning)，成功制备出了超高分子量聚乙烯(UHMWPE)纤维，并于1979年申请了专利。此后经过十年的努力研究，证实凝胶纺丝法是制造高强聚乙烯纤维的有效方法，具有工业化前途。超高分子量聚乙烯具有超强的耐磨性、自润滑性，强度比较高、化学性质稳定、抗老化性能强，在现代化战争和航空、航天、海域防御装备等领域发挥着举足轻重的作用。In 1975, the Netherlands invented the gel spinning method (Gelspinning) using decahydronaphthalene as a solvent, successfully produced ultra-high molecular weight polyethylene (UHMWPE) fiber, and applied for a patent in 1979. After ten years of hard research, it was confirmed that the gel spinning method is an effective method for manufacturing high-strength polyethylene fibers and has a promising industrialization prospect. Ultra-high molecular weight polyethylene has super wear resistance, self-lubrication, relatively high strength, stable chemical properties, and strong anti-aging performance. It plays a pivotal role in modern warfare and aviation, aerospace, and sea defense equipment.

超高分子量聚乙烯分子量较高，流动性很差较难加工。实现超高分子量聚乙烯的合成及性能加工对其工业应用具有重要意义，但是目前能够使用的催化剂很少。而且，几乎所有的商业化UHMWPE都是用Zieglar Natta催化剂(Z-N催化剂)生产。Z-N催化剂是非均相催化剂，含有多个活性位点，这些活性位点表现出不同的反应活性，因此得到的聚合物分子量分布较宽。同时由于反应温度较高，制备的UHMWPE会出现分子链缠结，使聚合物链运动能力受到抑制，从而影响产品的加工性能。而茂金属催化剂和非茂金属催化剂是单活性种催化剂，与Z-N催化剂相比，可以实现活性聚合，得到分子量分布较窄的聚合物，且聚合温度较低，可以有效规避分子链缠结的情况发生，但是，现有技术公开的茂金属催化剂或非茂金属催化剂均无法用于合成UHMWPE。Ultra-high molecular weight polyethylene has a high molecular weight, poor fluidity and is difficult to process. The synthesis and performance processing of ultra-high molecular weight polyethylene is of great significance for its industrial application, but there are few catalysts that can be used at present. Moreover, almost all commercial UHMWPE is produced using Zieglar Natta catalysts (Z-N catalysts). Z-N catalysts are heterogeneous catalysts containing multiple active sites, which exhibit different reactivity, so the molecular weight distribution of the obtained polymer is relatively wide. At the same time, due to the high reaction temperature, the prepared UHMWPE will have molecular chain entanglement, which inhibits the mobility of the polymer chain, thereby affecting the processing performance of the product. Metallocene catalysts and non-metallocene catalysts are single-active catalysts. Compared with Z-N catalysts, active polymerization can be achieved to obtain polymers with a narrow molecular weight distribution, and the polymerization temperature is low, which can effectively avoid the occurrence of molecular chain entanglement. However, metallocene catalysts or non-metallocene catalysts disclosed in the prior art cannot be used to synthesize UHMWPE.

发明内容Summary of the invention

有鉴于此，本发明所要解决的技术问题在于提供一种配合物、其制备方法及其用途，本申请提供的配合物为茂-非茂金属配合物，由配体和中心金属组成，可用于催化合成UHMWPE，分子量分布较窄，且分子链间缠结度较低。In view of this, the technical problem to be solved by the present invention is to provide a complex, a preparation method thereof and a use thereof. The complex provided in the present application is a metallocene-non-metallocene complex, which is composed of a ligand and a central metal, can be used for catalytic synthesis of UHMWPE, has a narrow molecular weight distribution, and has a low degree of entanglement between molecular chains.

本发明提供了式(I)、式(II)或式(III)所示的配合物：The present invention provides a complex represented by formula (I), formula (II) or formula (III):

其中，Z选自S、O、(CH2)n；n为1～5的整数；Wherein, Z is selected from S, O, (CH 2 ) n ; n is an integer of 1 to 5;

R1选自取代或未取代的C1～C12的烷基、取代或未取代的苯基或卤素； R1 is selected from substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted phenyl or halogen;

R2、R3分别独立的选自氢、取代或未取代的C1～C12的烷基或卤素；R 2 and R 3 are independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen;

R4、R5、R6、R7、R8分别独立的选自氢、取代或未取代的C1～C12的烷基或卤素；R 4 , R 5 , R 6 , R 7 and R 8 are independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen;

R9、R10、R11、R12、R13、R14、R15、R16、R17分别独立的选自氢、取代或未取代的硅基、取代或未取代的C1～C12的烷基、取代或未取代的芳基或卤素。R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently selected from hydrogen, substituted or unsubstituted silicon, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted aryl or halogen.

本发明提供的配合物为茂-非茂金属配合物，由配体和中心金属组成，配体是含有芳香基团杂原子类，中心金属是Ti，可用于催化超高分子量聚乙烯的合成，制备得到的超高分子量聚乙烯的粘均分子量为100～800万，分子链间缠结度较低，熔点在130℃～145℃之间，聚合活性较高达106。而且，本发明提供的配合物合成简单，收率较高，可达50％～60％。The complex provided by the present invention is a metallocene-non-metallocene complex, which is composed of a ligand and a central metal. The ligand is a heteroatom containing an aromatic group, and the central metal is Ti. It can be used to catalyze the synthesis of ultra-high molecular weight polyethylene. The prepared ultra-high molecular weight polyethylene has a viscosity average molecular weight of 1 to 8 million, a low degree of entanglement between molecular chains, a melting point between 130°C and 145°C, and a high polymerization activity of 10 6. Moreover, the complex provided by the present invention is simple to synthesize and has a high yield of 50% to 60%.

在一些具体的实现方式中，Z选自S或CH2；In some specific implementations, Z is selected from S or CH 2 ;

R1选自取代或未取代的C1～C5的烷基、卤素；R 1 is selected from substituted or unsubstituted C1-C5 alkyl, halogen;

R2、R3分别独立的选自氢、取代或未取代的C1～C5的烷基；R 2 and R 3 are independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl;

R4、R5、R6、R7、R8分别独立的选自氢、取代或未取代的C1～C12的烷基或卤素；R 4 , R 5 , R 6 , R 7 and R 8 are independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen;

R9、R10、R11、R12、R13、R14、R15、R16、R17分别独立的选自氢、烷基取代的硅基、取代或未取代的C1～C5的烷基。R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently selected from hydrogen, an alkyl-substituted silicon group, and a substituted or unsubstituted C1-C5 alkyl group.

在一些具体的实现方式中，所述Z选自S、CH2；In some specific implementations, the Z is selected from S, CH 2 ;

所述R1选自Cl、CH3；The R 1 is selected from Cl, CH 3 ;

所述R2、R3为叔丁基、甲基、辛基、卤素中的任意一种；The R 2 and R 3 are any one of tert-butyl, methyl, octyl and halogen;

所述R4、R5、R6、R7、R8分别独立的选自氢、甲基、叔丁基、卤素中的任意一种；The R 4 , R 5 , R 6 , R 7 and R 8 are independently selected from any one of hydrogen, methyl, tert-butyl and halogen;

所述R9、R10、R11、R12、R13、R14、R15、R16、R17分别独立的选自氢、甲基、乙基、叔丁基、辛基、三甲基硅基的任意一种；R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 are independently selected from any one of hydrogen, methyl, ethyl, tert-butyl, octyl, and trimethylsilyl;

在一些具体的实现方式中，所述配合物选自：In some specific implementations, the complex is selected from:

配合物1：Z＝S,R1＝Cl,R2＝C(CH3)3,R3＝C(CH3)3,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H；Complex 1: Z＝S, R 1 ＝Cl, R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 =H,R 8 =H,R 9 =H,R 10 =H,R 11 =H,R 12 =H,R 13 =H;

配合物2：Z＝S,R1＝Cl,R2＝C(CH3)3,R3＝C(CH3)3,R4＝F,R5＝F,R6＝F,R7＝F,R8＝F,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H；Complex 2: Z＝S, R 1 ＝Cl, R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝F, R 5 ＝F, R 6 ＝F, R 7 =F,R 8 =F,R 9 =H,R 10 =H,R 11 =H,R 12 =H,R 13 =H;

配合物3：Z＝S,R1＝CH3,R2＝C(CH3)3,R3＝C(CH3)3,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H；Complex 3: Z＝S, R 1 ＝CH 3 , R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 =H,R 8 =H,R 9 =H,R 10 =H,R 11 =H,R 12 =H,R 13 =H;

配合物4：Z＝CH2,R1＝Cl,,R2＝C(CH3)3,R3＝C(CH3)3,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H；Complex 4: Z＝CH 2 , R 1 ＝Cl,, R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 =H,R 8 =H,R 9 =H,R 10 =H,R 11 =H,R 12 =H,R 13 =H;

配合物5：Z＝CH2,R1＝Cl,R2＝H,R3＝H,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H；Complex 5: Z＝CH 2 , R 1 ＝Cl, R 2 ＝H, R 3 ＝H, R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 ＝H, R 8 ＝H, R 9 =H,R 10 =H,R 11 =H,R 12 =H,R 13 =H;

配合物6：Z＝CH2,R1＝CH3,R2＝C(CH3)3,R3＝C(CH3)3,R4＝F,R5＝F,R6＝F,R7＝F,R8＝F,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H；Complex 6: Z＝CH 2 , R 1 ＝CH 3 , R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝F, R 5 ＝F, R 6 ＝F, R 7 =F,R 8 =F,R 9 =H,R 10 =H,R 11 =H,R 12 =H,R 13 =H;

配合物7：Z＝S,R1＝Cl,R2＝C(CH3)3,R3＝C(CH3)3,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝CH3,R10＝CH3,R11＝Si(CH3)3,R12＝CH3,R13＝CH3；Complex 7: Z＝S, R 1 ＝Cl, R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 =H,R 8 =H,R 9 =CH 3 ,R 10 =CH 3 ,R 11 =Si(CH 3 ) 3 ,R 12 =CH 3 ,R 13 =CH 3 ;

配合物8：Z＝S,R1＝Cl,R2＝H,R3＝H,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝CH3,R10＝CH3,R11＝Si(CH3)3,R12＝CH3,R13＝CH3；Complex 8: Z＝S, R 1 ＝Cl, R 2 ＝H, R 3 ＝H, R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 ＝H, R 8 ＝H, R 9 ＝CH 3 ,R 10 ＝CH 3 ,R 11 ＝Si(CH 3 ) 3 ,R 12 ＝CH 3 ,R 13 ＝CH 3 ;

配合物9：Z＝S,R1＝Cl,R2＝H,R3＝H,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝H,R10＝H,R11＝Si(CH3)3,R12＝H,R13＝H；Complex 9: Z＝S, R 1 ＝Cl, R 2 ＝H, R 3 ＝H, R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 ＝H, R 8 ＝H, R 9 =H,R 10 =H,R 11 =Si(CH 3 ) 3 ,R 12 =H,R 13 =H;

配合物10：Z＝CH2,R1＝Cl,R2＝C(CH3)3,R3＝C(CH3)3,R4＝F,R5＝F,R6＝F,R7＝F,R8＝F,R9＝H,R10＝H,R11＝Si(CH3)3,R12＝H,R13＝H；Complex 10: Z＝CH 2 , R 1 ＝Cl, R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝F, R 5 ＝F, R 6 ＝F, R 7 =F,R 8 =F,R 9 =H,R 10 =H,R 11 =Si(CH 3 ) 3 ,R 12 =H,R 13 =H;

配合物11：Z＝S,R1＝Cl,R2＝C(CH3)3,R3＝C(CH3)3,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H,R14＝H，R15＝H；Complex 11: Z＝S, R 1 ＝Cl, R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 =H,R 8 =H,R 9 =H,R 10 =H,R 11 =H,R 12 =H,R 13 =H,R 14 =H,R 15 =H;

配合物12：Z＝S,R1＝Cl,R2＝C(CH3)3,R3＝C(CH3)3,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H,R14＝H,R15＝H,R16＝H，R17＝H。Complex 12: Z＝S, R 1 ＝Cl, R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H,R 14 ＝H,R 15 ＝H,R 16 ＝H,R 17 =H.

在一些具体的实现方式中，所述配合物具有式(1)～式(4)的结构：In some specific implementations, the complex has structures of formula (1) to formula (4):

本发明还提供了上述配合物的制备方法，包括以下步骤：The present invention also provides a method for preparing the above-mentioned complex, comprising the following steps:

将式(a)所示的配体与锂化试剂和CpTiX3混合反应，得到式(I)、(II)或式(III)所示的配合物，其中，R1选自X，X为卤素；The ligand represented by formula (a) is mixed with a lithiation agent and CpTiX 3 to obtain a complex represented by formula (I), (II) or formula (III), wherein R1 is selected from X, and X is a halogen;

其中，CpTiX3中，Cp选自取代的或非取代的环戊二烯基、取代的或非取代茚基、取代的或非取代芴基，X为卤素；Wherein, in CpTiX 3 , Cp is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted fluorenyl, and X is halogen;

可选的，将R1为卤素的式(I)、式(II)或式(III)所述的配合物和烷基试剂混合反应，得到R1不为卤素的式(I)、式(II)或式(III)所示的配合物。Optionally, the complex of formula (I), formula (II) or formula (III) in which R 1 is halogen and an alkyl reagent are mixed and reacted to obtain a complex of formula (I), formula (II) or formula (III) in which R 1 is not halogen.

其合成路线如下：Its synthetic route is as follows:

本申请对所述式(a)所示的化合物的来源没有特殊限制，可以为市场上购买，也可以按照本领域技术人员公知的方法进行制备。如下图为化合物(a)的制备方法。The present application has no particular restrictions on the source of the compound represented by formula (a), which can be purchased from the market or prepared according to methods known to those skilled in the art. The following figure shows the preparation method of compound (a).

首先在氮气气氛下，在0℃～150℃下将化合物b、化合物c混合，以FeCl3，MgCl2等作为催化剂，反应10～72h，反应结束后过滤，浓缩反应溶液，在进行柱层析分离，石油醚：乙酸乙酯为7～10：0～3，得到化合物a。First, under nitrogen atmosphere, compound b and compound c are mixed at 0°C to 150°C, and FeCl 3 , MgCl 2 and the like are used as catalysts, and the reaction is carried out for 10 to 72 hours. After the reaction is completed, the reaction solution is filtered and concentrated, and then column chromatography is performed for separation, and the ratio of petroleum ether to ethyl acetate is 7 to 10:0 to 3 to obtain compound a.

本发明首先在氮气气氛下，在-78℃～0℃条件下，将式(a)所示的化合物与锂化试剂溶液混合，进行反应。在一些具体的实现方式中，所述锂化试剂溶液的溶剂为正己烷，所述锂化试剂溶液的浓度为1～5M，优选为2～4M，更优选为2.5～3.2M。在一些具体的实现方式中，所述式(a)所示的化合物与锂化试剂的摩尔比为1:1～5，优选为1:1。在一些具体的实现方式中，所述锂化试剂选自烷基锂，包括但不限于正丁基锂等。在一些具体的实现方式中，所述反应的温度为-78℃～0℃，优选为-60～0℃，时间为10～24h，优选为12～20h。The present invention first mixes the compound shown in formula (a) with a lithiation reagent solution under a nitrogen atmosphere at -78°C to 0°C to react. In some specific implementations, the solvent of the lithiation reagent solution is n-hexane, and the concentration of the lithiation reagent solution is 1 to 5M, preferably 2 to 4M, and more preferably 2.5 to 3.2M. In some specific implementations, the molar ratio of the compound shown in formula (a) to the lithiation reagent is 1:1 to 5, preferably 1:1. In some specific implementations, the lithiation reagent is selected from alkyl lithium, including but not limited to n-butyl lithium, etc. In some specific implementations, the reaction temperature is -78°C to 0°C, preferably -60 to 0°C, and the reaction time is 10 to 24h, preferably 12 to 20h.

反应完毕后，将反应混合液过滤、浓缩、重结晶后，得到白色固体，然后将所述白色固体与CpTiX3中反应，得到R1为卤素的式(I)、式(II)或式(III)的配合物。本申请对CpTiX3的来源没有特殊限制，可以为市场上购买，也可以按照本领域技术人员公知的方法进行制备。其中，Cp选自取代的或非取代的环戊二烯基、取代的或非取代茚基、取代的或非取代芴；X为卤素，优选为Cl。After the reaction is completed, the reaction mixture is filtered, concentrated, and recrystallized to obtain a white solid, which is then reacted with CpTiX 3 to obtain a complex of formula (I), formula (II) or formula (III) in which R 1 is a halogen. The present application has no special restrictions on the source of CpTiX 3 , which can be purchased on the market or prepared according to methods known to those skilled in the art. Wherein, Cp is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted fluorene; X is a halogen, preferably Cl.

具体而言，本申请在-78℃～0℃和氮气条件下将得到的白色固体和CpTiX3分别溶解，混合后进行反应。在一些具体的实现方式中，所述溶解的溶剂为脂肪族饱和烃、芳香烃、芳基卤化物和环烷烃中的一种或多种，优选为甲苯。所述白色固体溶解后的浓度为0.05～5mmol/mL，优选为0.1～4mmol/mL，更优选0.15～2mmol/mL；所述CpTiX3溶解后的浓度为0.05～5mmol/mL，优选为0.1～4mmol/mL，更优选0.15～2mmol/mL。在一些具体的实现方式中，所述CpTiX3与得到的白色固体的摩尔比为1:1～5，优选为1:1。在一些具体的实现方式中，所述反应的温度为-78℃～0℃，优选为-60～0℃，时间为10～24h，优选为12～20h。反应完毕后，将反应混合液过滤、浓缩、重结晶后，得到R1为卤素的式(I)、式(II)或式(III)所述的配合物。Specifically, the present application dissolves the obtained white solid and CpTiX 3 separately under -78°C to 0°C and nitrogen conditions, and reacts after mixing. In some specific implementations, the dissolving solvent is one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aromatic halides and cycloalkanes, preferably toluene. The concentration of the white solid after dissolution is 0.05 to 5 mmol/mL, preferably 0.1 to 4 mmol/mL, more preferably 0.15 to 2 mmol/mL; the concentration of CpTiX 3 after dissolution is 0.05 to 5 mmol/mL, preferably 0.1 to 4 mmol/mL, more preferably 0.15 to 2 mmol/mL. In some specific implementations, the molar ratio of CpTiX 3 to the obtained white solid is 1:1 to 5, preferably 1:1. In some specific implementations, the reaction temperature is -78°C to 0°C, preferably -60 to 0°C, and the time is 10 to 24h, preferably 12 to 20h. After the reaction is completed, the reaction mixture is filtered, concentrated, and recrystallized to obtain a complex of formula (I), formula (II) or formula (III) wherein R 1 is a halogen.

可选的，本申请将R1为卤素的式(I)、式(II)或式(III)所述的配合物和烷基试剂混合反应，得到R1不为卤素的式(I)、式(II)或式(III)所示的配合物。在一些具体的实现方式中，所述烷基化试剂包括但不限于CH3BrMg等，所述烷基化试剂和所述R1为卤素的式(I)、式(II)或式(III)所述的配合物的摩尔比为1:2～10，优选为1:2。在一些具体的实现方式中，所述烷基化反应的温度为-78℃～0℃，优选为-60～0℃，时间为1～10h，优选为3～5h。反应完毕后，过滤除去溶剂，己烷萃取，浓缩后，即可得到R1不为卤素的式(I)、式(II)或式(III)所述的配合物。Optionally, the present application mixes the complex described in formula (I), formula (II) or formula (III) in which R 1 is a halogen and an alkyl reagent to obtain a complex described in formula (I), formula (II) or formula (III) in which R 1 is not a halogen. In some specific implementations, the alkylating agent includes but is not limited to CH 3 BrMg, etc., and the molar ratio of the alkylating agent to the complex described in formula (I), formula (II) or formula (III) in which R 1 is a halogen is 1:2 to 10, preferably 1:2. In some specific implementations, the temperature of the alkylation reaction is -78°C to 0°C, preferably -60 to 0°C, and the time is 1 to 10h, preferably 3 to 5h. After the reaction is completed, the solvent is filtered off, extracted with hexane, and concentrated to obtain the complex described in formula (I), formula (II) or formula (III) in which R 1 is not a halogen.

本发明还提供了上述茂-非茂金属配合物在催化乙烯聚合中的应用。采用上述配合物催化聚乙烯聚合可得到超高分子量聚乙烯，在一些具体的实现方式中，超高分子量聚乙烯粘均分子量为100～800万且分子链间缠结度较低，其分子量优选为100～600万，更优选为100～500万。所述超高分子量聚乙烯分子量分布为1～10，优选为1～6，更优选为1～4。在本发明中，所述超高分子量聚乙烯结晶度在60-90％之间、130-150℃的熔点。The present invention also provides the use of the metallocene-non-metallocene complex in catalyzing ethylene polymerization. Ultra-high molecular weight polyethylene can be obtained by catalyzing polyethylene polymerization with the complex. In some specific implementations, the viscosity-average molecular weight of the ultra-high molecular weight polyethylene is 1 to 8 million and the degree of entanglement between molecular chains is low. The molecular weight is preferably 1 to 6 million, and more preferably 1 to 5 million. The molecular weight distribution of the ultra-high molecular weight polyethylene is 1 to 10, preferably 1 to 6, and more preferably 1 to 4. In the present invention, the ultra-high molecular weight polyethylene has a crystallinity between 60-90% and a melting point of 130-150°C.

本发明还提供了一种催化剂组合物，包括上述技术方案所述的配合物、有机硼盐化合物和有机铝化合物。The present invention also provides a catalyst composition, comprising the complex described in the above technical solution, an organic boron salt compound and an organic aluminum compound.

在本发明中，所述有机硼盐化合物可以为由有机硼阴离子与阳离子组成的离子型化合物；所述有机硼阴离子包括但不限于四苯基硼酸根([BPh4]-)、四(单氟苯基)硼酸根、四(二氟苯基)硼酸根、四(三氟苯基)硼酸根、四(四氟苯基)硼酸根、四(五氟苯基)硼酸根([B(C6F5)4]-)、四(四氟甲基苯基)硼酸根、四(甲苯基)硼酸根、四(二甲苯基)硼酸根，(三苯基,五氟苯基)硼酸根、[三(五氟苯基),苯基]硼酸根或十一氢化-7、8-二碳十一硼酸根；所述阳离子包括但不限于碳鎓阳离子、氧鎓阳离子、铵阳离子、鏻阳离子、环庚三烯基阳离子或含有过渡金属的二茂铁鎓阳离子，所述碳鎓阳离子包含三取代的碳鎓阳离子如三苯基碳鎓阳离子([Ph3C]+)和三(取代的苯基)碳鎓阳离子，且三(取代的苯基)碳鎓阳离子的更具体的实例包括三(甲苯基)碳鎓阳离子；铵阳离子包括三烷基铵阳离子如三甲基铵阳离子、三乙基铵阳离子([NEt3H]+)、三丙基铵阳离子和三丁基铵阳离子；N,N-二烷基苯铵阳离子如N,N-二甲基苯铵阳离子([PhNMe2H]+)、N,N-二乙基苯铵阳离子和N,N-2,4,6-五甲基苯铵阳离子和二烷基铵阳离子如二异丙基铵阳离子和二环己基铵阳离子；鏻阳离子包括三芳基鏻阳离子如三苯基鏻阳离子、三(甲苯基)鏻阳离子和三(二甲苯基)鏻阳离子。In the present invention, the organic boron salt compound can be an ionic compound composed of an organic boron anion and a cation; the organic boron anion includes but is not limited to tetraphenylborate ([BPh 4 ] - ), tetrakis(monofluorophenyl)borate, tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl)borate, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate ([B(C 6 F 5 ) 4 ] - ), tetrakis(tetrafluoromethylphenyl)borate, tetrakis(tolyl)borate, tetrakis(xylyl)borate, (triphenyl, pentafluorophenyl)borate, [tris(pentafluorophenyl), phenyl]borate or undecyl-7,8-dicarbonundecaborate; the cation includes but is not limited to a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation or a ferrocenium cation containing a transition metal, the carbonium cation includes a trisubstituted carbonium cation such as a triphenylcarbonium cation ([Ph 3 C] + ) and a tri(substituted phenyl)carbonium cation, and a more specific example of the tri(substituted phenyl)carbonium cation includes a tri(tolyl)carbonium cation; the ammonium cation includes a trialkylammonium cation such as a trimethylammonium cation, a triethylammonium cation ([NEt 3 H] + ), tripropylammonium cation and tributylammonium cation; N,N-dialkylanilinium cation such as N,N-dimethylanilinium cation ([PhNMe 2 H] + ), N,N-diethylanilinium cation and N,N-2,4,6-pentamethylanilinium cation and dialkylammonium cation such as diisopropylammonium cation and dicyclohexylammonium cation; phosphonium cation includes triarylphosphonium cation such as triphenylphosphonium cation, tri(tolyl)phosphonium cation and tri(xylyl)phosphonium cation.

在本发明的一个实施例中，所述有机硼盐化合物具体选自[Ph3C][B(C6F5)4]、[PhNMe2H][BPh4]、[NEt3H][BPh4]、B(C6F5)3和[PhNMe2H][B(C6F5)4]中的一种或多种。In one embodiment of the present invention, the organic boron salt compound is specifically selected from one or more of [Ph 3 C][B(C 6 F 5 ) 4 ], [PhNMe 2 H][BPh 4 ], [NEt 3 H][BPh 4 ], B(C 6 F 5 ) 3 and [PhNMe 2 H][B(C 6 F 5 ) 4 ].

本发明催化剂组合物中，所述有机硼盐与茂-非茂杂配金属配合物的摩尔比优选为(0.5～10)：1，更优选为(1～5)：1，再优选为(1～3)：1。In the catalyst composition of the present invention, the molar ratio of the organic boron salt to the cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex is preferably (0.5-10):1, more preferably (1-5):1, and even more preferably (1-3):1.

在一些具体的实现方式中，所述有机铝化合物选自三甲基铝、三乙基铝、三丙基铝、三丁基铝、三异丙基铝、三异丁基铝、三戊基铝、三己基铝、三环己基铝、三辛基铝、三苯基铝、三对甲苯基铝、三苄基铝、乙基二苄基铝和乙基二(对甲苯基)铝中的一种或多种。In some specific implementations, the organoaluminum compound is selected from one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum and ethyldi(p-tolyl)aluminum.

催化剂组合物中烷基铝与茂-非茂杂配金属配合物的摩尔比优选为(1～200)：1，更优选为(1～100)：1，再优选为(1～20)：1。The molar ratio of the alkyl aluminum to the cyclopentadienyl-noncyclopentadienyl heteroleptic metal complex in the catalyst composition is preferably (1-200):1, more preferably (1-100):1, and even more preferably (1-20):1.

本发明对所述催化剂组合物的制备方法没有特殊限制，将配合物、有机硼盐化合物和有机铝化合物在溶剂中混合溶解即可。在一些具体的实现方式中，所述溶剂可以为脂肪族饱和烃、芳香烃、芳基卤化物和环烷烃中的一种或多种，优选为甲苯。在一些具体的实现方式中，所述溶剂的体积与所述催化剂中配合物的摩尔数的比例为100～1000L：1mol，优选为200～800L：1mol。The present invention has no particular restrictions on the preparation method of the catalyst composition, and the complex, the organic boron salt compound and the organic aluminum compound are mixed and dissolved in a solvent. In some specific implementations, the solvent can be one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aromatic halides and cycloalkanes, preferably toluene. In some specific implementations, the ratio of the volume of the solvent to the molar number of the complex in the catalyst is 100 to 1000 L: 1 mol, preferably 200 to 800 L: 1 mol.

本发明提供的催化剂组合物可以用于催化制备超高分子量聚乙烯，包括以下步骤：The catalyst composition provided by the present invention can be used for catalytic preparation of ultra-high molecular weight polyethylene, comprising the following steps:

以乙烯类单体为原料，在所述催化剂组合物的作用下进行聚合反应，得到超高分子量聚乙烯。Using ethylene monomers as raw materials, a polymerization reaction is carried out under the action of the catalyst composition to obtain ultra-high molecular weight polyethylene.

具体而言，本申请首先将乙烯类单体置于无水无氧处理的反应釜中，加入上述催化剂组合物溶液进行反应，即所述聚合反应在无水无氧的条件下进行。在一些具体的实现方式中，所述乙烯类单体包括但不限于苯乙烯、乙烯、丙烯等。在一些具体的实现方式中，所述乙烯类单体的压力为1～20atm。在一些具体的实现方式中，所述反应在烃类溶剂中进行，所述烃类溶剂包括但不限于甲苯等。在一些具体的实现方式中，所述烃类溶剂与所述茂-非茂金属的摩尔比为100～1000:1。所述聚合反应的温度为0～60℃，时间为30s～5h。聚合完毕后，加入盐酸酸化的乙醇溶液终止聚合反应，将反应溶液倒入乙醇中沉降，干燥后得到低缠结态超高分子量聚乙烯。Specifically, the present application first places the ethylene monomer in a reactor treated in anhydrous and oxygen-free conditions, and adds the above-mentioned catalyst composition solution to react, that is, the polymerization reaction is carried out under anhydrous and oxygen-free conditions. In some specific implementations, the ethylene monomers include but are not limited to styrene, ethylene, propylene, etc. In some specific implementations, the pressure of the ethylene monomers is 1 to 20 atm. In some specific implementations, the reaction is carried out in a hydrocarbon solvent, and the hydrocarbon solvent includes but is not limited to toluene, etc. In some specific implementations, the molar ratio of the hydrocarbon solvent to the metallocene-non-metallocene is 100 to 1000:1. The temperature of the polymerization reaction is 0 to 60°C, and the time is 30s to 5h. After the polymerization is completed, an ethanol solution acidified with hydrochloric acid is added to terminate the polymerization reaction, the reaction solution is poured into ethanol for sedimentation, and low entanglement state ultra-high molecular weight polyethylene is obtained after drying.

本发明提供的配合物为茂-非茂金属配合物，由配体和中心金属组成，配体是含有芳香基团杂原子类，中心金属是Ti，可用于催化超高分子量聚乙烯的合成，制备得到的超高分子量聚乙烯的粘均分子量为100～800万，分子量分布为1～10，结晶度在60-90％之间、熔点在130-150℃。而且，本发明提供的配合物合成简单，收率较高，可达50％～60％。The complex provided by the invention is a metallocene-non-metallocene complex, which is composed of a ligand and a central metal, wherein the ligand is a heteroatom containing an aromatic group, and the central metal is Ti, and can be used to catalyze the synthesis of ultra-high molecular weight polyethylene. The prepared ultra-high molecular weight polyethylene has a viscosity average molecular weight of 1 to 8 million, a molecular weight distribution of 1 to 10, a crystallinity of 60 to 90%, and a melting point of 130 to 150° C. Moreover, the complex provided by the invention is simple to synthesize and has a high yield of 50 to 60%.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1为本发明实施例14制备的超高分子量聚乙烯甲基支化的核磁共振氢谱图；FIG1 is a hydrogen nuclear magnetic resonance spectrum of ultra-high molecular weight polyethylene methyl branching prepared in Example 14 of the present invention;

图2为本发明实施例14制备的超高分子量聚乙烯的室温冷压3min图片；FIG2 is a picture of the ultra-high molecular weight polyethylene prepared in Example 14 of the present invention being cold pressed at room temperature for 3 minutes;

图3为本发明实施例14制备的超高分子量聚乙烯的DSC图；FIG3 is a DSC graph of the ultra-high molecular weight polyethylene prepared in Example 14 of the present invention;

图4为本发明实施例14制备的超高分子量聚乙烯的KPIC报表。FIG. 4 is a KPIC report of the ultra-high molecular weight polyethylene prepared in Example 14 of the present invention.

具体实施方式DETAILED DESCRIPTION

下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

为了进一步说明本发明，下面通过以下实施例进行详细说明。本发明以下实施例所用的原料均为市售商品。In order to further illustrate the present invention, the following examples are provided for detailed description. The raw materials used in the following examples of the present invention are all commercially available products.

实施例1：配合物1的制备Example 1: Preparation of Complex 1

在氮气条件下，以间二甲苯-2-磺酰氯(3mmol，0.52g)和2，4-二叔丁基苯酚(3mmol，0.62g)为原料，用二氯甲烷溶解，以FeCl3为催化剂在室温下反应12h得到灰绿色溶液，过滤浓缩反应溶液，进行柱层析分离，石油醚：乙酸乙酯为10：1，得到白色固体(化合物1)0.46g，产率为51％。Under nitrogen conditions, m-xylene-2-sulfonyl chloride (3 mmol, 0.52 g) and 2,4-di-tert-butylphenol (3 mmol, 0.62 g) were used as raw materials, dissolved in dichloromethane, and reacted at room temperature for 12 h with FeCl 3 as a catalyst to obtain a gray-green solution. The reaction solution was filtered and concentrated, and column chromatography was performed to separate the mixture with petroleum ether: ethyl acetate in a ratio of 10:1 to obtain 0.46 g of a white solid (compound 1) with a yield of 51%.

在-30℃和氮气条件下，将2.5M的正丁基锂的正己烷溶液(3mmol,1.2ml)滴加到含有杂原子配体(化合物1)(3mmol,0.94g)的正己烷(20ml)的溶液中，反应10h后，过滤，浓缩反应溶液，重结晶得到白色固体。在-30℃和氮气条件下将白色固体(3mmol，0.96g)和CpTiCl3(3mmol,0.63g)分别溶于甲苯(20ml)，将白色固体溶液加入CpTiCl3溶液中，反应10h，过滤，浓缩反应溶液，重结晶，得到橙红色茂-非茂金属配合物1，0.8g，产率为53％。At -30°C and nitrogen, a 2.5M n-butyllithium n-hexane solution (3mmol, 1.2ml) was added dropwise to a solution of n-hexane (20ml) containing a heteroatom ligand (compound 1) (3mmol, 0.94g), and the reaction was continued for 10h, filtered, the reaction solution was concentrated, and recrystallized to obtain a white solid. At -30°C and nitrogen, the white solid (3mmol, 0.96g) and CpTiCl 3 (3mmol, 0.63g) were dissolved in toluene (20ml), the white solid solution was added to the CpTiCl 3 solution, the reaction was continued for 10h, filtered, the reaction solution was concentrated, and recrystallized to obtain an orange-red metallocene-non-metallocene complex 1, 0.8g, with a yield of 53%.

核磁氢谱：1H NMR(500MHz，CDCl3)δ1.22(s,9H),1.62(s,9H),δ6.41(s,5H),δ6.98(tt,1H),δ7.08(tt,2H),δ7.34(dt,2H),δ7.54(s,2H)Hydrogen nuclear magnetic spectrum: 1 H NMR (500MHz, CDCl 3 ) δ1.22 (s, 9H), 1.62 (s, 9H), δ 6.41 (s, 5H), δ 6.98 (tt, 1H), δ 7.08 (tt,2H),δ7.34(dt,2H),δ7.54(s,2H)

元素分析目标分子式为C25H29Cl2OSTi(％)The target molecular formula of elemental analysis is C 25 H 29 Cl 2 OSTi (%)

理论分析值：C,60.50；H,5.89。实测值：C,60.20；H,6.53。Theoretical analysis value: C, 60.50; H, 5.89. Measured value: C, 60.20; H, 6.53.

实施例2：配合物2的制备Example 2: Preparation of Complex 2

在氮气条件下，以苄基氯(3mmol，0.38g)和2，4-二叔丁基苯酚(3mmol，0.62g)为原料，用二氯甲烷溶解，以FeCl3为催化剂在室温下反应12h得到灰绿色溶液，过滤，浓缩反应溶液，进行柱层析分离，石油醚：乙酸乙酯为10：0，得到白色固体(化合物2)0.40g，产率为45％。Under nitrogen conditions, benzyl chloride (3mmol, 0.38g) and 2,4-di-tert-butylphenol (3mmol, 0.62g) were used as raw materials, dissolved in dichloromethane, and reacted at room temperature for 12h with FeCl3 as a catalyst to obtain a gray-green solution. The reaction solution was filtered and concentrated, and column chromatography was performed for separation. The ratio of petroleum ether to ethyl acetate was 10:0 to obtain 0.40g of a white solid (compound 2) with a yield of 45%.

在-30℃和氮气条件下，将2.5M的正丁基锂的正己烷溶液(3mmol,1.2ml)滴加到配体(化合物2)(3mmol,1.21g)的正己烷(20ml)的溶液中，反应10h后，过滤，浓缩反应溶液，重结晶得到白色固体。在-30℃和氮气条件下将白色固体(3mmol，1.23g)和CpTiCl3(3mmol,0.63g)分别溶于甲苯(20ml)，将白色固体溶液加入CpTiCl3溶液中，反应10h，过滤，浓缩反应溶液，重结晶，得到橙红色茂-非茂金属配合物2，1.21g，产率为55％。At -30°C and nitrogen, a 2.5M n-butyllithium n-hexane solution (3mmol, 1.2ml) was added dropwise to a solution of the ligand (compound 2) (3mmol, 1.21g) in n-hexane (20ml). After reacting for 10h, the mixture was filtered, the reaction solution was concentrated, and recrystallized to obtain a white solid. At -30°C and nitrogen, the white solid (3mmol, 1.23g) and CpTiCl3 (3mmol, 0.63g) were dissolved in toluene (20ml), respectively, and the white solid solution was added to the CpTiCl3 solution . The mixture was reacted for 10h, filtered, the reaction solution was concentrated, and recrystallized to obtain an orange-red metallocene-non-metallocene complex 2, 1.21g, with a yield of 55%.

元素分析目标分子式为C25H24Cl2F5OSTi(％)The target molecular formula of elemental analysis is C 25 H 24 Cl 2 F 5 OSTi (%)

理论分析值：C,51.22；H,4.13。实测值：C,51.35；H,4.52。Theoretical analysis value: C, 51.22; H, 4.13. Measured value: C, 51.35; H, 4.52.

实施例3：配合物3的制备Example 3: Preparation of Complex 3

在-30℃和氮气条件下，将2.5M的正丁基锂的正己烷溶液(3mmol,1.2ml)滴加到含有杂原子配体(化合物1)(3mmol,0.94g)的正己烷(20ml)的溶液中，反应10h后，过滤，浓缩反应溶液，重结晶得到白色固体。在-30℃和氮气条件下将白色固体(3mmol，0.96g)和CpTiCl3(3mmol,0.63g)分别溶于甲苯(20ml)，将白色固体溶液加入CpTiCl3溶液中，反应10h，过滤，浓缩反应溶液，之后在-30℃加入(3mmol，1ml)3.0M甲基溴化镁的乙醚溶液，反应1h，用硅藻土过滤重结晶，得到橙红色茂-非茂金属配合物3，0.67g，产率为49％。At -30°C and nitrogen, 2.5M n-butyl lithium in n-hexane solution (3mmol, 1.2ml) was added dropwise to a solution of n-hexane (20ml) containing a heteroatom ligand (compound 1) (3mmol, 0.94g), and reacted for 10h, filtered, concentrated, and recrystallized to obtain a white solid. At -30°C and nitrogen, the white solid (3mmol, 0.96g) and CpTiCl 3 (3mmol, 0.63g) were dissolved in toluene (20ml), respectively, and the white solid solution was added to the CpTiCl 3 solution, reacted for 10h, filtered, and concentrated. Then, 3.0M methyl magnesium bromide in ether solution (3mmol, 1ml) was added at -30°C, reacted for 1h, filtered and recrystallized with diatomaceous earth to obtain an orange-red metallocene-non-metallocene complex 3, 0.67g, with a yield of 49%.

元素分析目标分子式为C27H36OSTi(％)The target molecular formula of elemental analysis is C 27 H 36 OSTi (%)

理论分析值：C,71.04；H,7.95。实测值：C,71.01；H,8.02。Theoretical analysis value: C, 71.04; H, 7.95. Measured value: C, 71.01; H, 8.02.

实施例4：配合物4的制备Example 4: Preparation of Complex 4

在-30℃和氮气条件下，将2.5M的正丁基锂的正己烷溶液(3mmol,1.2ml)滴加到配体(化合物2)(3mmol,0.89g)的正己烷(20ml)的溶液中，反应10h后，过滤，浓缩反应溶液，重结晶得到黄色固体。在-30℃和氮气条件下将黄色固体(3mmol，0.94g)和CpTiCl3(3mmol,0.63g)分别溶于甲苯(20ml)，将黄色固体溶液加入CpTiCl3溶液中，反应10h，过滤，浓缩反应溶液，重结晶，得到橙红色茂-非茂金属配合物4，0.7g，产率为50％。At -30°C and nitrogen, a 2.5M n-butyllithium n-hexane solution (3mmol, 1.2ml) was added dropwise to a solution of the ligand (compound 2) (3mmol, 0.89g) in n-hexane (20ml). After reacting for 10h, the mixture was filtered, the reaction solution was concentrated, and recrystallized to obtain a yellow solid. At -30°C and nitrogen, the yellow solid (3mmol, 0.94g) and CpTiCl3 (3mmol, 0.63g) were dissolved in toluene (20ml), respectively, and the yellow solid solution was added to the CpTiCl3 solution . The mixture was reacted for 10h, filtered, the reaction solution was concentrated, and recrystallized to obtain an orange-red metallocene-non-metallocene complex 4, 0.7g, with a yield of 50%.

核磁氢谱：1H NMR(500MHz，CDCl3)δ1.25(s,9H),1.44(s,9H),δ4.18(s,2H),δ6.54(s,5H),δ6.95(d,1H),δ7.22(q,4H),δ7.34(t,2H)Hydrogen nuclear magnetic spectrum: 1 H NMR (500MHz, CDCl 3 ) δ1.25 (s, 9H), 1.44 (s, 9H), δ 4.18 (s, 2H), δ 6.54 (s, 5H), δ 6.95 (d,1H),δ7.22(q,4H),δ7.34(t,2H)

元素分析目标分子式为C26H31Cl2OTi(％)The target molecular formula of elemental analysis is C 26 H 31 Cl 2 OTi (%)

理论分析值：C,65.29；H,6.53。实测值：C,64.98；H,6.89。Theoretical analysis value: C, 65.29; H, 6.53. Measured value: C, 64.98; H, 6.89.

实施例5：配合物5的制备Example 5: Preparation of Complex 5

在氮气条件下，以苄基氯(3mmol，0.38g)和苯酚(3mmol，0.30g)为原料，用二氯甲烷溶解，以FeCl3为催化剂在室温下反应12h得到灰绿色溶液，过滤，浓缩反应溶液，进行柱层析分离，石油醚：乙酸乙酯为10：1，得到黄色固体(化合物3)0.22g，产率为40％。Under nitrogen conditions, benzyl chloride (3mmol, 0.38g) and phenol (3mmol, 0.30g) were used as raw materials, dissolved in dichloromethane, and reacted at room temperature for 12h with FeCl3 as a catalyst to obtain a gray-green solution. The reaction solution was filtered and concentrated, and column chromatography was performed to separate the mixture with petroleum ether: ethyl acetate in a ratio of 10:1 to obtain 0.22g of a yellow solid (compound 3) with a yield of 40%.

在-30℃和氮气条件下，将2.5M的正丁基锂的正己烷溶液(3mmol,1.2ml)滴加到配体(化合物3)(3mmol,0.55g)的正己烷(20ml)的溶液中，反应10h后，过滤，浓缩反应溶液，重结晶得到黄色固体。在-30℃和氮气条件下将黄色固体(3mmol，0.57g)和CpTiCl3(3mmol,0.63g)分别溶于甲苯(20ml)，将黄色固体溶液加入CpTiCl3溶液中，反应10h，过滤，浓缩反应溶液，重结晶，得到橙红色茂-非茂金属配合物5，0.52g，产率为47％。At -30°C and nitrogen, a 2.5M solution of n-butyl lithium in n-hexane (3mmol, 1.2ml) was added dropwise to a solution of the ligand (compound 3) (3mmol, 0.55g) in n-hexane (20ml). After reacting for 10h, the mixture was filtered, concentrated, and recrystallized to obtain a yellow solid. At -30°C and nitrogen, the yellow solid (3mmol, 0.57g) and CpTiCl 3 (3mmol, 0.63g) were dissolved in toluene (20ml), respectively, and the yellow solid solution was added to the CpTiCl 3 solution. The mixture was reacted for 10h, filtered, concentrated, and recrystallized to obtain an orange-red metallocene-non-metallocene complex 5, 0.52g, with a yield of 47%.

元素分析目标分子式为C18H16Cl2OTi(％)The target molecular formula of elemental analysis is C 18 H 16 Cl 2 OTi (%)

理论分析值：C,58.89；H,4.39。实测值：C,58.85；H,4.44。Theoretical analysis value: C, 58.89; H, 4.39. Measured value: C, 58.85; H, 4.44.

实施例6：配合物6的制备Example 6: Preparation of Complex 6

在氮气条件下，以五氟苄基氯(3mmol，0.65g)和苯酚(3mmol，0.30g)为原料，用二氯甲烷溶解，以FeCl3为催化剂在室温下反应12h得到灰绿色溶液，过滤，浓缩反应溶液，进行柱层析分离，石油醚：乙酸乙酯为10：1，得到黄色固体(化合物4)0.48g，产率为42％。Under nitrogen conditions, pentafluorobenzyl chloride (3mmol, 0.65g) and phenol (3mmol, 0.30g) were used as raw materials, dissolved in dichloromethane, and reacted at room temperature for 12h with FeCl3 as a catalyst to obtain a gray-green solution. The reaction solution was filtered and concentrated, and column chromatography was performed to separate the mixture with petroleum ether: ethyl acetate in a ratio of 10:1 to obtain 0.48g of a yellow solid (compound 4) with a yield of 42%.

在-30℃和氮气条件下，将2.5M的正丁基锂的正己烷溶液(3mmol,1.2ml)滴加到配体(化合物4)(3mmol,1.15g)的正己烷(20ml)的溶液中，反应10h后，过滤，浓缩反应溶液，重结晶得到白色固体。在-30℃和氮气条件下将白色固体(3mmol，1.17g)和CpTiCl3(3mmol,0.63g)分别溶于甲苯(20ml)，将白色固体溶液加入CpTiCl3溶液中，反应10h，过滤，浓缩反应溶液，之后在-30℃加入(3mmol，1ml)3.0M甲基溴化镁的乙醚溶液，反应1h，用硅藻土过滤重结晶，得到橙红色茂-非茂金属配合物6，0.81g，产率为51％。At -30°C and nitrogen, 2.5M n-butyl lithium in n-hexane solution (3mmol, 1.2ml) was added dropwise to a solution of ligand (compound 4) (3mmol, 1.15g) in n-hexane (20ml), reacted for 10h, filtered, concentrated, and recrystallized to obtain a white solid. At -30°C and nitrogen, the white solid (3mmol, 1.17g) and CpTiCl 3 (3mmol, 0.63g) were dissolved in toluene (20ml), respectively, and the white solid solution was added to the CpTiCl 3 solution, reacted for 10h, filtered, and concentrated. Then, 3.0M methyl magnesium bromide in ether solution (3mmol, 1ml) was added at -30°C, reacted for 1h, filtered and recrystallized with diatomaceous earth to obtain an orange-red metallocene-non-metallocene complex 6, 0.81g, with a yield of 51%.

元素分析目标分子式为C28H33F5OTi(％)The target molecular formula of elemental analysis is C 28 H 33 F 5 OTi (%)

理论分析值：C,63.64；H,6.29。实测值：C,63.51；H,6.52。Theoretical analysis value: C, 63.64; H, 6.29. Measured value: C, 63.51; H, 6.52.

实施例7：配合物7的制备Example 7: Preparation of Complex 7

在-78℃和氮气条件下，将2.5M的正丁基锂的正己烷溶液(3mmol,1.2ml)滴加到含有杂原子配体(化合物1)(3mmol,0.94g)的正己烷(20ml)的溶液中，反应12h后，过滤，浓缩反应溶液，重结晶得到白色固体。在-78℃和氮气条件下将白色固体(3mmol，0.96g)和C12H21SiTiCl3(3mmol,1.03g)分别溶于甲苯(20ml)，将白色固体溶液加入C12H21SiTiCl3溶液中，反应12h，过滤，浓缩反应溶液，重结晶，得到橙红色茂-非茂金属配合物15，0.9g，产率为45％。At -78°C and nitrogen, a 2.5M n-butyllithium n-hexane solution (3mmol, 1.2ml) was added dropwise to a solution of n-hexane (20ml) containing a heteroatom ligand (compound 1) (3mmol, 0.94g), and the reaction was continued for 12h, filtered, the reaction solution was concentrated, and recrystallized to obtain a white solid. At -78°C and nitrogen, the white solid (3mmol, 0.96g) and C 12 H 21 SiTiCl 3 (3mmol, 1.03g) were dissolved in toluene (20ml), the white solid solution was added to the C 12 H 21 SiTiCl 3 solution, the reaction was continued for 12h, filtered, the reaction solution was concentrated, and recrystallized to obtain an orange-red metallocene-non-metallocene complex 15, 0.9g, with a yield of 45%.

核磁氢谱：1H NMR(500MHz，C6D6)δ0.48(s,9H),1.12(s,9H),δ1.56(s,9H),δ1.87(s,6H),δ2.46(d,6H),δ6.88(tt,1H),δ7.00(tt,2H),δ7.28(dt,2H),δ7.44(q,2H)。Hydrogen nuclear magnetic spectrum: 1 H NMR (500MHz, C 6 D 6 ) δ0.48 (s, 9H), 1.12 (s, 9H), δ 1.56 (s, 9H), δ 1.87 (s, 6H), δ 2 .46(d,6H), δ6.88(tt,1H), δ7.00(tt,2H), δ7.28(dt,2H), δ7.44(q,2H).

元素分析目标分子式为C33H48Cl2OSSiTi(％)The target molecular formula of elemental analysis is C 33 H 48 Cl 2 OSSiTi (%)

理论分析值：C,65.23；H,7.96。实测值：C,65.12；H,8.05。Theoretical analysis value: C, 65.23; H, 7.96. Measured value: C, 65.12; H, 8.05.

实施例8：配合物8的制备Example 8: Preparation of Complex 8

在氮气条件下，以间二甲苯-2-磺酰氯(3mmol，0.52g)和苯酚(3mmol，0.30g)为原料，用二氯甲烷溶解，以FeCl3为催化剂在室温下反应12h得到灰绿色溶液，过滤，浓缩反应溶液，进行柱层析分离，石油醚：乙酸乙酯为10：1，得到黄色固体(化合物5)0.10g，产率为40％。Under nitrogen conditions, m-xylene-2-sulfonyl chloride (3 mmol, 0.52 g) and phenol (3 mmol, 0.30 g) were used as raw materials, dissolved in dichloromethane, and reacted at room temperature for 12 h with FeCl 3 as a catalyst to obtain a gray-green solution. The reaction solution was filtered and concentrated, and column chromatography was performed to separate the mixture with petroleum ether: ethyl acetate in a ratio of 10:1 to obtain 0.10 g of a yellow solid (Compound 5) with a yield of 40%.

在-78℃和氮气条件下，将2.5M的正丁基锂的正己烷溶液(3mmol,1.2ml)滴加到配体(化合物5)(3mmol,0.61g)的正己烷(20ml)的溶液中，反应12h后，过滤，浓缩反应溶液，重结晶得到白色固体。在-78℃和氮气条件下将白色固体(3mmol，0.62g)和C12H21SiTiCl3(3mmol,1.22g)分别溶于甲苯(20ml)，将白色固体溶液加入C12H21SiTiCl3溶液中，反应12h，过滤，浓缩反应溶液，重结晶，得到橙红色茂-非茂金属配合物8，0.72g，产率为47％。At -78°C and nitrogen, a 2.5M n-butyllithium n-hexane solution (3mmol, 1.2ml) was added dropwise to a solution of the ligand (compound 5) (3mmol, 0.61g) in n-hexane (20ml), and the reaction was continued for 12h, filtered, the reaction solution was concentrated, and recrystallized to obtain a white solid. At -78°C and nitrogen, the white solid (3mmol, 0.62g) and C 12 H 21 SiTiCl 3 (3mmol, 1.22g) were dissolved in toluene (20ml), the white solid solution was added to the C 12 H 21 SiTiCl 3 solution, the reaction was continued for 12h, filtered, the reaction solution was concentrated, and recrystallized to obtain an orange-red metallocene-non-metallocene complex 8, 0.72g, with a yield of 47%.

元素分析目标分子式为C24H29Cl2OSSiTi(％)The target molecular formula of elemental analysis is C 24 H 29 Cl 2 OSSiTi (%)

理论分析值：C,56.26；H,5.70。实测值：C,56.03；H,5.92。Theoretical analysis value: C, 56.26; H, 5.70. Measured value: C, 56.03; H, 5.92.

实施例9：配合物9的制备Example 9: Preparation of Complex 9

在-78℃和氮气条件下，将2.5M的正丁基锂的正己烷溶液(3mmol,1.2ml)滴加到含有杂原子配体(化合物5)(3mmol,0.61g)的正己烷(20ml)的溶液中，反应12h后，过滤，浓缩反应溶液，重结晶得到白色固体。在-78℃和氮气条件下将白色固体(3mmol，0.62g)和C8H13SiTiCl3(3mmol,0.87g)分别溶于甲苯(20ml)，将白色固体溶液加入C8H13SiTiCl3溶液中，反应12h，过滤，浓缩反应溶液，重结晶，得到橙红色茂-非茂金属配合物8，0.68g，产率为50％。At -78°C and nitrogen, a 2.5M n-butyllithium n-hexane solution (3mmol, 1.2ml) was added dropwise to a solution of n-hexane (20ml) containing a heteroatom ligand (compound 5) (3mmol, 0.61g), and the reaction was continued for 12h, filtered, the reaction solution was concentrated, and recrystallized to obtain a white solid. At -78°C and nitrogen, the white solid (3mmol, 0.62g) and C 8 H 13 SiTiCl 3 (3mmol, 0.87g) were dissolved in toluene (20ml), the white solid solution was added to the C 8 H 13 SiTiCl 3 solution, the reaction was continued for 12h, filtered, the reaction solution was concentrated, and recrystallized to obtain an orange-red metallocene-non-metallocene complex 8, 0.68g, with a yield of 50%.

元素分析目标分子式为C20H22Cl2OSSiTi(％)The target molecular formula of elemental analysis is C 20 H 22 Cl 2 OSSiTi (%)

理论分析值：C,52.53；H,4.85。实测值：C,52.39；H,5.13。Theoretical analysis value: C, 52.53; H, 4.85. Measured value: C, 52.39; H, 5.13.

实施例10：配合物10的制备Example 10: Preparation of Complex 10

在-78℃和氮气条件下，将2.5M的正丁基锂的正己烷溶液(3mmol,1.2ml)滴加到配体(化合物4)(3mmol,1.16g)的正己烷(20ml)的溶液中，反应12h后，过滤，浓缩反应溶液，重结晶得到白色固体。在-78℃和氮气条件下将白色固体(3mmol，1.17g)和C8H13SiTiCl3(3mmol,0.87g)分别溶于甲苯(20ml)，将白色固体溶液加入C8H13SiTiCl3溶液中，反应12h，过滤，浓缩反应溶液，重结晶，得到橙红色茂-非茂金属配合物10，0.92g，产率为48％。At -78°C and nitrogen, a 2.5M n-butyllithium n-hexane solution (3mmol, 1.2ml) was added dropwise to a solution of the ligand (compound 4) (3mmol, 1.16g) in n-hexane (20ml), and the reaction was continued for 12h, filtered, the reaction solution was concentrated, and recrystallized to obtain a white solid. At -78°C and nitrogen, the white solid (3mmol, 1.17g) and C 8 H 13 SiTiCl 3 (3mmol, 0.87g) were dissolved in toluene (20ml), the white solid solution was added to the C 8 H 13 SiTiCl 3 solution, the reaction was continued for 12h, filtered, the reaction solution was concentrated, and recrystallized to obtain an orange-red metallocene-non-metallocene complex 10, 0.92g, with a yield of 48%.

元素分析目标分子式为C29H35Cl2F5OSiTi(％)The target molecular formula of elemental analysis is C 29 H 35 Cl 2 F 5 OSiTi (%)

理论分析值：C,54.30；H,5.50。实测值：C,54.21；H,5.62。Theoretical analysis value: C, 54.30; H, 5.50. Measured value: C, 54.21; H, 5.62.

实施例11：配合物11的制备Example 11: Preparation of Complex 11

在-78℃和氮气条件下，将2.5M的正丁基锂的正己烷溶液(3mmol,1.2ml)滴加到含有杂原子配体(化合物1)(3mmol,0.94g)的正己烷(20ml)的溶液中，反应12h后，过滤，浓缩反应溶液，重结晶得到白色固体。在-78℃和氮气条件下将白色固体(3mmol，0.96g)和C10H10TiCl3(3mmol,0.87g)分别溶于甲苯(20ml)，将白色固体溶液加入C10H10TiCl3溶液中，反应12h，过滤，浓缩反应溶液，重结晶，得到橙红色茂-非茂金属配合物12，0.85g，产率为51％。At -78°C and nitrogen, a 2.5M n-butyllithium n-hexane solution (3mmol, 1.2ml) was added dropwise to a solution of n-hexane (20ml) containing a heteroatom ligand (compound 1) (3mmol, 0.94g), and the reaction was continued for 12h, filtered, the reaction solution was concentrated, and recrystallized to obtain a white solid. At -78°C and nitrogen, the white solid (3mmol, 0.96g) and C10H10TiCl3 (3mmol , 0.87g) were dissolved in toluene (20ml), respectively, and the white solid solution was added to the C10H10TiCl3 solution , and the reaction was continued for 12h, filtered, the reaction solution was concentrated, and recrystallized to obtain an orange-red metallocene-non-metallocene complex 12, 0.85g, with a yield of 51%.

元素分析目标分子式为C30H35Cl2OSTi(％)The target molecular formula of elemental analysis is C 30 H 35 Cl 2 OSTi (%)

理论分析值：C,64.07；H,6.27。实测值：C,64.01；H,6.53。Theoretical analysis value: C, 64.07; H, 6.27. Measured value: C, 64.01; H, 6.53.

实施例12：配合物12的制备Example 12: Preparation of Complex 12

在-78℃和氮气条件下，将2.5M的正丁基锂的正己烷溶液(3mmol,1.2ml)滴加到含有杂原子配体(化合物1)(3mmol,0.94g)的正己烷(20ml)的溶液中，反应12h后，过滤，浓缩反应溶液，重结晶得到白色固体。在-78℃和氮气条件下将白色固体(3mmol，0.96g)和C10H10TiCl3(3mmol,0.87g)分别溶于甲苯(20ml)，将白色固体溶液加入C10H10TiCl3溶液中，反应12h，过滤，浓缩反应溶液，重结晶，得到橙红色茂-非茂金属配合物12，0.92g，产率为51％。At -78°C and nitrogen, a 2.5M n-butyllithium n-hexane solution (3mmol, 1.2ml) was added dropwise to a solution of n-hexane (20ml) containing a heteroatom ligand (compound 1) (3mmol, 0.94g), and the reaction was continued for 12h, filtered, the reaction solution was concentrated, and recrystallized to obtain a white solid. At -78°C and nitrogen, the white solid (3mmol, 0.96g) and C10H10TiCl3 (3mmol , 0.87g) were dissolved in toluene (20ml), respectively, and the white solid solution was added to the C10H10TiCl3 solution , and the reaction was continued for 12h, filtered, the reaction solution was concentrated, and recrystallized to obtain an orange-red metallocene-non-metallocene complex 12, 0.92g, with a yield of 51%.

元素分析目标分子式为C34H37Cl2OSTi(％)The target molecular formula of elemental analysis is C 34 H 37 Cl 2 OSTi (%)

理论分析值：C,66.67；H,6.09。实测值：C,66.53；H,6.23。Theoretical analysis value: C, 66.67; H, 6.09. Measured value: C, 66.53; H, 6.23.

实施例13Example 13

手套箱中，将40mL甲苯加入150mL聚合瓶中，放入乙烯装置抽换气，乙烯＝2atm；将配合物1(5mg,10μmol)、AliBu3(0.4ml,200μmol，0.5M甲苯溶剂)和硼酸三苯基碳盐[Ph3C][B(C6F5)4](9.2mg，10μmol)溶解于甲苯中，制备催化剂组合物；将催化剂组合物通过注射器快速注入聚合瓶中引发聚合，聚合反应在20min后，加入2ml的盐酸乙醇溶液(v/v,1:10)终止聚合反应，再将聚合反应液倒入100ml的乙醇中沉降，过滤，真空干燥24h，得到超高分子量聚乙烯净重为0.43g。In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, and an ethylene device was placed for ventilation, with ethylene = 2 atm; complex 1 (5 mg, 10 μmol), Al i Bu 3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and boric acid triphenyl carbendazim [Ph 3 C][B(C 6 F 5 ) 4 ] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into the polymerization bottle through a syringe to initiate polymerization, and after the polymerization reaction for 20 min, 2 ml of hydrochloric acid ethanol solution (v/v, 1:10) was added to terminate the polymerization reaction, and the polymerization reaction solution was poured into 100 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 h to obtain an ultra-high molecular weight polyethylene with a net weight of 0.43 g.

实施例14Embodiment 14

手套箱中，将40mL甲苯加入150mL聚合瓶中，放入乙烯装置抽换气，乙烯＝4atm；将配合物1(5mg，10μmol)、AliBu3(0.4ml，200μmol，0.5M甲苯溶剂)和硼酸三苯基碳盐[Ph3C][B(C6F5)4](9.2mg，10μmol)溶解于甲苯中，制备催化剂组合物；将催化剂组合物通过注射器快速注入聚和瓶中引发聚合，聚合反应在15min后，加入2ml的盐酸乙醇溶液(v/v，1:10)终止聚合反应，再将聚合反应液倒入100ml的乙醇中沉降，过滤，真空干燥24h，得到超高分子量聚乙烯净重为0.47g。In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, and an ethylene device was placed for ventilation, with ethylene = 4 atm; complex 1 (5 mg, 10 μmol), Al i Bu 3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and boric acid triphenyl carbendazim [Ph 3 C][B(C 6 F 5 ) 4 ] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into the polymerization bottle through a syringe to initiate polymerization, and after the polymerization reaction for 15 min, 2 ml of hydrochloric acid ethanol solution (v/v, 1:10) was added to terminate the polymerization reaction, and the polymerization reaction solution was poured into 100 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 h to obtain an ultra-high molecular weight polyethylene with a net weight of 0.47 g.

本实施例的产物的测定根据在C2D2Cl4中在110℃下测定的均聚物的1HNMR谱图得到；聚合物熔点(Tm)通过差示扫描量热法(DSC)测定；聚合物粘均分子量(Mn)通过粘度仪在135℃下，用十氢萘为流动相测定。The product of this example was determined based on the 1 HNMR spectrum of the homopolymer measured in C 2 D 2 Cl 4 at 110°C; the polymer melting point (T m ) was determined by differential scanning calorimetry (DSC); and the polymer viscosity average molecular weight (M n ) was determined by a viscometer at 135°C using decalin as the mobile phase.

利用核磁共振对实施例14中得到的超高分子量聚乙烯进行分析，得到其1H NMR谱图，The ultra-high molecular weight polyethylene obtained in Example 14 was analyzed by nuclear magnetic resonance to obtain its 1 H NMR spectrum.

利用差示扫描量热法对其测试分析，得到其DSC图，如图3所示。图3的DSC曲线显示所得聚乙烯Tg＝136.9℃以及结晶度X＝74.1％。利用粘度仪对其粘均分子量进行分析，得到KPIC图，如图4所示。The DSC graph was obtained by differential scanning calorimetry, as shown in Figure 3. The DSC curve in Figure 3 shows that the obtained polyethylene has a T g = 136.9°C and a crystallinity X = 74.1%. The viscosity average molecular weight was analyzed by a viscometer, and a KPIC graph was obtained, as shown in Figure 4.

实施例15Embodiment 15

手套箱中，将40mL甲苯加入150mL聚合瓶中，放入乙烯装置抽换气，乙烯＝6atm；将配合物1(5mg，10μmol)、AliBu3(0.4ml，200μmol，0.5M甲苯溶剂)和硼酸三苯基碳盐[Ph3C][B(C6F5)4](9.2mg，10μmol)溶解于甲苯中，制备催化剂组合物；将催化剂组合物通过注射器快速注入聚和瓶中引发聚合，聚合反应在2min后，加入2ml的盐酸乙醇溶液(v/v，1:10)终止聚合反应，再将聚合反应液倒入100ml的乙醇中沉降，过滤，真空干燥24h，得到超高分子量聚乙烯净重为0.53g。In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, and an ethylene device was placed for ventilation, with ethylene = 6 atm; complex 1 (5 mg, 10 μmol), Al i Bu 3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and boric acid triphenyl carbendazim [Ph 3 C][B(C 6 F 5 ) 4 ] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into the polymerization bottle through a syringe to initiate polymerization, and after the polymerization reaction for 2 min, 2 ml of hydrochloric acid ethanol solution (v/v, 1:10) was added to terminate the polymerization reaction, and then the polymerization reaction solution was poured into 100 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 h to obtain an ultra-high molecular weight polyethylene with a net weight of 0.53 g.

实施例16Example 16

手套箱中，将40mL甲苯加入150mL聚合瓶中，放入乙烯装置抽换气，乙烯＝6atm；将配合物2(4.5mg，10μmol)、AliBu3(0.4ml，200μmol，0.5M甲苯溶剂)和硼酸三苯基碳盐[Ph3C][B(C6F5)4](9.2mg，10μmol)溶解于甲苯中，制备催化剂组合物；将催化剂组合物通过注射器快速注入聚和瓶中引发聚合，聚合反应在10min后，加入2ml的盐酸乙醇溶液(v/v，1:10)终止聚合反应，再将聚合反应液倒入100ml的乙醇中沉降，过滤，真空干燥24h，得到超高分子量聚乙烯净重为0.18g。In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, and an ethylene device was placed for ventilation, with ethylene = 6 atm; complex 2 (4.5 mg, 10 μmol), Al i Bu 3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and triphenyl borate carbon salt [Ph 3 C][B(C 6 F 5 ) 4 ] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into the polymerization bottle through a syringe to initiate polymerization. After the polymerization reaction lasted for 10 min, 2 ml of hydrochloric acid ethanol solution (v/v, 1:10) was added to terminate the polymerization reaction, and the polymerization reaction solution was poured into 100 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 h to obtain an ultra-high molecular weight polyethylene with a net weight of 0.18 g.

实施例17Embodiment 17

手套箱中，将40mL甲苯加入150mL聚合瓶中，放入乙烯装置抽换气，乙烯＝6atm；将配合物3(4mg，10μmol)、AliBu3(0.4ml，200μmol，0.5M甲苯溶剂)和硼酸三苯基碳盐[Ph3C][B(C6F5)4](9.2mg，10μmol)溶解于甲苯中，制备催化剂组合物；将催化剂组合物通过注射器快速注入聚和瓶中引发聚合，聚合反应在10min后，加入2ml的盐酸乙醇溶液(v/v，1:10)终止聚合反应，再将聚合反应液倒入100ml的乙醇中沉降，过滤，真空干燥24h，得到超高分子量聚乙烯净重为0.19g。In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, and an ethylene device was placed for ventilation, with ethylene = 6 atm; complex 3 (4 mg, 10 μmol), Al i Bu 3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and triphenyl borate carbon salt [Ph 3 C][B(C 6 F 5 ) 4 ] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into the polymerization bottle through a syringe to initiate polymerization, and after the polymerization reaction for 10 min, 2 ml of hydrochloric acid ethanol solution (v/v, 1:10) was added to terminate the polymerization reaction, and the polymerization reaction solution was poured into 100 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 h to obtain an ultra-high molecular weight polyethylene with a net weight of 0.19 g.

实施例18Embodiment 18

手套箱中，将40mL甲苯加入150mL聚合瓶中，放入乙烯装置抽换气，乙烯＝6atm；将配合物4(4mg，10μmol)、AliBu3(0.4ml，200μmol，0.5M甲苯溶剂)和硼酸三苯基碳盐[Ph3C][B(C6F5)4](9.2mg，10μmol)溶解于甲苯中，制备催化剂组合物；将催化剂组合物通过注射器快速注入聚和瓶中引发聚合，聚合反应在10min后，加入2ml的盐酸乙醇溶液(v/v，1:10)终止聚合反应，再将聚合反应液倒入100ml的乙醇中沉降，过滤，真空干燥24h，得到超高分子量聚乙烯净重为0.07g。In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, and the bottle was placed in an ethylene device for ventilation, with ethylene = 6 atm; complex 4 (4 mg, 10 μmol), Al i Bu 3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and triphenyl borate carbon salt [Ph 3 C][B(C 6 F 5 ) 4 ] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into the polymerization bottle through a syringe to initiate polymerization. After the polymerization reaction lasted for 10 min, 2 ml of ethanol hydrochloric acid solution (v/v, 1:10) was added to terminate the polymerization reaction, and the polymerization reaction solution was poured into 100 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 h to obtain an ultra-high molecular weight polyethylene with a net weight of 0.07 g.

实施例19Embodiment 19

手套箱中，将40mL甲苯加入150mL聚合瓶中，放入乙烯装置抽换气，乙烯＝6atm；将配合物5(3.6mg，10μmol)、AliBu3(0.4ml，200μmol，0.5M甲苯溶剂)和硼酸三苯基碳盐[Ph3C][B(C6F5)4](9.2mg，10μmol)溶解于甲苯中，制备催化剂组合物；将催化剂组合物通过注射器快速注入聚和瓶中引发聚合，聚合反应在10min后，加入2ml的盐酸乙醇溶液(v/v，1:10)终止聚合反应，再将聚合反应液倒入100ml的乙醇中沉降，过滤，真空干燥24h，得到超高分子量聚乙烯净重为0.13g。In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, and an ethylene device was placed for ventilation, with ethylene = 6 atm; complex 5 (3.6 mg, 10 μmol), Al i Bu 3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and boric acid triphenyl carbendazim [Ph 3 C][B(C 6 F 5 ) 4 ] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into the polymerization bottle through a syringe to initiate polymerization, and after the polymerization reaction for 10 min, 2 ml of hydrochloric acid ethanol solution (v/v, 1:10) was added to terminate the polymerization reaction, and the polymerization reaction solution was poured into 100 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 h to obtain an ultra-high molecular weight polyethylene with a net weight of 0.13 g.

实施例20Embodiment 20

手套箱中，将40mL甲苯加入150mL聚合瓶中，放入乙烯装置抽换气，乙烯＝6atm；将配合物6(5mg，10μmol)、AliBu3(0.4ml，200μmol，0.5M甲苯溶剂)和硼酸三苯基碳盐[Ph3C][B(C6F5)4](9.2mg，10μmol)溶解于甲苯中，制备催化剂组合物；将催化剂组合物通过注射器快速注入聚和瓶中引发聚合，聚合反应在10min后，加入2ml的盐酸乙醇溶液(v/v，1:10)终止聚合反应，再将聚合反应液倒入100ml的乙醇中沉降，过滤，真空干燥24h，得到超高分子量聚乙烯净重为0.24g。In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, and an ethylene device was placed for ventilation, with ethylene = 6 atm; complex 6 (5 mg, 10 μmol), Al i Bu 3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and triphenyl borate carbon salt [Ph 3 C][B(C 6 F 5 ) 4 ] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into the polymerization bottle through a syringe to initiate polymerization. After the polymerization reaction lasted for 10 min, 2 ml of ethanol hydrochloric acid solution (v/v, 1:10) was added to terminate the polymerization reaction, and the polymerization reaction solution was poured into 100 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 h to obtain an ultra-high molecular weight polyethylene with a net weight of 0.24 g.

实施例21Embodiment 21

手套箱中，将40mL甲苯加入150mL聚合瓶中，放入乙烯装置抽换气，乙烯＝6atm；将配合物7(5mg，10μmol)、AliBu3(0.4ml，200μmol，0.5M甲苯溶剂)和硼酸三苯基碳盐[Ph3C][B(C6F5)4](9.2mg，10μmol)溶解于甲苯中，制备催化剂组合物；将催化剂组合物通过注射器快速注入聚和瓶中引发聚合，聚合反应在10min后，加入2ml的盐酸乙醇溶液(v/v，1:10)终止聚合反应，再将聚合反应液倒入100ml的乙醇中沉降，过滤，真空干燥24h，得到超高分子量聚乙烯净重为0.11g。In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, and an ethylene device was placed for ventilation, with ethylene = 6 atm; complex 7 (5 mg, 10 μmol), Al i Bu 3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and boric acid triphenyl carbendazim [Ph 3 C][B(C 6 F 5 ) 4 ] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into the polymerization bottle through a syringe to initiate polymerization, and after the polymerization reaction for 10 min, 2 ml of hydrochloric acid ethanol solution (v/v, 1:10) was added to terminate the polymerization reaction, and the polymerization reaction solution was poured into 100 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 h to obtain an ultra-high molecular weight polyethylene with a net weight of 0.11 g.

实施例22Example 22

手套箱中，将40mL甲苯加入150mL聚合瓶中，放入乙烯装置抽换气，乙烯＝6atm；将配合物8(5mg，10μmol)、AliBu3(0.4ml，200μmol，0.5M甲苯溶剂)和硼酸三苯基碳盐[Ph3C][B(C6F5)4](9.2mg，10μmol)溶解于甲苯中，制备催化剂组合物；将催化剂组合物通过注射器快速注入聚和瓶中引发聚合，聚合反应在10min后，加入2ml的盐酸乙醇溶液(v/v，1:10)终止聚合反应，再将聚合反应液倒入100ml的乙醇中沉降，过滤，真空干燥24h，得到超高分子量聚乙烯净重为0.05g。In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, and an ethylene device was placed for ventilation, with ethylene = 6 atm; complex 8 (5 mg, 10 μmol), Al i Bu 3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and triphenyl borate carbon salt [Ph 3 C][B(C 6 F 5 ) 4 ] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into the polymerization bottle through a syringe to initiate polymerization. After the polymerization reaction lasted for 10 min, 2 ml of ethanol hydrochloric acid solution (v/v, 1:10) was added to terminate the polymerization reaction, and the polymerization reaction solution was poured into 100 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 h to obtain an ultra-high molecular weight polyethylene with a net weight of 0.05 g.

实施例23Embodiment 23

手套箱中，将40mL甲苯加入150mL聚合瓶中，放入乙烯装置抽换气，乙烯＝6atm；将配合物9(4.5mg，10μmol)、AliBu3(0.4ml，200μmol，0.5M甲苯溶剂)和硼酸三苯基碳盐[Ph3C][B(C6F5)4](9.2mg，10μmol)溶解于甲苯中，制备催化剂组合物；将催化剂组合物通过注射器快速注入聚和瓶中引发聚合，聚合反应在2min后，加入2ml的盐酸乙醇溶液(v/v，1:10)终止聚合反应，再将聚合反应液倒入100ml的乙醇中沉降，过滤，真空干燥24h，得到超高分子量聚乙烯净重为0.16g。In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, and an ethylene device was placed for ventilation, with ethylene = 6 atm; complex 9 (4.5 mg, 10 μmol), Al i Bu 3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and triphenyl borate carbon salt [Ph 3 C][B(C 6 F 5 ) 4 ] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into the polymerization bottle through a syringe to initiate polymerization, and after the polymerization reaction for 2 minutes, 2 ml of hydrochloric acid ethanol solution (v/v, 1:10) was added to terminate the polymerization reaction, and then the polymerization reaction solution was poured into 100 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 hours to obtain an ultra-high molecular weight polyethylene with a net weight of 0.16 g.

实施例24Embodiment 24

手套箱中，将40mL甲苯加入150mL聚合瓶中，放入乙烯装置抽换气，乙烯＝6atm；将配合物10(6.4mg，10μmol)、AliBu3(0.4ml，200μmol，0.5M甲苯溶剂)和硼酸三苯基碳盐[Ph3C][B(C6F5)4](9.2mg，10μmol)溶解于甲苯中，制备催化剂组合物；将催化剂组合物通过注射器快速注入聚和瓶中引发聚合，聚合反应在10min后，加入2ml的盐酸乙醇溶液(v/v，1:10)终止聚合反应，再将聚合反应液倒入100ml的乙醇中沉降，过滤，真空干燥24h，得到超高分子量聚乙烯净重为0.21g。In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, and an ethylene device was placed for ventilation, with ethylene = 6 atm; complex 10 (6.4 mg, 10 μmol), Al i Bu 3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and triphenyl borate carbon salt [Ph 3 C][B(C 6 F 5 ) 4 ] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into the polymerization bottle through a syringe to initiate polymerization, and after the polymerization reaction for 10 min, 2 ml of ethanol hydrochloric acid solution (v/v, 1:10) was added to terminate the polymerization reaction, and the polymerization reaction solution was poured into 100 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 h to obtain an ultra-high molecular weight polyethylene with a net weight of 0.21 g.

实施例25Embodiment 25

手套箱中，将40mL甲苯加入150mL聚合瓶中，放入乙烯装置抽换气，乙烯＝6atm；将配合物11(5.6mg，10μmol)、AliBu3(0.4ml，200μmol，0.5M甲苯溶剂)和硼酸三苯基碳盐[Ph3C][B(C6F5)4](9.2mg，10μmol)溶解于甲苯中，制备催化剂组合物；将催化剂组合物通过注射器快速注入聚和瓶中引发聚合，聚合反应在10min后，加入2ml的盐酸乙醇溶液(v/v，1:10)终止聚合反应，再将聚合反应液倒入100ml的乙醇中沉降，过滤，真空干燥24h，得到超高分子量聚乙烯净重为0.75g。In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, and the bottle was placed in an ethylene device for ventilation, with ethylene = 6 atm; complex 11 (5.6 mg, 10 μmol), Al i Bu 3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and triphenyl borate carbon salt [Ph 3 C][B(C 6 F 5 ) 4 ] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into the polymerization bottle through a syringe to initiate polymerization. After the polymerization reaction lasted for 10 min, 2 ml of ethanol hydrochloric acid solution (v/v, 1:10) was added to terminate the polymerization reaction, and the polymerization reaction solution was poured into 100 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 h to obtain an ultra-high molecular weight polyethylene with a net weight of 0.75 g.

实施例26Embodiment 26

手套箱中，将40mL甲苯加入150mL聚合瓶中，放入乙烯装置抽换气，乙烯＝6atm；将配合物12(6.1mg，10μmol)、AliBu3(0.4ml，200μmol，0.5M甲苯溶剂)和硼酸三苯基碳盐[Ph3C][B(C6F5)4](9.2mg，10μmol)溶解于甲苯中，制备催化剂组合物；将催化剂组合物通过注射器快速注入聚和瓶中引发聚合，聚合反应在10min后，加入2ml的盐酸乙醇溶液(v/v，1:10)终止聚合反应，再将聚合反应液倒入100ml的乙醇中沉降，过滤，真空干燥24h，得到超高分子量聚乙烯净重为0.87g。In a glove box, 40 mL of toluene was added to a 150 mL polymerization bottle, and an ethylene device was placed for ventilation, with ethylene = 6 atm; complex 12 (6.1 mg, 10 μmol), Al i Bu 3 (0.4 ml, 200 μmol, 0.5 M toluene solvent) and boric acid triphenyl carbendazim [Ph 3 C][B(C 6 F 5 ) 4 ] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into the polymerization bottle through a syringe to initiate polymerization, and after the polymerization reaction for 10 min, 2 ml of hydrochloric acid ethanol solution (v/v, 1:10) was added to terminate the polymerization reaction, and the polymerization reaction solution was poured into 100 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 h to obtain an ultra-high molecular weight polyethylene with a net weight of 0.87 g.

参见表1，表1为本申请实施例13～26制备超高分子量聚乙烯的条件及结果数据。See Table 1, which shows the conditions and result data for preparing ultra-high molecular weight polyethylene in Examples 13 to 26 of the present application.

表1乙烯均聚合的条件以及结果数据表Table 1 Conditions and results of ethylene homopolymerization

结果表明：本公开实施例中的茂-非茂金属配合物在使用含硼助催化剂活化后可以催化乙烯进行聚合，聚合活性可高达1.59×106g/mol*h，熔点可达136.9℃，结晶度可达74.1％，超高分子量聚乙烯粘均分子量在100w～500w。The results show that the metallocene-non-metallocene complex in the embodiment of the present disclosure can catalyze the polymerization of ethylene after being activated with a boron-containing co-catalyst, and the polymerization activity can be as high as 1.59×10 6 g/mol*h, the melting point can reach 136.9°C, the crystallinity can reach 74.1%, and the viscosity average molecular weight of the ultra-high molecular weight polyethylene is between 100w and 500w.

以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims (10)

1.式(I)、式(II)或式(III)所示的配合物：1. Complexes represented by formula (I), formula (II) or formula (III): 其中，Z选自S、O、(CH2)n；n为1～5的整数；Wherein, Z is selected from S, O, (CH 2 ) n ; n is an integer from 1 to 5; R1选自取代或未取代的C1～C12的烷基、取代或未取代的苯基或卤素；R 1 is selected from substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted phenyl or halogen; R2、R3分别独立的选自氢、取代或未取代的C1～C12的烷基或卤素；R 2 and R 3 are independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen; R4、R5、R6、R7、R8分别独立的选自氢、取代或未取代的C1～C12的烷基或卤素；R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen; R9、R10、R11、R12、R13、R14、R15、R16、R17分别独立的选自氢、取代或未取代的硅基、取代或未取代的C1～C12的烷基、取代或未取代的芳基或卤素。R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently selected from hydrogen, substituted or unsubstituted silicon group, substituted or unsubstituted C1～C12 Alkyl, substituted or unsubstituted aryl or halogen. 2.根据权利要求1所述的配合物，其特征在于，Z选自S或CH2；2. The complex according to claim 1, characterized in that, Z is selected from S or CH2 ; R1选自取代或未取代的C1～C5的烷基、卤素；R 1 is selected from substituted or unsubstituted C1 to C5 alkyl and halogen; R2、R3分别独立的选自氢、取代或未取代的C1～C5的烷基；R 2 and R 3 are independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl groups; R4、R5、R6、R7、R8分别独立的选自氢、取代或未取代的C1～C12的烷基或卤素；R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen; R9、R10、R11、R12、R13、R14、R15、R16、R17分别独立的选自氢、烷基取代的硅基、取代或未取代的C1～C5的烷基。R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently selected from hydrogen, alkyl-substituted silicon group, substituted or unsubstituted C1-C5 alkane base. 3.根据权利要求2所述的茂-非茂金属配合物，其特征在于，所述Z选自S、CH2；3. The non-metallocene complex according to claim 2, characterized in that the Z is selected from S, CH 2 ; 所述R1选自Cl、CH3；The R 1 is selected from Cl, CH 3 ; 所述R2、R3为叔丁基、甲基、辛基、卤素中的任意一种；The R 2 and R 3 are any one of tert-butyl, methyl, octyl and halogen; 所述R4、R5、R6、R7、R8分别独立的选自氢、甲基、叔丁基、卤素中的任意一种；The R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from any one of hydrogen, methyl, tert-butyl, and halogen; 所述R9、R10、R11、R12、R13、R14、R15、R16、R17分别独立的选自氢、甲基、乙基、叔丁基、辛基、三甲基硅基的任意一种。The R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are independently selected from hydrogen, methyl, ethyl, tert- butyl , octyl, trimethyl Any kind of silicon base. 4.根据权利要求1～3任意一项所述的配合物，其特征在于，所述配合物选自：4. The complex according to any one of claims 1 to 3, characterized in that the complex is selected from: 配合物1：Z＝S,R1＝Cl,R2＝C(CH3)3,R3＝C(CH3)3,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H；Complex 1: Z＝S, R 1 ＝Cl, R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 =H,R 8 =H,R 9 =H,R 10 =H,R 11 =H,R 12 =H,R 13 =H; 配合物2：Z＝S,R1＝Cl,R2＝C(CH3)3,R3＝C(CH3)3,R4＝F,R5＝F,R6＝F,R7＝F,R8＝F,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H；Complex 2: Z＝S, R 1 ＝Cl, R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝F, R 5 ＝F, R 6 ＝F, R 7 =F,R 8 =F,R 9 =H,R 10 =H,R 11 =H,R 12 =H,R 13 =H; 配合物3：Z＝S,R1＝CH3,R2＝C(CH3)3,R3＝C(CH3)3,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H；Complex 3: Z＝S, R 1 ＝CH 3 , R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 =H,R 8 =H,R 9 =H,R 10 =H,R 11 =H,R 12 =H,R 13 =H; 配合物4：Z＝CH2,R1＝Cl,,R2＝C(CH3)3,R3＝C(CH3)3,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H；Complex 4: Z＝CH 2 , R 1 ＝Cl,, R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 =H,R 8 =H,R 9 =H,R 10 =H,R 11 =H,R 12 =H,R 13 =H; 配合物5：Z＝CH2,R1＝Cl,R2＝H,R3＝H,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H；Complex 5: Z＝CH 2 , R 1 ＝Cl, R 2 ＝H, R 3 ＝H, R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 ＝H, R 8 ＝ H, R 9 =H,R 10 =H,R 11 =H,R 12 =H,R 13 =H; 配合物6：Z＝CH2,R1＝CH3,R2＝C(CH3)3,R3＝C(CH3)3,R4＝F,R5＝F,R6＝F,R7＝F,R8＝F,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H；Complex 6: Z＝CH 2 , R 1 ＝CH 3 , R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝F, R 5 ＝F, R 6 ＝F, R 7 =F,R 8 =F,R 9 =H,R 10 =H,R 11 =H,R 12 =H,R 13 =H; 配合物7：Z＝S,R1＝Cl,R2＝C(CH3)3,R3＝C(CH3)3,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝CH3,R10＝CH3,R11＝Si(CH3)3,R12＝CH3,R13＝CH3；Complex 7: Z＝S, R 1 ＝Cl, R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 =H,R 8 =H,R 9 =CH 3 ,R 10 =CH 3 ,R 11 =Si(CH 3 ) 3 ,R 12 =CH 3 ,R 13 =CH 3 ; 配合物8：Z＝S,R1＝Cl,R2＝H,R3＝H,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝CH3,R10＝CH3,R11＝Si(CH3)3,R12＝CH3,R13＝CH3；Complex 8: Z＝S, R 1 ＝Cl, R 2 ＝H, R 3 ＝H, R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 ＝H, R 8 ＝H, R 9 =CH 3 ,R 10 =CH 3 ,R 11 =Si(CH 3 ) 3 ,R 12 =CH 3 ,R 13 =CH 3 ; 配合物9：Z＝S,R1＝Cl,R2＝H,R3＝H,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝H,R10＝H,R11＝Si(CH3)3,R12＝H,R13＝H；Complex 9: Z＝S, R 1 ＝Cl, R 2 ＝H, R 3 ＝H, R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 ＝H, R 8 ＝H, R 9 =H,R 10 =H,R 11 =Si(CH 3 ) 3 ,R 12 =H,R 13 =H; 配合物10：Z＝CH2,R1＝Cl,R2＝C(CH3)3,R3＝C(CH3)3,R4＝F,R5＝F,R6＝F,R7＝F,R8＝F,R9＝H,R10＝H,R11＝Si(CH3)3,R12＝H,R13＝H；Complex 10: Z＝CH 2 , R 1 ＝Cl, R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝F, R 5 ＝F, R 6 ＝F, R 7 =F,R 8 =F,R 9 =H,R 10 =H,R 11 =Si(CH 3 ) 3 ,R 12 =H,R 13 =H; 配合物11：Z＝S,R1＝Cl,R2＝C(CH3)3,R3＝C(CH3)3,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H,R14＝H，R15＝H；Complex 11: Z＝S, R 1 ＝Cl, R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 =H,R 8 =H,R 9 =H,R 10 =H,R 11 =H,R 12 =H,R 13 =H,R 14 =H,R 15 =H; 配合物12：Z＝S,R1＝Cl,R2＝C(CH3)3,R3＝C(CH3)3,R4＝H,R5＝H,R6＝H,R7＝H,R8＝H,R9＝H,R10＝H,R11＝H,R12＝H,R13＝H,R14＝H,R15＝H,R16＝H，R17＝H。Complex 12: Z＝S, R 1 ＝Cl, R 2 ＝C(CH 3 ) 3 , R 3 ＝C(CH 3 ) 3 , R 4 ＝H, R 5 ＝H, R 6 ＝H, R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H,R 14 ＝H,R 15 ＝H, R 16 ＝ H,R 17 =H. 5.根据权利要求4所述的配合物，其具有式(1)～式(4)的结构：5. The complex according to claim 4, which has the structure of formula (1) to formula (4): 6.权利要求1～5任意一项所述的配合物的制备方法，包括以下步骤：6. The preparation method of the complex according to any one of claims 1 to 5, comprising the following steps: 将式(a)所示的配体与锂化试剂和CpTiX3混合反应，得到R1为卤素的式(I)、(II)或式(III)所示的配合物，其中，；The ligand represented by formula (a) is mixed and reacted with a lithiation reagent and CpTiX 3 to obtain a complex represented by formula (I), (II) or formula (III) in which R 1 is halogen, wherein; 其中，CpTiX3中，Cp选自取代的或非取代的环戊二烯基、取代的或非取代茚基、取代的或非取代芴基，X为卤素；Among them, in CpTiX 3 , Cp is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted fluorenyl, and X is halogen; 可选的，将所述R1为卤素的式(I)、式(II)或式(III)所述的配合物和烷基试剂混合反应，得到R1不为卤素的式(I)、式(II)或式(III)所示的配合物。Optionally, the complex of formula (I), formula (II) or formula (III) in which R 1 is halogen and an alkyl reagent are mixed and reacted to obtain formula (I) in which R 1 is not halogen. A complex represented by formula (II) or formula (III). 7.根据权利要求4所述的制备方法，其特征在于，所述锂化试剂选自正丁基锂；7. The preparation method according to claim 4, characterized in that the lithiation reagent is selected from n-butyllithium; 所述式(a)所示的化合物和锂化试剂的摩尔比为1:(1～5)；The molar ratio of the compound represented by formula (a) and the lithiation reagent is 1: (1-5); 式(a)所示的化合物和CpTiCl3的摩尔比为1:(1～5)。The molar ratio of the compound represented by formula (a) and CpTiCl 3 is 1: (1 to 5). 8.一种催化剂组合物，包括权利要求1～5任意一项所述的配合物、有机硼盐化合物和有机铝化合物。8. A catalyst composition comprising the complex according to any one of claims 1 to 5, an organoboron salt compound and an organoaluminum compound. 9.根据权利要求7所述的组合物，其特征在于，所述配合物、有机硼盐化合物和有机铝化合物的摩尔比为1:0.5～5：1～100；9. The composition according to claim 7, wherein the molar ratio of the complex, the organoboron salt compound and the organoaluminum compound is 1:0.5-5:1-100; 所述有机硼盐化合物选自[Ph3C][B(C6F5)4]、[PhNMe2H][BPh4]、[NEt3H][BPh4]、B(C6F5)3和[PhNMe2H][B(C6F5)4]中的一种或多种；The organic boron salt compound is selected from the group consisting of [Ph 3 C] [B(C 6 F 5 ) 4 ], [PhNMe 2 H] [BPh 4 ], [NEt 3 H] [BPh 4 ], B(C 6 F 5 ) 3 and one or more of [PhNMe 2 H] [B(C 6 F 5 ) 4 ]; 所述有机铝化合物选自三甲基铝、三乙基铝、三丙基铝、三丁基铝、三异丙基铝、三异丁基铝、三戊基铝、三己基铝、三环己基铝、三辛基铝、三苯基铝、三对甲苯基铝、三苄基铝、乙基二苄基铝和乙基二(对甲苯基)铝中的一种或多种。The organoaluminum compound is selected from the group consisting of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclic One or more of hexylaluminum, trioctyl aluminum, triphenylaluminum, triphenyl aluminum, tribenzyl aluminum, ethyl dibenzyl aluminum and ethyl di(p-tolylaluminum). 10.一种超高分子量聚乙烯的制备方法，包括以下步骤：10. A method for preparing ultra-high molecular weight polyethylene, comprising the following steps: 以乙烯类单体为原料，在权利要求8或9所述的催化剂组合物的作用下进行聚合反应，得到超高分子量聚乙烯。Using vinyl monomers as raw materials, the polymerization reaction is carried out under the action of the catalyst composition according to claim 8 or 9 to obtain ultra-high molecular weight polyethylene.
CN202311032500.9A 2023-08-16 2023-08-16 Metallocene-non-metallocene complex, preparation method thereof and application thereof in preparation of disentangled ultra-high molecular weight polyethylene Pending CN117069771A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311032500.9A CN117069771A (en) 2023-08-16 2023-08-16 Metallocene-non-metallocene complex, preparation method thereof and application thereof in preparation of disentangled ultra-high molecular weight polyethylene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311032500.9A CN117069771A (en) 2023-08-16 2023-08-16 Metallocene-non-metallocene complex, preparation method thereof and application thereof in preparation of disentangled ultra-high molecular weight polyethylene

Publications (1)

Publication Number Publication Date
CN117069771A true CN117069771A (en) 2023-11-17

Family

ID=88710911

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311032500.9A Pending CN117069771A (en) 2023-08-16 2023-08-16 Metallocene-non-metallocene complex, preparation method thereof and application thereof in preparation of disentangled ultra-high molecular weight polyethylene

Country Status (1)

Country Link
CN (1) CN117069771A (en)

Similar Documents

Publication Publication Date Title
CN107922528B (en) Polymers produced by using vinyl transfer agents
CN105294778B (en) A kind of Ni-based complex and its preparation method and application
JP2994746B2 (en) Monocyclopentadienyl transition metal olefin polymerization catalyst
CN103025770B (en) Catalyst component for the polymerization of olefins having a guanidinate ligand
JP2000513399A (en) Mixed transition metal catalyst system for olefin polymerization
CN110698513B (en) Preparation of trihydroquinoline amine metal compound and application of trihydroquinoline amine metal compound in high-temperature solution polymerization of olefin
JPWO2006022355A1 (en) Olefin polymerization catalyst, process for producing olefin polymer, olefin copolymer, novel transition metal compound and process for producing transition metal compound
CN106349294A (en) Aniline anthraquinone late transition metal compound and preparation method and application thereof
JP2022549338A (en) Propylene copolymer, its production method and its use
KR101713065B1 (en) Hybrid supported metallocene catalyst, method for preparing polyolefin by using the same and polyolefin having improved melting strength
CN110655538A (en) Monocene trivalent transition metal complex containing neutral benzyl heteroatom ligand and its use
CN107312115B (en) A kind of bisindole rare earth metal catalyst, preparation method and application
KR101926833B1 (en) Metallocene compound
KR101973191B1 (en) Metallocene supported catalyst and method for preparing polyolefin using the same
CN117069771A (en) Metallocene-non-metallocene complex, preparation method thereof and application thereof in preparation of disentangled ultra-high molecular weight polyethylene
CN107722155B (en) A kind of alpha olefin-fluorostyrene polymer and preparation method thereof
CN117229444A (en) Vanadium catalyst system and preparation method and application thereof
KR20100100433A (en) A method for preparation of catalyst for ethylene (co)polymerization
CN106715483B (en) Ethene polymers and stretch forming thing and polyvinyl manufacture method obtained from being stretched
CN116023538B (en) Metallocene catalyst and preparation method thereof and method for preparing olefin copolymer
CN114426613B (en) Catalyst for olefin polymerization, application thereof, propylene-ethylene elastomer and preparation method thereof
WO2024078528A1 (en) Phosphine-phenol transition metal complex, preparation method therefor, and use thereof
CN100376604C (en) A kind of olefin polymerization catalyst and its application
CN116410239A (en) A heteroatom-containing metallocene compound and its preparation method and use
JP3142933B2 (en) Method for producing polyolefin

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination