WO2018090412A1 - 多嵌段支化聚乙烯及其制备方法 - Google Patents

多嵌段支化聚乙烯及其制备方法 Download PDF

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WO2018090412A1
WO2018090412A1 PCT/CN2016/109278 CN2016109278W WO2018090412A1 WO 2018090412 A1 WO2018090412 A1 WO 2018090412A1 CN 2016109278 W CN2016109278 W CN 2016109278W WO 2018090412 A1 WO2018090412 A1 WO 2018090412A1
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branch
branches
molecular weight
component
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French (fr)
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傅智盛
范志强
方实耿
成振美
朱良
傅信羽中
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浙江大学
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    • 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

Definitions

  • the invention belongs to the technical field of thermoplastic elastomers, in particular to multi-block branched polyethylene and a preparation method thereof.
  • This invention relates to the polymerization of a monomer from ethylene to form a polymer having a unique topology, to a process for preparing such a polymer, and to the resulting polymer product.
  • the invention relates to a method of using these polymers in the field of application requiring a unique combination of physical properties.
  • the invention relates to articles made from these polymers.
  • the polymer of the present invention is a novel polymer having a unique chain structure which allows the polymer to have unique physical properties.
  • Such polymers and blends comprising such polymers can be used to prepare solid articles such as molded articles, films, sheets, and foamed articles by molding, extrusion, or other methods, and can be used as an adhesive. , laminates, polymer blends, and other components or ingredients in end use.
  • the resulting product is used in the manufacture of automotive parts such as profiles, bumpers and decorative parts; packaging materials; wire and cable insulation and other uses.
  • Ethylene is the cheapest and most abundant olefin monomer. Ethylene homopolymerization can result in polymers with different topologies, such as linear polyethylene (HDPE), branched polyethylene (LDPE), and hyperbranched polyethylene (HBPE), all of which have their own uses.
  • HDPE has high crystallinity, tensile strength, abrasion resistance, cold resistance, etc. It is resistant to corrosion by acids, alkalis and various salts. It is often used as containers and pipes for industrial packaging and municipal construction.
  • LDPE has good molding processing properties and is mainly used as a film product for medical devices and food and pharmaceutical packaging materials.
  • HBPE has a low crystallinity and a low glass transition temperature, and is a rubber material with excellent comprehensive properties (ZL2014 1 0200113.6). We hope that a new type of topology of polyethylene will emerge, which will bring us new possibilities.
  • Rubber has excellent sealing, vibration damping, damping, fatigue resistance, wear resistance, insulation and other characteristics, and is indispensable for manufacturing aircraft, warships, automobiles, trains, wires and cables, agricultural machinery, medical equipment, sports equipment, etc.
  • the materials are also widely used in people's daily lives. It is not only an important raw material for the national economy, but also an internationally recognized national defense strategic material.
  • the molding process of rubber is more complex and consumes more energy than synthetic resin and plastic. It requires several processes such as gel breaking, high temperature mixing, molding and vulcanization. The process is complicated and the equipment is huge, which requires a large amount of energy.
  • vulcanized rubber is thermosetting and can no longer return to the original linear molecular state, so it can not be reused.
  • a large amount of rubber solid waste is generated during processing and use, which seriously pollutes the environment and wastes petroleum resources. .
  • Thermoplastic elastomers are a class of polymeric materials with physical properties between rubber and plastic. It has both rubber elasticity and plastic easy processing, and can be recycled, so it is known as "third generation rubber.” Since heat vulcanization like rubber is not required, the molding process is simple. The final product can be easily obtained by ordinary plastic processing machinery. The molding process can shorten the process by 1/4, improve the efficiency by 10 to 20 times, save energy by 25 to 40%, and reprocess the TPE after recycling. The performance of the products obtained has not been significantly lost. This is quite obvious compared to the traditional rubber, which is a revolution in the material and process technology of the rubber industry.
  • Thermoplastic elastomers mainly include six categories: polyolefin-based thermoplastic elastomers (TPO); styrenic thermoplastic elastomers; polyvinyl-based thermoplastic elastomers; polyurethane-based thermoplastic elastomers; polyester-based thermoplastic elastomers; Thermoplastic elastomer.
  • TPO polyolefin-based thermoplastic elastomers
  • styrenic thermoplastic elastomers polyvinyl-based thermoplastic elastomers
  • polyurethane-based thermoplastic elastomers polyurethane-based thermoplastic elastomers
  • polyester-based thermoplastic elastomers polyester-based thermoplastic elastomers
  • Thermoplastic elastomer Thermoplastic elastomer.
  • TPO has excellent weather resistance, ozone resistance, UV resistance and good high temperature and impact resistance, it can be used in ordinary thermoplastic processing equipment for molding processing and reusability. It has developed rapidly and has become the fastest growing thermoplastic elastomer. A variety, widely used in automotive, electrical and electronic, industrial and civil applications.
  • the blended composite type includes two routes of mechanical blending and dynamic vulcanization.
  • the mechanical blending method is the earliest and most mature TPO production process. The method combines ethylene propylene rubber and polypropylene by a twin-screw extruder, and the manufacturing process is simple and the cost is low. However, due to the low content of rubber components (mass fraction of about 20 to 30%), heat resistance, oil resistance, high temperature permanent deformation and elasticity are poorer than those prepared by other methods, and applications are limited, and are often used in automobile parts and home appliances. industry.
  • the dynamic vulcanization method is to dynamically vulcanize the rubber phase to obtain a vulcanizate.
  • the open-mixing equipment and the mixing process use batch blending equipment, which is simple in process and convenient in operation, and is suitable for small-scale and multi-variety blending rubber production. Due to the poor reproducibility of the process and the small blending shear force, it is not suitable for high temperature operation and the product quality is low.
  • the twin-screw extrusion process adopts continuous extrusion blending machinery. The processes of blending oil-filling, dynamic vulcanization and exhausting can be completed on the same unit, with high production capacity and automatic control level, and the process conditions can be strictly controlled. The quality of the polymer mixture is fully guaranteed and the degree of vulcanization is controlled, which is suitable for mass production.
  • the reactor synthesis process is developing late. Because the TPO rubber content produced by this method can reach more than 60% and the performance is superior, many companies in the world are actively researching, which is the main direction of TPO development.
  • the reactor synthesis method is to homogenize polypropylene in a propylene polymerization reactor, and then gradually introduce ethylene and propylene to form a block copolymer of polypropylene and ethylene propylene rubber.
  • the Unipol fluidized bed gas phase polymerization process and Himont's loop-tube bulk homopolymerization and gas phase block copolymerization process are widely used.
  • the synthetic rubber pulverization and blending extrusion process is omitted, so the cost is low, and the product has a higher flow than the TPO prepared by the blending composite process. And impact resistance.
  • Exxon's patented Exxpol patented technology the world's first metallocene polyethylene was created, creating a new era in the development of metallocene polyolefins. Since the metallocene catalyst has an ideal single active center, it is possible to precisely control the molecular weight of the polymer, the content of the comonomer and its distribution and crystal structure in the main chain, thereby obtaining a high-performance polyolefin material.
  • POE elastomer is an abbreviation of a class of polyolefin elastomers successfully developed by The Dow Chemical Company in 1993. It mainly refers to ethylene- ⁇ -olefin copolymers synthesized by metallocene catalysts (ethylene-1-octene copolymer, ethylene- 1-butene copolymer, etc.).
  • polyolefin elastomers with similar structural and performance characteristics, including propylene- ⁇ -olefin copolymers synthesized by metallocene catalysts, which can be classified into POE materials.
  • POE is characterized by high mass fraction of alpha-olefins (greater than 20%), low density, and the main characteristics are close to rubber, but have a certain degree of crystallinity.
  • the crystallizable polyethylene segments in the structure form a physical cross-linking point to bear the load, and the non-crystalline random copolymerized segments provide elasticity.
  • This special morphological structure allows POE to have special properties and a wide range of uses, both as a rubber and as a thermoplastic elastomer, and as a toughening agent for plastics.
  • Dow Chemical successfully developed a olefin block copolymer with the trade name Infuse, alternating semi-crystalline and amorphous segments based on chain shuttle polymerization using a new catalytic system for continuous solution polymerization in a single reactor.
  • Object (OBC) Infuse OBC forms a new family of polyolefin elastomers with higher melting points, crystallization temperatures and lower glass transition temperatures than POEs, with a more crystalline morphology.
  • two catalysts were used in the preparation of OBC.
  • the technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a multi-block branched polyethylene and a preparation method thereof.
  • the solution of the present invention is:
  • a multi-block branched polyethylene comprising a semi-crystalline, low-branched polyethylene segment as a hard segment and an amorphous, highly branched poly-polymer as a soft segment Vinyl segments in accordance with The connection methods are alternately connected;
  • the semi-crystalline means that the melting point of the hard segment is 80 to 133.5 ° C, the crystallinity is 9.7 to 47%, the glass transition temperature is -73 to -69 ° C, and the degree of branching is: the degree of branching is 1 to 60 branches / 1000 carbons;
  • the amorphous type means that the glass transition temperature of the soft segment is -70 to -56 ° C, no obvious melting point, and the crystallinity is 0 to 4.5%; the high degree of branching means: the branching degree is 50 to 250 branches. Chain / 1000 carbons.
  • the multi-block branched polyethylene has a weight average molecular weight of 11.1 ⁇ 10 4 to 29.1 ⁇ 10 4 g/mol, a molecular weight distribution index of 2.6 to 4.0, and a degree of branching of 31.6 to 118.3 branches/1000.
  • a carbon, 49 to 58.7 mol% of the branch is a methyl branch, 4.9 to 7.5 mol% is an ethyl branch, 3.3 to 4.7 mol% is a propyl branch, and 1.7 to 5.1 mol% is a butyl branch.
  • 15.1 ⁇ 20.5mol% is a pentyl branch
  • 12.4 ⁇ 17.5mol% is a branch with carbon number ⁇ 6
  • crystallinity is 5.7 ⁇ 42.9%
  • glass transition temperature is –69°C ⁇ –61°C
  • melting point is 116.5°C ⁇ 123.3 °C.
  • the molar percentage content of each branch in the hard segment is: 52 to 100 mol% is a methyl branch, 0 to 14.6 mol% is an ethyl branch, and 0 to 4.8 mol% is a propyl group.
  • Branched, 0 to 3.6 mol% is a butyl branch, 0 to 13.6 mol% is a pentyl branch, and 0 to 12.5 mol% is a branch having a carbon number ⁇ 6; a mole of each branch in the soft segment
  • the proportion of the fraction is: 44.5 to 56 mol% is a methyl branch, 3.5 to 11.7 mol% is an ethyl branch, 4.5 to 14.6 mol% is a propyl branch, and 2.5 to 6.6 mol% is a butyl branch, 11.0.
  • ⁇ 22.4 mol% is a pentyl branch, and 6.5 to 15 mol% is a branch having a carbon number ⁇ 6.
  • the multi-block branched polyethylene has a tensile strength of not less than 10 MPa and an elongation at break of not less than 500%.
  • the multi-block branched polyethylene has the property of rubber, and is a thermoplastic elastomer: it is stretched to 2 times the original length at room temperature of 18 to 29 ° C and left for 1 minute to remove the external force. It can be restored to less than 1.5 times the original length in 1 minute.
  • the multi-block branched polyethylene is a multi-component mixture, and at least 10 to 11 components can be separated by using a temperature rising elution fractionation (TREF) method using toluene as a solvent: wherein
  • TEZ temperature rising elution fractionation
  • the base branch chain 4.7 to 6.1 mol% is a butyl branch, 10 to 14 mol% is a pentyl branch, and 6.3 to 18.9 mol% is a branch having a carbon number ⁇ 6, and the glass transition temperature is -64.6 ° C to -61 °C, has two melting points, melting point one is 50-60 ° C, melting point two is 110-115 ° C, crystallinity is 0.3-2.5%, crystallization temperature is 70-80 ° C;
  • the content of the component eluted at 40 ° C is 5.8 to 10 wt%, and the weight average molecular weight of the component is 10 ⁇ 10 4 to 26 ⁇ 10 4 g / mol, and the molecular weight distribution index is 2.4 to 3.8.
  • the degree of conversion is 120 to 180 branches/1000 carbons, 45 to 60 mol% of the branches are methyl branches, 2 to 3.5 mol% are ethyl branches, and 11 to 15 mol% are propyl branches, 1 to 3 mol% is a butyl branch, 9-13 mol% is a pentyl branch, and 12.5 to 20.5 mol% is a branch having a carbon number ⁇ 6, and the glass transition temperature is from -64 ° C to -61 ° C, and has two melting points.
  • the melting point one is 65-80 ° C
  • the melting point two is 110-116 ° C
  • the crystallinity is 1.5-3.5%
  • there are two crystallization temperatures the crystallization temperature is 45-60 ° C
  • the crystallization temperature is 80-95 ° C;
  • the content of the component eluted at 50 ° C is 3.4 to 6.5 wt%, and the weight average molecular weight of the component is 12.8 ⁇ 10 4 to 30 ⁇ 10 4 g / mol, and the molecular weight distribution index is 2.6 to 3.6.
  • the degree of branching is 90 to 150 branches/1000 carbons, 58 to 67 mol% of the branches are methyl branches, 3 to 5.5 mol% are ethyl branches, and 7.9 to 11 mol% are propyl branches, 0 ⁇ 3 mol% is a butyl branch, 7-13 mol% is a pentyl branch, and 7.5-15 mol% is a branch with a carbon number ⁇ 6, and the glass transition temperature is from -69 ° C to 64 ° C, and has two melting points.
  • the melting point one is 80-90 ° C
  • the melting point two is 110-120 ° C
  • the crystallinity is 3-6%
  • there are two crystallization temperatures the crystallization temperature is 55-70 ° C
  • the crystallization temperature is 80-95 ° C;
  • the content of the component eluted at 60 ° C is 3.4 to 6.5 wt%, and the weight average molecular weight of the component is 14 ⁇ 10 4 to 34 ⁇ 10 4 g / mol, and the molecular weight distribution index is 3.2 to 3.8.
  • the degree of branching is 46 to 100 branches/1000 carbons, 75 to 90 mol% of the branches are methyl branches, 0 to 2.5 mol% are ethyl branches, and 0 to 2 mol% are propyl branches, 0 ⁇ 3 mol% is a butyl branch, 6-15 mol% is a pentyl branch, and 4-9 mol% is a branch with a carbon number ⁇ 6, and the glass transition temperature is from -72 ° C to -68 ° C, and the melting point is from 90 to 100. °C, crystallinity is 10-16%, crystallization temperature is 75-85 °C;
  • the content of the component eluted at 70 ° C is 5.5 to 8 wt%, and the weight average molecular weight of the component is 17 ⁇ 10 4 to 40 ⁇ 10 4 g / mol, and the molecular weight distribution index is 3.5 to 4.0.
  • the degree of conversion is 26 to 70 branches/1000 carbons, 80 to 95 mol% of the branches are methyl branches, 0 to 2 mol% are ethyl branches, 0 to 2 mol% are propyl branches, 0 to 3 mol % is a butyl branch, 3 to 17 mol% is a pentyl branch, and 1 to 5 mol% is a branch having a carbon number of ⁇ 6, a glass transition temperature of -72 ° C to -68 ° C, and a melting point of 95 to 110 ° C.
  • the crystallinity is 15 to 25%, and the crystallization temperature is 80 to 95 ° C;
  • the content of the component eluted at 80 ° C is 5.5 to 9 wt%, and the weight average molecular weight of the component is 20 ⁇ 10 4 to 48 ⁇ 10 4 g / mol, and the molecular weight distribution index is 2.7 to 3.2.
  • the degree of conversion is 17 to 60 branches/1000 carbons, 70 to 85 mol% of the branches are methyl branches, 10 to 18 mol% are ethyl branches, and 0 to 2 mol% are propyl branches, 0 to 3 mol.
  • % is a butyl branch, 0 to 3 mol% is a pentyl branch, and 5 to 12 mol% is a branch having a carbon number ⁇ 6, a glass transition temperature of -74 ° C to - 69 ° C, and a melting point of 105 to 115 ° C.
  • the crystallinity is 20 to 30%, and the crystallization temperature is 90 to 100 ° C;
  • the content of the component eluted at 90 ° C is 11.5 to 20 wt%, and the weight average molecular weight of the component is 23 ⁇ 10 4 to 60 ⁇ 10 4 g / mol, and the molecular weight distribution index is 2.5 to 3.2.
  • the degree of conversion is 10 to 40 branches/1000 carbons, 88 to 98 mol% of the branches are methyl branches, 0 to 2 mol% are ethyl branches, 0 to 2 mol% are propyl branches, 0 to 3 mol % is a butyl branch, 0 to 3 mol% is a pentyl branch, and 2 to 6 mol% is a branch having a carbon number of ⁇ 6, a glass transition temperature of -68 ° C to 60 ° C, and a melting point of 110 to 120 ° C.
  • the crystallinity is 25 to 35%, and the crystallization temperature is 95 to 105 ° C;
  • the content of the component eluted at 100 ° C is 9-16 wt%, and the weight average molecular weight of the component is 24 ⁇ 10 4 to 60 ⁇ 10 4 g/mol, and the molecular weight distribution index is 2.2-3.0.
  • the degree of conversion is 10 to 30 branches/1000 carbons, 90 to 100 mol% of the branches are methyl branches, 0 to 2 mol% are ethyl branches, and 0 to 2 mol% are propyl branches, 0 to 2 mol.
  • % is a butyl branch, 0 to 2 mol% is a pentyl branch, and 0 to 2 mol% is a branch having a carbon number of ⁇ 6, a glass transition temperature of -70 ° C to 64 ° C, and a melting point of 115 to 125 ° C.
  • the crystallinity is 25 to 33%, and the crystallization temperature is 100 to 110 ° C;
  • the content of the component eluted at 110 ° C is 7 to 14 wt%, and the weight average molecular weight of the component is 20 ⁇ 10 4 to 60 ⁇ 10 4 g / mol, and the molecular weight distribution index is 2.2 to 3.0.
  • the degree of conversion is 8 to 25 branches/1000 carbons, 70 to 80 mol% of the branches are methyl branches, 0 to 2 mol% are ethyl branches, 0 to 2 mol% are propyl branches, 0 to 2 mol % is a butyl branch, 0 to 2 mol% is a pentyl branch, and 20 to 30 mol% is a branch having a carbon number of ⁇ 6, a glass transition temperature of -68 ° C to 62 ° C, and a melting point of 120 to 130 ° C.
  • the crystallinity is 30 to 38%, and the crystallization temperature is 105 to 115 ° C;
  • the content of the component eluted at 120 ° C is 2.5 to 7 wt%, and the weight average molecular weight of the component is 20 ⁇ 10 4 to 60 ⁇ 10 4 g / mol, and the molecular weight distribution index is 2.5 to 3.0.
  • the degree of conversion is 5 to 20 branches/1000 carbons, 95 to 100 mol% of the branches are methyl branches, 0 to 1 mol% are ethyl branches, and 0 to 1 mol% are propyl branches, 0 to 1 mol.
  • % is a butyl branch, 0 to 1 mol% is a pentyl branch, and 0 to 1 mol% is a branch having a carbon number of ⁇ 6, a glass transition temperature of -71 ° C to -67 ° C, and a melting point of 120 to 130 ° C.
  • the crystallinity is 36 to 40%, and the crystallization temperature is 105 to 115 ° C;
  • the content of the component having a rinsing temperature higher than 120 ° C is 0 to 5 wt%, and the weight average molecular weight of the component is 15 ⁇ 10 4 to 40 ⁇ 10 4 g/mol, and the molecular weight distribution index is 2.5 to 3.0.
  • the degree of conversion is 0 to 10 branches/1000 carbons, 100 mol% of the branches are methyl branches, the glass transition temperature is -63.8 ° C to -61 ° C, the melting point is 122 to 130 ° C, and the crystallinity is 35 °. 40%, the crystallization temperature is 108 to 115 °C.
  • the invention further provides a preparation method of the multi-block branched polyethylene, which is a dinuclear ruthenium ( ⁇ -diimine) nickel catalyst as a main catalyst, an alkyl aluminum as a cocatalyst, and a chain shuttling agent diethyl Zinc-catalyzed ethylene is homopolymerized, and the multi-block branched polyethylene is obtained by chain shuttle polymerization;
  • the chemical structure of the dinuclear ruthenium ( ⁇ -diimine) nickel catalyst is as shown in formula I, wherein R is methyl or isopropyl;
  • the aluminum alkyl is one of diethylaluminum chloride, sesquiethylaluminum chloride or ethylaluminum dichloride.
  • the aluminum alkyl, the chain shuttling agent diethyl zinc and the dinuclear ruthenium ( ⁇ -diimine) nickel catalyst are dissolved in a solvent, and ethylene is fed at a pressure of 0.4-2.0 MPa, followed by chain shuttle polymerization to control the polymerization temperature. 25 ⁇ 40°C, the polymerization time is 30-60 minutes; after the end of the polymerization, the polymerization reaction is terminated by adding acidified ethanol; the polymerization product is precipitated, filtered and washed to obtain a multi-block branched polyethylene;
  • the concentration of the dinuclear ruthenium ( ⁇ -diimine) nickel catalyst is 2.5 to 45.5 ⁇ mol/L, and the molar ratio of aluminum in the aluminum alkyl to nickel in the dinuclear ruthenium ( ⁇ -diimine) nickel catalyst The (Al/Ni ratio) is 50 to 200, and the molar ratio of zinc in the chain shuttling agent diethyl zinc to nickel in the dinuclear ruthenium ( ⁇ -diimine) nickel catalyst is 10 to 100.
  • the solvent used is one of n-hexane and n-heptane; or a mixture of n-heptane and toluene, and the volume ratio of n-heptane to toluene in the mixture is from 99:1 to 10:1. .
  • the present invention also provides the use of the aforementioned multi-block branched polyethylene or a composition comprising the multi-block branched polyethylene polymer as any of the following products, or in the manufacture of any of the following products: film , at least one layer of a multilayer film, at least one layer of a laminate, a foamed article, a polypropylene impact modifier, a fiber, a nonwoven fabric, an injection molded article, a blow molded article, a rotational molded article or a binder .
  • composition comprising the multi-block branched polyethylene polymer of the present invention means, in addition to the multi-block branched polyethylene polymer of the present invention, a multi-block branched polyethylene polymer Other polymers or additives used in blending. Compositions that can be known by those skilled in the art based on their knowledge, or that can be derived from existing experimental techniques, should be included.
  • the applicant has provided a dinuclear ruthenium ( ⁇ -diimine) nickel catalyst (the specific structure is shown in the following formula) and a preparation method thereof in the Chinese invention patent ZL 2012 1 0276244.3.
  • the catalyst has high activity, good stability, simple preparation process, short synthetic route, low cost, high yield and easy industrialization.
  • the Applicant discovered that the catalyst can be modified to produce two active sites with different catalytic behaviors during the polymerization of ethylene.
  • One active center produces semi-crystalline, low-branched polyethylene, and the other active.
  • the center produces an amorphous, highly branched polyethylene.
  • Ethylene is homopolymerized by using a dinuclear ruthenium ( ⁇ -diimine) nickel catalyst as a main catalyst, an alkyl aluminum as a cocatalyst, and a chain shuttling agent (this is a difference between the present invention and the Chinese invention patent ZL 2012 1 0276244.3).
  • MBBPE multi-block branched polyethylene
  • the amorphous, highly branched polyethylene segments in MBBPE provide elasticity, and the semi-crystalline, low-branched polyethylene segments form physical cross-linking points to withstand loads, so MBBPE is a completely new thermoplastic elastomer.
  • the present invention has the following advantages:
  • the multi-block branched polyethylene prepared by the present invention requires only one monomer of ethylene, which is the most inexpensive and abundant source of olefin, and does not require the use of expensive long-chain ⁇ -olefins, such as - Octene, 1-decene, etc., the production cost is low, and it is not necessary to add a monomer which consumes quickly in the polymerization process, which greatly simplifies the production process and is suitable for large-scale industrial production.
  • the multi-block branched polyethylene prepared by the present invention only requires a dinuclear ruthenium ( ⁇ -diimine) nickel catalyst, an olefin catalyst, without using two catalysts having a large difference in polymerization behavior, so that it is not necessary to consider
  • the matching problem of the two catalysts simplifies the production process, reduces the production cost, and is suitable for large-scale industrial production.
  • the multi-block branched polyethylene prepared by the present invention uses only a dinuclear ruthenium ( ⁇ -diimine) nickel catalyst as an olefin catalyst, and the chain shuttle reaction is carried out between two identical metal active centers in the molecule,
  • the advantages of high efficiency and rapidity are uniform, the chain structure and composition of the polymerization product are mild, the polymerization reaction conditions are mild, and it is not required to be carried out at a high temperature, and the energy consumption is greatly reduced, which is more in line with the requirements of the current "low carbon economy".
  • Ethylene polymerization is carried out under anhydrous anaerobic conditions. 100 ml of n-heptane was placed in a 200 ml stainless steel autoclave with mechanical stirring, and the temperature of the polymerization vessel was controlled to 25 ° C by means of jacketed circulating water, and stirring was started.
  • Ethylene was fed to the reactor pressure of 1.2 MPa. After the polymerization for 30 minutes, the reaction vessel was vented to normal pressure, the lid was opened, the polymer solution was poured out, and the solvent was evaporated to give 22 g of a polymer.
  • the catalyst activity was 4400 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 12.9 ⁇ 10 4 g/mol, the polydispersity coefficient was 3.0, the glass transition temperature was -67 ° C, the melting point was 120.4 ° C, and the crystallinity was obtained. It is 10.5%.
  • the tensile properties of the polymerized product were tested according to GB/T 528-2009, the tensile strength was 18.0 MPa, and the elongation at break was 1230%.
  • the polymerization product was stretched to 2 times the original length at room temperature and after removing the external force for 1 minute, it was able to recover to 1.33 times the original length in 1 minute.
  • the degree of branching of the polymerization product was 80 branches/1000 carbon atoms as determined by 1 H-NMR, 52.0 mol% in the branch chain was methyl branch, 6.5 mol% was ethyl branch, and 4.5 mol% was C.
  • the base branch 3.9 mol% is a butyl branch, 17.6 mol% is a pentyl branch, and 15.5 mol% is a branch having a carbon number ⁇ 6.
  • the degree of branching of the hard segment is 42 branches/1000 carbon atoms
  • the degree of branching of the soft segment is 139 branches/1000 carbon atoms.
  • 82 mol% of the branch in the hard segment is a methyl branch
  • 3 mol% is an ethyl branch
  • 1 mol% is a propyl branch
  • 1 mol% is a butyl branch
  • 7 mol% is a pentyl branch
  • 6 mol% is a carbon.
  • Branches with a number ⁇ 6. 51.8 mol% of the branches in the soft segment are methyl branches
  • 4.2 mol% are ethyl branches
  • 13.6 mol% are propyl branches
  • 5.4 mol% are butyl branches
  • 11.9 mol% are pentyl branches.
  • 13.1 mol% is a branch having a carbon number of ⁇ 6.
  • the hard segment has a melting point of 118.0 ° C, a crystallinity of 10.3%, a glass transition temperature of -72 ° C, a soft segment glass transition temperature of -67 ° C, no significant melting point, and a crystallinity of 0%.
  • the polymerization product can be separated into 11 components by the method of temperature rising elution fractionation (TREF) using toluene as a solvent: (1) the content of the component eluted at 30 ° C is 27.1 wt% (weight percentage). The weight average molecular weight of the component is 9.6 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.4, the degree of branching is 177 branches/1000 carbons, and 58.9 mol% of the branch is methyl branch, 3.5 mol.
  • TEZ temperature rising elution fractionation
  • % is ethyl branch, 11.2 mol% is propyl branch, 5.3 mol% is butyl branch, 11.9 mol% is pentyl branch, 9.2 mol% is branch with carbon number ⁇ 6, glass transition temperature
  • melting point one is 55.7 ° C
  • melting point two is 113.6 ° C
  • crystallinity is 1.41%
  • crystallization temperature is 75.8 ° C
  • the content of the component eluted at 40 ° C is 8.5 Wwt%, the component has a weight average molecular weight of 10.7 ⁇ 10 4 g/mol, a molecular weight distribution index of 2.4, a branching degree of 149 branches/1000 carbons, and a branching chain of 58.3 mol% being a methyl branch.
  • 3.0 mol% is an ethyl branch
  • 13.6 mol% is a propyl branch
  • 1.6 mol% is a butyl branch
  • 10.4 mol% is a pentyl branch
  • 13.1 mol% is a branch having a carbon number ⁇ 6, vitrification Change temperature
  • melting point one is 75.2 ° C
  • melting point two is 113.8 ° C
  • crystallinity is 2.62%
  • crystallization temperatures crystallization temperature is 54.5 ° C
  • crystallization temperature is 86.3 ° C
  • (3 The content of the component eluted at 50 ° C is 4.4 wt%
  • the weight average molecular weight of the component is 13.5 ⁇ 10 4 g / mol
  • the molecular weight distribution index is 3.0
  • the degree of branching is 108 branches / 1000 Carbon
  • 64.2 mol% in the branch is a methyl branch
  • 4.2 mol% is an ethyl branch
  • the content of the component eluted at 70 ° C is 6.2 wt%, the weight average molecular weight of the component is 17.6 ⁇ 10 4 g / mol, the molecular weight distribution index is 3.8, and the branching degree is 38 branches.
  • mol% of the branches are methyl branches, 0 mol% is ethyl branch, 0 mol% is propyl branch, 0 mol% is butyl branch, and 13.6 mol% is pentyl branch, 1.7 mol% is a branch with carbon number ⁇ 6, glass transition temperature is -71 ° C, melting point is 101.9 ° C, crystallinity is 19.26%, crystallization temperature is 86.7 ° C; (6) group ejected at 80 ° C The content of the component is 7.0 wt%, the weight average molecular weight of the component is 23.3 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.7, the degree of branching is 27 branches/1000 carbons, and 76.3 mol% of the branch is A.
  • One carbon, 74.1 mol% of the branch is methyl branch, 25.9 mol% is a branch with carbon number ⁇ 6, the glass transition temperature is -64.8 ° C, the melting point is 123.3 ° C, the crystallinity is 34.01%, and the crystallization temperature is 109.1 ° C; (10) The content of the component eluted at 120 ° C is 3.4 wt%, the weight average molecular weight of the component is 22.4 ⁇ 10 4 g / mol, the molecular weight distribution index is 2.5, and the degree of branching is 11 Branched / 1000 carbons, 100 mol% of the branches are methyl branches, glass transition temperature is -68.9 ° C, melting point is 122.0 ° C, crystallinity is 37.09%, crystallization temperature is 107.7 ° C; (11) rinsing temperature The component content higher than 120 ° C is 0.9 wt%, the weight average molecular weight of the component is 16.6 ⁇ 10 4 g
  • the polymerization pressure of ethylene was lowered to 0.7 MPa, and other conditions were the same as in Example 1, to obtain 18.5 g of a polymer.
  • the catalyst activity was 3700 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 12.6 ⁇ 10 4 g/mol, the polydispersity coefficient was 3.0, the glass transition temperature was -68 ° C, the melting point was 120.6 ° C, and the crystallinity was obtained. It is 9.2%.
  • the tensile properties of the polymerized product were tested according to GB/T 528-2009, and the tensile strength was 14.0 MPa, and the elongation at break was 900%.
  • the polymerization product was stretched to 2 times the original length at room temperature and after removing the external force for 1 minute, it was able to recover to 1.21 times the original length in 1 minute.
  • the degree of branching of the polymerized product was 82.3 branches/1000 carbon atoms as determined by 1 H-NMR, 49 mol% of the branch was methyl branch, 6.8 mol% was ethyl branch, and 4.7 mol% was propyl.
  • the degree of branching of the hard segment is 51 branches/1000 carbon atoms
  • the degree of branching of the soft segment is 162 branches/1000 carbon atoms.
  • 79 mol% of the branches in the hard segment are methyl branches, 3.2 mol% are ethyl branches, 1.1 mol% are propyl branches, 1.2 mol% are butyl branches, and 7.3 mol% are pentyl branches.
  • 8.2 mol% is a branch having a carbon number of ⁇ 6.
  • 49.6 mol% of the branches in the soft segment are methyl branches, 4.3 mol% are ethyl branches, 13.8 mol% are propyl branches, 5.6 mol% are butyl branches, and 12.1 mol% are pentyl branches.
  • 14.6 mol% is a branch having a carbon number of ⁇ 6.
  • the hard segment has a melting point of 117 ° C, a crystallinity of 9.8%, a glass transition temperature of -73 ° C, a soft segment glass transition temperature of -68 ° C, no significant melting point, and a crystallinity of 0%.
  • the polymerization product can be separated into 11 components by the method of temperature rising elution fractionation (TREF), using toluene as a solvent: (1) the content of the component eluted at 30 ° C is 29.8 wt% (weight percentage) The weight average molecular weight of the component is 9.2 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.4, the degree of branching is 178.8 branches/1000 carbons, and 58.4 mol% of the branches are methyl branches, 3.6 mol.
  • TEZ temperature rising elution fractionation
  • % is ethyl branch, 11.3 mol% is propyl branch, 5.4 mol% is butyl branch, 12.0 mol% is pentyl branch, 9.3 mol% is branch with carbon number ⁇ 6, glass transition temperature
  • melting point one is 53.5 ° C
  • melting point two is 112.8 ° C
  • crystallinity is 1.23%
  • crystallization temperature is 74.5 ° C
  • the content of the component eluted at 40 ° C is 8.9 Wwt%, the component has a weight average molecular weight of 10.5 ⁇ 10 4 g/mol, a molecular weight distribution index of 2.4, a degree of branching of 149.9 branches/1000 carbons, and 57.8 mol% of the branches are methyl branches.
  • 3.1 mol% is ethyl branch, 13.7 mol% is propyl branch, 1.7 mol% is butyl branch, 10.5 mol% is pentyl branch, and 13.2 mol% is branch with carbon number ⁇ 6, vitrification change
  • the temperature is -63.2 ° C, there are two melting points, the melting point one is 73.2 ° C, the melting point two is 113.1 ° C, the crystallinity is 2.41%, there are two crystallization temperatures, the crystallization temperature is 54.2 ° C, and the crystallization temperature is 86.0 ° C; 3)
  • the content of the component eluted at 50 ° C is 4.9 wt%, the weight average molecular weight of the component is 13.0 ⁇ 10 4 g / mol, the molecular weight distribution index is 2.9, and the degree of branching is 109.8 branches / 1000 Carbon, 63.5 mol% of the branch is a methyl branch, 4.4 mol% is an ethyl branch,
  • 12.7mol% is a branch with carbon number ⁇ 6, glass transition temperature is –65.8°C, has two melting points, melting point is 84.2°C, melting point is 115.0°C, crystallinity is 4.29%, and there are two crystallization temperatures.
  • the crystallization temperature is 65.1 ° C, the crystallization temperature is 86.5 ° C; (4) the component content eluted at 60 ° C is 4.2 wt%, and the weight average molecular weight of the component is 15.1 ⁇ 10 4 g / mol,
  • the molecular weight distribution index is 3.2, the degree of branching is 57.8 branches/1000 carbons, 81.5 mol% in the branch chain is methyl branch, 0.1% is ethyl branch, and 0.1 mol% is propyl branch.
  • 0.1 mol% is a butyl branch, 11.6 mol% is a pentyl branch, and 6.6 mol% is a branch having a carbon number ⁇ 6, a glass transition temperature of -70.9 ° C, a melting point of 94.0 ° C, and a crystallinity of 13.12%.
  • the crystallization temperature is 79.2 ° C; (5) the content of the component eluted at 70 ° C is 6.2 wt%, the weight average molecular weight of the component is 17.2 ⁇ 10 4 g / mol, the molecular weight distribution index is 3.6, branching The degree is 37.9 branches/1000 carbons, 84.1 mol% of the branches are methyl branches, 0.2 mol% is ethyl branch, 0.1 mol% is propyl branch, and 0.1 mol% is butyl branch.
  • 13.7 mol% is a pentyl branch, 1.8 mol% is a branch with a carbon number ⁇ 6, a glass transition temperature of -71.1 ° C, a melting point of 101.4 ° C, a crystallinity of 18.78%, and a crystallization temperature of 86.1 ° C; (6)
  • the content of the component eluted at 80 ° C was 7.0 wt%, the weight average molecular weight of the component was 23.0 ⁇ 10 4 g / mol, the molecular weight distribution index was 2.7, and the degree of branching was 27.8 branches / 1000 carbons.
  • mol% in the branch is a methyl branch
  • 14.7 mol% is an ethyl branch
  • 0.1 mol% is a propyl branch
  • 0.1 mol% is a butyl branch
  • 0.1 mol% is a pentyl branch
  • 9.2 Mol% is carbon number ⁇ 6 Chain
  • glass transition temperature is -72.1 ° C
  • melting point is 109.2 ° C
  • crystallinity is 27.07%
  • crystallization temperature is 95.1 ° C
  • component content eluted at 90 ° C is 16.0 wt%
  • the component The weight average molecular weight is 24.4 ⁇ 10 4 g/mol
  • the molecular weight distribution index is 2.6
  • the degree of branching is 22.4 branches/1000 carbons
  • 95.7 mol% of the branches are methyl branches
  • 0.1 mol% is ethyl group.
  • the molecular weight distribution index is 2.4
  • the degree of branching is 17.8 branches/1000 carbons
  • 100 mol% of the branches are methyl branches
  • the glass transition temperature is -66.5 ° C
  • the melting point is 120.1 ° C
  • the crystallinity is 28.5%
  • (9) is rinsed out at 110 °C ingredients content of 10.0 wt% of the component of weight average molecular weight 20.5 ⁇ 10 4 g / mol
  • molecular The distribution index is 2.5
  • the degree of branching is 15.9 branches/1000 carbons
  • 72.9 mol% of the branches are methyl branches
  • 27.1 mol% are branches with carbon number ⁇ 6, and the glass transition temperature is –64.9 °C.
  • the melting point is 123.2 ° C, the crystallinity is 39.87%, the crystallization temperature is 109.1 ° C; (10) the component content eluted at 120 ° C is 3.2 wt%, and the weight average molecular weight of the component is 22.2 ⁇ 10 4 g /mol, the molecular weight distribution index is 2.5, the degree of branching is 10.9 branches/1000 carbons, 100 mol% of the branches are methyl branches, the glass transition temperature is -68.7 ° C, the melting point is 121.0 ° C, and the crystallinity is 37.01%, the crystallization temperature is 107.5 ° C; (11) the component having a rinsing temperature higher than 120 ° C is 1.0 wt%, the weight average molecular weight of the component is 16.0 ⁇ 10 4 g / mol, and the molecular weight distribution index is 2.6.
  • the degree of branching is 8 branches/1000 carbons, 100 mol% of the branches are methyl branches, the glass transition temperature is -63.1 ° C, the melting point is 122.0 ° C, the crystallinity is 35.40%, and the crystallization temperature is 108.1 ° C.
  • the polymerization pressure of ethylene was lowered to 0.4 MPa, and other conditions were the same as in Example 1, to obtain 16.3 g of a polymer.
  • the catalyst activity was 3260 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 11.9 ⁇ 10 4 g/mol, the polydispersity coefficient was 2.9, the glass transition temperature was -69 ° C, the melting point was 120.1 ° C, and the crystallinity was obtained. It is 8.7%.
  • the tensile properties of the polymerized product were tested in accordance with GB/T 528-2009, the tensile strength was 12.0 MPa, and the elongation at break was 850%.
  • the polymerized product was stretched to 2 times the original length at room temperature and after removing the external force for 1 minute, it was able to recover to 1.20 times the original length in 1 minute.
  • the degree of branching of the polymerization product was 93.2 branches/1000 carbon atoms as determined by 1 H-NMR, 54.8 mol% in the branch chain was methyl branch, 7.3 mol% was ethyl branch, and 3.8 mol% was C.
  • the base branch 3.5 mol% is a butyl branch, 15.1 mol% is a pentyl branch, and 15.5 mol% is a branch having a carbon number ⁇ 6.
  • the degree of branching of the hard segment is 50 branches/1000 carbon atoms
  • the degree of branching of the soft segment is 189 branches/1000 carbon atoms.
  • 65 mol% of the branches in the hard segment are methyl branches, 5 mol% are ethyl branches, 3 mol% are propyl branches, 2 mol% are butyl branches, 12.5 mol% are pentyl branches, 12.5 mol% It is a branch with a carbon number of ⁇ 6. 46.9 mol% of the branches in the soft segment are methyl branches, 4.1 mol% are ethyl branches, 14.6 mol% are propyl branches, 5.5 mol% are butyl branches, and 22.4 mol% are pentyl branches. 6.5 mol% is a branch having a carbon number of ⁇ 6.
  • the hard segment has a melting point of 115.0 ° C, a crystallinity of 10.1%, a glass transition temperature of -72 ° C, a soft segment glass transition temperature of -67 ° C, no significant melting point, and a crystallinity of 0%.
  • the polymerization product can be separated into 10 components by a temperature rising elution fractionation (TREF) method using toluene as a solvent: (1) the content of the component eluted at 30 ° C is 30 wt% (weight percentage), The component has a weight average molecular weight of 9.0 ⁇ 10 4 g/mol, a molecular weight distribution index of 2.4, a degree of branching of 190.9 branches/1000 carbons, and 56.5 mol% of the branches are methyl branches, and 4 mol% is Ethyl branch, 12 mol% is propyl branch, 4.7 mol% is butyl branch, 10 mol% is pentyl branch, 12.8 mol% is branch with carbon number ⁇ 6, glass transition temperature is -63 °C , having two melting points, melting point one is 53 ° C, melting point two is 112 ° C, crystallinity is 1.2%, crystallization temperature is 74 ° C; (2) component content eluted at 40 ° C is 10 w
  • Branched, 12 mol% is a propyl branch, 2 mol% is a butyl branch, 10.7 mol% is a pentyl branch, 16.5 mol% is a branch with a carbon number ⁇ 6, and the glass transition temperature is -64 ° C, One melting point, melting point one is 73 ° C, melting point two is 113 ° C, crystallinity is 2.2%, there are two crystallization temperatures, crystallization temperature is 54 ° C, crystallization temperature is 86 ° C; (3) rinsing at 50 ° C
  • the component content was 6.5 wt%, the weight average molecular weight of the component was 12.8 ⁇ 10 4 g/mol, the molecular weight distribution index was 2.9, the degree of branching was 116 branches/1000 carbons, and the branch chain was 63.1 mol.
  • % is a methyl branch
  • 5.5 mol% is an ethyl branch
  • 7.9 mol% is a propyl branch
  • 3 mol% is a butyl branch
  • 13 mol% is a pentyl branch
  • 7.5 mol% is a carbon number ⁇ 6.
  • mol% is ethyl branch
  • 0 mol% is propyl branch
  • 0 mol% is butyl branch
  • 17 mol% is pentyl branch
  • 2 mol% is branch with carbon number ⁇ 6
  • the glass transition temperature is - 71.5 ° C, melting point of 101.2 ° C, crystallinity of 18.3%, crystallization temperature of 85.9 ° C
  • (6) component content of leaching at 80 ° C is 9 wt%, the weight average molecular weight of the component is 22.3 ⁇ 10 4 g/mol, molecular weight distribution index of 2.7, branching degree of 35 branches/1000 carbons
  • 77 mol% of branches are methyl branches
  • 0 mol% of propyl branches 0 mol% is butyl branch
  • 0 mol% is pentyl branch
  • 5 mol% is a branch with carbon number ⁇ 6
  • glass transition temperature is -72.5 ° C
  • branches/1000 carbons 88 mol% of the branches are methyl branches, 2 mol% are ethyl branches, 2 mol% are propyl branches, 3 mol% are butyl branches, and 3 mol% are pentyl branches.
  • 2 mol% is a branch with carbon number ⁇ 6, glass transition temperature is -64.5 ° C, melting point is 115 ° C, crystallinity is 28.9%, crystallization temperature is 100 ° C; (8) group ejected at 100 ° C
  • the content of the component is 9wt%, the weight average molecular weight of the component is 24.5 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.4, the degree of branching is 22 branches/1000 carbons, and 95 mol% of the branch is methyl branch.
  • 0.1 mol% is a butyl branch, 0.1 mol% is a pentyl branch, and 0.1 mol% is a branch having a carbon number ⁇ 6, a glass transition temperature of -68.9 ° C, a melting point of 120 ° C, and a crystallinity of 37%.
  • the crystallization temperature was 107 ° C; (11) the component having a rinsing temperature higher than 120 ° C was 0 wt%.
  • the amount of diethyl zinc was changed to 0.1 mmol [the molar ratio between zinc in the control zinc zinc and nickel in the dinuclear ruthenium ( ⁇ -diimine) nickel catalyst was 10], and other conditions were the same as in Example 1. 24.5 g of the polymer was obtained.
  • the catalyst activity was 4900 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 11.1 ⁇ 10 4 g/mol, the polydispersity coefficient was 3.1, the glass transition temperature was -69 ° C, the melting point was 120.8 ° C, and the crystallinity was obtained. It is 7.1%.
  • the tensile properties of the polymerized product were tested in accordance with GB/T 528-2009, the tensile strength was 18.0 MPa, and the elongation at break was 1240%.
  • the polymerization product was stretched to 2 times the original length at room temperature and after 1 minute, the external force was removed, and it was restored to 1.30 times the original length in 1 minute.
  • the degree of branching of the polymerized product was 87.3 branches/1000 carbon atoms as determined by 1 H-NMR, 50 mol% of the branch was methyl branch, 6.6 mol% was ethyl branch, and 4.6 mol% was propyl.
  • the branched chain, 4 mol% is a butyl branch, 17.7 mol% is a pentyl branch, and 17.1 mol% is a branch having a carbon number ⁇ 6.
  • the degree of branching of the hard segment is 49 branches/1000 carbon atoms
  • the degree of branching of the soft segment is 167 branches/1000 carbon atoms.
  • 80 mol% of the branches in the hard segment are methyl branches, 3.1 mol% are ethyl branches, 1.2 mol% are propyl branches, 1.1 mol% are butyl branches, and 7.2 mol% are pentyl branches.
  • 7.4 mol% is a branch having a carbon number of ⁇ 6.
  • 50 mol% of the branches of the soft segment are methyl branches, 4.3 mol% are ethyl branches, 13.8 mol% are propyl branches, 5.6 mol% are butyl branches, and 11.9 mol% are pentyl branches.
  • 14.4 mol% is a branch having a carbon number of ⁇ 6.
  • the hard segment has a melting point of 122 ° C, a crystallinity of 10.2%, a glass transition temperature of -71 ° C, a soft segment glass transition temperature of -67 ° C, no significant melting point, and a crystallinity of 0%.
  • the polymerization product can be separated into 10 components by the method of temperature rising elution fractionation (TREF), and the content of the component eluted at 30 ° C is 27.5 wt% (weight percentage).
  • the weight average molecular weight of the component is 9.2 ⁇ 10 4 g/mol
  • the molecular weight distribution index is 2.4
  • the degree of branching is 184 branches/1000 carbons
  • 56 mol% of the branches are methyl branches, 3.7 mol%.
  • 63.5 mol% in the branch is a methyl branch, 4.5 mol% is an ethyl branch, 9.5 mol% is a propyl branch, 0.2 mol% is a butyl branch, and 9.8 mol% is a pentyl branch, 12.5 Mol% is a branch with carbon number ⁇ 6, glass transition temperature is –65.5°C, has two melting points, melting point is 84.1°C, melting point is 114°C, crystallinity is 4.2%, there are two crystallization temperatures, crystallization The temperature is 65.2 ° C, the crystallization temperature is 86 ° C; (4) the content of the component eluted at 60 ° C is 4.2 wt%, the weight average molecular weight of the component is 14.8 ⁇ 10 4 g / mol, molecular weight distribution
  • the index is 3.6, the degree of branching is 64 branches/1000 carbons, 80 mol% of the branches are methyl branches, 0.1% is ethyl branch, 0.2
  • Base branch 14.8 mol% is ethyl branch, 0.1 mol% is propyl branch, 0.2 mol% is butyl branch, 0.2 mol% is pentyl branch, and 9.7 mol% is branch with carbon number ⁇ 6 Chain, glass transition temperature is –72 ° C A melting point of 109.1 deg.] C, a crystallinity of 27.1%, a crystallization temperature of 95 °C; (7) rinsed out at 90 deg.] C ingredients content proportion of 16.3 wt% of the set of parts weight average molecular weight 24.2 ⁇ 10 4 g / Mol, the molecular weight distribution index is 2.6, the degree of branching is 22 branches/1000 carbons, 95 mol% of the branches are methyl branches, 0.1 mol% is ethyl branch, and 0.1 mol% is propyl branch.
  • 0.1 mol% is a butyl branch
  • 0.1 mol% is a pentyl branch
  • 4.6 mol% is a branch having a carbon number ⁇ 6, a glass transition temperature of -64.2 ° C, a melting point of 115.3 ° C, and a crystallinity of 29%.
  • the crystallization temperature is 100 ° C; (8) the content of the component eluted at 100 ° C is 11 wt%, the weight average molecular weight of the component is 25 ⁇ 10 4 g / mol, the molecular weight distribution index is 2.4, and the degree of branching is 18 branches/1000 carbons, 98 mol% of the branches are methyl branches, 0.2 mol% is ethyl branch, 0.2 mol% is propyl branch, 0.2 mol% is butyl branch, 0.2 mol% Is a pentyl branch, 1.2 mol% is a branch with a carbon number ⁇ 6, a glass transition temperature of -67 ° C, a melting point of 120 ° C, a crystallinity of 28.4%, a crystallization temperature of 105.2 ° C; (9) at 110 ° C Sublimed components An amount of 10.2wt%, the component of weight average molecular weight 20.8 ⁇ 10 4 g / mol, a
  • % is a methyl branch
  • 0.1 mol% is an ethyl branch
  • 0.1 mol% is a propyl branch
  • 0.1 mol% is a butyl branch
  • 0.1 mol% is a pentyl branch
  • 1 mol% is a carbon number ⁇ 6
  • the branch has a glass transition temperature of -69 ° C, a melting point of 122.0 ° C, a crystallinity of 37%, and a crystallization temperature of 107.2 ° C
  • (11) a component having a rinsing temperature of more than 120 ° C is 0 wt%.
  • the amount of diethyl zinc was changed to 0.3 mmol [the molar ratio between the zinc in the control zinc and the nickel in the dinuclear ruthenium ( ⁇ -diimine) nickel catalyst was 30], and other conditions were the same as in Example 1. 21.5 g of polymer were obtained.
  • the catalyst activity was 4300 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 17.2 ⁇ 10 4 g/mol, the polydispersity coefficient was 3.1, the glass transition temperature was -68 ° C, the melting point was 120.9 ° C, crystallinity. At 11.6%.
  • the tensile properties of the polymerized product were tested in accordance with GB/T 528-2009, the tensile strength was 17.1 MPa, and the elongation at break was 1060%.
  • the polymerization product was stretched to 2 times the original length at room temperature and after 1 minute, the external force was removed, and it was restored to 1.30 times the original length in 1 minute.
  • the degree of branching of the polymerized product was 76.3 branches/1000 carbon atoms as determined by 1 H-NMR, 54.8 mol% of the branch was methyl branch, 6 mol% was ethyl branch, and 4.2 mol% was propyl.
  • the degree of branching of the hard segment is 35 branches/1000 carbon atoms
  • the degree of branching of the soft segment is 132 branches/1000 carbon atoms.
  • mol% of the branches in the hard segment are methyl branches
  • 2 mol% are ethyl branches
  • 0.5 mol% are propyl branches
  • 0.5 mol% are butyl branches
  • 6.8 mol% are pentyl branches
  • 5.2 Mol% is a branch with a carbon number of ⁇ 6.
  • 53 mol% of the branches in the soft segment are methyl branches
  • 4 mol% are ethyl branches
  • 13.2 mol% are propyl branches
  • 5.1 mol% are butyl branches
  • 11.2 mol% are pentyl branches
  • 13.5 Mol% is a branch with a carbon number of ⁇ 6.
  • the hard segment has a melting point of 122 ° C, a crystallinity of 13.3%, a glass transition temperature of -70 ° C, a soft segment glass transition temperature of -66 ° C, no significant melting point, and a crystallinity of 1%.
  • the polymerization product can be separated into 11 components by the method of temperature rising elution fractionation (TREF), and the content of the component eluted at 30 ° C is 26.5 wt% (weight percentage).
  • the weight average molecular weight of the component is 13.8 ⁇ 10 4 g/mol
  • the molecular weight distribution index is 2.4
  • the degree of branching is 167 branches/1000 carbons
  • the branching chain is 61.8 mol% of methyl branch, 3.2 mol.
  • % is ethyl branch, 11.1 mol% is propyl branch, 5.1 mol% is butyl branch, 11.7 mol% is pentyl branch, 7.1 mol% is branch with carbon number ⁇ 6, glass transition temperature
  • melting point one is 55.9 ° C
  • melting point two is 113.9 ° C
  • crystallinity is 1.49%
  • crystallization temperature is 75.9 ° C
  • the content of the component eluted at 40 ° C is 8.2 Wwt%
  • the component has a weight average molecular weight of 16.7 ⁇ 10 4 g/mol, a molecular weight distribution index of 2.4, a degree of branching of 146 branches/1000 carbons, and 59.2 mol% of the branches are methyl branches.
  • 3.0 mol% is an ethyl branch
  • 13.3 mol% is a propyl branch
  • 1.4 mol% is a butyl branch
  • 10.2 mol% is a pentyl branch
  • 12.9 mol% is a branch having a carbon number ⁇ 6, vitrification Change temperature
  • the degree is -62.3 ° C, there are two melting points, the melting point one is 75.5 ° C, the melting point is 114.2 ° C, the crystallinity is 2.69%, there are two crystallization temperatures, the crystallization temperature is 54.9 ° C, and the crystallization temperature is 86.9 ° C; 3) leaching out at 50 deg.] C ingredients content of 4wt%, the component of the weight average molecular weight 17.8 ⁇ 10 4 g / mol, a molecular weight distribution index of 3.0, the degree of branching of 106 branches / 1000 Carbon, 64.9 mol% in the branch is a methyl branch, 4.1 mol% is an
  • 12.3mol% is a branch with carbon number ⁇ 6, the glass transition temperature is –65.1°C, has two melting points, the melting point is 84.9°C, the melting point is 115.6°C, the crystallinity is 4.5%, and there are two crystallization temperatures.
  • the crystallization temperature is 65.9 ° C, the crystallization temperature is 87.8 ° C; (4) the component content eluted at 60 ° C is 3.8 wt%, the weight average molecular weight of the component is 19.6 ⁇ 10 4 g / mol, the molecular weight
  • the distribution index is 3.6, the degree of branching is 54 branches/1000 carbons, 83 mol% of the branches are methyl branches, 0% is ethyl branch, 0 mol% is propyl branch, 0 mol% is The base branch chain, 11.2mol% is a pentyl branch, 5.8mol% is a branch with a carbon number ⁇ 6, the glass transition temperature is -70.2 ° C, the melting point is 94.6 ° C, the crystallinity is 13.7%, and the crystallization temperature is 79.9 ° C.
  • the content of the component eluted at 70 ° C is 6 wt%, the weight average molecular weight of the component is 21.4 ⁇ 10 4 g / mol, the molecular weight distribution index is 3.5, and the degree of branching is 36.4 branches / 1000 carbons, 85 mol% of the branches are methyl branches, 0 mol% is ethyl branch, 0 mol% is propyl branch, 0 mol% is butyl branch, 13.3 mol% is pentyl branch, 1.7 mol % is a branch with carbon number ⁇ 6, glass transition temperature is -70 ° C, melting point is 102 ° C, crystallinity is 19.6%, crystallization temperature is 87 ° C; (6) component content eluted at 80 ° C
  • the composition has a weight average molecular weight of 25.7 ⁇ 10 4 g/mol, a molecular weight distribution index of 2.8, a branching degree of 26.5 branches/1000 carbons, and a branching
  • Branched / 1000 carbons 100 mol% of the branches are methyl branches, glass transition temperature is -66.5 ° C, melting point is 120.8 ° C, crystallinity is 28.9%, crystallization temperature is 105.9 ° C; (9) at 110 ° C
  • the content of the component eluted by the lower elution is 10.5 wt%, the weight average molecular weight of the component is 29.3 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.5, and the degree of branching is 15.4 branches/1000 carbons.
  • 74.8mol% in the chain is a methyl branch, and 25.2mol% is a branch with a carbon number ⁇ 6, a glass transition temperature of -64.5 ° C, a melting point of 123.6 ° C, a crystallinity of 34.5%, and a crystallization temperature of 109.6 ° C; 10)
  • the content of the component eluted at 120 ° C is 3.8 wt%, the weight average molecular weight of the component is 29.9 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.5, and the degree of branching is 9.8 branches/1000.
  • One carbon, 100 mol% of the branch is a methyl branch
  • the glass transition temperature is -68.6 ° C
  • the melting point is 122.5 ° C
  • the crystallinity is 37.3%
  • the crystallization temperature is 107.9 ° C
  • the rinsing temperature is higher than 120 ° C
  • the component content is 1.7 wt%
  • the weight average molecular weight of the component is 29.3 ⁇ 10 4 g/mol
  • the molecular weight distribution index is 2.5
  • the degree of branching is 4 branches/1000 carbons
  • 100 mol% of the branches are
  • the methyl branch has a glass transition temperature of -63.1 ° C, a melting point of 122.6 ° C, a crystallinity of 35.7%, and a crystallization temperature of 108.6 ° C.
  • the amount of diethyl zinc is changed to 0.5 mmol [controlling the molar ratio between zinc in diethyl zinc and nickel in the dinuclear ruthenium ( ⁇ -diimine) nickel catalyst is 50], and other conditions are the same as in the first embodiment.
  • the polymer was obtained in an amount of 18.0 g.
  • the catalyst activity was 3600 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 17.6 ⁇ 10 4 g/mol, the polydispersity coefficient was 3.6, the glass transition temperature was -68 ° C, the melting point was 120.7 ° C, and the crystallinity was obtained. It is 17.7%.
  • the tensile properties of the polymerized product were tested in accordance with GB/T 528-2009, the tensile strength was 19.4 MPa, and the elongation at break was 1180%.
  • the polymerization product was stretched to 2 times the original length at room temperature and after removing the external force for 1 minute, it was able to recover to 1.33 times the original length in 1 minute.
  • the degree of branching of the polymerized product was 63.2 branches/1000 carbon atoms as determined by 1 H-NMR, 55.3 mol% of the branch was methyl branch, 5.8 mol% was ethyl branch, and 4.1 mol% was C.
  • the degree of branching of the hard segment is 32 branches/1000 carbon atoms
  • the degree of branching of the soft segment is 113 branches/1000 carbon atoms.
  • 87 mol% of the branches in the hard segment are methyl branches, 2 mol% are ethyl branches, 0.5 mol% are propyl branches, 0.5 mol% are butyl branches, and 6.1 mol% are pentyl branches, 3.9 Mol% is a branch with a carbon number of ⁇ 6.
  • 54 mol% of the branches in the soft segment are methyl branches, 3.8 mol% are ethyl branches, 13.1 mol% are propyl branches, 5 mol% are butyl branches, 11 mol% are pentyl branches, 13.1 mol % is a branch with a carbon number ⁇ 6.
  • the hard segment has a melting point of 122.1 ° C, a crystallinity of 23.6%, a glass transition temperature of -70 ° C, a soft segment glass transition temperature of -66 ° C, no significant melting point, and a crystallinity of 1.4%.
  • the polymerization product can be separated into 11 components by the method of temperature rising elution fractionation (TREF), and the content of the component eluted at 30 ° C is 26.2 wt% (weight percentage).
  • the weight average molecular weight of the component is 13.9 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.5, the degree of branching is 155 branches/1000 carbons, and 62.4 mol% in the branch chain is methyl branch, 3.1 mol.
  • % is an ethyl branch, 11 mol% is a propyl branch, 5 mol% is a butyl branch, 11.5 mol% is a pentyl branch, 7 mol% is a branch with a carbon number ⁇ 6, and the glass transition temperature is -63.1 °C, has two melting points, melting point one is 56 ° C, melting point two is 114 ° C, crystallinity is 1.5%, crystallization temperature is 76 ° C; (2) the content of the component eluted at 40 ° C is 8 wt%, The weight average molecular weight of the component is 16.9 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.6, the degree of branching is 138 branches/1000 carbons, the branching chain is 59.8 mol%, and the methyl branch is 2.8 mol%.
  • Ethyl branch 13.3 mol% is a propyl branch, 1.2 mol% is a butyl branch, 10.1 mol% is a pentyl branch, 12.8 mol% is a branch with a carbon number ⁇ 6, and the glass transition temperature is – 62.2 , has two melting points, melting point one is 75.8 ° C, melting point two is 114.6 ° C, crystallinity is 2.7%, there are two crystallization temperatures, crystallization temperature one is 55 ° C, crystallization temperature two is 87 ° C; (3) at 50 ° C The content of the component eluted by the lower rinse was 3.7 wt%, the weight average molecular weight of the component was 17.9 ⁇ 10 4 g/mol, the molecular weight distribution index was 3.1, the degree of branching was 103 branches/1000 carbons, and the branching was carried out.
  • 65 mol% is a methyl branch
  • 4 mol% is an ethyl branch
  • 9.2 mol% is a propyl branch
  • 0.1 mol% is a butyl branch
  • 9.4 mol% is a pentyl branch
  • 12.3 mol% is a carbon number.
  • the degree of conversion is 52 branches/1000 carbons, 84 mol% of the branches are methyl branches, 0% is ethyl branch, 0 mol% is propyl branch, 0 mol% is butyl branch, 11 mol% is Amyl Branch chain, 5 mol% is a branch with carbon number ⁇ 6, glass transition temperature is -70.1 ° C, melting point is 94.8 ° C, crystallinity is 13.9%, crystallization temperature is 80 ° C; (5) leaching at 70 ° C
  • the component content is 5.8 wt%, the weight average molecular weight of the component is 21.8 ⁇ 10 4 g/mol, the molecular weight distribution index is 3.6, the degree of branching is 35 branches/1000 carbons, and 86 mol% of the branches are Methyl branch, 0 mol% is ethyl branch, 0 mol% is propyl branch, 0 mol% is butyl branch, 13 mol% is pentyl branch, 1 mol% is branch
  • the base branch has a glass transition temperature of -66 ° C, a melting point of 121 ° C, a crystallinity of 29%, and a crystallization temperature of 106 ° C; (9) a component content of 10.9 wt % eluted at 110 ° C,
  • the weight average molecular weight of the component is 29.8 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.5, the degree of branching is 14 branches/1000 carbons, 75 mol% of the branch is methyl branch, and 25 mol% is carbon number.
  • the glass transition temperature is -64 ° C, the melting point is 124 ° C, the crystallinity is 35%, the crystallization temperature is 109.9 ° C; (10) the component content eluted at 120 ° C is 4.5 wt%, the weight of the component
  • the average molecular weight is 31.2 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.5, the degree of branching is 8 branches/1000 carbons, 100 mol% of the branches are methyl branches, and the glass transition temperature is ⁇ 68° C.
  • the melting point is 123 ° C, the crystallinity is 37.8%, the crystallization temperature is 108 ° C; (11) the component having a rinsing temperature higher than 120 ° C is 1.4 wt%, and the weight average molecular weight of the component is 29.9 ⁇ 10 4 g/ Mol, molecular weight distribution index of 2.5, branching degree of 3 branches / 1000 carbons, 100 mol% of branches is methyl branch, glass transition temperature of -63 ° C, melting point of 122.9 ° C, crystallinity of 35.9 %, the crystallization temperature was 108.8 °C.
  • the amount of diethyl zinc was changed to 1.0 mmol [the molar ratio between the zinc in the control zinc and the nickel in the dinuclear ruthenium ( ⁇ -diimine) nickel catalyst was 100], and the other conditions were the same as in Example 1.
  • the polymer was obtained in an amount of 15.5 g.
  • the catalyst activity was 3100 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 18.5 ⁇ 10 4 g/mol, the polydispersity coefficient was 3.3, the glass transition temperature was -67 ° C, the melting point was 121.8 ° C, and the crystallinity was obtained. It is 27.3%.
  • the tensile properties of the polymerized product were tested according to GB/T 528-2009, the tensile strength was 33.7 MPa, and the elongation at break was 1130%.
  • the polymerization product was stretched to 2 times the original length at room temperature and after 1 minute, the external force was removed, and it was restored to 1.30 times the original length in 1 minute.
  • the degree of branching of the polymerization product was 59.6 branches/1000 carbon atoms as determined by 1 H-NMR, 56 mol% of the branches were methyl branches, 5.5 mol% were ethyl branches, and 4 mol% were propyl groups.
  • the degree of branching of the hard segment is 30 branches/1000 carbon atoms, and the degree of branching of the soft segment is 110 branches/1000 carbon atoms.
  • 89 mol% of the branches in the hard segment are methyl branches, 1 mol% is ethyl branch, 0.5 mol% is propyl branch, 0.5 mol% is butyl branch, 6 mol% is pentyl branch, 3 mol% It is a branch with a carbon number of ⁇ 6.
  • 56 mol% of the branches in the soft segment are methyl branches, 3.5 mol% are ethyl branches, 13 mol% are propyl branches, 4.5 mol% are butyl branches, 11 mol% are pentyl branches, 12 mol% It is a branch with a carbon number of ⁇ 6.
  • the hard segment has a melting point of 122.6 ° C, a crystallinity of 24%, a glass transition temperature of -69 ° C, a soft segment glass transition temperature of -65 ° C, no significant melting point, and a crystallinity of 1.8%.
  • the polymerization product can be separated into 11 components by a temperature rising elution fractionation (TREF) method using toluene as a solvent: (1) the content of the component eluted at 30 ° C is 26 wt% (weight percentage), The component has a weight average molecular weight of 14.6 ⁇ 10 4 g/mol, a molecular weight distribution index of 2.5, a degree of branching of 137 branches/1000 carbons, and 62.8 mol% of the branches are methyl branches, and 3 mol% is Ethyl branch, 10.8 mol% is propyl branch, 4.8 mol% is butyl branch, 11.3 mol% is pentyl branch, 7.3 mol% is branch with carbon number ⁇ 6, glass transition temperature is – At 63 ° C, there are two melting points, melting point one is 57 ° C, melting point two is 115 ° C, crystallinity is 1.8%, crystallization temperature is 79 ° C; (2) component content eluted at 40 ° C
  • 67 mol% is a methyl branch
  • 3 mol% is an ethyl branch
  • 9 mol% is a propyl branch
  • 0.1 mol% is a butyl branch
  • 9.2 mol% is a pentyl branch
  • 11.7 mol% is a carbon number ⁇ 6
  • the branch has a glass transition temperature of –64 ° C, two melting points, a melting point of 87 ° C, a melting point of 117 ° C, a crystallinity of 5%, two crystallization temperatures, a crystallization temperature of 68 ° C, and crystallization.
  • the temperature is 90 ° C; (4) the content of the component eluted at 60 ° C is 3.4 wt%, the weight average molecular weight of the component is 21.8 ⁇ 10 4 g / mol, the molecular weight distribution index is 3.6, the degree of branching It is 46 branches/1000 carbons, 85 mol% of the branches are methyl branches, 0% is ethyl branch, 0 mol% is propyl branch, 0 mol% is butyl branch, 10 mol% is pentyl Branch, 5mol
  • the glass transition temperature is -70 ° C, the melting point is 95 ° C, the crystallinity is 14.5%, the crystallization temperature is 83 ° C; (5) the content of the component eluted at 70 ° C is 5.5wt%, the weight average molecular weight of the component is 22.4 ⁇ 10 4 g/mol, the molecular weight distribution index is 3.5, the degree of branching is 26 branches/1000 carbon
  • 0 mol% is ethyl branch, 0 mol% is propyl branch, 0 mol% is butyl branch, 12 mol% is pentyl branch, 1 mol% is a branch with carbon number ⁇ 6, and the glass transition temperature is -68 °C, melting point is 106 ° C, crystallinity is 20.3%, crystallization temperature is 90 ° C; (6) component content eluted at 80 ° C is 6.3 wt%, the weight average molecular weight of the component is 26.4 ⁇ 10 4 g/mol, molecular weight distribution index is 2.9, degree of branching is 17 branches/1000 carbons, 79 mol% of branches is methyl branch, 12 mol% is ethyl branch, 0 mol% is propyl branch, 0 mol% is a butyl branch, 0 mol% is a pentyl branch, 9 mol% is a branch with a carbon number ⁇ 6, a glass transition temperature of -69
  • the polymerization temperature was raised to 35 ° C, and other conditions were the same as in Example 1 to obtain 18 g of a polymer.
  • the catalyst activity was 3600 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 11.6 ⁇ 10 4 g/mol, the polydispersity coefficient was 2.8, the glass transition temperature was -68 ° C, the melting point was 120.2 ° C, crystallinity. It is 9.2%.
  • the tensile properties of the polymerized product were tested according to GB/T 528-2009, the tensile strength was 17 MPa, and the elongation at break was 1280%.
  • the polymerization product was stretched to 2 times the original length at room temperature and after 1 minute, the external force was removed, and it was restored to 1.30 times the original length in 1 minute.
  • the degree of branching of the polymerization product was 92.5 branches/1000 carbon atoms as determined by 1 H-NMR, 50.6 mol% in the branch chain was methyl branch, 6.7 mol% was ethyl branch, and 4.6 mol% was C.
  • the degree of branching of the hard segment is 54 branches/1000 carbon atoms
  • the degree of branching of the soft segment is 168 branches/1000 carbon atoms.
  • 80 mol% of the branches in the hard segment are methyl branches, 3.1 mol% are ethyl branches, 1.2 mol% are propyl branches, 1.1 mol% are butyl branches, and 7.2 mol% are pentyl branches. 7.4 mol% is a branch having a carbon number of ⁇ 6. 50 mol% of the branch of the soft segment is a methyl branch, 4.5 mol% is an ethyl branch, 13.8 mol% is a propyl branch, 5.5 mol% is a butyl branch, and 12.2 mol% is a pentyl branch. 14 mol% is a branch having a carbon number of ⁇ 6.
  • the hard segment has a melting point of 117 ° C, a crystallinity of 9.7%, a glass transition temperature of -73 ° C, a soft segment glass transition temperature of -69 ° C, no significant melting point, and a crystallinity of 0%.
  • the polymerization product can be separated into 11 components by the method of temperature rising elution fractionation (TREF), and the content of the component eluted at 30 ° C is 27.3 wt% (weight percentage).
  • the weight average molecular weight of the component is 9.2 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.5, the degree of branching is 184 branches/1000 carbons, and 57.2 mol% of the branches are methyl branches, 3.6 mol.
  • % is an ethyl branch, 11.3 mol% is a propyl branch, 5.5 mol% is a butyl branch, 12 mol% is a pentyl branch, and 10.4 mol% is a branch having a carbon number ⁇ 6, and the glass transition temperature is – 63.8 ° C, with two melting points, melting point 1 is 55.4 ° C, melting point 2 is 113.2 ° C, crystallinity is 1.32%, crystallization temperature is 75.3 ° C; (2) component content eluted at 40 ° C is 8.7 wt %, the weight average molecular weight of the component is 10.1 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.6, the degree of branching is 165 branches/1000 carbons, and 56.6 mol% of the branches are methyl branches, 3.1 Mol% is ethyl branch, 13.8 mol% is propyl branch, 1.8 mol% is butyl branch, 10.6 mol% is pentyl branch,
  • mol% is a branch with carbon number ⁇ 6, glass transition temperature is -65.7 ° C, has two melting points, melting point one is 84.2 ° C, melting point two is 115 ° C, crystallinity is 4.2%, and there are two crystallization temperatures.
  • the crystallization temperature was 65.2 ° C, the crystallization temperature was 87 ° C; (4) the content of the component eluted at 60 ° C was 4.1 wt%, and the weight average molecular weight of the component was 15.1 ⁇ 10 4 g / mol.
  • the distribution index is 3.4, the degree of branching is 63 branches/1000 carbons, 80 mol% in the branch chain is methyl branch, 0.2% is ethyl branch, 0.1 mol% is propyl branch, 0.2 mol% is Butyl branch, 11.3 mol% is a pentyl branch, 8.2 mol% is a branch with carbon number ⁇ 6, glass transition temperature is -70.9 ° C, melting point is 94 ° C, crystallinity is 13.3%, crystallization temperature is 79.3 °C; (5) The content of the component eluted at 70 ° C is 6.3 wt%, the weight average molecular weight of the component is 17.2 ⁇ 10 4 g / mol, the molecular weight distribution index is 3.6, and the branching degree is 45 Chain / 1000 carbons, 82.5 mol% of the branches are methyl branches, 0.1 mol% is ethyl branch, 0.1 mol% is propyl branch, 0.2 mol% is buty
  • Mol% is a methyl branch, 14.7 mol% is an ethyl branch, 0.1 mol% is a propyl branch, 0.1 mol% is a butyl branch, 0.2 mol% is a pentyl branch, and 9.3 mol% is a carbon number.
  • the content of the component eluted at 110 ° C is 10.5 wt%, the weight average molecular weight of the component is 20.3 ⁇ 10 4 g / mol, the molecular weight distribution index is 2.6, and the branching degree is 17 Chain/10 00 carbons, 73.5 mol% of the branches are methyl branches, 26.5 mol% are branches with carbon number ⁇ 6, glass transition temperature is -64.9 ° C, melting point is 123.1 ° C, crystallinity is 34%, crystallization temperature It is 109 ° C; (10) the content of the component eluted at 120 ° C is 3.7 wt%, the weight average molecular weight of the component is 22.2 ⁇ 10 4 g / mol, the molecular weight distribution index is 2.5, and the degree of branching is 13.
  • Branches / 1000 carbons 100 mol% of the branches are methyl branches, glass transition temperature of -68.9 ° C, melting point of 122.0 ° C, crystallinity of 37%, crystallization temperature of 107.7 ° C; (11) leaching
  • the component content of the temperature higher than 120 ° C is 0.3 wt%
  • the weight average molecular weight of the component is 16.5 ⁇ 10 4 g / mol
  • the molecular weight distribution index is 2.6
  • the degree of branching is 8 branches / 1000 carbons.
  • 100 mol% of the chain is a methyl branch, a glass transition temperature of -63.8 ° C, a melting point of 122 ° C, a crystallinity of 35%, and a crystallization temperature of 108 ° C.
  • the cocatalyst was changed to sesquiethylaluminum, and other conditions were the same as in Example 1, to obtain 21.5 g of a polymer.
  • the catalyst activity was 4300 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 13.5 ⁇ 10 4 g/mol, the polydispersity coefficient was 2.8, the glass transition temperature was -67 ° C, the melting point was 120.8 ° C, and the crystallinity was obtained. It is 11.3%.
  • the tensile properties of the polymerized product were tested according to GB/T 528-2009, the tensile strength was 17.9 MPa, and the elongation at break was 1190%.
  • the polymerization product was stretched to 2 times the original length at room temperature and after 1 minute, the external force was removed, and it was restored to 1.30 times the original length in 1 minute.
  • the degree of branching of the polymerization product was 80.5 branches/1000 carbon atoms as determined by 1 H-NMR, 52.2 mol% in the branch chain was methyl branch, 6.4 mol% was ethyl branch, and 4.4 mol% was C.
  • the base branch 3.7 mol% is a butyl branch, 17.5 mol% is a pentyl branch, and 15.4 mol% is a branch having a carbon number of ⁇ 6.
  • the degree of branching of the hard segment is 41 branches/1000 carbon atoms, and the degree of branching of the soft segment is 138 branches/1000 carbon atoms.
  • 81 mol% of the branches in the hard segment are methyl branches, 3 mol% are ethyl branches, 2 mol% are propyl branches, 1 mol% are butyl branches, 7 mol% are pentyl branches, and 6 mol% are carbon.
  • Branches with a number ⁇ 6. 52.8 mol% of the branches in the soft segment are methyl branches, 4.1 mol% are ethyl branches, 13.2 mol% are propyl branches, 5.1 mol% are butyl branches, and 11.8 mol% are pentyl branches.
  • 13 mol% is a branch with a carbon number of ⁇ 6.
  • the hard segment has a melting point of 118.5 ° C, a crystallinity of 10.8%, a glass transition temperature of -72 ° C, a soft segment glass transition temperature of -67 ° C, no significant melting point, and a crystallinity of 0%.
  • the polymerization product can be separated into 11 components by the method of temperature rising elution fractionation (TREF), and the content of the component eluted at 30 ° C is 27.3 wt% (weight percentage).
  • the weight average molecular weight of the component is 9.8 ⁇ 10 4 g/mol
  • the molecular weight distribution index is 2.4
  • the degree of branching is 176.4 branches/1000 carbons
  • the branching chain is 58.3 mol% of methyl branch, 3.6 mol.
  • % is ethyl branch, 11.4 mol% is propyl branch, 5.5 mol% is butyl branch, 11.9 mol% is pentyl branch, 9.3 mol% is branch with carbon number ⁇ 6, glass transition temperature
  • melting point one is 55.8 ° C
  • melting point two is 113.7 ° C
  • crystallinity is 1.44%
  • crystallization temperature is 75.9 ° C
  • the content of the component eluted at 40 ° C is 8.3 Wwt%, the component has a weight average molecular weight of 10.9 ⁇ 10 4 g/mol, a molecular weight distribution index of 2.5, a degree of branching of 149.7 branches/1000 carbons, and 58.2 mol% of the branches are methyl branches.
  • mol% is ethyl branch, 13.5 mol% is propyl branch, 1.7 mol% is butyl branch, 10.5 mol% is pentyl branch, 13 mol% is branch with carbon number ⁇ 6, glass transition Degree is -62.8 ° C, has two melting points, melting point one is 75.5 ° C, melting point two is 113.7 ° C, crystallinity is 2.61%, there are two crystallization temperatures, crystallization temperature one is 54.7 ° C, crystallization temperature two is 86.5 ° C; 3) The content of the component eluted at 50 ° C is 4.5 wt%, the weight average molecular weight of the component is 13.7 ⁇ 10 4 g / mol, the molecular weight distribution index is 3.0, and the degree of branching is 108.2 branches / 1000 One carbon, 64.5 mol% of the branch is a methyl branch, 4.1 mol% is an ethyl branch, 9.3 mol% is a propyl branch,
  • 12.6mol% is a branch with carbon number ⁇ 6, glass transition temperature is –65.2°C, has two melting points, melting point is 84.8°C, melting point is 115.3°C, crystallinity is 4.5%, and there are two crystallization temperatures.
  • the crystallization temperature is 65.9 ° C, the crystallization temperature is 87.4 ° C; (4) the component content eluted at 60 ° C is 3.9 wt%, the weight average molecular weight of the component is 15.8 ⁇ 10 4 g / mol, the molecular weight
  • the distribution index is 3.5, the degree of branching is 56.6 branches/1000 carbons, 81 mol% of the branches are methyl branches, 0.2% are ethyl branches, 0.2 mol% are propyl branches, 0.2 Mol% is butyl branch, 11.7 mol% is pentyl branch, 6.8 mol% is branch with carbon number ⁇ 6, glass transition temperature is -70.7 ° C, melting point is 94.5 ° C
  • mol% of the chain is a methyl branch, 14.6 mol% is an ethyl branch, 0.1 mol% is a propyl branch, 0.1 mol% is a butyl branch, 0.1 mol% is a pentyl branch, and 9.1 mol% is Branches with carbon number ⁇ 6,
  • the glass transition temperature is -71 ° C, the melting point is 109.8 ° C, the crystallinity is 27.2%, the crystallization temperature is 95.6 ° C; (7) the component content eluted at 90 ° C is 16.5 wt%, the weight of the component
  • the average molecular weight is 24.9 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.5, the degree of branching is 23 branches/1000 carbons, 95.7 mol% in the branch chain is methyl branch, and 0.1 mol% is ethyl branch.
  • 0.1 mol% is a propyl branch, 0.1 mol% is a butyl branch, 0.1 mol% is a pentyl branch, and 3.9 mol% is a branch having a carbon number ⁇ 6, and the glass transition temperature is -64.2 ° C, melting point It is 115.6 ° C, the crystallinity is 29.2%, the crystallization temperature is 100.3 ° C; (8) the content of the component eluted at 100 ° C is 11.8 wt%, and the weight average molecular weight of the component is 25.8 ⁇ 10 4 g/mol.
  • the molecular weight distribution index is 2.5, the degree of branching is 18 branches / 1000 carbons, 100 mol% of the branches are methyl branches, the glass transition temperature is -66.8 ° C, the melting point is 120.3 ° C, and the crystallinity is 28.7%.
  • the crystallization temperature is 105.8 ° C; (9) the content of the component eluted at 110 ° C is 10.5 wt%, the weight average molecular weight of the component is 21 ⁇ 10 4 g / mol, and the molecular weight distribution index is 2.
  • the degree of branching is 16 branches / 1000 carbons, 74 mol% of the branches are methyl branches, 26 mol% is the branch with carbon number ⁇ 6, the glass transition temperature is -64.5 ° C, the melting point is 123.6 ° C , crystallinity is 34%, crystallization temperature is 109.3 ° C; (10) component content eluted at 120 ° C is 3.1 wt%, the weight average molecular weight of the component is 22.8 ⁇ 10 4 g / mol, molecular weight distribution The index is 2.5, the degree of branching is 11 branches/1000 carbons, 100 mol% of the branches are methyl branches, the glass transition temperature is -68.9 ° C, the melting point is 122.0 ° C, the crystallinity is 37.09%, and the crystallization temperature It is 107.7 ° C; (11) the content of the component having a rinsing temperature higher than 120 ° C is 0.9 wt%, the weight average molecular weight of the component
  • One branch/1000 carbons, 100 mol% of the branches are methyl branches, the glass transition temperature is -63.3 ° C, the melting point is 122.2 ° C, the crystallinity is 35.46%, and the crystallization temperature is 108.3 ° C.
  • the cocatalyst was changed to diethylaluminum chloride, and other conditions were the same as in Example 1, to obtain 20.5 g of a polymer.
  • the catalyst activity was 4100 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 15.6 ⁇ 10 4 g/mol, the polydispersity coefficient was 2.9, the glass transition temperature was -67 ° C, the melting point was 121 ° C, and the crystallinity was obtained. At 12.6%.
  • the tensile properties of the polymerized product were tested according to GB/T 528-2009, the tensile strength was 19 MPa, and the elongation at break was 1250%.
  • the polymerization product was stretched to 2 times the original length at room temperature and after removing the external force for 1 minute, it was able to recover to 1.31 times the original length in 1 minute.
  • the degree of branching of the polymerized product was 79 branches/1000 carbon atoms as determined by 1 H-NMR, 51.7 mol% in the branch chain was methyl branch, 6.5 mol% was ethyl branch, and 4.5 mol% was C.
  • the degree of branching of the hard segment is 37 branches/1000 carbon atoms
  • the degree of branching of the soft segment is 133 branches/1000 carbon atoms.
  • mol% of the branches in the hard segment are methyl branches, 2 mol% are ethyl branches, 1 mol% is propyl branch, 1 mol% is butyl branch, 6 mol% is pentyl branch, and 6 mol% is carbon.
  • 53.3 mol% of the branches in the soft segment are methyl branches, 4 mol% are ethyl branches, 13.1 mol% are propyl branches, 5 mol% are butyl branches, and 11.7 mol% are pentyl branches, 12.9 Mol% is a branch with a carbon number of ⁇ 6.
  • the hard segment has a melting point of 118.8 ° C, a crystallinity of 12.2%, a glass transition temperature of -72 ° C, a soft segment glass transition temperature of -67 ° C, no significant melting point, and a crystallinity of 0%.
  • the polymerization product can be separated into 11 components by the method of temperature rising elution fractionation (TREF), wherein toluene is used as a solvent: (1) the content of the component eluted at 30 ° C is 26.8 wt% (weight percentage).
  • the weight average molecular weight of the component is 11.2 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.5, the degree of branching is 164 branches/1000 carbons, and 58.8 mol% of the branches are methyl branches, 3.5 mol.
  • % is ethyl branch, 11.3 mol% is propyl branch, 5.4 mol% is butyl branch, 11.8 mol% is pentyl branch, 9.2 mol% is branch with carbon number ⁇ 6, glass transition temperature
  • melting point one is 55.9 ° C
  • melting point two is 113.9 ° C
  • crystallinity is 1.52%
  • crystallization temperature is 76 ° C
  • the content of the component eluted at 40 ° C is 8.8 Wt%
  • the component has a weight average molecular weight of 12.7 ⁇ 10 4 g/mol, a molecular weight distribution index of 2.5, a degree of branching of 137 branches/1000 carbons, and 58.7 mol% of the branches are methyl branches.
  • 3 mol% is ethyl branch, 13.4 mol% is propyl branch, 1.6 mol% is butyl branch, 10.4 mol% is pentyl branch, 12.9 mol% is branch with carbon number ⁇ 6, glass transition temperature – 62.5 ° C, with two melting points, melting point 1 is 75.7 ° C, melting point 2 is 113.9 ° C, crystallinity is 2.7%, there are two crystallization temperatures, crystallization temperature is 54.9 ° C, crystallization temperature is 86.9 ° C; (3) The content of the component eluted at 50 ° C was 4.2 wt%, the weight average molecular weight of the component was 14.3 ⁇ 10 4 g / mol, the molecular weight distribution index was 3.0, and the degree of branching was 102 branches / 1000 carbons.
  • 64.9 mol% in the branch is methyl branch, 4 mol% is ethyl branch, 9.2 mol% is propyl branch, 0 mol% is butyl branch, 9.4 mol% is pentyl branch, 12.5 mol%
  • the glass transition temperature is –65.5°C, there are two melting points, the melting point is 84.9°C, the melting point is 115.8°C, the crystallinity is 5%, there are two crystallization temperatures, and the crystallization temperature is The temperature is 66 ° C at 66 ° C; (4) the content of the component eluted at 60 ° C is 4.2 wt%, the weight average molecular weight of the component is 16.8 ⁇ 10 4 g / mol, and the molecular weight distribution index is 3.5, the degree of branching is 53 branches/1000 carbons, 82 mol% of the branches are methyl branches, 0.1% are ethyl branches, 0.1 mol% are propyl
  • mol% is a pentyl branch
  • 6.6 mol% is a branch with a carbon number ⁇ 6, a glass transition temperature of -71 ° C, a melting point of 95 ° C, a crystallinity of 13.6%, and a crystallization temperature of 80 ° C; 5)
  • the content of the component eluted at 70 ° C is 6.8 wt%
  • the weight average molecular weight of the component is 18.5 ⁇ 10 4 g / mol
  • the molecular weight distribution index is 3.8
  • the degree of branching is 34 branches / 1000
  • One carbon, 84.9 mol% of the branch is a methyl branch
  • 0.1 mol% is an ethyl branch
  • 0.1 mol% is a propyl branch
  • 0.1 mol% is a butyl branch
  • 13.2 mol% is a pentyl branch.
  • 1.6 mol% is a branch with carbon number ⁇ 6, glass transition temperature is -71.2 ° C, melting point is 102 ° C, crystallinity is 19.8%, crystallization temperature is 87 ° C; (6) leaching at 80 ° C
  • the component content is 6.4% by weight, the weight average molecular weight of the component is 24.9 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.8, the degree of branching is 25 branches/1000 carbons, and 78 mol% of the branch is A.
  • Base branch 14.1 mol% is ethyl branch, 0.1 mol% is propyl branch, 0.1 mol% is butyl branch, 0.1 mol% is pentyl branch, and 7.6 mol% is branch with carbon number ⁇ 6 Chain, glass transition temperature is –71 ° C, The melting point is 110 ° C, the crystallinity is 27.8%, the crystallization temperature is 95.9 ° C; (7) the content of the component eluted at 90 ° C is 16.2 wt%, and the weight average molecular weight of the component is 26.2 ⁇ 10 4 g / Mol, the molecular weight distribution index is 2.5, the degree of branching is 21 branches/1000 carbons, 96 mol% of the branches are methyl branches, 0.1 mol% is ethyl branch, and 0.1 mol% is propyl branch.
  • 0.1 mol% is a butyl branch
  • 0.1 mol% is a pentyl branch
  • 3.6 mol% is a branch having a carbon number ⁇ 6, a glass transition temperature of -64 ° C, a melting point of 116 ° C, and a crystallinity of 29.7%.
  • the crystallization temperature is 100.8 ° C; (8) the content of the component eluted at 100 ° C is 12.1 wt%, the weight average molecular weight of the component is 27.3 ⁇ 10 4 g / mol, the molecular weight distribution index is 2.5, the degree of branching It is 14 branches/1000 carbons, 100 mol% of the branches is methyl branch, the glass transition temperature is -66.8 ° C, the melting point is 120.3 ° C, the crystallinity is 28.7%, and the crystallization temperature is 105.8 ° C; (9) The content of the component eluted at 110 ° C was 10.8 wt%, the weight average molecular weight of the component was 23 ⁇ 10 4 g / mol, the molecular weight distribution index was 2.6, and the degree of branching was 13 branches / 1000 carbons.
  • 76 mol% of the branches are methyl branches, 24 mol% are branches with carbon number ⁇ 6, glass transition temperature is -64 ° C, melting point is 124 ° C, crystallinity is 35%, crystallization temperature is 109.8 ° C; ) leaching out at 120 °C ingredients content of 2.9wt%, the component of weight average molecular weight 23.7 ⁇ 10 4 g / mol, a molecular weight distribution index of 2.5, the degree of branching of 10 branches / 1000 Carbon, 100 mol% of the branches are methyl branches, glass transition temperature is -68.9 ° C, melting point is 122.0 ° C, crystallinity is 37.09%, crystallization temperature is 107.7 ° C; (11) rinsing temperature is higher than 120 ° C The component content is 0.8% by weight, the weight average molecular weight of the component is 19 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.6, the degree of branching is 4 branches/1000 carbon
  • the polymerization temperature was lowered to 25 ° C, the ethylene pressure was increased to 2.0 MPa, and the catalyst was changed to catalyst 1 (R was a methyl group, previously dissolved in 10 ml of toluene), and other conditions were the same as in Example 1 to obtain 18.0 g of a polymer.
  • the catalyst activity is 3600kgPE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product is 18.5 ⁇ 10 4 g/mol, the polydispersity coefficient is 4.0, the glass transition temperature is –61 ° C, the melting point is 123.3 ° C, crystallinity It is 42.9%.
  • the tensile properties of the polymerized product were tested according to GB/T 528-2009, the tensile strength was 33.7 MPa, and the elongation at break was 500%.
  • the polymerization product was stretched to 2 times the original length at room temperature and after 1 minute, the external force was removed, and it was restored to 1.49 times the original length in 1 minute.
  • the degree of branching of the polymerization product was 31.6 branches/1000 carbon atoms as determined by 1 H-NMR, 58.7 mol% of the branch was methyl branch, 4.9 mol% was ethyl branch, and 3.3 mol% was C.
  • the base branch 1.7 mol% is a butyl branch, 16.5 mol% is a pentyl branch, and 14.9 mol% is a branch having a carbon number of ⁇ 6.
  • the degree of branching of the hard segment is 1 branch/1000 carbon atoms
  • the degree of branching of the soft segment is 50 branches/1000 carbon atoms. 100 mol% of the branches in the hard segment are methyl branches.
  • the hard segment has a melting point of 133.5 ° C, a crystallinity of 47%, a glass transition temperature of -72 ° C, a soft segment glass transition temperature of -56 ° C, no significant melting point, and a crystallinity of 4.5%.
  • the polymerization product can be separated into 11 components by the method of temperature rising elution fractionation (TREF), using toluene as a solvent: (1) the content of the component eluted at 30 ° C is 3.3 wt% (weight percentage) The weight average molecular weight of the component is 3.0 ⁇ 10 4 g/mol, the molecular weight distribution index is 3.8, the degree of branching is 110 branches/1000 carbons, 62 mol% of the branches are methyl branches, and 3 mol% is Ethyl branch, 10 mol% is a propyl branch, 4.7 mol% is a butyl branch, 10 mol% is a pentyl branch, 7 mol% is a branch with a carbon number ⁇ 6, and the glass transition temperature is -61 ° C.
  • TEZ temperature rising elution fractionation
  • melting point one is 60 ° C
  • melting point two is 115 ° C
  • crystallinity is 2.5%
  • crystallization temperature is 80 ° C
  • component content eluted at 40 ° C is 7.7 wt%
  • the group The weight average molecular weight of the part is 10 ⁇ 10 4 g/mol
  • the molecular weight distribution index is 3.8
  • the degree of branching is 120 branches/1000 carbons
  • 60 mol% of the branches are methyl branches
  • 2.5 mol% is ethyl group.
  • Branched, 11 mol% is a propyl branch, 1 mol% is a butyl branch, 9 mol% is a pentyl branch, 16.5 mol% is a branch with a carbon number ⁇ 6, and the glass transition temperature is -61 ° C, there are two Melting point , melting point one is 80 ° C, melting point two is 115 ° C, crystallinity is 3.5%, there are two crystallization temperatures, crystallization temperature is 60 ° C, crystallization temperature is 95 ° C; (3) leaching at 50 ° C
  • the component content is 6.5 wt%, the weight average molecular weight of the component is 13.0 ⁇ 10 4 g/mol, the molecular weight distribution index is 3.6, the degree of branching is 90 branches/1000 carbons, and 66 mol% of the branches is A.
  • Base branch 5.5 mol% is ethyl branch, 11 mol% is propyl branch, 3 mol% is butyl branch, 7 mol% is pentyl branch, 7.5 mol% is branch with carbon number ⁇ 6, glass
  • the transformation temperature is -64 ° C, there are two melting points, the melting point is 90 ° C, the melting point is 120 ° C, the crystallinity is 6%, there are two crystallization temperatures, the crystallization temperature is 70 ° C, the crystallization temperature is 95 ° C (4)
  • the content of the component eluted at 60 ° C is 6.5 wt%, the weight average molecular weight of the component is 14 ⁇ 10 4 g / mol, the molecular weight distribution index is 3.8, and the branching degree is 50 branches.
  • 0 mol% is propyl branch, 0 mol% is butyl branch, 3 mol% is pentyl branch, 2 mol% is a branch with carbon number ⁇ 6, glass transition temperature is -68 ° C, melting point is 110 ° C, crystallization The degree is 25%, the crystallization temperature is 95 ° C; (6) the content of the component eluted at 80 ° C is 9 wt%, the weight average molecular weight of the component is 20 ⁇ 10 4 g / mol, and the molecular weight distribution index is 3.2.
  • the degree of branching is 20 branches/1000 carbons, 85 mol% of the branches are methyl branches, 10 mol% is ethyl branch, 0 mol% is propyl branch, 0 mol% is butyl branch, 0 mol % is a pentyl branch, 5 mol% is a branch with a carbon number ⁇ 6, a glass transition temperature of -69 ° C, a melting point of 115 ° C, a crystallinity of 30%, a crystallization temperature of 100 ° C; (7) at 90 ° C Sublimed components In an amount of 20wt%, the weight average molecular weight component of 23 ⁇ 10 4 g / mol, a molecular weight distribution index of 3.2, the degree of branching of 10 branches / 1000 carbons, branched chain 98mol% of methyl branches 0 mol% is ethyl branch, 0 mol% is propyl branch, 0 mol% is butyl branch, 0 mol
  • Ethylene polymerization is carried out under anhydrous anaerobic conditions.
  • a 10 liter stainless steel autoclave with mechanical stirring 4.95 liters of n-heptane was added, and the temperature of the polymerization vessel was controlled to 25 ° C by means of jacketed circulating water, and stirring was started.
  • Ethylene was introduced to the reactor pressure of 2.0 MPa. After the polymerization for 60 minutes, the reaction vessel was vented to normal pressure, the lid was opened, the polymer solution was poured out, and the solvent was distilled off to obtain 430 g of a polymer.
  • the catalyst activity was 17200 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 29.1 ⁇ 10 4 g/mol, the polydispersity coefficient was 3.0, the glass transition temperature was -61 ° C, the melting point was 122.3 ° C, crystallinity. It is 22.5%.
  • the tensile properties of the polymerized product were tested according to GB/T 528-2009, the tensile strength was 51.8 MPa, and the elongation at break was 820%.
  • the polymerization product was stretched to 2 times the original length at room temperature and after 1 minute, the external force was removed, and it was restored to 1.30 times the original length in 1 minute.
  • the degree of branching of the polymerization product was 86 branches/1000 carbon atoms as determined by 1 H-NMR, 55.6 mol% in the branch was methyl branch, 7.5 mol% was ethyl branch, and 4.3 mol% was C.
  • the degree of branching of the hard segment is 38 branches/1000 carbon atoms, and the degree of branching of the soft segment is 125 branches/1000 carbon atoms.
  • mol% of the branches in the hard segment are methyl branches, 3 mol% are ethyl branches, 1 mol% is propyl branch, 1 mol% is butyl branch, 8 mol% is pentyl branch, and 2 mol% is carbon.
  • the mol% is a pentyl branch, and 11.3 mol% is a branch having a carbon number of ⁇ 6.
  • the hard segment has a melting point of 125.9 ° C, a crystallinity of 27%, a glass transition temperature of -71 ° C, a soft segment glass transition temperature of -66 ° C, no significant melting point, and a crystallinity of 1.5%.
  • the polymerization product can be separated into 11 components by the method of temperature rising elution fractionation (TREF) using toluene as a solvent: (1) the content of the component eluted at 30 ° C is 22.8 wt% (weight percentage) The weight average molecular weight of the component is 21.4 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.8, the degree of branching is 158 branches/1000 carbons, 60 mol% in the branch chain is methyl branch, and 4 mol% is Ethyl branch, 12 mol% is propyl branch, 5.7 mol% is butyl branch, 12 mol% is pentyl branch, 6.3 mol% is branch with carbon number ⁇ 6, glass transition temperature is -61 °C , having two melting points, melting point one is 57 ° C, melting point two is 114 ° C, crystallinity is 1.5%, crystallization temperature is 76 ° C; (2) the content of the component eluted at 40 ° C is 5.8
  • Base branch 14 mol% is propyl branch, 2 mol% is butyl branch, 9 mol% is pentyl branch, 12.5 mol% is branch with carbon number ⁇ 6, glass transition temperature is -62 ° C, Two Point, melting point one is 76 ° C, melting point two is 114 ° C, crystallinity is 2.8%, there are two crystallization temperatures, crystallization temperature is 55 ° C, crystallization temperature is 87 ° C; (3) leaching at 50 ° C
  • the component content is 4.0% by weight, the weight average molecular weight of the component is 30 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.6, the degree of branching is 103 branches/1000 carbons, and 65.8 mol% in the branch.
  • the chain has a glass transition temperature of -64 ° C, two melting points, a melting point of 85 ° C, a melting point of 116 ° C, a crystallinity of 4.6%, two crystallization temperatures, a crystallization temperature of 67 ° C, and a crystallization temperature of two.
  • Branches/1000 carbons 83 mol% of the branches are methyl branches, 0% are ethyl branches, 0 mol% are propyl branches, 0 mol% are butyl branches, and 11.6 mol% are pentyl groups Chain, 5.4mol% is Branches with ⁇ 6, glass transition temperature of -70 ° C, melting point of 95 ° C, crystallinity of 15%, crystallization temperature of 81 ° C; (5) leaching component content of 5.8 wt at 70 ° C %, the component has a weight average molecular weight of 40 ⁇ 10 4 g/mol, a molecular weight distribution index of 3.8, a degree of branching of 35 branches/1000 carbons, and 85 mol% of the branches are methyl branches, 0 mol%.
  • the temperature is 121.5%, the crystallinity is 29.5%, the crystallization temperature is 107 ° C; (9) the content of the component eluted at 110 ° C is 13 wt%, and the weight average molecular weight of the component is 60 ⁇ 10 4 g / mol, The molecular weight distribution index is 2.2, the degree of branching is 14 branches/1000 carbons, 76 mol% of the branches are methyl branches, 24 mol% is the branch with carbon number ⁇ 6, and the glass transition temperature is -63 ° C.
  • Point of 124 deg.] C a crystallinity of 36%, a crystallization temperature of 110 °C; (10) rinsed out at 120 °C ingredients content of 4.7 wt .-% parts of a weight average molecular weight of the set of 60 ⁇ 10 4 g / Mol, molecular weight distribution index of 2.5, degree of branching is 10 branches / 1000 carbons, 100 mol% of branches is methyl branch, glass transition temperature is -68 ° C, melting point is 123 ° C, crystallinity is 38 %, the crystallization temperature is 108 ° C; (11) the rinsing temperature is higher than 120 ° C, the content of the component is 5 wt%, the weight average molecular weight of the component is 40 ⁇ 10 4 g / mol, the molecular weight distribution index is 2.6, branching The degree is 4 branches/1000 carbons, 100 mol% of the branches are methyl branches, the glass transition temperature is -63 ° C, the melting point
  • Ethylene polymerization is carried out under anhydrous anaerobic conditions. 990 ml of n-heptane was placed in a 2-liter stainless steel autoclave with mechanical stirring, and the temperature of the polymerization vessel was controlled to 40 ° C by means of jacketed circulating water, and stirring was started.
  • Ethylene was introduced to the reactor pressure of 1.5 MPa. After the polymerization for 45 minutes, the reaction vessel was vented to normal pressure, the lid was opened, the polymer solution was poured out, and the solvent was evaporated to give 53 g of a polymer.
  • the catalyst activity was 7067 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 15.9 ⁇ 10 4 g/mol, the polydispersity coefficient was 2.6, the glass transition temperature was -67 ° C, the melting point was 116.5 ° C, and the crystallinity was obtained. It is 5.7%.
  • the tensile properties of the polymerized product were tested in accordance with GB/T 528-2009, the tensile strength was 10 MPa, and the elongation at break was 500%.
  • the polymerization product was stretched to 2 times the original length at room temperature and after removing the external force for 1 minute, it was restored to 1.35 times the original length in 1 minute.
  • the degree of branching of the polymerization product was 118.3 branches/1000 carbon atoms as determined by 1 H-NMR, 49.9 mol% in the branch chain was methyl branch, 4.9 mol% was ethyl branch, and 4.1 mol% was C.
  • the degree of branching of the hard segment is 60 branches/1000 carbon atoms, and the degree of branching of the soft segment is 250 branches/1000 carbon atoms.
  • 52 mol% of the branches in the hard segment are methyl branches, 14.6 mol% are ethyl branches, 4.8 mol% are propyl branches, 3.6 mol% are butyl branches, and 13.6 mol% are pentyl branches.
  • 11.4 mol% is a branch with a carbon number ⁇ 6; 44.5 mol% of the branch of the soft segment is a methyl branch, 11.7 mol% is an ethyl branch, 6.2 mol% is a propyl branch, and 6.6 mol% is a butyl group.
  • the base branch, 16 mol% is a pentyl branch, and 15 mol% is a branch having a carbon number ⁇ 6.
  • the hard segment has a melting point of 80 ° C, a crystallinity of 10.1%, a glass transition temperature of -72 ° C, a soft segment glass transition temperature of -70 ° C, no significant melting point, and a crystallinity of 0%.
  • the polymerization product can be separated into 10 components by a temperature rising elution fractionation (TREF) method using toluene as a solvent: (1) the content of the component eluted at 30 ° C is 28 wt% (weight percentage), The weight average molecular weight of the component is 11.4 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.4, the degree of branching is 220 branches/1000 carbons, 48 mol% of the branches are methyl branches, and 3 mol% is B.
  • TEZ temperature rising elution fractionation
  • the base branch chain 10 mol% is a propyl branch, 6.1 mol% is a butyl branch, 14 mol% is a pentyl branch, and 18.9 mol% is a branch having a carbon number ⁇ 6, and the glass transition temperature is -64 ° C.
  • melting point one is 50 ° C
  • melting point two is 110 ° C
  • crystallinity is 0.3%
  • crystallization temperature is 70 ° C
  • component content eluted at 40 ° C is 9 wt%
  • the component The weight average molecular weight is 12 ⁇ 10 4 g/mol
  • the molecular weight distribution index is 2.6
  • the degree of branching is 180 branches/1000 carbons
  • 45 mol% of the branches are methyl branches
  • 3.5 mol% is ethyl branch.
  • the branch of 6 has a glass transition temperature of -72 ° C, a melting point of 90 ° C, a crystallinity of 10%, a crystallization temperature of 75 ° C, and (5) a component content of 6 wt% eluted at 70 ° C.
  • the weight average molecular weight of the component is 20 ⁇ 10 4 g/mol, the molecular weight distribution index is 3.8, the degree of branching is 70 branches/1000 carbons, 80 mol% of the branch is methyl branch, and 2 mol% is ethyl.
  • Base branch 1 mol% is propyl branch, 1 mol% is butyl branch, 1 mol% is pentyl branch, 1 mol% is branch with carbon number ⁇ 6, glass transition temperature is -71 ° C, melting point is 120 ° C, crystallinity of 36%, crystallization temperature of 105 ° C; (11) rinsing temperature of more than 120 ° C component content of 0 wt%.
  • Ethylene polymerization is carried out under anhydrous anaerobic conditions. 100 ml of n-hexane was placed in a 200 ml stainless steel autoclave with mechanical stirring, and the temperature of the polymerization vessel was controlled to 25 ° C by means of jacketed circulating water, and stirring was started.
  • Ethylene was fed to the reactor pressure of 1.2 MPa. After the polymerization for 30 minutes, the reaction vessel was vented to normal pressure, the lid was opened, the polymer solution was poured out, and the solvent was evaporated to give 22 g of a polymer.
  • the catalyst activity was 4400 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 12.9 ⁇ 10 4 g/mol, the polydispersity coefficient was 3.0, the glass transition temperature was -67 ° C, the melting point was 120.4 ° C, and the crystallinity was obtained. It is 10.5%.
  • the tensile properties of the polymerized product were tested according to GB/T 528-2009, the tensile strength was 18.0 MPa, and the elongation at break was 1230%.
  • the polymerization product was stretched to 2 times the original length at room temperature and after removing the external force for 1 minute, it was able to recover to 1.33 times the original length in 1 minute.
  • the degree of branching of the polymerization product was 80 branches/1000 carbon atoms as determined by 1 H-NMR, 52.0 mol% in the branch chain was methyl branch, 6.5 mol% was ethyl branch, and 4.5 mol% was C.
  • the base branch 3.9 mol% is a butyl branch, 17.6 mol% is a pentyl branch, and 15.5 mol% is a branch having a carbon number ⁇ 6.
  • the degree of branching of the hard segment is 42 branches/1000 carbon atoms
  • the degree of branching of the soft segment is 139 branches/1000 carbon atoms.
  • 82 mol% of the branch in the hard segment is a methyl branch
  • 3 mol% is an ethyl branch
  • 1 mol% is a propyl branch
  • 1 mol% is a butyl branch
  • 7 mol% is a pentyl branch
  • 6 mol% is a carbon.
  • Branches with a number ⁇ 6. 51.8 mol% of the branches in the soft segment are methyl branches
  • 4.2 mol% are ethyl branches
  • 13.6 mol% are propyl branches
  • 5.4 mol% are butyl branches
  • 11.9 mol% are pentyl branches.
  • 13.1 mol% is a branch having a carbon number of ⁇ 6.
  • the hard segment has a melting point of 118.0 ° C, a crystallinity of 10.3%, a glass transition temperature of -72 ° C, a soft segment glass transition temperature of -67 ° C, no significant melting point, and a crystallinity of 0%.
  • the polymerization product can be separated into 11 components by the method of temperature rising elution fractionation (TREF) using toluene as a solvent: (1) the content of the component eluted at 30 ° C is 27.1 wt% (weight percentage). The weight average molecular weight of the component is 9.6 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.4, the degree of branching is 177 branches/1000 carbons, and 58.9 mol% of the branch is methyl branch, 3.5 mol.
  • TEZ temperature rising elution fractionation
  • % is ethyl branch, 11.2 mol% is propyl branch, 5.3 mol% is butyl branch, 11.9 mol% is pentyl branch, 9.2 mol% is branch with carbon number ⁇ 6, glass transition temperature
  • melting point one is 55.7 ° C
  • melting point two is 113.6 ° C
  • crystallinity is 1.41%
  • crystallization temperature is 75.8 ° C
  • the content of the component eluted at 40 ° C is 8.5 Wwt%, the component has a weight average molecular weight of 10.7 ⁇ 10 4 g/mol, a molecular weight distribution index of 2.4, a branching degree of 149 branches/1000 carbons, and a branching chain of 58.3 mol% being a methyl branch.
  • 3.0 mol% is an ethyl branch
  • 13.6 mol% is a propyl branch
  • 1.6 mol% is a butyl branch
  • 10.4 mol% is a pentyl branch
  • 13.1 mol% is a branch having a carbon number ⁇ 6, vitrification Change temperature
  • melting point one is 75.2 ° C
  • melting point two is 113.8 ° C
  • crystallinity is 2.62%
  • crystallization temperatures crystallization temperature is 54.5 ° C
  • crystallization temperature is 86.3 ° C
  • (3 The content of the component eluted at 50 ° C is 4.4 wt%
  • the weight average molecular weight of the component is 13.5 ⁇ 10 4 g / mol
  • the molecular weight distribution index is 3.0
  • the degree of branching is 108 branches / 1000 Carbon
  • 64.2 mol% in the branch is a methyl branch
  • 4.2 mol% is an ethyl branch
  • the content of the component eluted at 70 ° C is 6.2 wt%, the weight average molecular weight of the component is 17.6 ⁇ 10 4 g / mol, the molecular weight distribution index is 3.8, and the branching degree is 38 branches.
  • mol% of the branches are methyl branches, 0 mol% is ethyl branch, 0 mol% is propyl branch, 0 mol% is butyl branch, and 13.6 mol% is pentyl branch, 1.7 mol% is a branch with carbon number ⁇ 6, glass transition temperature is -71 ° C, melting point is 101.9 ° C, crystallinity is 19.26%, crystallization temperature is 86.7 ° C; (6) group ejected at 80 ° C The content of the component is 7.0 wt%, the weight average molecular weight of the component is 23.3 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.7, the degree of branching is 27 branches/1000 carbons, and 76.3 mol% of the branch is A.
  • One carbon, 74.1 mol% of the branch is methyl branch, 25.9 mol% is a branch with carbon number ⁇ 6, the glass transition temperature is -64.8 ° C, the melting point is 123.3 ° C, the crystallinity is 34.01%, and the crystallization temperature is 109.1 ° C; (10) The content of the component eluted at 120 ° C is 3.4 wt%, the weight average molecular weight of the component is 22.4 ⁇ 10 4 g / mol, the molecular weight distribution index is 2.5, and the degree of branching is 11 Branched / 1000 carbons, 100 mol% of the branches are methyl branches, glass transition temperature is -68.9 ° C, melting point is 122.0 ° C, crystallinity is 37.09%, crystallization temperature is 107.7 ° C; (11) rinsing temperature The component content higher than 120 ° C is 0.9 wt%, the weight average molecular weight of the component is 16.6 ⁇ 10 4 g
  • Ethylene polymerization is carried out under anhydrous anaerobic conditions.
  • 1490 ml of n-heptane was added, and the temperature of the polymerization vessel was controlled to 25 ° C by means of jacketed circulating water, and stirring was started.
  • Ethylene was fed to the reactor pressure of 1.2 MPa. After the polymerization for 30 minutes, the reaction vessel was vented to normal pressure, the lid was opened, the polymer solution was poured out, and the solvent was evaporated to give 65.6 g of a polymer.
  • the catalyst activity was 4370 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 26.9 ⁇ 10 4 g/mol, the polydispersity coefficient was 3.6, the glass transition temperature was -67 ° C, the melting point was 121.5 ° C, and the crystallinity was obtained. It is 30.6%.
  • the tensile properties of the polymerized product were tested in accordance with GB/T 528-2009, the tensile strength was 49.5 MPa, and the elongation at break was 870%.
  • the polymerization product was stretched to 2 times the original length at room temperature and after removing the external force for 1 minute, it was able to recover to 1.33 times the original length in 1 minute.
  • the degree of branching of the polymerization product was 80.2 branches/1000 carbon atoms as determined by 1 H-NMR, 52.0 mol% in the branch chain was methyl branch, 6.5 mol% was ethyl branch, and 4.5 mol% was C.
  • the base branch 3.9 mol% is a butyl branch, 17.6 mol% is a pentyl branch, and 15.5 mol% is a branch having a carbon number ⁇ 6.
  • the degree of branching of the hard segment is 42 branches/1000 carbon atoms
  • the degree of branching of the soft segment is 139 branches/1000 carbon atoms.
  • 82 mol% of the branch in the hard segment is a methyl branch
  • 3 mol% is an ethyl branch
  • 1 mol% is a propyl branch
  • 1 mol% is a butyl branch
  • 7 mol% is a pentyl branch
  • 6 mol% is a carbon.
  • Branches with a number ⁇ 6. 51.8 mol% of the branches in the soft segment are methyl branches
  • 4.2 mol% are ethyl branches
  • 13.6 mol% are propyl branches
  • 5.4 mol% are butyl branches
  • 11.9 mol% are pentyl branches.
  • 13.1 mol% is a branch having a carbon number of ⁇ 6.
  • the hard segment has a melting point of 118.0 ° C, a crystallinity of 10.3%, a glass transition temperature of -72 ° C, a soft segment glass transition temperature of -67 ° C, no significant melting point, and a crystallinity of 0%.
  • the polymerization product can be separated into 11 components by the method of temperature rising elution fractionation (TREF) using toluene as a solvent: (1) the content of the component eluted at 30 ° C is 27.1 wt% (weight percentage). The weight average molecular weight of the component is 9.6 ⁇ 10 4 g/mol, the molecular weight distribution index is 2.4, the degree of branching is 177.4 branches/1000 carbons, and 58.9 mol% of the branches are methyl branches, 3.5 mol.
  • TEZ temperature rising elution fractionation
  • % is ethyl branch, 11.2 mol% is propyl branch, 5.3 mol% is butyl branch, 11.9 mol% is pentyl branch, 9.2 mol% is branch with carbon number ⁇ 6, glass transition temperature
  • melting point one is 55.7 ° C
  • melting point two is 113.6 ° C
  • crystallinity is 1.41%
  • crystallization temperature is 75.8 ° C
  • the content of the component eluted at 40 ° C is 8.5 Wwt%, the component has a weight average molecular weight of 10.7 ⁇ 10 4 g/mol, a molecular weight distribution index of 2.4, a degree of branching of 148.8 branches/1000 carbons, and a branching chain of 58.3 mol% of methyl groups.
  • 3.0 mol% is an ethyl branch
  • 13.6 mol% is a propyl branch
  • 1.6 mol% is a butyl branch
  • 10.4 mol% is a pentyl branch
  • 13.1 mol% is a branch having a carbon number ⁇ 6, vitrification change
  • the temperature is -62.6 ° C, there are two melting points, the melting point one is 75.2 ° C, the melting point two is 113.8 ° C, the crystallinity is 2.62%, there are two crystallization temperatures, the crystallization temperature is 54.5 ° C, and the crystallization temperature is 86.3 ° C; 3)
  • the content of the component eluted at 50 ° C is 4.4 wt%
  • the weight average molecular weight of the component is 13.5 ⁇ 10 4 g / mol
  • the molecular weight distribution index is 3.0
  • the degree of branching is 108.4 branches / 1000 Carbon
  • 64.2 mol% of the branch is a
  • 12.6mol% is a branch with carbon number ⁇ 6, the glass transition temperature is –65.3°C, has two melting points, the melting point is 84.7°C, the melting point is 115.1°C, the crystallinity is 4.45%, and there are two crystallization temperatures.
  • the crystallization temperature is 65.7 ° C, the crystallization temperature is 87.1 ° C; (4) the component content eluted at 60 ° C is 4.0 wt%, the weight average molecular weight of the component is 15.3 ⁇ 10 4 g / mol, the molecular weight
  • the distribution index is 3.6, the degree of branching is 56.9 branches/1000 carbons, 82 mol% of the branches are methyl branches, 0% is ethyl branch, 0 mol% is propyl branch, 0 mol % is a butyl branch, 11.5 mol% is a pentyl branch, and 6.6 mol% is a branch with a carbon number ⁇ 6, a glass transition temperature of -70.8 ° C, a melting point of 94.2 ° C, a crystallinity of 13.43%, and a crystallization temperature.
  • Branches / 1000 carbons 84.7 mol% of the branches are methyl branches, 0 mol% of ethyl branches, 0 mol% of propyl branches, 0 mol% of butyl branches, 13.6 mol% of pentyl Branch, 1.7 mol% is a branch with carbon number ⁇ 6, glass transition temperature is -71 ° C, melting point is 101.9 ° C, crystallinity is 19.26%, crystallization temperature is 86.7 ° C; (6) rinsing at 80 ° C The content of the component was 7.0 wt%, the weight average molecular weight of the component was 23.3 ⁇ 10 4 g/mol, the molecular weight distribution index was 2.7, the degree of branching was 27.2 branches/1000 carbons, and 76.3 mol in the branch.
  • % is a methyl branch, 14.6 mol% is an ethyl branch, 0 mol% is a propyl branch, 0 mol% is a butyl branch, 0 mol% is a pentyl branch, and 9.1 mol% is a branch having a carbon number ⁇ 6 Chain, glass transition
  • the degree is -72 ° C, the melting point is 109.5 ° C, the crystallinity is 27.17%, the crystallization temperature is 95.3 ° C; (7) the content of the component eluted at 90 ° C is 16.1 wt%, and the weight average molecular weight of the component is 24.7 ⁇ 10 4 g/mol, molecular weight distribution index is 2.6
  • branching degree is 20.0 branches/1000 carbons, 96.2 mol% in branch is methyl branch, 0 mol% is ethyl branch, 0 mol% is a propyl branch, 0 mol% is a butyl branch, 0 mol%
  • the degree of branching is 16.8 branches/1000 carbons, 100 mol% of the branches are methyl branches, the glass transition temperature is -66.8 ° C, the melting point is 120.3 ° C, the crystallinity is 28.7%, and the crystallization temperature is 105.8 ° C; (9)
  • the content of the component eluted at 110 ° C is 10.2 wt%, the weight average molecular weight of the component is 20.8 ⁇ 10 4 g / mol, the molecular weight distribution index is 2.5, and the degree of branching is 15.8 branches/1000 carbons, 74.1 mol% of the branches are methyl branches, 25.9 mol% are branches with carbon number ⁇ 6, the glass transition temperature is -64.8 ° C, the melting point is 123.3 ° C, and the crystallinity is 34.01%, the crystallization temperature was 109.1 ° C; (10) the content of the component eluted at 120 ° C was 3.4 wt%, the weight average molecular
  • the degree of branching is 10.7 branches/1000 carbons, 100 mol% of the branches are methyl branches, the glass transition temperature is -68.9 ° C, the melting point is 122.0 ° C, the crystallinity is 37.09%, and the crystallization temperature is 107.7 ° C; (11)
  • the component having a rinsing temperature higher than 120 ° C is 0.9 wt%, the weight average molecular weight of the component is 16.6 ⁇ 10 4 g / mol, the molecular weight distribution index is 2.6, and the branching degree is 5 branches / 1000 carbons, 100 mol% of the branches are methyl branches, the glass transition temperature is -63.3 ° C, the melting point is 122.2 ° C, the crystallinity is 35.46%, and the crystallization temperature is 108.3 ° C.
  • the tensile strength of the multi-block branched polyethylene prepared by the present invention exceeds 10 MPa
  • the elongation at break exceeds 500%
  • the stress-strain curve of the sample does not exhibit yielding, indicating that the multi-inlay prepared by the present invention is prepared.
  • Segmented polyethylene is not a plastic, but an elastomer, which has a good application value.
  • the multi-block branched polyethylene obtained in the preparation of Example 1 of the present invention was melted in an extruder, passed through an annular shape, expanded with air, cooled, and cut into a biaxially oriented film having a thickness of 50 ⁇ m.
  • the single-layer film made of the multi-block branched polyethylene of the invention has high tear resistance and blocking resistance, and its performance meets the requirements of GB/T 4456-2008 "Polyethylene blown film for packaging". It can be used for packaging of daily necessities, food, medicines, etc.
  • the three-layer film structure is an adhesive layer/core layer/separation layer, wherein the adhesive layer (thickness: 4.5 ⁇ m) is a multi-block branched polyethylene prepared in the third embodiment of the present invention, and the core layer (thickness: 21 ⁇ m) is Linear low density polyethylene with a density of 0.918 g/cm 3 and a melt index of 0.85 g/10 min (190 ° C / 2.16 kg).
  • the separator (thickness 4.5 ⁇ m) has a density of 0.923 g/cm 3 and a melt index of 0.75. ⁇ /10 minutes (190 ° C / 2.16 kg) of low density polyethylene.
  • the three-layer film has an adhesive force of 80 g, an elongation at break of 440%, and a puncture resistance of 0.4 kg in the form of 250%, which can be used for foods such as poultry, vegetables, fresh red meat, cheese, and non-food. Packaging of industrial and retail items.
  • the sheets from the rolling mill were preheated in an oven to 90 ° C for 15 minutes, then added to a mold preheated to 180 ° C, pressed and cured at this temperature for 10 minutes.
  • the sample When taken out, the sample is expanded to form a foamed article with lower shrinkage, lower compression set and higher split tear and elongation, and its performance is in accordance with HG/T 3082-2010 "Rubber Sole” Requires that it can be used in the fields of soles, floors, building materials, etc.
  • Example 12 of the present invention was obtained at a spinning head temperature of 260 ° C, a solution temperature of 302 ° C and a winding speed of 70 m / min.
  • the multi-block branched polyethylene is spun into a multifilament bundle composed of 24 fibers having a circular cross section, and the tow has a tensile strength of 7 g/d, a modulus of 270 g/d, and an elongation at break of 820%.
  • Fiber materials made from multi-block branched polyethylene can be used in the textile industry (including non-woven fabrics), environmental protection, medicine and construction.
  • the multi-block branched polyethylene obtained by the preparation of Example 7 of the present invention was injection-molded using a melting temperature of 200 ° C to prepare a sheet of 60 ⁇ 60 ⁇ 1 cm 3 , and the tensile strength of the product was 33.7 MPa, and the fracture was broken.
  • the elongation is 1130%, and it can be used for automotive interior parts such as automobile pillars, household appliances such as washing machine covers, toilet covers such as toilets, syringes, bottles for powders and tablets.
  • the multi-block branched polyethylene obtained in the preparation of Example 12 of the present invention was ground to a particle size of 150 to 500 ⁇ m, and the rotational molding method was carried out in a test apparatus FSP M20 "Clamshell" to grind the multi-block branching.
  • the polyethylene is placed in a cast aluminum mold that is biaxially rotated in a gas fired oven. Hot air is circulated through the blower through the chamber while the temperature is increased to 288 ° C in 4 minutes. The temperature was maintained for 15 minutes, then the oven was opened while still rotating, and the mold was cooled by forced air circulation for 7 minutes, followed by spraying water mist for 7 minutes and then air cooling for 2 minutes.
  • the rotary molded product has a shrinkage of 2.24%, a maximum warp of 1.41 mm, and an impact strength of 10.3 J/mm at -40 ° C, and can be used for cans, containers, toys, boats, furniture, medical equipment, underground storage. Cans, fuel tanks, mobile toilets, combination bathrooms, telephone booths, hulls, trash cans, lampshades, ice buckets, device enclosures, etc.
  • the invention can be widely applied to industrial, military, medical and health care. , food, daily life and other fields.
  • the polymers of the present invention are useful in a variety of conventional thermoplastic manufacturing processes to produce useful articles, including at least one film layer (e.g., a single layer film or more) formed by casting, calendering, blow molding, or extrusion coating.
  • Thermoplastic compositions comprising the polymers of the present invention include and other natural or synthetic polymers, reinforcing agents, additives, flame retardant additives, stabilizers, antioxidants, colorants, crosslinking agents, extenders, blowing agents, and A blend of plasticizers.
  • Particularly useful are multicomponent fibers comprising an outer surface layer, such as core/sheath fibers, at least in part comprising one or more polymers of the invention.
  • Fibers that can be made from the polymers or blends of the present invention include staple fibers, multicomponent fibers, tows, sheath/core fibers, stranded fibers, and monofilaments.
  • Suitable fiber forming methods include melt blow molding techniques, spin bonding, or spinning into fibers by gelation, from which woven or nonwoven fabrics, or structures composed of these fibers, including blends with other fibers, can be obtained.
  • compositions comprising multi-block branched polyethylene can also be made into finished products using conventional polyolefin processing techniques well known to those skilled in the art of polyolefin processing.
  • Dispersions can also be formed using the polymers of the invention or formulations comprising the polymers.
  • a foam material comprising the polymer of the present invention can also be formed.
  • the multi-block branched polyethylene can also be crosslinked by any known means, for example using peroxides, silanes, electron beams, azides or other crosslinking techniques.
  • the multi-block branched polyethylene can also be chemically modified, for example by grafting (for example using maleic anhydride, silane or other grafting agents), amination, halogenation, sulfonation or other chemical modification.
  • Additives and adjuvants may be included in any formulation comprising the polymer of the invention.
  • Suitable additives include fillers such as organic or inorganic particles (including clays, silica, talc, zeolites, powdered metals), organic or inorganic fibers (including carbon fibers, steel or mesh, silicon nitride fibers, and nylon or polyester). Noose, nanoscale particles, clay, etc.; thickeners, extender oils, including paraffinic or naphthenic oils; and other natural and synthetic polymers, including other polymers of the invention.
  • fillers such as organic or inorganic particles (including clays, silica, talc, zeolites, powdered metals), organic or inorganic fibers (including carbon fibers, steel or mesh, silicon nitride fibers, and nylon or polyester). Noose, nanoscale particles, clay, etc.; thickeners, extender oils, including paraffinic or naphthenic oils; and other natural and synthetic polymers, including other
  • Suitable polymers for blending with the polymers of the present invention include both thermoplastic and non-thermoplastic polymers, including natural and synthetic polymers.
  • Exemplary polymers for blending include polypropylene (impact modified polypropylene, isotactic polypropylene, random polypropylene, and random ethylene/propylene copolymer), various types of polyethylene, including low Density polyethylene, high density polyethylene, linear low density polyethylene, metallocene polyethylene, including reactor type polyethylene (reactor type alloy of Ziegler-Natta polyethylene and metallocene polyethylene), ethylene-ethylene Alcohol copolymer, ethylene-vinyl acetate copolymer, polystyrene, impact modified polystyrene, SBS, ABS, SEBS and thermoplastic polyurethane.
  • Homogeneous polymers, ethylene and propylene-based copolymers of olefin plastomers and elastomers can also be used as components in blends comprising the polymers of the
  • Suitable end uses for the foregoing products include elastic films and fibers; adhesives (including hot melt adhesives and pressure sensitive adhesives); soft touch products such as toothbrush handles and handles; footwear (including soles and shoes) ); gaskets and profiles; automotive interior parts and profiles; foam products (open and closed); impact modification for other thermoplastic polymers such as high density polyethylene, isotactic polypropylene or other olefin polymers Cap; pad; coated fabric; hose; weather strip; pipe; floor; and viscosity index improver for lubricants, also known as pour point modifier.
  • thermoplastic compositions comprising a thermoplastic graft copolymer (especially isotactic polypropylene) and a multi-block branched polyethylene of the invention are particularly capable of forming core-shell particles comprising hard crystalline or semi-crystalline blocks - Wherein the core is surrounded by a soft or elastomeric block to form a "shell" around the enclosed area of the hard polymer.
  • These particles are formed and dispersed in the graft copolymer by forces induced during hot melt mixing or blending. Upon curing, these areas become closed elastomeric particles encased in a polymeric matrix.
  • thermoplastic elastomers such as thermoplastic polyolefins (TPO), dynamically crosslinked thermoplastic elastomers (TPV) and styrene based thermoplastic elastomers (SBS, SEBS).
  • TPE thermoplastic polyolefins
  • TPV dynamically crosslinked thermoplastic elastomers
  • SBS styrene based thermoplastic elastomers
  • TPE and TPV blends were prepared by combining or vulcanizing agents.
  • the above blends can be used to form molded articles, and are optionally used to crosslink the resulting molded articles.
  • Suitable conventional block copolymers for this purpose have a Mooney viscosity (ML 1+4@100 ° C) of from 10 to 135, more preferably from 25 to 100, most preferably from 30 to 80.
  • Suitable polyolefins include, inter alia, linear or low density polyethylene, polypropylene (including its atactic, isotactic, syndiotactic and impact modified forms) and poly(4-methyl-1-pentyl) Alkene).
  • Suitable styrenic polymers include polystyrene, rubber modified polystyrene, styrene/acrylonitrile copolymer (SAN), rubber modified SAN, and styrene-maleic anhydride copolymers.
  • the blend can be prepared by mixing or kneading the respective components near or above the melting temperature of one or both components.
  • this temperature can be above 130 °C, most typically above 145 °C, and most preferably above 150 °C.
  • a typical polymer mixing or kneading apparatus capable of achieving the desired temperature and melt-plasticizing the mixture can be used. These include kneaders, mills, extruders (single and twin screw), Banbury mixers, calenders, and the like. The mixing sequence and method depend on the final composition.
  • the TPE or TPV composition has a higher content of crosslinkable polymer (typically a conventional block copolymer containing unsaturated bonds) than the TPO composition.
  • the weight ratio of multi-block branched polyethylene to block copolymer can range from 90:10 to 10:90, more preferably from 80:20 to 20:80, and most preferably from 75:25 to 25:75.
  • the weight ratio of multi-block branched polyethylene to TPO can range from 49:51 to 5:95, more preferably from 35:65 to 10:90.
  • the weight ratio of the multi-block branched polyethylene to the polyolefin is from 49:51 to 5:95, more preferably from 35:65 to 10:90.
  • the blend composition can comprise a processing oil, a plasticizer, and a processing aid.
  • Rubber processing oils have specific ASTM names and are suitable for paraffinic, naphthenic or aromatic processing oils. For every 100 parts of total polymer, 0 to 150 parts, preferably 0 to 100 parts, and most preferably 0 to 50 parts of oil are usually used. Higher amounts of oil may readily improve the processability of the resulting product at the expense of some physical properties.
  • Additional processing aids include conventional waxes, fatty acid salts (such as calcium stearate or zinc stearate) (poly) alcohols (including ethylene glycol), (poly)ol ethers (including glycol ethers), Poly)esters (including (poly)propylene glycols) and their metal salts, especially Group 1 or 2 metal or zinc salt derivatives.
  • fatty acid salts such as calcium stearate or zinc stearate
  • poly) alcohols including ethylene glycol
  • (poly)ol ethers including glycol ethers
  • Poly)esters including (poly)propylene glycols
  • metal salts especially Group 1 or 2 metal or zinc salt derivatives.
  • non-hydrogenated rubbers such as those comprising butadiene or isoprene in polymerized form, including block copolymers (hereinafter referred to as diene rubbers)
  • diene rubbers block copolymers
  • the fully saturated multi-block branched polyethylene of the present invention is particularly useful as a protective surface layer (coated, coextruded or adhered to articles made from conventional diene rubber modified polymer compositions) Laminated) or weather resistant film.
  • carbon black is an additive for UV absorption and stability.
  • Representative examples of carbon black include ASTM N110, N121, N220, N231, N234, N242, N293, N299, S315, N326, N330, M332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991.
  • the multi-block branched polyethylenes of the present invention and blends thereof require little or no carbon black, thereby resulting in considerable design freedom including other alternative pigments or no pigment at all. Multi-tone tires that match the color of the vehicle are a possible use.
  • compositions comprising the thermoplastic blends of the present invention may also contain antiozonants and antioxidants known to ordinary rubber chemists.
  • the antiozonant may be a physical protectant such as a wax material that covers the surface and protects the portion from oxygen or ozone, or they may be a chemical protectant that reacts with oxygen or ozone.
  • Suitable chemical protective agents include styrenated phenol, butylated bis(dimethylbenzyl)phenol, butylated octylated phenol, p-phenylenediamine, p-cresol and dicyclopentadiene.
  • Wingstay TM S antioxidant Polystay TM 100 antioxidant, Polystay TM 100AZ antioxidant, Polystay TM 200 antioxidant, Wingstay TM L antioxidant, Wingstay TM LHLS antioxidant, Wingstay TM K antioxidant , Wingstay TM 29 antioxidant, Wingstay TM SN-1 antioxidant, and Irganox TM antioxidants.
  • the antioxidants and antiozonants used are preferably non-staining and non-migrating.
  • hindered amine light stabilizers and UV absorbers can also be used. Suitable examples include those available from Ciba Specialty Chemicals of Tinuvin TM 123, Tinuvin TM 144, Tinuvin TM 622, Tinuvin TM 765, Tinuvin TM 770 and Tinuvin TM 780, and available from Cytex Plastics, Houston TX, USA of Chemisorb TM T944 .
  • an additional mixing process can be used to pre-disperse the antioxidant, antiozonant, carbon black, UV absorber, and/or light stabilizer to form a masterbatch, and subsequently form a polymer blend therefrom.
  • Suitable crosslinking agents for use herein include thio, peroxide or phenol based compounds.
  • an accelerator and a vulcanization activator can also be used.
  • the accelerator is used to control the time and/or temperature required for dynamic vulcanization and to improve the properties of the resulting crosslinked article.
  • a single accelerator or primary accelerator can be used.
  • the total amount of primary accelerator may range from 0.5 to 4 phr, preferably from 0.8 to 1.5, based on the total weight of the composition.
  • a primary accelerator in combination with a second accelerator, wherein the second accelerator is used in a small amount, for example 0.05 to 3 phr, to activate and improve the properties of the vulcanized article.
  • the combined use of accelerators produces articles that are generally slightly better than articles made with a single accelerator.
  • delayed action accelerators can be used which are not affected by normal processing temperatures, but which produce satisfactory vulcanization at ordinary vulcanization temperatures.
  • a vulcanization retarder can also be used.
  • Suitable accelerator types which can be used in the present invention are amines, guanidines, thioureas, thiazoles, thiurams, disulfides, sulfenamides, dithiocarbamates and xanthates.
  • the primary accelerator is a sulfinamide.
  • the second promoter is preferably a guanidine, dithiocarbamate or thiuram compound.
  • Certain processing aids and vulcanization activators can also be used.
  • a peroxide-based vulcanizing agent is used, a co-activator or a co-agent such as stearic acid and ZnO may be used in combination therewith.
  • Suitable coagents include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triallyl isocyanurate, triallyl cyanurate.
  • peroxide crosslinking agents and optional coagents for partial or complete dynamic vulcanization is well known in the art.
  • the degree of crosslinking can be measured by dissolving the composition in a solvent for a specified duration and calculating the percentage of gel or non-extractable components.
  • the percentage of gel generally increases as the degree of crosslinking increases.
  • the gel content percentage is from 5 to 100%.
  • the multi-block branched polyethylenes of the present invention and blends thereof have improved processability compared to prior art compositions because their unique branched chain structure reduces solution viscosity.
  • the composition or blend exhibits an improved surface appearance, especially when forming a molded or extruded article.
  • the present compositions and blends thereof uniquely have improved melt strength properties, thereby allowing the multi-block branched polyethylenes of the present invention and blends thereof, especially TPO blends, to be used in current melts. Insufficient foam and thermoforming applications.
  • thermoplastic composition of the present invention may also contain organic or inorganic fillers or other additives such as starch, glass fibers, talc, calcium carbonate, polymeric fibers (including nylon, rayon, cotton, polyester, and polyaramid), metals.
  • silane groups or other coupling agents can also be used.
  • thermoplastic composition of the present invention comprising the foregoing blends can be processed by conventional molding techniques such as injection molding, thermoforming, extrusion, mesoporous molding, insert molding, double-cover molding, blow molding, and other techniques.
  • the film including the multilayer film can be produced by a casting or tenter method, including a blown film method.
  • DSC Differential Scanning Calorimetry
  • crystallization temperature (T c ) and crystallization ⁇ ( ⁇ H crystal ) can be measured by the temperature drop curve, and the glass transition temperature (T g ) and melting enthalpy ( ⁇ H m ) can be measured by the second heating curve, crystallinity ⁇ can be calculated by dividing ⁇ H m by the melting enthalpy (292.6 J/g) of fully crystalline polyethylene under ideal conditions.
  • Sample preparation Weigh about 15 mg of the sample, and then add 0.5 ml of deuterated o-dichlorobenzene as a solvent. Test conditions: temperature 120 ° C, sampling time 1.998 seconds, relaxation time 1.0 seconds, test frequency 300 MHz, scanning 256 times.
  • the degree of branching of the polymer can be obtained by the following formula:
  • sample preparation Weigh about 50 mg of sample, add 10% of the sample mass of relaxation reagent into the nuclear magnetic tube, and then add 0.5 ml of deuterated o-dichlorobenzene as solvent.
  • Test conditions temperature 120 ° C, sampling time 0.8 seconds, relaxation time 3.0 seconds, test frequency 300 MHz, scanning times 5000 to 10000 times.
  • the degree of branching in terms of the number of branches per 1000 carbons
  • the branches are calculated according to the formulas 1.2 and 1.3. proportion
  • Methyl: ethyl: propyl: butyl: pentyl: branch with carbon number ⁇ 6 (I Me / 0.90): (I Et / 0.84): (I Pr / 0.83): (I Bu / 0.90) :(I Pe /0.90):(I Lg /0.80) Equation 1.3
  • the obtained rinse fraction was concentrated by rotary evaporation, and the product was precipitated with isopropyl alcohol. After standing for 12 hours, the product was filtered with a funnel, and the product was placed in a vacuum oven (temperature: 60 ° C) and baked for 24 hours.

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Abstract

本发明涉及热塑性弹性体技术，旨在提供一种多嵌段支化聚乙烯及其制备方法，并进一步提供该聚乙烯的应用。本发明所述多嵌段支化聚乙烯由作为硬段的半结晶、低支化度的聚乙烯链段和作为软段的无定型、高支化度的聚乙烯链段按照式（Ａ）的连接方式交替连接而成。本发明制备过程中，所用原料仅需乙烯单体，生产成本低；仅需一种催化剂，不必考虑两种催化剂的匹配问题，大大简化了生产工艺，适宜大规模的工业化生产。本发明的链穿梭反应在分子内的两个相同金属活性中心之间进行，具有高效、快速的优点，聚合产物的链结构和组成均匀，聚合反应条件温和，不需要在高温下进行，能耗大幅度降低。

Description

多嵌段支化聚乙烯及其制备方法 技术领域
本发明属于热塑性弹性体技术领域，尤其涉及多嵌段支化聚乙烯及其制备方法。
背景技术
本发明涉及用乙烯一种单体聚合以形成具有独特拓扑结构的聚合物，涉及制备这种聚合物的方法、并涉及所得聚合物产品。另一方面，本发明涉及在要求物理性能的独特组合的应用领域使用这些聚合物的方法。再一方面，本发明涉及由这些聚合物制成的制品。本发明的聚合物是一种新型的聚合物，具有独特的链结构，这使得聚合物具有独特的物理性能。这种聚合物和包含这种聚合物的掺合物可用于通过模塑、挤出或其它方法制备模制品、薄膜、片材和发泡制品之类的固体制品，并可用作粘合剂、层压制品、聚合物掺合物和其它最终用途中的组分或成分。所得产品用于制造汽车部件，例如型材、缓冲器和装饰部件等；包装材料；电线电缆绝缘材料和其它用途。
每一次新材料的出现都会极大地推动人类社会的进步，提高人们的生活水平。乙烯是最便宜、来源最丰富的烯烃单体。乙烯均聚可以得到不同拓扑结构的聚合物，如线性聚乙烯(HDPE)、支化聚乙烯(LDPE)和超支化聚乙烯(HBPE)，它们都有各自的用途。HDPE结晶度高、拉伸强度、耐磨性、耐寒性等均较好，耐酸、碱和各种盐类的腐蚀，常用作容器和管道，用于工业包装和市政建设。LDPE成型加工性能好，主要用作薄膜产品，用于医疗器具和食品、药品包装材料。HBPE结晶度低、玻璃化转变温度低，是一种综合性能优异的橡胶材料(ZL2014 1 0200113.6)。我们希望有新型拓扑结构的聚乙烯出现，它将带给我们新的可能。
橡胶(弹性体)具有优良的密封、减振、阻尼、耐疲劳、耐磨、绝缘等特性，是制造飞机、军舰、汽车、火车、电线电缆、农用机械、医疗器械、运动器械等不可或缺的材料，在人们的日常生活中也被广泛地应用。它不仅是国民经济的重要原材料，也是国际公认的国防战略物资。然而，橡胶的成型加工比合成树脂与塑料复杂、耗能更大，需要经切胶破胶、高温混炼、成型和硫化几个过程，工艺复杂、设备庞大，需要消耗大量的能量。更为严重的是，硫化后的橡胶呈热固性，再也无法回到原来的线性分子状态，因而不可回用，加工和使用过程中均产生大量的橡胶固体废弃物，严重污染环境，浪费石油资源。
热塑性弹性体(TPE)是物理性能介于橡胶和塑料之间的一类高分子材料。它既有橡胶的弹性，又有塑料的易加工性，且可回收利用，故被誉为“第三代橡胶”。由于不需要像橡胶那样的热硫化，因而成型加工简单。用普通的塑料加工机械即可容易地制得它的最终产品，仅成型加工即可缩短流程1/4，提高效率10～20倍，节约能耗25～40％；而且TPE回收后重新加工制得的产品性能并没有明显的流失。这相对于传统橡胶优势十分明显，堪称是橡胶工业的一次材料和工艺技术的革命。热塑性弹性体主要包括6大类：聚烯烃类热塑性弹性体(TPO)；苯乙烯类热塑性弹性体；聚氯乙烯类热塑性弹性体；聚氨酯类热塑性弹性体；聚酯类热塑性弹性体；聚酰胺类热塑性弹性体。
由于TPO具有优异的耐候、耐臭氧、耐紫外线及良好的耐高温、耐冲击性能，可用普通热塑性塑料加工设备进行成型加工及可重复使用的优点，发展迅速，成为热塑性弹性体中增长最快的一个品种，广泛应用于汽车、电子电气、工业及民用等领域。
TPO的生产方法主要有两种：一种是共混复合型，另一种是反应器型。共混复合型又包括机械掺混法和动态硫化法2种路线。机械掺混法是开发最早、技术最成熟的TPO生产工艺。该法通过双螺杆挤出机将乙丙橡胶和聚丙烯进行掺混挤出，制造工艺简单、成本低。但由于橡胶组分含量低(质量分数约20～30％)，耐热性、耐油性、耐高温永久变形性和弹性较其它方法制备的TPO差，应用受到限制，常用于汽车部件及家电等行业。动态硫化法是将橡胶相动态硫化获得硫化胶。动态硫化法TPO工艺路线有3种：开炼工艺、密炼工艺和双螺杆挤出工艺。其中开炼工艺和密炼工艺采用间歇共混设备，工艺简单、操作方便，适于小规模、多品种共混胶生产。由于该工艺再现性差、共混剪切力小，不适于高温操作，产品质量较低。双螺杆挤出工艺采用连续挤出式共混机械，其共混充油、动态硫化、排气等工序可在同一机组上完成，具有较高的生产能力和自动控制水平，可严格控制工艺条件，充分保证聚合物混合质量和控制硫化程度，适于大规模生产。
反应器合成法工艺发展较晚，由于该法生产的TPO橡胶含量可达60％以上，性能优越，世界上很多公司都在积极研究，是TPO发展的主要方向。反应器合成法是在丙烯聚合反应器中先生成均聚丙烯，再逐步通入乙烯、丙烯，生成聚丙烯和乙丙橡胶的嵌段共聚物。目前应用较多的是Unipol流化床气相聚合工艺和Himont的环管式本体均聚、气相嵌段共聚工艺。由于反应器合成工艺制备的TPO是在聚合反应过程中得到的，省去了合成橡胶粉碎及共混挤出过程，故成本较低，产品与共混复合工艺制备的TPO相比具有较高的流动和抗冲击性能。随着埃克森-美孚公司采用Exxpol专利技术在世界上首次生产出茂金属聚乙烯，开创了茂金属聚烯烃发展的新时代。由于茂金属催化剂具有理想的单活性中心，从而能够精确控制聚合物的分子量、共聚单体的含量及其在主链上的分布和结晶结构，从而获得高性能的聚烯烃材料。利用茂金属催化剂开发生产反应器型TPO已进入商业化生产阶段，埃克森和陶氏化学在该领域的研究十 分活跃，处于领先水平。POE弹性体是陶氏化学公司于1993年开发成功的一类聚烯烃弹性体的简称，主要指采用茂金属催化剂合成的乙烯—α-烯烃共聚物(乙烯—1-辛烯共聚物，乙烯—1-丁烯共聚物等)。在陶氏化学之后，又有其他公司开发出有类似结构和性能特点的聚烯烃弹性体，包括茂金属催化剂合成的丙烯—α-烯烃共聚物等，均可归入POE材料。POE的特点是α-烯烃质量分数高(大于20％)，密度较低，主要特性接近橡胶，却有一定的结晶度。其结构中的可结晶聚乙烯链段形成物理交联点承受载荷，非结晶的无规共聚链段提供弹性。这种特殊的形态结构使得POE具有特殊的性质和广泛的用途，既可用作橡胶，也可用作热塑性弹性体，还可用作塑料的增韧剂。2007年，陶氏化学基于链穿梭聚合反应，利用全新的催化体系在单一反应器内进行连续溶液聚合，成功开发了商品名为Infuse、具有交替的半结晶和无定形链段的烯烃嵌段共聚物(OBC)。Infuse OBC构成了聚烯烃弹性体的新家族，与POE相比，具有更高的熔点、结晶温度和更低的玻璃化转变温度，结晶形态更为有序。不过，OBC的制备过程中使用了两种催化剂，这两种催化剂是陶氏化学经过1600多次聚合实验才筛选出来的。聚合单体中用到的1-辛烯的价格昂贵。在连续法生产OBC的过程中，为了保证产品品质的均一、稳定，需要连续补充聚合过程中消耗得快的催化剂和乙烯，这就造成生产工艺比较复杂。另外，为了保证结晶的聚乙烯链段的充分溶解，聚合需要在130℃以上进行。这些均导致OBC的生产成本较高。
发明内容
本发明要解决的技术问题是，克服现有技术的不足，提供一种多嵌段支化聚乙烯及其制备方法。
为解决技术问题，本发明的解决方案是：
提供一种多嵌段支化聚乙烯，该多嵌段支化聚乙烯由作为硬段的半结晶、低支化度的聚乙烯链段和作为软段的无定型、高支化度的聚乙烯链段按照
Figure PCTCN2016109278-appb-000001
的连接方式交替连接而成；
所述半结晶是指：硬段的熔点为80～133.5℃，结晶度为9.7～47％，玻璃化转变温度为-73～-69℃；低支化度是指：支化度为1～60个支链/1000个碳；
所述无定型是指：软段的玻璃化转变温度为-70～-56℃，无明显熔点，结晶度为0～4.5％；高支化度是指：支化度为50～250个支链/1000个碳。
本发明中，该多嵌段支化聚乙烯的重均分子量为11.1×104～29.1×104g/mol，分子量分布指数为2.6～4.0，支化度为31.6～118.3个支链/1000个碳，支链中49～58.7mol％为甲基支链，4.9～7.5mol％为乙基支链，3.3～4.7mol％为丙基支链，1.7～5.1mol％为丁基支链，15.1～20.5mol％为戊基支链，12.4～17.5mol％为碳数≥6的支链，结晶度为5.7～42.9％，玻璃化转变温度为–69℃～–61℃，熔点为116.5℃～123.3℃。
本发明中，所述硬段中各支链的摩尔百分含量占比是：52～100mol％为甲基支链，0～14.6mol％为乙基支链，0～4.8mol％为丙基支链，0～3.6mol％为丁基支链，0～13.6mol％为戊基支链，0～12.5mol％为碳数≥6的支链；所述软段中各支链的摩尔百分含量占比是：44.5～56mol％为甲基支链，3.5～11.7mol％为乙基支链，4.5～14.6mol％为丙基支链，2.5～6.6mol％为丁基支链，11.0～22.4mol％为戊基支链，6.5～15mol％为碳数≥6的支链。
本发明中，该多嵌段支化聚乙烯的拉伸强度不低于10MPa，断裂伸长率不低于500％。
本发明中，该多嵌段支化聚乙烯具备橡胶的特性，是一种热塑性弹性体：在18～29℃室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，能在1分钟内恢复到原来长度的1.5倍以下。
本发明中，该多嵌段支化聚乙烯是一种多组份的混合物，通过升温淋洗分级(TREF)的方法，以甲苯为溶剂至少可以分离出10～11种组份：其中，
(1)在30℃下淋洗出来的组份含量为3.3～30wt％(重量百分含量)，该组份的重均分子量为3.0×104～21.4×104g/mol，分子量分布指数为2.4～3.8，支化度为110～220个支链/1000个碳，支链中48～62.8mol％为甲基支链，3～4mol％为乙基支链，10～12mol％为丙基支链，4.7～6.1mol％为丁基支链，10～14mol％为戊基支链，6.3～18.9mol％为碳数≥6的支链，玻璃化转变温度为–64.6℃～–61℃，有两个熔点，熔点一为50～60℃，熔点二为110～115℃，结晶度为0.3～2.5％，结晶温度为70～80℃；
(2)在40℃下淋洗出来的组份含量为5.8～10wt％，该组份的重均分子量为10×104～26×104g/mol，分子量分布指数为2.4～3.8，支化度为120～180个支链/1000个碳，支链中45～60mol％为甲基支链，2～3.5mol％为乙基支链，11～15mol％为丙基支链，1～3mol％为丁基支链，9～13mol％为戊基支链，12.5～20.5mol％为碳数≥6的支链，玻璃化转变温度为–64℃～–61℃，有两个熔点，熔点一为65～80℃，熔点二为110～116℃，结晶度为1.5～3.5％，有两个结晶温度，结晶温度一为45～60℃，结晶温度二为80～95℃；
(3)在50℃下淋洗出来的组份含量为3.4～6.5wt％，该组份的重均分子量为12.8×104～30×104g/mol，分子量分布指数为2.6～3.6，支化度为90～150个支链/1000个碳，支链中58～67mol％为甲基支链，3～5.5mol％为乙基支链，7.9～11mol％为丙基支链，0～3mol％为丁基支链，7～13mol％为戊基支链，7.5～15mol％为碳数≥6的支链，玻璃化转变温度为–69℃～–64℃，有两个熔点，熔点一为80～90℃，熔点二为110～120℃，结晶度为3～6％，有两个结晶温度，结晶温度一为55～70℃，结晶温度二为80～95℃；
(4)在60℃下淋洗出来的组份含量为3.4～6.5wt％，该组份的重均分子量为14×104～34×104g/mol，分子量分布指数为3.2～3.8，支化度为46～100个支链/1000个碳，支链中75～90mol％为甲基支链，0～2.5mol％为乙基支链，0～2mol％为丙基支链，0～3mol％为丁基支链，6～15mol％为戊基支链，4～9mol％为碳数≥6的支链，玻璃化转变温度为–72℃～–68℃，熔点为90～100℃，结晶度为10～16％，结晶温度为75～85℃；
(5)在70℃下淋洗出来的组份含量为5.5～8wt％，该组份的重均分子量为17×104～40×104g/mol，分子量分布指数为3.5～4.0，支化度为26～70个支链/1000个碳，支链中80～95mol％为甲基支链，0～2mol％为乙基支链，0～2mol％为丙基支链，0～3mol％为丁基支链，3～17mol％为戊基支链，1～5mol％为碳数≥6的支链，玻璃化转变温度为–72℃～–68℃，熔点为95～110℃，结晶度为15～25％，结晶温度为80～95℃；
(6)在80℃下淋洗出来的组份含量为5.5～9wt％，该组份的重均分子量为20×104～48×104g/mol，分子量分布指数为2.7～3.2，支化度为17～60个支链/1000个碳，支链中70～85mol％为甲基支链，10～18mol％为乙基支链，0～2mol％为丙基支链，0～3mol％为丁基支链，0～3mol％为戊基支链，5～12mol％为碳数≥6的支链，玻璃化转变温度为–74℃～–69℃，熔点为105～115℃，结晶度为20～30％，结晶温度为90～100℃；
(7)在90℃下淋洗出来的组份含量为11.5～20wt％，该组份的重均分子量为23×104～60×104g/mol，分子量分布指数为2.5～3.2，支化度为10～40个支链/1000个碳，支链中88～98mol％为甲基支链，0～2mol％为乙基支链，0～2mol％为丙基支链，0～3mol％为丁基支链，0～3mol％为戊基支链，2～6mol％为碳数≥6的支链，玻璃化转变温度为–68℃～–60℃，熔点为110～120℃，结晶度为25～35％，结晶温度为95～105℃；
(8)在100℃下淋洗出来的组份含量为9～16wt％，该组份的重均分子量为24×104～60×104g/mol，分子量分布指数为2.2～3.0，支化度为10～30个支链/1000个碳，支链中90～100mol％为甲基支链，0～2mol％为乙基支链，0～2mol％为丙基支链，0～2mol％为丁基支链，0～2mol％为戊基支链，0～2mol％为碳数≥6的支链，玻璃化转变温度为–70℃～–64℃，熔点为115～125℃，结晶度为25～33％，结晶温度为100～110℃；
(9)在110℃下淋洗出来的组份含量为7～14wt％，该组份的重均分子量为20×104～60×104g/mol，分子量分布指数为2.2～3.0，支化度为8～25个支链/1000个碳，支链中70～80mol％为甲基支链，0～2mol％为乙基支链，0～2mol％为丙基支链，0～2mol％为丁基支链，0～2mol％为戊基支链，20～30mol％为碳数≥6的支链，玻璃化转变温度为–68℃～–62℃，熔点为120～130℃，结晶度为30～38％，结晶温度为105～115℃；
(10)在120℃下淋洗出来的组份含量为2.5～7wt％，该组份的重均分子量为20×104～60×104g/mol，分子量分布指数为2.5～3.0，支化度为5～20个支链/1000个碳，支链中95～100mol％为甲基支链，0～1mol％为乙基支链，0～1mol％为丙基支链，0～1mol％为丁基支链，0～1mol％为戊基支链，0～1mol％为碳数≥6的支链，玻璃化转变温度为–71℃～–67℃，熔点为120～130℃，结晶度为36～40％，结晶温度为105～115℃；
(11)淋洗温度高于120℃的组份含量为0～5wt％，该组份的重均分子量为15×104～40×104g/mol，分子量分布指数为2.5～3.0，支化度为0～10个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–63.8℃～–61℃，熔点为122～130℃，结晶度为35～40％，结晶温度为108～115℃。
本发明进一步提供了所述多嵌段支化聚乙烯的制备方法，是以双核苊(α-二亚胺)镍催化剂为主催化剂、烷基铝为助催化剂，再加以链穿梭剂二乙基锌催化乙烯进行均聚，通过链穿梭聚合反应获得所述多嵌段支化聚乙烯；
Figure PCTCN2016109278-appb-000002
所述双核苊(α-二亚胺)镍催化剂的化学结构如式I所示，其中R为甲基或异丙基；
所述烷基铝为一氯二乙基铝、倍半乙基氯化铝或二氯乙基铝中的一种。
本发明中，该制备方法的具体步骤为：
将烷基铝、链穿梭剂二乙基锌和双核苊(α-二亚胺)镍催化剂溶于溶剂中，通入压力为0.4～2.0MPa的乙烯后进行链穿梭聚合反应，控制聚合温度为25～40℃，聚合时间为30～60分钟；聚合结束后，加入酸化乙醇终止聚合反应；将聚合产物沉淀出来，经过滤、洗涤，得到多嵌段支化聚乙烯；
在聚合体系中，双核苊(α-二亚胺)镍催化剂的浓度为2.5～45.5μmol/L，烷基铝中的铝与双核苊(α-二亚胺)镍催化剂中的镍的摩尔比(Al/Ni比)为50～200，链穿梭剂二乙基锌中的锌与双核苊(α-二亚胺)镍催化剂中的镍的摩尔比为10～100。
本发明中，在聚合体系中，所用的溶剂为正己烷、正庚烷中的一种；或者是正庚烷与甲苯的混合物，混合物中正庚烷与甲苯的体积比为99:1～10:1。
本发明还提供了前述多嵌段支化聚乙烯或包含该多嵌段支化聚乙烯聚合物的组合物作为下述任一产品的应用，或在制造下述任一产品中的应用：薄膜、多层膜的至少一层、层压制品的至少一层、发泡制品、聚丙烯冲击改性剂、纤维、无纺布、注射成型制品、吹塑制品、旋转模塑制品或粘合剂。
本发明所述包含多嵌段支化聚乙烯聚合物的组合物是指，除本发明所述多嵌段支化聚乙烯聚合物之外，还包括能够与多嵌段支化聚乙烯聚合物掺混使用的其它聚合物或添加剂。凡是本领域技术人员依据其所掌握的知识能够知晓，或根据现有试验技术能够推演得到的组合物，均应被包括在内。
发明原理描述：
申请人曾在中国发明专利ZL 2012 1 0276244.3中提供了一种双核苊(α-二亚胺)镍催化剂(具体结构如下式所示)及其制备方法。
Figure PCTCN2016109278-appb-000003
该催化剂活性高，稳定性好，制备工艺简单，合成路线短，成本低，产率高，易于工业化。在后续的研究中，申请人发现该催化剂经过调控可以在乙烯聚合过程中产生两种催化行为迥异的活性中心，一种活性中心生成半结晶的、低支化度的聚乙烯，另一种活性中心生成无定型的、高支化度的聚乙烯。
以双核苊(α-二亚胺)镍催化剂为主催化剂、烷基铝为助催化剂，再加入链穿梭剂(这是本发明与中国发明专利ZL 2012 1 0276244.3不同的地方)催化乙烯进行均聚，通过链穿梭聚合(Science,2006,312,714)获得无定型的高度支化聚乙烯链段(软段)和半结晶的低支化度聚乙烯链段(硬段)交替连接的新型聚合物，称之为“多嵌段支化聚乙烯”，简称为MBBPE。在MBBPE中无定型的高度支化聚乙烯链段提供弹性，半结晶的低支化度聚乙烯链段形成物理交联点承受载荷，所以MBBPE是一种全新的热塑性弹性体。
与现有技术相比，本发明具有如下优点：
(1)本发明制备的多嵌段支化聚乙烯仅需要乙烯一种单体，它是价格最便宜、来源非常丰富的烯烃，而不需要用到价格昂贵的长链α-烯烃，如1-辛烯、1-癸烯等，生产成本低，而且不需要在聚合过程中补加消耗得快的单体，大大简化了生产工艺，适宜大规模的工业化生产。
(2)本发明制备的多嵌段支化聚乙烯仅需要双核苊(α-二亚胺)镍催化剂一种烯烃催化剂，而不需要使用两种聚合行为相差很大的催化剂，这样就不必考虑两种催化剂的匹配问题，从而简化了生产工艺，降低了生产成本，适宜大规模的工业化生产。
(3)本发明制备的多嵌段支化聚乙烯仅使用双核苊(α-二亚胺)镍催化剂一种烯烃催化剂，链穿梭反应在分子内的两个相同金属活性中心之间进行，具有高效、快速的优点，聚合产物的链结构和组成均匀，聚合反应条件温和，不需要在高温下进行，能耗大幅度降低，更加符合当下“低碳经济”的要求。
具体实施方式
为了更好地对本发明进行详细说明，列举如下实施例：
实施例1
乙烯聚合是在无水无氧条件下进行的。在带机械搅拌的200毫升不锈钢反应釜中加入100毫升正庚烷，通过夹套循环水控制聚合釜温度为25℃，并开始搅拌。向聚合釜中依次加入2.0mmol助催化剂二氯乙基铝[控制二氯乙基铝中的铝与双核苊(α-二亚胺)镍催化剂中的镍之间的摩尔比为200]，0.2mmol二乙基锌[控制二乙基锌中的锌与双核苊(α-二亚胺)镍催化剂中的镍之间的摩尔比为20]，5μmol双核苊(α-二亚胺)镍催化剂2(R为异丙基，事先溶解在10毫升甲苯中)，催化剂在聚合体系中的浓度为45.5μmol/L。通入乙烯至反应釜压力为1.2MPa。聚合30分钟后，反应釜放空至常压，打开釜盖，倒出聚合物溶液，蒸出溶剂得到聚合物22克。催化剂活性为4400kgPE[mol(Ni)h]-1，聚合产物重均分子量为12.9×104g/mol,多分散系数为3.0，玻璃化转变温度为–67℃，熔点为120.4℃，结晶度为10.5％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为18.0MPa，断裂伸长率为1230％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.33倍。
经1H-NMR测定，聚合产物的支化度为80个支链/1000个碳原子，支链中52.0mol％为甲基支链、6.5mol％为乙基支链、4.5mol％为丙基支链、3.9mol％为丁基支链、17.6mol％为戊基支链、15.5mol％为碳 数≥6的支链。硬段的支化度为42个支链/1000个碳原子，软段的支化度为139个支链/1000个碳原子。硬段的支链中82mol％为甲基支链，3mol％为乙基支链，1mol％为丙基支链，1mol％为丁基支链，7mol％为戊基支链，6mol％为碳数≥6的支链。软段的支链中51.8mol％为甲基支链，4.2mol％为乙基支链，13.6mol％为丙基支链，5.4mol％为丁基支链，11.9mol％为戊基支链，13.1mol％为碳数≥6的支链。硬段的熔点为118.0℃，结晶度为10.3％，玻璃化转变温度为–72℃；软段的玻璃化转变温度为–67℃，无明显熔点，结晶度为0％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出11种组份：其中(1)在30℃下淋洗出来的组份含量为27.1wt％(重量百分含量)，该组份的重均分子量为9.6×104g/mol，分子量分布指数为2.4，支化度为177个支链/1000个碳，支链中58.9mol％为甲基支链，3.5mol％为乙基支链，11.2mol％为丙基支链，5.3mol％为丁基支链，11.9mol％为戊基支链，9.2mol％为碳数≥6的支链，玻璃化转变温度为–63.5℃，有两个熔点，熔点一为55.7℃，熔点二为113.6℃，结晶度为1.41％，结晶温度为75.8℃；(2)在40℃下淋洗出来的组份含量为8.5wt％，该组份的重均分子量为10.7×104g/mol，分子量分布指数为2.4，支化度为149个支链/1000个碳，支链中58.3mol％为甲基支链，3.0mol％为乙基支链，13.6mol％为丙基支链，1.6mol％为丁基支链，10.4mol％为戊基支链，13.1mol％为碳数≥6的支链，玻璃化转变温度为–62.6℃，有两个熔点，熔点一为75.2℃，熔点二为113.8℃，结晶度为2.62％，有两个结晶温度，结晶温度一为54.5℃，结晶温度二为86.3℃；(3)在50℃下淋洗出来的组份含量为4.4wt％，该组份的重均分子量为13.5×104g/mol，分子量分布指数为3.0，支化度为108个支链/1000个碳，支链中64.2mol％为甲基支链，4.2mol％为乙基支链，9.4mol％为丙基支链，0mol％为丁基支链，9.6mol％为戊基支链，12.6mol％为碳数≥6的支链，玻璃化转变温度为–65.3℃，有两个熔点，熔点一为84.7℃，熔点二为115.1℃，结晶度为4.45％，有两个结晶温度，结晶温度一为65.7℃，结晶温度二为87.1℃；(4)在60℃下淋洗出来的组份含量为4.0wt％，该组份的重均分子量为15.3×104g/mol，分子量分布指数为3.6，支化度为57个支链/1000个碳，支链中82mol％为甲基支链，0％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，11.5mol％为戊基支链，6.6mol％为碳数≥6的支链，玻璃化转变温度为–70.8℃，熔点为94.2℃，结晶度为13.43％，结晶温度为79.7℃；(5)在70℃下淋洗出来的组份含量为6.2wt％，该组份的重均分子量为17.6×104g/mol，分子量分布指数为3.8，支化度为38个支链/1000个碳，支链中84.7mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，13.6mol％为戊基支链，1.7mol％为碳数≥6的支链，玻璃化转变温度为–71℃，熔点为101.9℃，结晶度为19.26％，结晶温度为86.7℃；(6)在80℃下淋洗出来的组份含量为7.0wt％，该组份的重均分子量为23.3×104g/mol，分子量分布指数为2.7，支化度为27个支链/1000个碳，支链中76.3mol％为甲基支链，14.6mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，9.1mol％为碳数≥6的支链，玻璃化转变温度为–72℃，熔点为109.5℃，结晶度为27.17％，结晶温度为95.3℃；(7)在90℃下淋洗出来的组份含量为16.1wt％，该组份的重均分子量为24.7×104g/mol，分子量分布指数为2.6，支化度为20个支链/1000个碳，支链中96.2mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，3.8mol％为碳数≥6的支链，玻璃化转变温度为–64℃，熔点为115.8℃，结晶度为29.12％，结晶温度为100.6℃；(8)在100℃下淋洗出来的组份含量为12.2wt％，该组份的重均分子量为25.1×104g/mol，分子量分布指数为2.4，支化度为17个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–66.8℃，熔点为120.3℃，结晶度为28.7％，结晶温度为105.8℃；(9)在110℃下淋洗出来的组份含量为10.2wt％，该组份的重均分子量为20.8×104g/mol，分子量分布指数为2.5，支化度为16个支链/1000个碳，支链中74.1mol％为甲基支链，25.9mol％为碳数≥6的支链，玻璃化转变温度为–64.8℃，熔点为123.3℃，结晶度为34.01％，结晶温度为109.1℃；(10)在120℃下淋洗出来的组份含量为3.4wt％，该组份的重均分子量为22.4×104g/mol，分子量分布指数为2.5，支化度为11个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–68.9℃，熔点为122.0℃，结晶度为37.09％，结晶温度为107.7℃；(11)淋洗温度高于120℃的组份含量为0.9wt％，该组份的重均分子量为16.6×104g/mol，分子量分布指数为2.6，支化度为5个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–63.3℃，熔点为122.2℃，结晶度为35.46％，结晶温度为108.3℃。
实施例2
将乙烯的聚合压力降低到0.7MPa，其它条件同实施例1，得到聚合物18.5克。催化剂活性为3700kgPE[mol(Ni)h]-1，聚合产物重均分子量为12.6×104g/mol,多分散系数为3.0，玻璃化转变温度为–68℃，熔点为120.6℃，结晶度为9.2％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为14.0MPa，断裂伸长率为900％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.21倍。
经1H-NMR测定，聚合产物的支化度为82.3个支链/1000个碳原子，支链中49mol％为甲基支链、6.8mol％为乙基支链、4.7mol％为丙基支链、4.2mol％为丁基支链、17.8mol％为戊基支链、17.5mol％为碳 数≥6的支链。硬段的支化度为51个支链/1000个碳原子，软段的支化度为162个支链/1000个碳原子。硬段的支链中79mol％为甲基支链，3.2mol％为乙基支链，1.1mol％为丙基支链，1.2mol％为丁基支链，7.3mol％为戊基支链，8.2mol％为碳数≥6的支链。软段的支链中49.6mol％为甲基支链，4.3mol％为乙基支链，13.8mol％为丙基支链，5.6mol％为丁基支链，12.1mol％为戊基支链，14.6mol％为碳数≥6的支链。硬段的熔点为117℃，结晶度为9.8％，玻璃化转变温度为–73℃；软段的玻璃化转变温度为–68℃，无明显熔点，结晶度为0％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出11种组份：其中(1)在30℃下淋洗出来的组份含量为29.8wt％(重量百分含量)，该组份的重均分子量为9.2×104g/mol，分子量分布指数为2.4，支化度为178.8个支链/1000个碳，支链中58.4mol％为甲基支链，3.6mol％为乙基支链，11.3mol％为丙基支链，5.4mol％为丁基支链，12.0mol％为戊基支链，9.3mol％为碳数≥6的支链，玻璃化转变温度为–64.6℃，有两个熔点，熔点一为53.5℃，熔点二为112.8℃，结晶度为1.23％，结晶温度为74.5℃；(2)在40℃下淋洗出来的组份含量为8.9wt％，该组份的重均分子量为10.5×104g/mol，分子量分布指数为2.4，支化度为149.9个支链/1000个碳，支链中57.8mol％为甲基支链，3.1mol％为乙基支链，13.7mol％为丙基支链，1.7mol％为丁基支链，10.5mol％为戊基支链，13.2mol％为碳数≥6的支链，玻璃化转变温度为–63.2℃，有两个熔点，熔点一为73.2℃，熔点二为113.1℃，结晶度为2.41％，有两个结晶温度，结晶温度一为54.2℃，结晶温度二为86.0℃；(3)在50℃下淋洗出来的组份含量为4.9wt％，该组份的重均分子量为13.0×104g/mol，分子量分布指数为2.9，支化度为109.8个支链/1000个碳，支链中63.5mol％为甲基支链，4.4mol％为乙基支链，9.6mol％为丙基支链，0.1mol％为丁基支链，9.7mol％为戊基支链，12.7mol％为碳数≥6的支链，玻璃化转变温度为–65.8℃，有两个熔点，熔点一为84.2℃，熔点二为115.0℃，结晶度为4.29％，有两个结晶温度，结晶温度一为65.1℃，结晶温度二为86.5℃；(4)在60℃下淋洗出来的组份含量为4.2wt％，该组份的重均分子量为15.1×104g/mol，分子量分布指数为3.2，支化度为57.8个支链/1000个碳，支链中81.5mol％为甲基支链，0.1％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，11.6mol％为戊基支链，6.6mol％为碳数≥6的支链，玻璃化转变温度为–70.9℃，熔点为94.0℃，结晶度为13.12％，结晶温度为79.2℃；(5)在70℃下淋洗出来的组份含量为6.2wt％，该组份的重均分子量为17.2×104g/mol，分子量分布指数为3.6，支化度为37.9个支链/1000个碳，支链中84.1mol％为甲基支链，0.2mol％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，13.7mol％为戊基支链，1.8mol％为碳数≥6的支链，玻璃化转变温度为–71.1℃，熔点为101.4℃，结晶度为18.78％，结晶温度为86.1℃；(6)在80℃下淋洗出来的组份含量为7.0wt％，该组份的重均分子量为23.0×104g/mol，分子量分布指数为2.7，支化度为27.8个支链/1000个碳，支链中75.8mol％为甲基支链，14.7mol％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，0.1mol％为戊基支链，9.2mol％为碳数≥6的支链，玻璃化转变温度为–72.1℃，熔点为109.2℃，结晶度为27.07％，结晶温度为95.1℃；(7)在90℃下淋洗出来的组份含量为16.0wt％，该组份的重均分子量为24.4×104g/mol，分子量分布指数为2.6，支化度为22.4个支链/1000个碳，支链中95.7mol％为甲基支链，0.1mol％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，0.1mol％为戊基支链，3.9mol％为碳数≥6的支链，玻璃化转变温度为–64.2℃，熔点为115.5℃，结晶度为29.0％，结晶温度为100.1℃；(8)在100℃下淋洗出来的组份含量为12.0wt％，该组份的重均分子量为25.0×104g/mol，分子量分布指数为2.4，支化度为17.8个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–66.5℃，熔点为120.1℃，结晶度为28.5％，结晶温度为105.5℃；(9)在110℃下淋洗出来的组份含量为10.0wt％，该组份的重均分子量为20.5×104g/mol，分子量分布指数为2.5，支化度为15.9个支链/1000个碳，支链中72.9mol％为甲基支链，27.1mol％为碳数≥6的支链，玻璃化转变温度为–64.9℃，熔点为123.2℃，结晶度为39.87％，结晶温度为109.1℃；(10)在120℃下淋洗出来的组份含量为3.2wt％，该组份的重均分子量为22.2×104g/mol，分子量分布指数为2.5，支化度为10.9个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–68.7℃，熔点为121.0℃，结晶度为37.01％，结晶温度为107.5℃；(11)淋洗温度高于120℃的组份含量为1.0wt％，该组份的重均分子量为16.0×104g/mol，分子量分布指数为2.6，支化度为8个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–63.1℃，熔点为122.0℃，结晶度为35.40％，结晶温度为108.1℃。
实施例3
将乙烯的聚合压力降低到0.4MPa，其它条件同实施例1，得到聚合物16.3克。催化剂活性为3260kgPE[mol(Ni)h]-1，聚合产物重均分子量为11.9×104g/mol,多分散系数为2.9，玻璃化转变温度为–69℃，熔点为120.1℃，结晶度为8.7％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为12.0MPa，断裂伸长率为850％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.20倍。
经1H-NMR测定，聚合产物的支化度为93.2个支链/1000个碳原子，支链中54.8mol％为甲基支链、7.3mol％为乙基支链、3.8mol％为丙基支链、3.5mol％为丁基支链、15.1mol％为戊基支链、15.5mol％为碳 数≥6的支链。硬段的支化度为50个支链/1000个碳原子，软段的支化度为189个支链/1000个碳原子。硬段的支链中65mol％为甲基支链，5mol％为乙基支链，3mol％为丙基支链，2mol％为丁基支链，12.5mol％为戊基支链，12.5mol％为碳数≥6的支链。软段的支链中46.9mol％为甲基支链，4.1mol％为乙基支链，14.6mol％为丙基支链，5.5mol％为丁基支链，22.4mol％为戊基支链，6.5mol％为碳数≥6的支链。硬段的熔点为115.0℃，结晶度为10.1％，玻璃化转变温度为–72℃；软段的玻璃化转变温度为–67℃，无明显熔点，结晶度为0％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出10种组份：其中(1)在30℃下淋洗出来的组份含量为30wt％(重量百分含量)，该组份的重均分子量为9.0×104g/mol，分子量分布指数为2.4，支化度为190.9个支链/1000个碳，支链中56.5mol％为甲基支链，4mol％为乙基支链，12mol％为丙基支链，4.7mol％为丁基支链，10mol％为戊基支链，12.8mol％为碳数≥6的支链，玻璃化转变温度为–63℃，有两个熔点，熔点一为53℃，熔点二为112℃，结晶度为1.2％，结晶温度为74℃；(2)在40℃下淋洗出来的组份含量为10wt％，该组份的重均分子量为10.1×104g/mol，分子量分布指数为2.4，支化度为161个支链/1000个碳，支链中56.8mol％为甲基支链，2mol％为乙基支链，12mol％为丙基支链，2mol％为丁基支链，10.7mol％为戊基支链，16.5mol％为碳数≥6的支链，玻璃化转变温度为–64℃，有两个熔点，熔点一为73℃，熔点二为113℃，结晶度为2.2％，有两个结晶温度，结晶温度一为54℃，结晶温度二为86℃；(3)在50℃下淋洗出来的组份含量为6.5wt％，该组份的重均分子量为12.8×104g/mol，分子量分布指数为2.9，支化度为116个支链/1000个碳，支链中63.1mol％为甲基支链，5.5mol％为乙基支链，7.9mol％为丙基支链，3mol％为丁基支链，13mol％为戊基支链，7.5mol％为碳数≥6的支链，玻璃化转变温度为–66℃，有两个熔点，熔点一为84℃，熔点二为114.0℃，结晶度为4.1％，有两个结晶温度，结晶温度一为65℃，结晶温度二为86℃；(4)在60℃下淋洗出来的组份含量为6.5wt％，该组份的重均分子量为14.8×104g/mol，分子量分布指数为3.2，支化度为75个支链/1000个碳，支链中80.5mol％为甲基支链，0.2％为乙基支链，0.2mol％为丙基支链，0.1mol％为丁基支链，15mol％为戊基支链，4mol％为碳数≥6的支链，玻璃化转变温度为–70.5℃，熔点为93.0℃，结晶度为13.0％，结晶温度为79℃；(5)在70℃下淋洗出来的组份含量为8wt％，该组份的重均分子量为17×104g/mol，分子量分布指数为3.6，支化度为49个支链/1000个碳，支链中81mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，17mol％为戊基支链，2mol％为碳数≥6的支链，玻璃化转变温度为–71.5℃，熔点为101.2℃，结晶度为18.3％，结晶温度为85.9℃；(6)在80℃下淋洗出来的组份含量为9wt％，该组份的重均分子量为22.3×104g/mol，分子量分布指数为2.7，支化度为35个支链/1000个碳，支链中77mol％为甲基支链，18mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，5mol％为碳数≥6的支链，玻璃化转变温度为–72.5℃，熔点为109℃，结晶度为27％，结晶温度为95℃；(7)在90℃下淋洗出来的组份含量为11.5wt％，该组份的重均分子量为24.1×104g/mol，分子量分布指数为2.6，支化度为31个支链/1000个碳，支链中88mol％为甲基支链，2mol％为乙基支链，2mol％为丙基支链，3mol％为丁基支链，3mol％为戊基支链，2mol％为碳数≥6的支链，玻璃化转变温度为–64.5℃，熔点为115℃，结晶度为28.9％，结晶温度为100℃；(8)在100℃下淋洗出来的组份含量为9wt％，该组份的重均分子量为24.5×104g/mol，分子量分布指数为2.4，支化度为22个支链/1000个碳，支链中95mol％为甲基支链，1mol％为乙基支链，1mol％为丙基支链，1mol％为丁基支链，1mol％为戊基支链，1mol％为碳数≥6的支链，玻璃化转变温度为–66.8℃，熔点为120℃，结晶度为28％，结晶温度为105℃；(9)在110℃下淋洗出来的组份含量为7wt％，该组份的重均分子量为20.5×104g/mol，分子量分布指数为2.5，支化度为18个支链/1000个碳，支链中70mol％为甲基支链，30mol％为碳数≥6的支链，玻璃化转变温度为–65℃，熔点为123℃，结晶度为39％，结晶温度为109℃；(10)在120℃下淋洗出来的组份含量为2.5wt％，该组份的重均分子量为22×104g/mol，分子量分布指数为2.5，支化度为12个支链/1000个碳，支链中99.5mol％为甲基支链，0.1mol％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，0.1mol％为戊基支链，0.1mol％为碳数≥6的支链，玻璃化转变温度为–68.9℃，熔点为120℃，结晶度为37％，结晶温度为107℃；(11)淋洗温度高于120℃的组份含量为0wt％。
实施例4
二乙基锌的用量改为0.1mmol[控制二乙基锌中的锌与双核苊(α-二亚胺)镍催化剂中的镍之间的摩尔比为10]，其它条件同实施例1，得到聚合物24.5克。催化剂活性为4900kgPE[mol(Ni)h]-1，聚合产物重均分子量为11.1×104g/mol,多分散系数为3.1，玻璃化转变温度为–69℃，熔点为120.8℃，结晶度为7.1％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为18.0MPa，断裂伸长率为1240％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.30倍。
经1H-NMR测定，聚合产物的支化度为87.3个支链/1000个碳原子，支链中50mol％为甲基支链、6.6mol％为乙基支链、4.6mol％为丙基支链、4mol％为丁基支链、17.7mol％为戊基支链、17.1mol％为碳数 ≥6的支链。硬段的支化度为49个支链/1000个碳原子，软段的支化度为167个支链/1000个碳原子。硬段的支链中80mol％为甲基支链，3.1mol％为乙基支链，1.2mol％为丙基支链，1.1mol％为丁基支链，7.2mol％为戊基支链，7.4mol％为碳数≥6的支链。软段的支链中50mol％为甲基支链，4.3mol％为乙基支链，13.8mol％为丙基支链，5.6mol％为丁基支链，11.9mol％为戊基支链，14.4mol％为碳数≥6的支链。硬段的熔点为122℃，结晶度为10.2％，玻璃化转变温度为–71℃；软段的玻璃化转变温度为–67℃，无明显熔点，结晶度为0％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出10种组份：其中(1)在30℃下淋洗出来的组份含量为27.5wt％(重量百分含量)，该组份的重均分子量为9.2×104g/mol，分子量分布指数为2.4，支化度为184个支链/1000个碳，支链中56mol％为甲基支链，3.7mol％为乙基支链，11.5mol％为丙基支链，5.4mol％为丁基支链，12.4mol％为戊基支链，11mol％为碳数≥6的支链，玻璃化转变温度为–63.7℃，有两个熔点，熔点一为55.4℃，熔点二为113.2℃，结晶度为1.34％，结晶温度为75.2℃；(2)在40℃下淋洗出来的组份含量为8.8wt％，该组份的重均分子量为10.2×104g/mol，分子量分布指数为2.4，支化度为158个支链/1000个碳，支链中58mol％为甲基支链，3.1mol％为乙基支链，13.7mol％为丙基支链，1.6mol％为丁基支链，10.4mol％为戊基支链，13.2mol％为碳数≥6的支链，玻璃化转变温度为–62.9℃，有两个熔点，熔点一为75℃，熔点二为113.6℃，结晶度为2.61％，有两个结晶温度，结晶温度一为54.3℃，结晶温度二为86.1℃；(3)在50℃下淋洗出来的组份含量为4.6wt％，该组份的重均分子量为13.1×104g/mol，分子量分布指数为3.0，支化度为114个支链/1000个碳，支链中63.5mol％为甲基支链，4.5mol％为乙基支链，9.5mol％为丙基支链，0.2mol％为丁基支链，9.8mol％为戊基支链，12.5mol％为碳数≥6的支链，玻璃化转变温度为–65.5℃，有两个熔点，熔点一为84.1℃，熔点二为114℃，结晶度为4.2％，有两个结晶温度，结晶温度一为65.2℃，结晶温度二为86℃；(4)在60℃下淋洗出来的组份含量为4.2wt％，该组份的重均分子量为14.8×104g/mol，分子量分布指数为3.6，支化度为64个支链/1000个碳，支链中80mol％为甲基支链，0.1％为乙基支链，0.2mol％为丙基支链，0.1mol％为丁基支链，11.7mol％为戊基支链，7.9mol％为碳数≥6的支链，玻璃化转变温度为–70.9℃，熔点为94℃，结晶度为13.2％，结晶温度为79.2℃；(5)在70℃下淋洗出来的组份含量为6.3wt％，该组份的重均分子量为17.2×104g/mol，分子量分布指数为3.6，支化度为45个支链/1000个碳，支链中83mol％为甲基支链，0.2mol％为乙基支链，0.2mol％为丙基支链，0.2mol％为丁基支链，13.8mol％为戊基支链，2.6mol％为碳数≥6的支链，玻璃化转变温度为–71℃，熔点为101.2℃，结晶度为19％，结晶温度为86℃；(6)在80℃下淋洗出来的组份含量为7.5wt％，该组份的重均分子量为23×104g/mol，分子量分布指数为2.7，支化度为32个支链/1000个碳，支链中75mol％为甲基支链，14.8mol％为乙基支链，0.1mol％为丙基支链，0.2mol％为丁基支链，0.2mol％为戊基支链，9.7mol％为碳数≥6的支链，玻璃化转变温度为–72℃，熔点为109.1℃，结晶度为27.1％，结晶温度为95℃；(7)在90℃下淋洗出来的组份含量为16.3wt％，该组份的重均分子量为24.2×104g/mol，分子量分布指数为2.6，支化度为22个支链/1000个碳，支链中95mol％为甲基支链，0.1mol％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，0.1mol％为戊基支链，4.6mol％为碳数≥6的支链，玻璃化转变温度为–64.2℃，熔点为115.3℃，结晶度为29％，结晶温度为100℃；(8)在100℃下淋洗出来的组份含量为11wt％，该组份的重均分子量为25×104g/mol，分子量分布指数为2.4，支化度为18个支链/1000个碳，支链中98mol％为甲基支链，0.2mol％为乙基支链，0.2mol％为丙基支链，0.2mol％为丁基支链，0.2mol％为戊基支链，1.2mol％为碳数≥6的支链，玻璃化转变温度为–67℃，熔点为120℃，结晶度为28.4％，结晶温度为105.2℃；(9)在110℃下淋洗出来的组份含量为10.2wt％，该组份的重均分子量为20.8×104g/mol，分子量分布指数为2.5，支化度为15.8个支链/1000个碳，支链中74.1mol％为甲基支链，25.9mol％为碳数≥6的支链，玻璃化转变温度为–64.8℃，熔点为123.3℃，结晶度为34.01％，结晶温度为109.1℃；(10)在120℃下淋洗出来的组份含量为3.6wt％，该组份的重均分子量为22.2×104g/mol，分子量分布指数为2.5，支化度为13个支链/1000个碳，支链中98.6mol％为甲基支链，0.1mol％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，0.1mol％为戊基支链，1mol％为碳数≥6的支链，玻璃化转变温度为–69℃，熔点为122.0℃，结晶度为37％，结晶温度为107.2℃；(11)淋洗温度高于120℃的组份含量为0wt％。
实施例5
二乙基锌的用量改为0.3mmol[控制二乙基锌中的锌与双核苊(α-二亚胺)镍催化剂中的镍之间的摩尔比为30]，其它条件同实施例1，得到聚合物21.5克。催化剂活性为4300kgPE[mol(Ni)h]-1，聚合产物重均分子量为17.2×104g/mol,多分散系数为3.1，玻璃化转变温度为–68℃，熔点为120.9℃，结晶度为11.6％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为17.1MPa，断裂伸长率为1060％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.30倍。
经1H-NMR测定，聚合产物的支化度为76.3个支链/1000个碳原子，支链中54.8mol％为甲基支链、6mol％为乙基支链、4.2mol％为丙基支链、3.7mol％为丁基支链、17.1mol％为戊基支链、14.2mol％为碳数 ≥6的支链。硬段的支化度为35个支链/1000个碳原子，软段的支化度为132个支链/1000个碳原子。硬段的支链中85mol％为甲基支链，2mol％为乙基支链，0.5mol％为丙基支链，0.5mol％为丁基支链，6.8mol％为戊基支链，5.2mol％为碳数≥6的支链。软段的支链中53mol％为甲基支链，4mol％为乙基支链，13.2mol％为丙基支链，5.1mol％为丁基支链，11.2mol％为戊基支链，13.5mol％为碳数≥6的支链。硬段的熔点为122℃，结晶度为13.3％，玻璃化转变温度为–70℃；软段的玻璃化转变温度为–66℃，无明显熔点，结晶度为1％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出11种组份：其中(1)在30℃下淋洗出来的组份含量为26.5wt％(重量百分含量)，该组份的重均分子量为13.8×104g/mol，分子量分布指数为2.4，支化度为167个支链/1000个碳，支链中61.8mol％为甲基支链，3.2mol％为乙基支链，11.1mol％为丙基支链，5.1mol％为丁基支链，11.7mol％为戊基支链，7.1mol％为碳数≥6的支链，玻璃化转变温度为–63.2℃，有两个熔点，熔点一为55.9℃，熔点二为113.9℃，结晶度为1.49％，结晶温度为75.9℃；(2)在40℃下淋洗出来的组份含量为8.2wt％，该组份的重均分子量为16.7×104g/mol，分子量分布指数为2.4，支化度为146个支链/1000个碳，支链中59.2mol％为甲基支链，3.0mol％为乙基支链，13.3mol％为丙基支链，1.4mol％为丁基支链，10.2mol％为戊基支链，12.9mol％为碳数≥6的支链，玻璃化转变温度为–62.3℃，有两个熔点，熔点一为75.5℃，熔点二为114.2℃，结晶度为2.69％，有两个结晶温度，结晶温度一为54.9℃，结晶温度二为86.9℃；(3)在50℃下淋洗出来的组份含量为4wt％，该组份的重均分子量为17.8×104g/mol，分子量分布指数为3.0，支化度为106个支链/1000个碳，支链中64.9mol％为甲基支链，4.1mol％为乙基支链，9.2mol％为丙基支链，0.1mol％为丁基支链，9.4mol％为戊基支链，12.3mol％为碳数≥6的支链，玻璃化转变温度为–65.1℃，有两个熔点，熔点一为84.9℃，熔点二为115.6℃，结晶度为4.5％，有两个结晶温度，结晶温度一为65.9℃，结晶温度二为87.8℃；(4)在60℃下淋洗出来的组份含量为3.8wt％，该组份的重均分子量为19.6×104g/mol，分子量分布指数为3.6，支化度为54个支链/1000个碳，支链中83mol％为甲基支链，0％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，11.2mol％为戊基支链，5.8mol％为碳数≥6的支链，玻璃化转变温度为–70.2℃，熔点为94.6℃，结晶度为13.7％，结晶温度为79.9℃；(5)在70℃下淋洗出来的组份含量为6wt％，该组份的重均分子量为21.4×104g/mol，分子量分布指数为3.5，支化度为36.4个支链/1000个碳，支链中85mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，13.3mol％为戊基支链，1.7mol％为碳数≥6的支链，玻璃化转变温度为–70℃，熔点为102℃，结晶度为19.6％，结晶温度为87℃；(6)在80℃下淋洗出来的组份含量为6.7wt％，该组份的重均分子量为25.7×104g/mol，分子量分布指数为2.8，支化度为26.5个支链/1000个碳，支链中76.8mol％为甲基支链，14.5mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，8.7mol％为碳数≥6的支链，玻璃化转变温度为–71℃，熔点为110℃，结晶度为29％，结晶温度为95.9℃；(7)在90℃下淋洗出来的组份含量为16.4wt％，该组份的重均分子量为27.8×104g/mol，分子量分布指数为2.7，支化度为19个支链/1000个碳，支链中96.7mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，3.3mol％为碳数≥6的支链，玻璃化转变温度为–63℃，熔点为116℃，结晶度为29.6％，结晶温度为101℃；(8)在100℃下淋洗出来的组份含量为12.4wt％，该组份的重均分子量为28.1×104g/mol，分子量分布指数为2.5，支化度为16.6个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–66.5℃，熔点为120.8℃，结晶度为28.9％，结晶温度为105.9℃；(9)在110℃下淋洗出来的组份含量为10.5wt％，该组份的重均分子量为29.3×104g/mol，分子量分布指数为2.5，支化度为15.4个支链/1000个碳，支链中74.8mol％为甲基支链，25.2mol％为碳数≥6的支链，玻璃化转变温度为–64.5℃，熔点为123.6℃，结晶度为34.5％，结晶温度为109.6℃；(10)在120℃下淋洗出来的组份含量为3.8wt％，该组份的重均分子量为29.9×104g/mol，分子量分布指数为2.5，支化度为9.8个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–68.6℃，熔点为122.5℃，结晶度为37.3％，结晶温度为107.9℃；(11)淋洗温度高于120℃的组份含量为1.7wt％，该组份的重均分子量为29.3×104g/mol，分子量分布指数为2.5，支化度为4个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–63.1℃，熔点为122.6℃，结晶度为35.7％，结晶温度为108.6℃。
实施例6
二乙基锌的用量改为0.5mmol[控制二乙基锌中的锌与双核苊(α-二亚胺)镍催化剂中的镍之间的摩尔比为50]，其它条件同实施例1，得到聚合物18.0克。催化剂活性为3600kgPE[mol(Ni)h]-1，聚合产物重均分子量为17.6×104g/mol,多分散系数为3.6，玻璃化转变温度为–68℃，熔点为120.7℃，结晶度为17.7％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为19.4MPa，断裂伸长率为1180％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.33倍。
经1H-NMR测定，聚合产物的支化度为63.2个支链/1000个碳原子，支链中55.3mol％为甲基支链、5.8mol％为乙基支链、4.1mol％为丙基支链、3.6mol％为丁基支链、17mol％为戊基支链、14.2mol％为碳数≥6的支链。硬段的支化度为32个支链/1000个碳原子，软段的支化度为113个支链/1000个碳原子。硬段的支链中87mol％为甲基支链，2mol％为乙基支链，0.5mol％为丙基支链，0.5mol％为丁基支链，6.1mol％为戊基支链，3.9mol％为碳数≥6的支链。软段的支链中54mol％为甲基支链，3.8mol％为乙基支链，13.1mol％为丙基支链，5mol％为丁基支链，11mol％为戊基支链，13.1mol％为碳数≥6的支链。硬段的熔点为122.1℃，结晶度为23.6％，玻璃化转变温度为–70℃；软段的玻璃化转变温度为–66℃，无明显熔点，结晶度为1.4％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出11种组份：其中(1)在30℃下淋洗出来的组份含量为26.2wt％(重量百分含量)，该组份的重均分子量为13.9×104g/mol，分子量分布指数为2.5，支化度为155个支链/1000个碳，支链中62.4mol％为甲基支链，3.1mol％为乙基支链，11mol％为丙基支链，5mol％为丁基支链，11.5mol％为戊基支链，7mol％为碳数≥6的支链，玻璃化转变温度为–63.1℃，有两个熔点，熔点一为56℃，熔点二为114℃，结晶度为1.5％，结晶温度为76℃；(2)在40℃下淋洗出来的组份含量为8wt％，该组份的重均分子量为16.9×104g/mol，分子量分布指数为2.6，支化度为138个支链/1000个碳，支链中59.8mol％为甲基支链，2.8mol％为乙基支链，13.3mol％为丙基支链，1.2mol％为丁基支链，10.1mol％为戊基支链，12.8mol％为碳数≥6的支链，玻璃化转变温度为–62.2℃，有两个熔点，熔点一为75.8℃，熔点二为114.6℃，结晶度为2.7％，有两个结晶温度，结晶温度一为55℃，结晶温度二为87℃；(3)在50℃下淋洗出来的组份含量为3.7wt％，该组份的重均分子量为17.9×104g/mol，分子量分布指数为3.1，支化度为103个支链/1000个碳，支链中65mol％为甲基支链，4mol％为乙基支链，9.2mol％为丙基支链，0.1mol％为丁基支链，9.4mol％为戊基支链，12.3mol％为碳数≥6的支链，玻璃化转变温度为–65℃，有两个熔点，熔点一为85℃，熔点二为115.9℃，结晶度为4.7％，有两个结晶温度，结晶温度一为66℃，结晶温度二为88℃；(4)在60℃下淋洗出来的组份含量为3.6wt％，该组份的重均分子量为19.9×104g/mol，分子量分布指数为3.5，支化度为52个支链/1000个碳，支链中84mol％为甲基支链，0％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，11mol％为戊基支链，5mol％为碳数≥6的支链，玻璃化转变温度为–70.1℃，熔点为94.8℃，结晶度为13.9％，结晶温度为80℃；(5)在70℃下淋洗出来的组份含量为5.8wt％，该组份的重均分子量为21.8×104g/mol，分子量分布指数为3.6，支化度为35个支链/1000个碳，支链中86mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，13mol％为戊基支链，1mol％为碳数≥6的支链，玻璃化转变温度为–69℃，熔点为104℃，结晶度为19.9％，结晶温度为88℃；(6)在80℃下淋洗出来的组份含量为6.5wt％，该组份的重均分子量为25.9×104g/mol，分子量分布指数为2.8，支化度为25个支链/1000个碳，支链中77mol％为甲基支链，14mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，9mol％为碳数≥6的支链，玻璃化转变温度为–70℃，熔点为112℃，结晶度为30％，结晶温度为96℃；(7)在90℃下淋洗出来的组份含量为16.8wt％，该组份的重均分子量为28×104g/mol，分子量分布指数为2.7，支化度为17个支链/1000个碳，支链中97mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，3mol％为碳数≥6的支链，玻璃化转变温度为–63℃，熔点为117℃，结晶度为29.7％，结晶温度为102℃；(8)在100℃下淋洗出来的组份含量为12.6wt％，该组份的重均分子量为28.8×104g/mol，分子量分布指数为2.5，支化度为15个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–66℃，熔点为121℃，结晶度为29％，结晶温度为106℃；(9)在110℃下淋洗出来的组份含量为10.9wt％，该组份的重均分子量为29.8×104g/mol，分子量分布指数为2.5，支化度为14个支链/1000个碳，支链中75mol％为甲基支链，25mol％为碳数≥6的支链，玻璃化转变温度为–64℃，熔点为124℃，结晶度为35％，结晶温度为109.9℃；(10)在120℃下淋洗出来的组份含量为4.5wt％，该组份的重均分子量为31.2×104g/mol，分子量分布指数为2.5，支化度为8个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–68℃，熔点为123℃，结晶度为37.8％，结晶温度为108℃；(11)淋洗温度高于120℃的组份含量为1.4wt％，该组份的重均分子量为29.9×104g/mol，分子量分布指数为2.5，支化度为3个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–63℃，熔点为122.9℃，结晶度为35.9％，结晶温度为108.8℃。
实施例7
二乙基锌的用量改为1.0mmol[控制二乙基锌中的锌与双核苊(α-二亚胺)镍催化剂中的镍之间的摩尔比为100]，其它条件同实施例1，得到聚合物15.5克。催化剂活性为3100kgPE[mol(Ni)h]-1，聚合产物重均分子量为18.5×104g/mol,多分散系数为3.3，玻璃化转变温度为–67℃，熔点为121.8℃，结晶度为27.3％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为33.7MPa，断裂伸长率为1130％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.30倍。
经1H-NMR测定，聚合产物的支化度为59.6个支链/1000个碳原子，支链中56mol％为甲基支链、5.5mol％为乙基支链、4mol％为丙基支链、3.4mol％为丁基支链、16.7mol％为戊基支链、14.4mol％为碳数≥6的支链。硬段的支化度为30个支链/1000个碳原子，软段的支化度为110个支链/1000个碳原子。硬段的支链中89mol％为甲基支链，1mol％为乙基支链，0.5mol％为丙基支链，0.5mol％为丁基支链，6mol％为戊基支链，3mol％为碳数≥6的支链。软段的支链中56mol％为甲基支链，3.5mol％为乙基支链，13mol％为丙基支链，4.5mol％为丁基支链，11mol％为戊基支链，12mol％为碳数≥6的支链。硬段的熔点为122.6℃，结晶度为24％，玻璃化转变温度为–69℃；软段的玻璃化转变温度为–65℃，无明显熔点，结晶度为1.8％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出11种组份：其中(1)在30℃下淋洗出来的组份含量为26wt％(重量百分含量)，该组份的重均分子量为14.6×104g/mol，分子量分布指数为2.5，支化度为137个支链/1000个碳，支链中62.8mol％为甲基支链，3mol％为乙基支链，10.8mol％为丙基支链，4.8mol％为丁基支链，11.3mol％为戊基支链，7.3mol％为碳数≥6的支链，玻璃化转变温度为–63℃，有两个熔点，熔点一为57℃，熔点二为115℃，结晶度为1.8％，结晶温度为79℃；(2)在40℃下淋洗出来的组份含量为7.8wt％，该组份的重均分子量为17.9×104g/mol，分子量分布指数为2.6，支化度为125个支链/1000个碳，支链中60mol％为甲基支链，2.6mol％为乙基支链，13.2mol％为丙基支链，1.1mol％为丁基支链，10mol％为戊基支链，13.1mol％为碳数≥6的支链，玻璃化转变温度为–62℃，有两个熔点，熔点一为76℃，熔点二为116℃，结晶度为2.9％，有两个结晶温度，结晶温度一为57℃，结晶温度二为89℃；(3)在50℃下淋洗出来的组份含量为3.4wt％，该组份的重均分子量为18.5×104g/mol，分子量分布指数为3.0，支化度为97个支链/1000个碳，支链中67mol％为甲基支链，3mol％为乙基支链，9mol％为丙基支链，0.1mol％为丁基支链，9.2mol％为戊基支链，11.7mol％为碳数≥6的支链，玻璃化转变温度为–64℃，有两个熔点，熔点一为87℃，熔点二为117℃，结晶度为5％，有两个结晶温度，结晶温度一为68℃，结晶温度二为90℃；(4)在60℃下淋洗出来的组份含量为3.4wt％，该组份的重均分子量为21.8×104g/mol，分子量分布指数为3.6，支化度为46个支链/1000个碳，支链中85mol％为甲基支链，0％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，10mol％为戊基支链，5mol％为碳数≥6的支链，玻璃化转变温度为–70℃，熔点为95℃，结晶度为14.5％，结晶温度为83℃；(5)在70℃下淋洗出来的组份含量为5.5wt％，该组份的重均分子量为22.4×104g/mol，分子量分布指数为3.5，支化度为26个支链/1000个碳，支链中87mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，12mol％为戊基支链，1mol％为碳数≥6的支链，玻璃化转变温度为–68℃，熔点为106℃，结晶度为20.3％，结晶温度为90℃；(6)在80℃下淋洗出来的组份含量为6.3wt％，该组份的重均分子量为26.4×104g/mol，分子量分布指数为2.9，支化度为17个支链/1000个碳，支链中79mol％为甲基支链，12mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，9mol％为碳数≥6的支链，玻璃化转变温度为–69℃，熔点为115℃，结晶度为33％，结晶温度为98℃；(7)在90℃下淋洗出来的组份含量为17wt％，该组份的重均分子量为28.9×104g/mol，分子量分布指数为2.8，支化度为13个支链/1000个碳，支链中98mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，2mol％为碳数≥6的支链，玻璃化转变温度为–62℃，熔点为119℃，结晶度为30％，结晶温度为105℃；(8)在100℃下淋洗出来的组份含量为13wt％，该组份的重均分子量为29.6×104g/mol，分子量分布指数为2.4，支化度为10个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–65℃，熔点为123℃，结晶度为32％，结晶温度为109℃；(9)在110℃下淋洗出来的组份含量为11.6wt％，该组份的重均分子量为30.3×104g/mol，分子量分布指数为2.4，支化度为12个支链/1000个碳，支链中78mol％为甲基支链，22mol％为碳数≥6的支链，玻璃化转变温度为–63℃，熔点为126℃，结晶度为38％，结晶温度为112℃；(10)在120℃下淋洗出来的组份含量为5wt％，该组份的重均分子量为31.9×104g/mol，分子量分布指数为2.6，支化度为6个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–67℃，熔点为125℃，结晶度为40％，结晶温度为110℃；(11)淋洗温度高于120℃的组份含量为1wt％，该组份的重均分子量为30.6×104g/mol，分子量分布指数为2.5，支化度为1个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–63℃，熔点为126℃，结晶度为36％，结晶温度为109℃。
实施例8
将聚合温度提高到35℃，其它条件同实施例1，得到聚合物18克。催化剂活性为3600kgPE[mol(Ni)h]-1，聚合产物重均分子量为11.6×104g/mol,多分散系数为2.8，玻璃化转变温度为–68℃，熔点为120.2℃，结晶度为9.2％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为17MPa，断裂伸长率为1280％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.30倍。
经1H-NMR测定，聚合产物的支化度为92.5个支链/1000个碳原子，支链中50.6mol％为甲基支链、6.7mol％为乙基支链、4.6mol％为丙基支链、3.8mol％为丁基支链、17.5mol％为戊基支链、16.8mol％为碳数≥6的支链。硬段的支化度为54个支链/1000个碳原子，软段的支化度为168个支链/1000个碳原子。硬 段的支链中80mol％为甲基支链，3.1mol％为乙基支链，1.2mol％为丙基支链，1.1mol％为丁基支链，7.2mol％为戊基支链，7.4mol％为碳数≥6的支链。软段的支链中50mol％为甲基支链，4.5mol％为乙基支链，13.8mol％为丙基支链，5.5mol％为丁基支链，12.2mol％为戊基支链，14mol％为碳数≥6的支链。硬段的熔点为117℃，结晶度为9.7％，玻璃化转变温度为–73℃；软段的玻璃化转变温度为–69℃，无明显熔点，结晶度为0％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出11种组份：其中(1)在30℃下淋洗出来的组份含量为27.3wt％(重量百分含量)，该组份的重均分子量为9.2×104g/mol，分子量分布指数为2.5，支化度为184个支链/1000个碳，支链中57.2mol％为甲基支链，3.6mol％为乙基支链，11.3mol％为丙基支链，5.5mol％为丁基支链，12mol％为戊基支链，10.4mol％为碳数≥6的支链，玻璃化转变温度为–63.8℃，有两个熔点，熔点一为55.4℃，熔点二为113.2℃，结晶度为1.32％，结晶温度为75.3℃；(2)在40℃下淋洗出来的组份含量为8.7wt％，该组份的重均分子量为10.1×104g/mol，分子量分布指数为2.6，支化度为165个支链/1000个碳，支链中56.6mol％为甲基支链，3.1mol％为乙基支链，13.8mol％为丙基支链，1.8mol％为丁基支链，10.6mol％为戊基支链，14.1mol％为碳数≥6的支链，玻璃化转变温度为–62.9℃，有两个熔点，熔点一为75℃，熔点二为113.1℃，结晶度为2.58％，有两个结晶温度，结晶温度一为54.2℃，结晶温度二为86.1℃；(3)在50℃下淋洗出来的组份含量为4.5wt％，该组份的重均分子量为13.2×104g/mol，分子量分布指数为2.9，支化度为112.8个支链/1000个碳，支链中62.1mol％为甲基支链，4.3mol％为乙基支链，9.5mol％为丙基支链，0.1mol％为丁基支链，9.7mol％为戊基支链，14.3mol％为碳数≥6的支链，玻璃化转变温度为–65.7℃，有两个熔点，熔点一为84.2℃，熔点二为115℃，结晶度为4.2％，有两个结晶温度，结晶温度一为65.2℃，结晶温度二为87℃；(4)在60℃下淋洗出来的组份含量为4.1wt％，该组份的重均分子量为15.1×104g/mol，分子量分布指数为3.4，支化度为63个支链/1000个碳，支链中80mol％为甲基支链，0.2％为乙基支链，0.1mol％为丙基支链，0.2mol％为丁基支链，11.3mol％为戊基支链，8.2mol％为碳数≥6的支链，玻璃化转变温度为–70.9℃，熔点为94℃，结晶度为13.3％，结晶温度为79.3℃；(5)在70℃下淋洗出来的组份含量为6.3wt％，该组份的重均分子量为17.2×104g/mol，分子量分布指数为3.6，支化度为45个支链/1000个碳，支链中82.5mol％为甲基支链，0.1mol％为乙基支链，0.1mol％为丙基支链，0.2mol％为丁基支链，13.9mol％为戊基支链，3.2mol％为碳数≥6的支链，玻璃化转变温度为–72℃，熔点为101.5℃，结晶度为19％，结晶温度为86.2℃；(6)在80℃下淋洗出来的组份含量为7.1wt％，该组份的重均分子量为23×104g/mol，分子量分布指数为2.8，支化度为32个支链/1000个碳，支链中75.6mol％为甲基支链，14.7mol％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，0.2mol％为戊基支链，9.3mol％为碳数≥6的支链，玻璃化转变温度为–72℃，熔点为109.1℃，结晶度为27％，结晶温度为95℃；(7)在90℃下淋洗出来的组份含量为15.2wt％，该组份的重均分子量为24.2×104g/mol，分子量分布指数为2.6，支化度为23个支链/1000个碳，支链中95.1mol％为甲基支链，0.1mol％为乙基支链，0.2mol％为丙基支链，0.1mol％为丁基支链，0.2mol％为戊基支链，4.3mol％为碳数≥6的支链，玻璃化转变温度为–65℃，熔点为115.3℃，结晶度为29％，结晶温度为100.1℃；(8)在100℃下淋洗出来的组份含量为12.3wt％，该组份的重均分子量为25×104g/mol，分子量分布指数为2.4，支化度为18个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–67℃，熔点为120.1℃，结晶度为28.2％，结晶温度为105.3℃；(9)在110℃下淋洗出来的组份含量为10.5wt％，该组份的重均分子量为20.3×104g/mol，分子量分布指数为2.6，支化度为17个支链/1000个碳，支链中73.5mol％为甲基支链，26.5mol％为碳数≥6的支链，玻璃化转变温度为–64.9℃，熔点为123.1℃，结晶度为34％，结晶温度为109℃；(10)在120℃下淋洗出来的组份含量为3.7wt％，该组份的重均分子量为22.2×104g/mol，分子量分布指数为2.5，支化度为13个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–68.9℃，熔点为122.0℃，结晶度为37％，结晶温度为107.7℃；(11)淋洗温度高于120℃的组份含量为0.3wt％，该组份的重均分子量为16.5×104g/mol，分子量分布指数为2.6，支化度为8个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–63.8℃，熔点为122℃，结晶度为35％，结晶温度为108℃。
实施例9
将助催化剂改为倍半乙基铝，其它条件同实施例1，得到聚合物21.5克。催化剂活性为4300kgPE[mol(Ni)h]-1，聚合产物重均分子量为13.5×104g/mol,多分散系数为2.8，玻璃化转变温度为–67℃，熔点为120.8℃，结晶度为11.3％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为17.9MPa，断裂伸长率为1190％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.30倍。
经1H-NMR测定，聚合产物的支化度为80.5个支链/1000个碳原子，支链中52.2mol％为甲基支链、6.4mol％为乙基支链、4.4mol％为丙基支链、3.7mol％为丁基支链、17.5mol％为戊基支链、15.4mol％为碳数≥6的支链。硬段的支化度为41个支链/1000个碳原子，软段的支化度为138个支链/1000个碳原子。硬段的支链中81mol％为甲基支链，3mol％为乙基支链，2mol％为丙基支链，1mol％为丁基支链，7mol％为 戊基支链，6mol％为碳数≥6的支链。软段的支链中52.8mol％为甲基支链，4.1mol％为乙基支链，13.2mol％为丙基支链，5.1mol％为丁基支链，11.8mol％为戊基支链，13mol％为碳数≥6的支链。硬段的熔点为118.5℃，结晶度为10.8％，玻璃化转变温度为–72℃；软段的玻璃化转变温度为–67℃，无明显熔点，结晶度为0％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出11种组份：其中(1)在30℃下淋洗出来的组份含量为27.3wt％(重量百分含量)，该组份的重均分子量为9.8×104g/mol，分子量分布指数为2.4，支化度为176.4个支链/1000个碳，支链中58.3mol％为甲基支链，3.6mol％为乙基支链，11.4mol％为丙基支链，5.5mol％为丁基支链，11.9mol％为戊基支链，9.3mol％为碳数≥6的支链，玻璃化转变温度为–63.5℃，有两个熔点，熔点一为55.8℃，熔点二为113.7℃，结晶度为1.44％，结晶温度为75.9℃；(2)在40℃下淋洗出来的组份含量为8.3wt％，该组份的重均分子量为10.9×104g/mol，分子量分布指数为2.5，支化度为149.7个支链/1000个碳，支链中58.2mol％为甲基支链，3.1mol％为乙基支链，13.5mol％为丙基支链，1.7mol％为丁基支链，10.5mol％为戊基支链，13mol％为碳数≥6的支链，玻璃化转变温度为–62.8℃，有两个熔点，熔点一为75.5℃，熔点二为113.7℃，结晶度为2.61％，有两个结晶温度，结晶温度一为54.7℃，结晶温度二为86.5℃；(3)在50℃下淋洗出来的组份含量为4.5wt％，该组份的重均分子量为13.7×104g/mol，分子量分布指数为3.0，支化度为108.2个支链/1000个碳，支链中64.5mol％为甲基支链，4.1mol％为乙基支链，9.3mol％为丙基支链，0mol％为丁基支链，9.5mol％为戊基支链，12.6mol％为碳数≥6的支链，玻璃化转变温度为–65.2℃，有两个熔点，熔点一为84.8℃，熔点二为115.3℃，结晶度为4.5％，有两个结晶温度，结晶温度一为65.9℃，结晶温度二为87.4℃；(4)在60℃下淋洗出来的组份含量为3.9wt％，该组份的重均分子量为15.8×104g/mol，分子量分布指数为3.5，支化度为56.6个支链/1000个碳，支链中81mol％为甲基支链，0.2％为乙基支链，0.2mol％为丙基支链，0.2mol％为丁基支链，11.7mol％为戊基支链，6.8mol％为碳数≥6的支链，玻璃化转变温度为–70.7℃，熔点为94.5℃，结晶度为13.48％，结晶温度为79.9℃；(5)在70℃下淋洗出来的组份含量为6.5wt％，该组份的重均分子量为17.9×104g/mol，分子量分布指数为3.7，支化度为37.9个支链/1000个碳，支链中84.2mol％为甲基支链，0.1mol％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，13.7mol％为戊基支链，1.8mol％为碳数≥6的支链，玻璃化转变温度为–71.5℃，熔点为101.7℃，结晶度为19.3％，结晶温度为86.9℃；(6)在80℃下淋洗出来的组份含量为6.7wt％，该组份的重均分子量为23.8×104g/mol，分子量分布指数为2.8，支化度为27.9个支链/1000个碳，支链中76mol％为甲基支链，14.6mol％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，0.1mol％为戊基支链，9.1mol％为碳数≥6的支链，玻璃化转变温度为–71℃，熔点为109.8℃，结晶度为27.2％，结晶温度为95.6℃；(7)在90℃下淋洗出来的组份含量为16.5wt％，该组份的重均分子量为24.9×104g/mol，分子量分布指数为2.5，支化度为23个支链/1000个碳，支链中95.7mol％为甲基支链，0.1mol％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，0.1mol％为戊基支链，3.9mol％为碳数≥6的支链，玻璃化转变温度为–64.2℃，熔点为115.6℃，结晶度为29.2％，结晶温度为100.3℃；(8)在100℃下淋洗出来的组份含量为11.8wt％，该组份的重均分子量为25.8×104g/mol，分子量分布指数为2.5，支化度为18个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–66.8℃，熔点为120.3℃，结晶度为28.7％，结晶温度为105.8℃；(9)在110℃下淋洗出来的组份含量为10.5wt％，该组份的重均分子量为21×104g/mol，分子量分布指数为2.5，支化度为16个支链/1000个碳，支链中74mol％为甲基支链，26mol％为碳数≥6的支链，玻璃化转变温度为–64.5℃，熔点为123.6℃，结晶度为34％，结晶温度为109.3℃；(10)在120℃下淋洗出来的组份含量为3.1wt％，该组份的重均分子量为22.8×104g/mol，分子量分布指数为2.5，支化度为11个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–68.9℃，熔点为122.0℃，结晶度为37.09％，结晶温度为107.7℃；(11)淋洗温度高于120℃的组份含量为0.9wt％，该组份的重均分子量为16.9×104g/mol，分子量分布指数为2.6，支化度为6个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–63.3℃，熔点为122.2℃，结晶度为35.46％，结晶温度为108.3℃。
实施例10
将助催化剂改为一氯二乙基铝，其它条件同实施例1，得到聚合物20.5克。催化剂活性为4100kgPE[mol(Ni)h]-1，聚合产物重均分子量为15.6×104g/mol,多分散系数为2.9，玻璃化转变温度为–67℃，熔点为121℃，结晶度为12.6％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为19MPa，断裂伸长率为1250％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.31倍。
经1H-NMR测定，聚合产物的支化度为79个支链/1000个碳原子，支链中51.7mol％为甲基支链、6.5mol％为乙基支链、4.5mol％为丙基支链、3.8mol％为丁基支链、17.6mol％为戊基支链、15.5mol％为碳数≥6的支链。硬段的支化度为37个支链/1000个碳原子，软段的支化度为133个支链/1000个碳原子。硬段的支链中84mol％为甲基支链，2mol％为乙基支链，1mol％为丙基支链，1mol％为丁基支链，6mol％为 戊基支链，6mol％为碳数≥6的支链。软段的支链中53.3mol％为甲基支链，4mol％为乙基支链，13.1mol％为丙基支链，5mol％为丁基支链，11.7mol％为戊基支链，12.9mol％为碳数≥6的支链。硬段的熔点为118.8℃，结晶度为12.2％，玻璃化转变温度为–72℃；软段的玻璃化转变温度为–67℃，无明显熔点，结晶度为0％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出11种组份：其中(1)在30℃下淋洗出来的组份含量为26.8wt％(重量百分含量)，该组份的重均分子量为11.2×104g/mol，分子量分布指数为2.5，支化度为164个支链/1000个碳，支链中58.8mol％为甲基支链，3.5mol％为乙基支链，11.3mol％为丙基支链，5.4mol％为丁基支链，11.8mol％为戊基支链，9.2mol％为碳数≥6的支链，玻璃化转变温度为–63.8℃，有两个熔点，熔点一为55.9℃，熔点二为113.9℃，结晶度为1.52％，结晶温度为76℃；(2)在40℃下淋洗出来的组份含量为8.8wt％，该组份的重均分子量为12.7×104g/mol，分子量分布指数为2.5，支化度为137个支链/1000个碳，支链中58.7mol％为甲基支链，3mol％为乙基支链，13.4mol％为丙基支链，1.6mol％为丁基支链，10.4mol％为戊基支链，12.9mol％为碳数≥6的支链，玻璃化转变温度为–62.5℃，有两个熔点，熔点一为75.7℃，熔点二为113.9℃，结晶度为2.7％，有两个结晶温度，结晶温度一为54.9℃，结晶温度二为86.9℃；(3)在50℃下淋洗出来的组份含量为4.2wt％，该组份的重均分子量为14.3×104g/mol，分子量分布指数为3.0，支化度为102个支链/1000个碳，支链中64.9mol％为甲基支链，4mol％为乙基支链，9.2mol％为丙基支链，0mol％为丁基支链，9.4mol％为戊基支链，12.5mol％为碳数≥6的支链，玻璃化转变温度为–65.5℃，有两个熔点，熔点一为84.9℃，熔点二为115.8℃，结晶度为5％，有两个结晶温度，结晶温度一为66℃，结晶温度二为88℃；(4)在60℃下淋洗出来的组份含量为4.2wt％，该组份的重均分子量为16.8×104g/mol，分子量分布指数为3.5，支化度为53个支链/1000个碳，支链中82mol％为甲基支链，0.1％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，11.2mol％为戊基支链，6.6mol％为碳数≥6的支链，玻璃化转变温度为–71℃，熔点为95℃，结晶度为13.6％，结晶温度为80℃；(5)在70℃下淋洗出来的组份含量为6.8wt％，该组份的重均分子量为18.5×104g/mol，分子量分布指数为3.8，支化度为34个支链/1000个碳，支链中84.9mol％为甲基支链，0.1mol％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，13.2mol％为戊基支链，1.6mol％为碳数≥6的支链，玻璃化转变温度为–71.2℃，熔点为102℃，结晶度为19.8％，结晶温度为87℃；(6)在80℃下淋洗出来的组份含量为6.4wt％，该组份的重均分子量为24.9×104g/mol，分子量分布指数为2.8，支化度为25个支链/1000个碳，支链中78mol％为甲基支链，14.1mol％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，0.1mol％为戊基支链，7.6mol％为碳数≥6的支链，玻璃化转变温度为–71℃，熔点为110℃，结晶度为27.8％，结晶温度为95.9℃；(7)在90℃下淋洗出来的组份含量为16.2wt％，该组份的重均分子量为26.2×104g/mol，分子量分布指数为2.5，支化度为21个支链/1000个碳，支链中96mol％为甲基支链，0.1mol％为乙基支链，0.1mol％为丙基支链，0.1mol％为丁基支链，0.1mol％为戊基支链，3.6mol％为碳数≥6的支链，玻璃化转变温度为–64℃，熔点为116℃，结晶度为29.7％，结晶温度为100.8℃；(8)在100℃下淋洗出来的组份含量为12.1wt％，该组份的重均分子量为27.3×104g/mol，分子量分布指数为2.5，支化度为14个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–66.8℃，熔点为120.3℃，结晶度为28.7％，结晶温度为105.8℃；(9)在110℃下淋洗出来的组份含量为10.8wt％，该组份的重均分子量为23×104g/mol，分子量分布指数为2.6，支化度为13个支链/1000个碳，支链中76mol％为甲基支链，24mol％为碳数≥6的支链，玻璃化转变温度为–64℃，熔点为124℃，结晶度为35％，结晶温度为109.8℃；(10)在120℃下淋洗出来的组份含量为2.9wt％，该组份的重均分子量为23.7×104g/mol，分子量分布指数为2.5，支化度为10个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–68.9℃，熔点为122.0℃，结晶度为37.09％，结晶温度为107.7℃；(11)淋洗温度高于120℃的组份含量为0.8wt％，该组份的重均分子量为19×104g/mol，分子量分布指数为2.6，支化度为4个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–63.3℃，熔点为122.2℃，结晶度为35.46％，结晶温度为108.3℃。
实施例11
将聚合温度降低到25℃，乙烯压力提高到2.0MPa，催化剂改成催化剂1(R为甲基，事先溶解在10毫升甲苯中)，其它条件同实施例1，得到聚合物18.0克。催化剂活性为3600kgPE[mol(Ni)h]-1，聚合产物重均分子量为18.5×104g/mol,多分散系数为4.0，玻璃化转变温度为–61℃，熔点为123.3℃，结晶度为42.9％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为33.7MPa，断裂伸长率为500％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.49倍。
经1H-NMR测定，聚合产物的支化度为31.6个支链/1000个碳原子，支链中58.7mol％为甲基支链、4.9mol％为乙基支链、3.3mol％为丙基支链、1.7mol％为丁基支链、16.5mol％为戊基支链、14.9mol％为碳数≥6的支链。硬段的支化度为1个支链/1000个碳原子，软段的支化度为50个支链/1000个碳原子。硬段的支链中100mol％为甲基支链。软段的支链中55.8mol％为甲基支链，5.2mol％为乙基支链，4.5mol％为丙 基支链，2.5mol％为丁基支链，17.0mol％为戊基支链，8.6mol％为碳数≥6的支链。硬段的熔点为133.5℃，结晶度为47％，玻璃化转变温度为–72℃；软段的玻璃化转变温度为–56℃，无明显熔点，结晶度为4.5％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出11种组份：其中(1)在30℃下淋洗出来的组份含量为3.3wt％(重量百分含量)，该组份的重均分子量为3.0×104g/mol，分子量分布指数为3.8，支化度为110个支链/1000个碳，支链中62mol％为甲基支链，3mol％为乙基支链，10mol％为丙基支链，4.7mol％为丁基支链，10mol％为戊基支链，7mol％为碳数≥6的支链，玻璃化转变温度为–61℃，有两个熔点，熔点一为60℃，熔点二为115℃，结晶度为2.5％，结晶温度为80℃；(2)在40℃下淋洗出来的组份含量为7.7wt％，该组份的重均分子量为10×104g/mol，分子量分布指数为3.8，支化度为120个支链/1000个碳，支链中60mol％为甲基支链，2.5mol％为乙基支链，11mol％为丙基支链，1mol％为丁基支链，9mol％为戊基支链，16.5mol％为碳数≥6的支链，玻璃化转变温度为–61℃，有两个熔点，熔点一为80℃，熔点二为115℃，结晶度为3.5％，有两个结晶温度，结晶温度一为60℃，结晶温度二为95℃；(3)在50℃下淋洗出来的组份含量为6.5wt％，该组份的重均分子量为13.0×104g/mol，分子量分布指数为3.6，支化度为90个支链/1000个碳，支链中66mol％为甲基支链，5.5mol％为乙基支链，11mol％为丙基支链，3mol％为丁基支链，7mol％为戊基支链，7.5mol％为碳数≥6的支链，玻璃化转变温度为–64℃，有两个熔点，熔点一为90℃，熔点二为120℃，结晶度为6％，有两个结晶温度，结晶温度一为70℃，结晶温度二为95℃；(4)在60℃下淋洗出来的组份含量为6.5wt％，该组份的重均分子量为14×104g/mol，分子量分布指数为3.8，支化度为50个支链/1000个碳，支链中90mol％为甲基支链，0％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，6mol％为戊基支链，4mol％为碳数≥6的支链，玻璃化转变温度为–68℃，熔点为100℃，结晶度为16％，结晶温度为85℃；(5)在70℃下淋洗出来的组份含量为8wt％，该组份的重均分子量为17×104g/mol，分子量分布指数为4.0，支化度为35个支链/1000个碳，支链中95mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，3mol％为戊基支链，2mol％为碳数≥6的支链，玻璃化转变温度为–68℃，熔点为110℃，结晶度为25％，结晶温度为95℃；(6)在80℃下淋洗出来的组份含量为9wt％，该组份的重均分子量为20×104g/mol，分子量分布指数为3.2，支化度为20个支链/1000个碳，支链中85mol％为甲基支链，10mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，5mol％为碳数≥6的支链，玻璃化转变温度为–69℃，熔点为115℃，结晶度为30％，结晶温度为100℃；(7)在90℃下淋洗出来的组份含量为20wt％，该组份的重均分子量为23×104g/mol，分子量分布指数为3.2，支化度为10个支链/1000个碳，支链中98mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，2mol％为碳数≥6的支链，玻璃化转变温度为–60℃，熔点为120℃，结晶度为35％，结晶温度为105℃；(8)在100℃下淋洗出来的组份含量为16wt％，该组份的重均分子量为24.0×104g/mol，分子量分布指数为3.0，支化度为10个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–64℃，熔点为125℃，结晶度为33％，结晶温度为110℃；(9)在110℃下淋洗出来的组份含量为14wt％，该组份的重均分子量为20×104g/mol，分子量分布指数为3.0，支化度为8个支链/1000个碳，支链中80mol％为甲基支链，20mol％为碳数≥6的支链，玻璃化转变温度为–62℃，熔点为130℃，结晶度为36％，结晶温度为115℃；(10)在120℃下淋洗出来的组份含量为7wt％，该组份的重均分子量为20×104g/mol，分子量分布指数为3.0，支化度为5个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–67℃，熔点为130℃，结晶度为40％，结晶温度为115℃；(11)淋洗温度高于120℃的组份含量为2wt％，该组份的重均分子量为15.0×104g/mol，分子量分布指数为3.0，支化度为1个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–61℃，熔点为130℃，结晶度为40％，结晶温度为115℃。
实施例12
乙烯聚合是在无水无氧条件下进行的。在带机械搅拌的10升不锈钢反应釜中加入4.95升正庚烷，通过夹套循环水控制聚合釜温度为25℃，并开始搅拌。向聚合釜中依次加入1.25mmol助催化剂二氯乙基铝[控制二氯乙基铝中的铝与双核苊(α-二亚胺)镍催化剂中的镍之间的摩尔比为50]，0.5mmol二乙基锌[控制二乙基锌中的锌与双核苊(α-二亚胺)镍催化剂中的镍之间的摩尔比为20]，12.5μmol双核苊(α-二亚胺)镍催化剂2(R为异丙基，事先溶解在50毫升甲苯中)，催化剂在聚合体系中的浓度为2.5μmol/L。通入乙烯至反应釜压力为2.0MPa。聚合60分钟后，反应釜放空至常压，打开釜盖，倒出聚合物溶液，蒸出溶剂得到聚合物430克。催化剂活性为17200kgPE[mol(Ni)h]-1，聚合产物重均分子量为29.1×104g/mol,多分散系数为3.0，玻璃化转变温度为–61℃，熔点为122.3℃，结晶度为22.5％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为51.8MPa，断裂伸长率为820％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.30倍。
经1H-NMR测定，聚合产物的支化度为86个支链/1000个碳原子，支链中55.6mol％为甲基支链、7.5mol％为乙基支链、4.3mol％为丙基支链、2.7mol％为丁基支链、17.5mol％为戊基支链、12.4mol％为碳数≥6的支链。硬段的支化度为38个支链/1000个碳原子，软段的支化度为125个支链/1000个碳原子。硬 段的支链中85mol％为甲基支链，3mol％为乙基支链，1mol％为丙基支链，1mol％为丁基支链，8mol％为戊基支链，2mol％为碳数≥6的支链；软段的支链中52.8mol％为甲基支链，5.2mol％为乙基支链，14.5mol％为丙基支链，3.5mol％为丁基支链，12.7mol％为戊基支链，11.3mol％为碳数≥6的支链。硬段的熔点为125.9℃，结晶度为27％，玻璃化转变温度为–71℃；软段的玻璃化转变温度为–66℃，无明显熔点，结晶度为1.5％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出11种组份：其中(1)在30℃下淋洗出来的组份含量为22.8wt％(重量百分含量)，该组份的重均分子量为21.4×104g/mol，分子量分布指数为2.8，支化度为158个支链/1000个碳，支链中60mol％为甲基支链，4mol％为乙基支链，12mol％为丙基支链，5.7mol％为丁基支链，12mol％为戊基支链，6.3mol％为碳数≥6的支链，玻璃化转变温度为–61℃，有两个熔点，熔点一为57℃，熔点二为114℃，结晶度为1.5％，结晶温度为76℃；(2)在40℃下淋洗出来的组份含量为5.8wt％，该组份的重均分子量为26×104g/mol，分子量分布指数为2.6，支化度为145个支链/1000个碳，支链中59mol％为甲基支链，3.5mol％为乙基支链，14mol％为丙基支链，2mol％为丁基支链，9mol％为戊基支链，12.5mol％为碳数≥6的支链，玻璃化转变温度为–62℃，有两个熔点，熔点一为76℃，熔点二为114℃，结晶度为2.8％，有两个结晶温度，结晶温度一为55℃，结晶温度二为87℃；(3)在50℃下淋洗出来的组份含量为4.0wt％，该组份的重均分子量为30×104g/mol，分子量分布指数为2.6，支化度为103个支链/1000个碳，支链中65.8mol％为甲基支链，4.5mol％为乙基支链，10mol％为丙基支链，0mol％为丁基支链，8.8mol％为戊基支链，10.9mol％为碳数≥6的支链，玻璃化转变温度为–64℃，有两个熔点，熔点一为85℃，熔点二为116℃，结晶度为4.6％，有两个结晶温度，结晶温度一为67℃，结晶温度二为88℃；(4)在60℃下淋洗出来的组份含量为3.8wt％，该组份的重均分子量为34×104g/mol，分子量分布指数为3.2，支化度为54个支链/1000个碳，支链中83mol％为甲基支链，0％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，11.6mol％为戊基支链，5.4mol％为碳数≥6的支链，玻璃化转变温度为–70℃，熔点为95℃，结晶度为15％，结晶温度为81℃；(5)在70℃下淋洗出来的组份含量为5.8wt％，该组份的重均分子量为40×104g/mol，分子量分布指数为3.8，支化度为35个支链/1000个碳，支链中85mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，14mol％为戊基支链，1mol％为碳数≥6的支链，玻璃化转变温度为–69℃，熔点为103℃，结晶度为22.5％，结晶温度为88℃；(6)在80℃下淋洗出来的组份含量为5.5wt％，该组份的重均分子量为48×104g/mol，分子量分布指数为2.7，支化度为25个支链/1000个碳，支链中78mol％为甲基支链，15mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，7mol％为碳数≥6的支链，玻璃化转变温度为–71℃，熔点为111℃，结晶度为29％，结晶温度为96℃；(7)在90℃下淋洗出来的组份含量为15.6wt％，该组份的重均分子量为60×104g/mol，分子量分布指数为2.6，支化度为18个支链/1000个碳，支链中97mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，3mol％为碳数≥6的支链，玻璃化转变温度为–63℃，熔点为116℃，结晶度为30％，结晶温度为101.5℃；(8)在100℃下淋洗出来的组份含量为14wt％，该组份的重均分子量为60.0×104g/mol，分子量分布指数为2.2，支化度为15个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–66℃，熔点为121℃，结晶度为29.5％，结晶温度为107℃；(9)在110℃下淋洗出来的组份含量为13wt％，该组份的重均分子量为60×104g/mol，分子量分布指数为2.2，支化度为14个支链/1000个碳，支链中76mol％为甲基支链，24mol％为碳数≥6的支链，玻璃化转变温度为–63℃，熔点为124℃，结晶度为36％，结晶温度为110℃；(10)在120℃下淋洗出来的组份含量为4.7wt％，该组份的重均分子量为60×104g/mol，分子量分布指数为2.5，支化度为10个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–68℃，熔点为123℃，结晶度为38％，结晶温度为108℃；(11)淋洗温度高于120℃的组份含量为5wt％，该组份的重均分子量为40×104g/mol，分子量分布指数为2.6，支化度为4个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–63℃，熔点为123℃，结晶度为37％，结晶温度为110℃。
实施例13
乙烯聚合是在无水无氧条件下进行的。在带机械搅拌的2升不锈钢反应釜中加入990毫升正庚烷，通过夹套循环水控制聚合釜温度为40℃，并开始搅拌。向聚合釜中依次加入1mmol助催化剂二氯乙基铝[控制二氯乙基铝中的铝与双核苊(α-二亚胺)镍催化剂中的镍之间的摩尔比为100]，0.2mmol二乙基锌[控制二乙基锌中的锌与双核苊(α-二亚胺)镍催化剂中的镍之间的摩尔比为20]，5μmol双核苊(α-二亚胺)镍催化剂2(R为异丙基，事先溶解在10毫升甲苯中)，催化剂在聚合体系中的浓度为5μmol/L。通入乙烯至反应釜压力为1.5MPa。聚合45分钟后，反应釜放空至常压，打开釜盖，倒出聚合物溶液，蒸出溶剂得到聚合物53克。催化剂活性为7067kgPE[mol(Ni)h]-1，聚合产物重均分子量为15.9×104g/mol,多分散系数为2.6，玻璃化转变温度为–67℃，熔点为116.5℃，结晶度为5.7％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为10MPa，断裂伸长率为500％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.35倍。
经1H-NMR测定，聚合产物的支化度为118.3个支链/1000个碳原子，支链中49.9mol％为甲基支链、4.9mol％为乙基支链、4.1mol％为丙基支链、5.1mol％为丁基支链、20.5mol％为戊基支链、15.5mol％为碳数≥6的支链。硬段的支化度为60个支链/1000个碳原子，软段的支化度为250个支链/1000个碳原子。硬段的支链中52mol％为甲基支链，14.6mol％为乙基支链，4.8mol％为丙基支链，3.6mol％为丁基支链，13.6mol％为戊基支链，11.4mol％为碳数≥6的支链；软段的支链中44.5mol％为甲基支链，11.7mol％为乙基支链，6.2mol％为丙基支链，6.6mol％为丁基支链，16mol％为戊基支链，15mol％为碳数≥6的支链。硬段的熔点为80℃，结晶度为10.1％，玻璃化转变温度为–72℃；软段的玻璃化转变温度为–70℃，无明显熔点，结晶度为0％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出10种组份：其中(1)在30℃下淋洗出来的组份含量为28wt％(重量百分含量)，该组份的重均分子量为11.4×104g/mol，分子量分布指数为2.4，支化度为220个支链/1000个碳，支链中48mol％为甲基支链，3mol％为乙基支链，10mol％为丙基支链，6.1mol％为丁基支链，14mol％为戊基支链，18.9mol％为碳数≥6的支链，玻璃化转变温度为–64℃，有两个熔点，熔点一为50℃，熔点二为110℃，结晶度为0.3％，结晶温度为70℃；(2)在40℃下淋洗出来的组份含量为9wt％，该组份的重均分子量为12×104g/mol，分子量分布指数为2.6，支化度为180个支链/1000个碳，支链中45mol％为甲基支链，3.5mol％为乙基支链，15mol％为丙基支链，3mol％为丁基支链，13mol％为戊基支链，20.5mol％为碳数≥6的支链，玻璃化转变温度为–64℃，有两个熔点，熔点一为65℃，熔点二为110℃，结晶度为1.5％，有两个结晶温度，结晶温度一为45℃，结晶温度二为80℃；(3)在50℃下淋洗出来的组份含量为4.5wt％，该组份的重均分子量为15×104g/mol，分子量分布指数为2.6，支化度为150个支链/1000个碳，支链中58mol％为甲基支链，5.5mol％为乙基支链，11mol％为丙基支链，1mol％为丁基支链，9.5mol％为戊基支链，15mol％为碳数≥6的支链，玻璃化转变温度为–69℃，有两个熔点，熔点一为80℃，熔点二为110℃，结晶度为3％，有两个结晶温度，结晶温度一为55℃，结晶温度二为80℃；(4)在60℃下淋洗出来的组份含量为4.0wt％，该组份的重均分子量为17×104g/mol，分子量分布指数为3.2，支化度为100个支链/1000个碳，支链中75mol％为甲基支链，2.5％为乙基支链，2mol％为丙基支链，3mol％为丁基支链，8.5mol％为戊基支链，9mol％为碳数≥6的支链，玻璃化转变温度为–72℃，熔点为90℃，结晶度为10％，结晶温度为75℃；(5)在70℃下淋洗出来的组份含量为6wt％，该组份的重均分子量为20×104g/mol，分子量分布指数为3.8，支化度为70个支链/1000个碳，支链中80mol％为甲基支链，2mol％为乙基支链，2mol％为丙基支链，3mol％为丁基支链，8mol％为戊基支链，5mol％为碳数≥6的支链，玻璃化转变温度为–72℃，熔点为95℃，结晶度为15％，结晶温度为80℃；(6)在80℃下淋洗出来的组份含量为7wt％，该组份的重均分子量为24×104g/mol，分子量分布指数为2.7，支化度为60个支链/1000个碳，支链中70mol％为甲基支链，10mol％为乙基支链，2mol％为丙基支链，3mol％为丁基支链，3mol％为戊基支链，12mol％为碳数≥6的支链，玻璃化转变温度为–74℃，熔点为105℃，结晶度为20％，结晶温度为90℃；(7)在90℃下淋洗出来的组份含量为16wt％，该组份的重均分子量为30×104g/mol，分子量分布指数为2.6，支化度为40个支链/1000个碳，支链中90mol％为甲基支链，1mol％为乙基支链，1mol％为丙基支链，1mol％为丁基支链，1mol％为戊基支链，6mol％为碳数≥6的支链，玻璃化转变温度为–68℃，熔点为110℃，结晶度为25％，结晶温度为95℃；(8)在100℃下淋洗出来的组份含量为13wt％，该组份的重均分子量为30.0×104g/mol，分子量分布指数为2.4，支化度为30个支链/1000个碳，支链中90mol％为甲基支链，2mol％为乙基支链，2mol％为丙基支链，2mol％为丁基支链，2mol％为戊基支链，2mol％为碳数≥6的支链，玻璃化转变温度为–70℃，熔点为115℃，结晶度为25％，结晶温度为100℃；(9)在110℃下淋洗出来的组份含量为10wt％，该组份的重均分子量为30×104g/mol，分子量分布指数为2.5，支化度为25个支链/1000个碳，支链中70mol％为甲基支链，2mol％为乙基支链，2mol％为丙基支链，2mol％为丁基支链，2mol％为戊基支链，22％为碳数≥6的支链，玻璃化转变温度为–68℃，熔点为120℃，结晶度为30％，结晶温度为105℃；(10)在120℃下淋洗出来的组份含量为2.5wt％，该组份的重均分子量为30×104g/mol，分子量分布指数为2.5，支化度为20个支链/1000个碳，支链中95mol％为甲基支链，1mol％为乙基支链，1mol％为丙基支链，1mol％为丁基支链，1mol％为戊基支链，1mol％为碳数≥6的支链，玻璃化转变温度为–71℃，熔点为120℃，结晶度为36％，结晶温度为105℃；(11)淋洗温度高于120℃的组份含量为0wt％。
实施例14
乙烯聚合是在无水无氧条件下进行的。在带机械搅拌的200毫升不锈钢反应釜中加入100毫升正己烷，通过夹套循环水控制聚合釜温度为25℃，并开始搅拌。向聚合釜中依次加入2.0mmol助催化剂二氯乙基铝[控制二氯乙基铝中的铝与双核苊(α-二亚胺)镍催化剂中的镍之间的摩尔比为200]，0.2mmol二乙基锌[控制二乙基锌中的锌与双核苊(α-二亚胺)镍催化剂中的镍之间的摩尔比为20]，用10毫升正己烷将5μmol双核苊(α-二亚胺)镍催化剂2(R为异丙基)冲入聚合釜中，催化剂在聚合体系中的浓度为45.5μmol/L。通入乙烯至反应釜压力为1.2MPa。聚合30分钟后，反应釜放空至常压，打开釜盖，倒出聚 合物溶液，蒸出溶剂得到聚合物22克。催化剂活性为4400kgPE[mol(Ni)h]-1，聚合产物重均分子量为12.9×104g/mol,多分散系数为3.0，玻璃化转变温度为–67℃，熔点为120.4℃，结晶度为10.5％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为18.0MPa，断裂伸长率为1230％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.33倍。
经1H-NMR测定，聚合产物的支化度为80个支链/1000个碳原子，支链中52.0mol％为甲基支链、6.5mol％为乙基支链、4.5mol％为丙基支链、3.9mol％为丁基支链、17.6mol％为戊基支链、15.5mol％为碳数≥6的支链。硬段的支化度为42个支链/1000个碳原子，软段的支化度为139个支链/1000个碳原子。硬段的支链中82mol％为甲基支链，3mol％为乙基支链，1mol％为丙基支链，1mol％为丁基支链，7mol％为戊基支链，6mol％为碳数≥6的支链。软段的支链中51.8mol％为甲基支链，4.2mol％为乙基支链，13.6mol％为丙基支链，5.4mol％为丁基支链，11.9mol％为戊基支链，13.1mol％为碳数≥6的支链。硬段的熔点为118.0℃，结晶度为10.3％，玻璃化转变温度为–72℃；软段的玻璃化转变温度为–67℃，无明显熔点，结晶度为0％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出11种组份：其中(1)在30℃下淋洗出来的组份含量为27.1wt％(重量百分含量)，该组份的重均分子量为9.6×104g/mol，分子量分布指数为2.4，支化度为177个支链/1000个碳，支链中58.9mol％为甲基支链，3.5mol％为乙基支链，11.2mol％为丙基支链，5.3mol％为丁基支链，11.9mol％为戊基支链，9.2mol％为碳数≥6的支链，玻璃化转变温度为–63.5℃，有两个熔点，熔点一为55.7℃，熔点二为113.6℃，结晶度为1.41％，结晶温度为75.8℃；(2)在40℃下淋洗出来的组份含量为8.5wt％，该组份的重均分子量为10.7×104g/mol，分子量分布指数为2.4，支化度为149个支链/1000个碳，支链中58.3mol％为甲基支链，3.0mol％为乙基支链，13.6mol％为丙基支链，1.6mol％为丁基支链，10.4mol％为戊基支链，13.1mol％为碳数≥6的支链，玻璃化转变温度为–62.6℃，有两个熔点，熔点一为75.2℃，熔点二为113.8℃，结晶度为2.62％，有两个结晶温度，结晶温度一为54.5℃，结晶温度二为86.3℃；(3)在50℃下淋洗出来的组份含量为4.4wt％，该组份的重均分子量为13.5×104g/mol，分子量分布指数为3.0，支化度为108个支链/1000个碳，支链中64.2mol％为甲基支链，4.2mol％为乙基支链，9.4mol％为丙基支链，0mol％为丁基支链，9.6mol％为戊基支链，12.6mol％为碳数≥6的支链，玻璃化转变温度为–65.3℃，有两个熔点，熔点一为84.7℃，熔点二为115.1℃，结晶度为4.45％，有两个结晶温度，结晶温度一为65.7℃，结晶温度二为87.1℃；(4)在60℃下淋洗出来的组份含量为4.0wt％，该组份的重均分子量为15.3×104g/mol，分子量分布指数为3.6，支化度为57个支链/1000个碳，支链中82mol％为甲基支链，0％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，11.5mol％为戊基支链，6.6mol％为碳数≥6的支链，玻璃化转变温度为–70.8℃，熔点为94.2℃，结晶度为13.43％，结晶温度为79.7℃；(5)在70℃下淋洗出来的组份含量为6.2wt％，该组份的重均分子量为17.6×104g/mol，分子量分布指数为3.8，支化度为38个支链/1000个碳，支链中84.7mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，13.6mol％为戊基支链，1.7mol％为碳数≥6的支链，玻璃化转变温度为–71℃，熔点为101.9℃，结晶度为19.26％，结晶温度为86.7℃；(6)在80℃下淋洗出来的组份含量为7.0wt％，该组份的重均分子量为23.3×104g/mol，分子量分布指数为2.7，支化度为27个支链/1000个碳，支链中76.3mol％为甲基支链，14.6mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，9.1mol％为碳数≥6的支链，玻璃化转变温度为–72℃，熔点为109.5℃，结晶度为27.17％，结晶温度为95.3℃；(7)在90℃下淋洗出来的组份含量为16.1wt％，该组份的重均分子量为24.7×104g/mol，分子量分布指数为2.6，支化度为20个支链/1000个碳，支链中96.2mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，3.8mol％为碳数≥6的支链，玻璃化转变温度为–64℃，熔点为115.8℃，结晶度为29.12％，结晶温度为100.6℃；(8)在100℃下淋洗出来的组份含量为12.2wt％，该组份的重均分子量为25.1×104g/mol，分子量分布指数为2.4，支化度为17个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–66.8℃，熔点为120.3℃，结晶度为28.7％，结晶温度为105.8℃；(9)在110℃下淋洗出来的组份含量为10.2wt％，该组份的重均分子量为20.8×104g/mol，分子量分布指数为2.5，支化度为16个支链/1000个碳，支链中74.1mol％为甲基支链，25.9mol％为碳数≥6的支链，玻璃化转变温度为–64.8℃，熔点为123.3℃，结晶度为34.01％，结晶温度为109.1℃；(10)在120℃下淋洗出来的组份含量为3.4wt％，该组份的重均分子量为22.4×104g/mol，分子量分布指数为2.5，支化度为11个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–68.9℃，熔点为122.0℃，结晶度为37.09％，结晶温度为107.7℃；(11)淋洗温度高于120℃的组份含量为0.9wt％，该组份的重均分子量为16.6×104g/mol，分子量分布指数为2.6，支化度为5个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–63.3℃，熔点为122.2℃，结晶度为35.46％，结晶温度为108.3℃。
实施例15
乙烯聚合是在无水无氧条件下进行的。在带机械搅拌的2升不锈钢反应釜中加入1490毫升正庚烷，通过夹套循环水控制聚合釜温度为25℃，并开始搅拌。向聚合釜中依次加入6mmol助催化剂二氯乙基铝[控制二氯乙基铝中的铝与双核苊(α-二亚胺)镍催化剂中的镍之间的摩尔比为200]，0.6mmol二乙基锌[控制二乙基锌中的锌与双核苊(α-二亚胺)镍催化剂中的镍之间的摩尔比为20]，用10毫升正庚烷将15μmol双核苊(α-二亚胺)镍催化剂2(R为异丙基)冲入聚合釜中，催化剂在聚合体系中的浓度为10μmol/L。通入乙烯至反应釜压力为1.2MPa。聚合30分钟后，反应釜放空至常压，打开釜盖，倒出聚合物溶液，蒸出溶剂得到聚合物65.6克。催化剂活性为4370kgPE[mol(Ni)h]-1，聚合产物重均分子量为26.9×104g/mol,多分散系数为3.6，玻璃化转变温度为–67℃，熔点为121.5℃，结晶度为30.6％。聚合产物的拉伸性能按GB/T 528-2009进行测试，拉伸强度为49.5MPa，断裂伸长率为870％。聚合产物在室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，它能在1分钟内恢复到原来长度的1.33倍。
经1H-NMR测定，聚合产物的支化度为80.2个支链/1000个碳原子，支链中52.0mol％为甲基支链、6.5mol％为乙基支链、4.5mol％为丙基支链、3.9mol％为丁基支链、17.6mol％为戊基支链、15.5mol％为碳数≥6的支链。硬段的支化度为42个支链/1000个碳原子，软段的支化度为139个支链/1000个碳原子。硬段的支链中82mol％为甲基支链，3mol％为乙基支链，1mol％为丙基支链，1mol％为丁基支链，7mol％为戊基支链，6mol％为碳数≥6的支链。软段的支链中51.8mol％为甲基支链，4.2mol％为乙基支链，13.6mol％为丙基支链，5.4mol％为丁基支链，11.9mol％为戊基支链，13.1mol％为碳数≥6的支链。硬段的熔点为118.0℃，结晶度为10.3％，玻璃化转变温度为–72℃；软段的玻璃化转变温度为–67℃，无明显熔点，结晶度为0％。
聚合产物通过升温淋洗分级(TREF)的方法，以甲苯为溶剂可以分离出11种组份：其中(1)在30℃下淋洗出来的组份含量为27.1wt％(重量百分含量)，该组份的重均分子量为9.6×104g/mol，分子量分布指数为2.4，支化度为177.4个支链/1000个碳，支链中58.9mol％为甲基支链，3.5mol％为乙基支链，11.2mol％为丙基支链，5.3mol％为丁基支链，11.9mol％为戊基支链，9.2mol％为碳数≥6的支链，玻璃化转变温度为–63.5℃，有两个熔点，熔点一为55.7℃，熔点二为113.6℃，结晶度为1.41％，结晶温度为75.8℃；(2)在40℃下淋洗出来的组份含量为8.5wt％，该组份的重均分子量为10.7×104g/mol，分子量分布指数为2.4，支化度为148.8个支链/1000个碳，支链中58.3mol％为甲基支链，3.0mol％为乙基支链，13.6mol％为丙基支链，1.6mol％为丁基支链，10.4mol％为戊基支链，13.1mol％为碳数≥6的支链，玻璃化转变温度为–62.6℃，有两个熔点，熔点一为75.2℃，熔点二为113.8℃，结晶度为2.62％，有两个结晶温度，结晶温度一为54.5℃，结晶温度二为86.3℃；(3)在50℃下淋洗出来的组份含量为4.4wt％，该组份的重均分子量为13.5×104g/mol，分子量分布指数为3.0，支化度为108.4个支链/1000个碳，支链中64.2mol％为甲基支链，4.2mol％为乙基支链，9.4mol％为丙基支链，0mol％为丁基支链，9.6mol％为戊基支链，12.6mol％为碳数≥6的支链，玻璃化转变温度为–65.3℃，有两个熔点，熔点一为84.7℃，熔点二为115.1℃，结晶度为4.45％，有两个结晶温度，结晶温度一为65.7℃，结晶温度二为87.1℃；(4)在60℃下淋洗出来的组份含量为4.0wt％，该组份的重均分子量为15.3×104g/mol，分子量分布指数为3.6，支化度为56.9个支链/1000个碳，支链中82mol％为甲基支链，0％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，11.5mol％为戊基支链，6.6mol％为碳数≥6的支链，玻璃化转变温度为–70.8℃，熔点为94.2℃，结晶度为13.43％，结晶温度为79.7℃；(5)在70℃下淋洗出来的组份含量为6.2wt％，该组份的重均分子量为17.6×104g/mol，分子量分布指数为3.8，支化度为37.5个支链/1000个碳，支链中84.7mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，13.6mol％为戊基支链，1.7mol％为碳数≥6的支链，玻璃化转变温度为–71℃，熔点为101.9℃，结晶度为19.26％，结晶温度为86.7℃；(6)在80℃下淋洗出来的组份含量为7.0wt％，该组份的重均分子量为23.3×104g/mol，分子量分布指数为2.7，支化度为27.2个支链/1000个碳，支链中76.3mol％为甲基支链，14.6mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，9.1mol％为碳数≥6的支链，玻璃化转变温度为–72℃，熔点为109.5℃，结晶度为27.17％，结晶温度为95.3℃；(7)在90℃下淋洗出来的组份含量为16.1wt％，该组份的重均分子量为24.7×104g/mol，分子量分布指数为2.6，支化度为20.0个支链/1000个碳，支链中96.2mol％为甲基支链，0mol％为乙基支链，0mol％为丙基支链，0mol％为丁基支链，0mol％为戊基支链，3.8mol％为碳数≥6的支链，玻璃化转变温度为–64℃，熔点为115.8℃，结晶度为29.12％，结晶温度为100.6℃；(8)在100℃下淋洗出来的组份含量为12.2wt％，该组份的重均分子量为25.1×104g/mol，分子量分布指数为2.4，支化度为16.8个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–66.8℃，熔点为120.3℃，结晶度为28.7％，结晶温度为105.8℃；(9)在110℃下淋洗出来的组份含量为10.2wt％，该组份的重均分子量为20.8×104g/mol，分子量分布指数为2.5，支化度为15.8个支链/1000个碳，支链中74.1mol％为甲基支链，25.9mol％为碳数≥6的支链，玻璃化转变温度为–64.8℃，熔点为123.3℃，结晶度为34.01％，结晶温度为109.1℃；(10)在120℃下淋洗出来的组份含量为3.4wt％，该组份的重均分子量为22.4×104g/mol，分子量分布指数为2.5，支化度为10.7个支链/1000个碳，支链中100mol％ 为甲基支链，玻璃化转变温度为–68.9℃，熔点为122.0℃，结晶度为37.09％，结晶温度为107.7℃；(11)淋洗温度高于120℃的组份含量为0.9wt％，该组份的重均分子量为16.6×104g/mol，分子量分布指数为2.6，支化度为5个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–63.3℃，熔点为122.2℃，结晶度为35.46％，结晶温度为108.3℃。
由以上实施例可见，本发明制备的多嵌段支化聚乙烯的拉伸强度超过10MPa，断裂伸长率超过500％，样品的应力应变曲线没有出现屈服的现象，说明本发明制备的多嵌段支化聚乙烯不是塑料，而是弹性体，具备了很好的应用价值。
应用实例
1、将本发明实施例1制备获得的多嵌段支化聚乙烯在挤出机中熔融，通过环形口型，用空气膨胀，冷却，并切成厚度为50微米的双向取向膜。由本发明的多嵌段支化聚乙烯制成的单层薄膜具有较高的抗撕裂性和抗粘连性，其性能符合GB/T 4456-2008《包装用聚乙烯吹塑薄膜》的要求，可用于日用品、食品、药品等的包装。
2、使用三个挤出机的生产线(两个挤出机的螺杆直径为33毫米和一个挤出机的螺杆直径为25毫米)，使用205℃的熔融温度，30厘米的模头宽度，0.8毫米的模头间隙，18米/分钟的线速度和6公斤/小时的产量，制备总厚度为30微米的3层流延膜。该三层膜结构为粘着层/芯层/隔离层，其中粘着层(厚度为4.5微米)是本发明实施例3制备获得的多嵌段支化聚乙烯，芯层(厚度为21微米)是密度为0.918克/立方厘米和熔融指数0.85克/10分钟(190℃/2.16公斤)的线性低密度聚乙烯，隔离层(厚度为4.5微米)是密度为0.923克/立方厘米和熔融指数为0.75克/10分钟(190℃/2.16公斤)的低密度聚乙烯。三层膜的粘着力为80克，断裂伸长率为440％，在形变为250％的抗刺穿性为0.4公斤，可用于食品例如家禽、蔬菜、新鲜的红肉、奶酪以及非食品的工业和零售物品的包装。
3、将100份本发明实施例15制备获得的多嵌段支化聚乙烯与1.3份叠氮化物发泡剂(AZ130，偶氮二碳酰胺发泡剂)、2份氧化锌、0.2份硬脂酸和2份过氧化物交联剂(二叔丁基过氧基异丙基苯过氧化物，40％活性物在二氧化硅载体上，PerkadoxTM 1440过氧化物)一起热熔混合，压缩模塑成板材并使其膨胀。混合条件：轧制机@130℃，10分钟。将来自轧制机的板材在烘箱中预热至90℃达15分钟，然后加入预热至180℃的模具中，压制并在该温度固化10分钟。取出时，使样品膨胀，制成发泡制品，具有较低的收缩、较低的压缩变定和较高的剖层撕裂和伸长，其性能符合HG/T 3082-2010《橡胶鞋底》的要求，可用于鞋底、地板、建筑材料等领域。
4、在配有24个25×1毫米喷丝头的纤维纺丝生产线中，以260℃纺丝头温度、302℃溶体温度和70米/分钟缠绕速度，将本发明实施例12制备获得的多嵌段支化聚乙烯纺成由具有圆形横截面的24根纤维构成的复丝束，丝束的拉伸强度为7g/d，模量为270g/d，断裂伸长率为820％，由多嵌段支化聚乙烯制成的纤维材料可用于纺织业(包括无纺布)、环保、医药和建筑等领域。
6、将本发明实施例7制备获得的多嵌段支化聚乙烯使用200℃的熔融温度进行注射成型，制成60×60×1立方厘米的板材，制品的拉伸强度为33.7MPa，断裂伸长率为1130％，可用于汽车的车柱等汽车内饰件、洗衣机的盖板等家电产品、卫生间的马桶盖等住宅设备用品、注射器、装粉末和片剂的瓶子。
7、将本发明实施例12制备获得的多嵌段支化聚乙烯研磨至150～500微米粒度，旋转模塑法在试验用设备FSP M20“Clamshell”中进行，将研磨的多嵌段支化聚乙烯放在铸塑铝模具中，模具在煤气燃烧烘箱中双轴旋转。热空气通过鼓风机在室中循环，同时温度在4分钟内提高到288℃。保持该温度15分钟，随后打开烘箱，同时仍旋转，将模具用强制空气循环冷却7分钟，其后是喷水雾7分钟，再进行空气冷却2分钟。在整个加热和冷却过程中，主轴的速度保持6转/分钟，旋转比为4.5:1。冷却结束后，打开模具取出中空物体。该旋转模塑制品的收缩率为2.24％，最大翘曲1.41毫米，-40℃下的抗冲击强度为10.3J/mm，可用于罐、容器、玩具、舟皿、家具、医疗器材、地下储罐、燃油箱、移动式厕所、组合浴室、电话亭、船体、垃圾桶、灯罩、冰桶、装置外壳等领域。
8、将39克本发明实施例13制备获得的多嵌段支化聚乙烯在Haake RheomixTM 600混合机中于190℃熔融，之后加入17克石蜡油，继续混合15分钟，然后停止转子，打开滚筒，并取出所得掺合物，在压机中弄平并冷却。所得掺合物表现出较好的吃油性，肖氏A硬度为54，通过热机械分析测得的转变温度为85℃，可用于许多软弹性体应用领域，例如软触模制品和压敏粘合剂。
9、将6克本发明实施例12制备获得的多嵌段支化聚乙烯和49克全同立构聚丙烯在Haake RheomixTM 600混合机中于190℃熔融15分钟，然后停止转子，打开滚筒，并取出所得掺合物。该掺合物的常温缺口冲击强度达到了52.83KJ/m2，弯曲模量为610MPa，而相应的全同立构聚丙烯的常温缺口冲击强度为19.53KJ/m2，弯曲模量为710MPa，表明多嵌段支化聚乙烯是有效的聚丙烯冲击改性剂。
应用或最终用途的示例
鉴于多嵌段支化聚乙烯或包含该多嵌段支化聚乙烯聚合物的组合物在作为上述产品，或在制造上述产品中的应用情形，本发明可广泛应用于工业、军事、医疗卫生、食品、日常生活等多种领域。
本发明的聚合物可有效用于各种传统的热塑性制造法以制造有用制品，包括通过浇铸、压延、吹塑或挤塑涂布法制成的含有至少一层膜层(例如单层膜或多层膜中的至少一层)的物体；挤出件；模制品，例如吹塑、注射成型、或旋转模塑制品；纤维；和纺织或无纺布。包含本发明的聚合物的热塑性组合物包括与其它天然或合成聚合物、补强剂、添加剂、阻燃添加剂、稳定剂、抗氧化剂、色料、交联剂、增量剂、发泡剂和增塑剂的掺合物。特别有用的是含有外表面层的多组分纤维，例如芯/鞘纤维，至少部分包括一种或多种本发明的聚合物。
可以由本发明的聚合物或掺合物制成的纤维包括短纤维、多组分纤维、丝束、鞘/芯纤维、绞合纤维和单丝。合适的纤维形成方法包括溶体吹塑技术，旋转粘合、或通过凝胶纺成纤维，由这些纤维可以获得纺织或无纺织物，或由这些纤维构成的结构，包括与其它纤维的掺合物，例如尼龙、聚酯或棉、热成型制品、挤出型材(包括异型挤出件和共挤出件)、压延制品、和拉出、绞合或卷曲纱线或纤维。本文所述的新型聚合物还可用于线材和线缆涂布操作，以及用于真空成形操作的板材挤塑、或旋转模塑法。包含多嵌段支化聚乙烯的组合物也可以用聚烯烃加工领域技术人员公知的传统聚烯烃加工技术制成成品。
还可以使用本发明的聚合物或包含该聚合物的制剂形成分散体(水性和非水性的)。也可以形成包含本发明的聚合物的泡沫材料。多嵌段支化聚乙烯也可以通过任何已知方式，例如使用过氧化物、硅烷、电子束、叠氮化物或其它交联技术交联。多嵌段支化聚乙烯还可以化学改性，例如通过接枝(例如使用马来酸酐、硅烷或其它接枝剂)、胺化、卤化、磺化或其它化学改性法进行改性。
在包含本发明的聚合物的任何制剂中都可以包含添加剂和辅助剂。合适的添加剂包括填料，例如有机或无机粒子(包括粘土、二氧化硅、滑石、沸石、粉状金属)、有机或无机纤维(包括碳纤维、钢丝或网、氮化硅纤维、和尼龙或聚酯绞索)、纳米级粒子、粘土等；增稠剂、增量油、包括石蜡油或环烷油；和其它天然和合成聚合物，包括本发明的其它聚合物。
与本发明的聚合物掺合的合适的聚合物包括热塑性和非热塑性聚合物，包括天然和合成聚合物。用于掺合的示例性聚合物包括聚丙烯(冲击改性聚丙烯、全同立构聚丙烯、无规聚丙烯，和无规乙烯/丙烯共聚物)、各种类型的聚乙烯，包括低密度聚乙烯、高密度聚乙烯、线性低密度聚乙烯、茂金属聚乙烯，包括反应器型聚乙烯(齐格勒-纳塔聚乙烯和茂金属聚乙烯的反应器型合金)、乙烯-乙烯基醇共聚物、乙烯-醋酸乙烯酯共聚物、聚苯乙烯、冲击改性聚苯乙烯、SBS、ABS、SEBS和热塑性聚氨酯。烯烃塑性体和弹性体之类的均相聚合物、乙烯和丙烯基共聚物也可用作包含本发明的聚合物的掺合物中的组分。
前述产品的合适的最终用途包括弹性膜和纤维；粘合剂(包括热熔粘合剂和压敏粘合剂)；软触产品，如牙刷柄和器具柄；鞋类(包括鞋底和鞋里)；垫圈和型材；汽车内部部件和型材；泡沫产品(开孔和闭孔)；用于其它热塑性聚合物(例如高密度聚乙烯、全同立构聚丙烯或其它烯烃聚合物)的冲击改性；瓶盖垫；涂布织物；软管；挡风雨条；管材；地板；和用于润滑剂的粘度指数改进剂，也称作倾点改性剂。
包含热塑性接枝共聚物(尤其是全同立构聚丙烯)和本发明的多嵌段支化聚乙烯的热塑性组合物特别能够形成含有硬结晶或半结晶嵌段的芯-壳型粒子——其中芯被软或弹性嵌段围绕，从而在硬聚合物的封闭区域周围形成“壳”。这些粒子在通过热熔混合或掺合过程中引起的力在接枝共聚物中形成和分散。在固化时，这些区域变成包在聚合母体中的封闭的弹性体粒子。
特别优选的掺合物是热塑性弹性体(TPE)，如热塑性聚烯烃(TPO)、动态交联热塑性弹性体(TPV)和苯乙烯基热塑性弹性体(SBS、SEBS)。可以通过将本发明的多嵌段支化聚乙烯(包括其官能化或不饱和衍生物)与任选橡胶(包括传统的嵌段共聚物，尤其是SBS嵌段共聚物)和任选的交联或硫化剂结合，制备TPE和TPV掺合物。上述掺合物可用于形成模制品，并任选用于使所得模制品交联。
用于此用途的合适的传统嵌段共聚物具有10至135，更优选25至100，最优选30至80的门尼粘度(ML 1+4@100℃)。合适的聚烯烃尤其包括线性或低密度聚乙烯、聚丙烯(包括它的无规立构、全同立构、间同立构和冲击改性形式)和聚(4-甲基-1-戊烯)。合适的苯乙烯聚合物包括聚苯乙烯、橡胶改性聚苯乙烯、苯乙烯/丙烯腈共聚物(SAN)、橡胶改性SAN和苯乙烯-马来酸酐共聚物。
通过在一种或两种组分的熔点温度附近或以上混合或捏和各个组分，可以制备掺合物。对于多数多嵌段支化聚乙烯，这种温度可以高于130℃，最通常高于145℃，且最优选高于150℃。可以使用能够达到所需温度并将混合物熔融塑化的典型聚合物混合或捏和设备。这些包括捏合机、磨机、挤出机(单螺杆和双螺杆)、班伯里密炼机、压延机、和类似物。混合顺序和方法取决于最终组合物。也可以使用班伯里分批密炼机和连续密炼机的组合，例如使用班伯里密炼机，然后使用粉碎混合机，然后使用挤出机。通常，TPE或TPV组合物与TPO组合物相比，具有更高的可交联聚合物(通常是传统的含有不饱和键的嵌段共聚物)含量。通常，对于TPE和TPV组合物，多嵌段支化聚乙烯与嵌段共聚物的重量比可以为90:10至10:90，更优选80:20至20:80，最优选75:25至25:75。对于TPO组合物，多嵌段支化聚乙烯与TPO的重量比可以为49:51至5:95，更优选35:65至10:90。对于改性苯乙烯类聚合物，多嵌段支化聚乙烯与聚烯烃的重量比为49:51至5:95，更优选35:65至10:90。
掺合物组合物可以包含加工油、增塑剂和加工助剂。橡胶加工油具有特定的ASTM名称，并且石蜡油、环烷油或芳族加工油都适用。对于每100份总聚合物，通常使用0至150份，优选0至100份，最优选0至50份油。较高量的油可能容易以损害一些物理性能为代价改进所得产品的加工性。附加的加工助剂包括传统的蜡、脂肪酸盐(例如硬脂酸钙或硬脂酸锌)(聚)醇(包括乙二醇)、(聚)醇醚(包括乙二醇醚)、(聚)酯(包括(聚)丙二醇)和它们的金属盐、尤其是第1或2族金属盐或锌盐衍生物。
众所周知，非氢化橡胶[例如包含聚合形式的丁二烯或异戊二烯的那些橡胶，包括嵌段共聚物(下文称作二烯橡胶)]与主要或高度饱和橡胶相比，具有较低的抗UV、臭氧和抗氧化性。在由包含较高浓度二烯橡胶的组合物制成的轮胎之类的用途中，已知与抗臭氧添加剂和抗氧化剂一起加入炭黑可以改进橡胶稳定性。本发明的完全饱和的多嵌段支化聚乙烯特别可用作粘附到由传统二烯橡胶改性的聚合物组合物制成的制品上的保护性表面层(涂布、共挤出或层压)或耐候性膜。
对于传统的热塑性弹性体应用，炭黑是用于UV吸收和稳定性能的添加剂。炭黑的代表性例子包括ASTM N110、N121、N220、N231、N234、N242、N293、N299、S315、N326、N330、M332、N339、N343、N347、N351、N358、N375、N539、N550、N582、N630、N642、N650、N683、N754、N762、N765、N774、N787、N907、N908、N990和N991。对于许多这样的用途，本发明的多嵌段支化聚乙烯及其掺合物几乎或完全不需要炭黑，由此产生包括其它备选颜料或完全不使用颜料的相当大的设计自由度。与车辆颜色匹配的多色调轮胎是一种可能的用途。
包含本发明的热塑性掺合物的组合物还可以含有普通橡胶化学家已知的抗臭氧剂和抗氧化剂。抗臭氧剂可以是物理保护剂，例如覆盖在表面并保护该部分免受氧或臭氧作用的蜡材料，或者它们可以是与氧或臭氧反应的化学保护剂。合适的化学保护剂包括苯乙烯化苯酚、丁基化二(二甲基苄基)苯酚、丁基化辛基化苯酚、对亚苯基二胺、对甲酚和二环戊二烯的丁基化反应产物、多酚抗氧化剂、喹啉、氢醌衍生物、二亚苯基抗氧化剂、硫酯抗氧化剂、和它们的掺合物。这些产品的一些典型的商品名是WingstayTM S抗氧化剂、PolystayTM 100抗氧化剂、PolystayTM 100AZ抗氧化剂、PolystayTM 200抗氧化剂、WingstayTML抗氧化剂、WingstayTMLHLS抗氧化剂、WingstayTMK抗氧化剂、WingstayTM29抗氧化剂、WingstayTMSN-1抗氧化剂和IrganoxTM抗氧化剂。一些应用中，所用抗氧化剂和抗臭氧剂优选为非染色和非迁移性的。
为了提供额外的抗UV辐射稳定性，也可以使用受阻胺光稳定剂和UV吸收剂。合适的例子包括可获自Ciba Specialty Chemicals的TinuvinTM 123、TinuvinTM 144、TinuvinTM622、TinuvinTM765、TinuvinTM770和TinuvinTM780，和可获自Cytex Plastics，Houston TX,USA的ChemisorbTM T944。
对于一些组合物，可以使用附加混合过程使抗氧化剂、抗臭氧剂、炭黑、UV吸收剂和/或光稳定剂预分散以形成母炼胶，并随后由其形成聚合物掺合物。
此处使用的合适的交联剂(也称作硫化剂)包括硫基、过氧化物基或苯酚基化合物。当使用硫基硫化剂时，也可以使用促进剂和硫化活化剂。使用促进剂控制动态硫化所需的时间和/或温度并改进所得交联制品的性能。可以使用单种促进剂或主促进剂。主促进剂的总量可以为组合物总重量的0.5至4phr，优选0.8至1.5。也可以主促进剂和第二促进剂结合使用，其中第二促进剂以较少的量使用，例如0.05至3phr，从而激活并改进硫化制品的性质。促进剂的结合使用产生的制品性能通常略好于使用单种促进剂制成的制品。此外，可以使用延迟作用促进剂，其不受正常加工温度影响，但是在普通硫化温度产生令人满意的硫化。也可以使用硫化延缓剂。本发明中可以使用的合适的促进剂类型是胺、胍、硫脲、噻唑、秋兰姆、二硫化物、亚磺酰胺、二硫代氨基甲酸酯和黄原酸盐。优选地，主促进剂是亚磺酰胺。如果使用第二促进剂，第二促进剂优选为胍、二硫代氨基甲酸酯或秋兰姆化合物。也可以使用某些加工助剂和硫化活化剂。当使用过氧化物基硫化剂时，可以与其结合使用共活化剂或活性助剂，例如硬脂酸和ZnO。合适的活性助剂包括三丙烯酸三羟甲基丙烷、三甲基丙烯酸三羟甲基丙烷、异氰脲酸三烯丙酯、氰脲酸三烯丙酯。用于部分或完全的动态硫化的过氧化物交联剂和任选活性助剂的使用是本领域中公知的。
当包含多嵌段支化聚乙烯的组合物至少部分交联时，可以通过将该组合物在溶剂中溶解指定持续时间并计算凝胶或不可萃取组分的百分比来测量交联程度。凝胶百分比通常随着交联程度的提高而提高。对于本发明的硫化制品，凝胶含量百分比为5至100％。
本发明的多嵌段支化聚乙烯及其掺合物与现有技术的组合物相比，具有改进的加工性能，因为其独特的支化链结构降低了溶体粘度。因此，该组合物或掺合物表现出改进的表面外观，尤其是形成模制或挤出制品时。同时，本组合物及其掺合物独特地具有改进的熔体强度性能，由此使本发明的多嵌段支化聚乙烯及其掺合物，尤其是TPO掺合物可用于目前熔体强度不足的泡沫和热成型应用领域。
本发明的热塑性组合物还可以含有有机或无机填料或其它添加剂，例如淀粉、玻璃纤维、滑石、碳酸钙、聚合纤维(包括尼龙、人造丝、棉、聚酯和聚芳族聚酰胺)、金属纤维、薄片或粒子、可膨胀层状硅酸盐、磷酸盐或碳酸盐，例如二氧化硅、粘土、氧化铝、云母、碳须晶、碳纤维、铝硅酸盐或铝磷 酸盐、纳米粒子(包括纳米管)、硅灰石、石墨(包括石墨烯)、沸石和陶瓷，例如碳化硅、氮化硅或二氧化钛。为了更好的填料粘合性，也可以使用硅烷基或其它偶联剂。
包括前述掺合物的本发明的热塑性组合物可以通过传统的模制技术加工，例如注射成型、热成型、挤塑、中孔模塑、夹物模压、双料覆盖成型、吹塑和、其它技术。可以通过浇铸或拉幅法，包括吹塑薄膜法，制造包括多层膜在内的薄膜。
测试方法
(1)高温GPC：采用英国Polymer Laboratories公司生产的PL-220型凝胶渗透色谱仪，称取10-15毫克样品溶于5毫升1,2,4-三氯苯中，配成浓度为2～3‰的溶液。在160℃下加热3～4小时，使之完全溶解，之后过滤，用专用滤枪过滤大约1毫升至专用GPC测试瓶中。测试过程中采用三根PLgel1010μmMIXED-B型色谱柱，色谱柱分离范围为500～1×107，以1,2,4-三氯苯为流动相，流动速率为1.0毫升/分钟，样品浓度2～3毫克/毫升，测试温度为150℃。用窄分布聚苯乙烯作标样，采用普适校正法校正数据，计算中采用的聚乙烯Mark-Houwink常数为：K＝1.56×10-4，α＝0.76。
(2)差示扫描量热(DSC)：采用美国TA Instruments公司生产的TA-Q200型差示扫描量热仪。制样：称取3～5毫克的样品置于小坩埚中，压实后放入样品池。测试：在氮气保护气氛下，将初始温度设定为40℃，以10℃/分钟的速率升温至150℃，保温5分钟使样品完全熔融，消除热历史。再以20℃/分钟的速率降温至-80℃，保温5分钟。最后以10℃/分钟的速率升温至150℃，得到DSC曲线。数据处理：结晶温度(Tc)和结晶焓(△Hcrystal)可由降温曲线测得，玻璃化转变温度(Tg)和熔融焓(△Hm)可由第二条升温曲线测得，结晶度χ可由△Hm除以理想状态下完全结晶聚乙烯的熔融焓(292.6J/g)算得
(3)高温NMR：采用美国Varian公司生产的核磁共振Mercury Plus 300。
1H-NMR：
制样：称取15毫克左右的样品，随后加入0.5毫升的氘代邻二氯苯做溶剂。测试条件：温度120℃，采样时间1.998秒，弛豫时间1.0秒，测试频率300MHz，扫描256次。通过以下公式1.1可以得到聚合物的支化度：
Figure PCTCN2016109278-appb-000004
①制样：称取50毫克左右的样品，加入样品质量10％的弛豫试剂加入核磁管中，随后加入0.5毫升的氘代邻二氯苯做溶剂。
②测试条件：温度120℃，采样时间0.8秒，弛豫时间3.0秒，测试频率300MHz，扫描次数5000～10000次。根据Usami和Takiyama提出的聚乙烯支链命名方法，再将碳谱中各个特征峰进行归属，根据公式1.2和1.3计算支化度(以每1000个碳中支链数目计)和各支链的比例
Figure PCTCN2016109278-appb-000005
甲基:乙基:丙基:丁基:戊基：碳数≥6的支链＝(IMe/0.90):(IEt/0.84):(IPr/0.83):(IBu/0.90):(IPe/0.90):(ILg/0.80)                  公式1.3
(4)聚合物的混炼和力学性能测试
①混炼:采用RM-200C哈普转矩流变仪。称取40克样品，加入样品质量3‰～5‰的抗氧剂，混炼条件设定温度为165℃，转速为60转/分钟，混炼时间6～8分钟。混匀后用热压机在165℃下将样品压成薄膜，用裁刀进行切割制得哑铃型样条。
②力学性能测试：采用深圳新三思材料有限公司生产的UTM-2103型电子拉力机测试。选择试验方法GB/T528，拉伸速率500毫米/分钟，分别测试拉伸强度、断裂伸长率。
(5)升温林洗分级(TREF)
①烤石英砂：将石英砂加入8个坩埚中放入马弗炉在800℃下烘烤2小时。
②溶解样品：将2克样品加入300毫升二甲苯中，加入5～8‰抗氧剂，在130℃条件下使之完全溶解。
③装填石英砂。
④结晶：在程序控温条件下，使溶液缓慢结晶。从130℃降至27℃，降温速率为1.5℃/小时。
⑤淋洗：从30℃开始，每10℃为一个级份，共分为11个级份。
⑥将所得的淋洗级份通过旋转蒸发进行浓缩，再用异丙醇将产物沉淀出来，静置12小时后用漏斗过滤产物，将产物放入真空烘箱(温度60℃)，烘24小时。

Claims (10)

  1. 一种多嵌段支化聚乙烯，其特征在于，该多嵌段支化聚乙烯由作为硬段的半结晶、低支化度的聚乙烯链段和作为软段的无定型、高支化度的聚乙烯链段按照
    Figure PCTCN2016109278-appb-100001
    的连接方式交替连接而成；
    所述半结晶是指：硬段的熔点为80～133.5℃，结晶度为9.7～47％，玻璃化转变温度为-73～-69℃；低支化度是指：支化度为1～60个支链/1000个碳；
    所述无定型是指：软段的玻璃化转变温度为-70～-56℃，无明显熔点，结晶度为0～4.5％；高支化度是指：支化度为50～250个支链/1000个碳。
  2. 根据权利要求1所述的多嵌段支化聚乙烯，其特征在于，该多嵌段支化聚乙烯的重均分子量为11.1×104～29.1×104g/mol，分子量分布指数为2.6～4.0，支化度为31.6～118.3个支链/1000个碳，支链中49～58.7mol％为甲基支链，4.9～7.5mol％为乙基支链，3.3～4.7mol％为丙基支链，1.7～5.1mol％为丁基支链，15.1～20.5mol％为戊基支链，12.4～17.5mol％为碳数≥6的支链，结晶度为5.7～42.9％，玻璃化转变温度为–69℃～–61℃，熔点为116.5℃～123.3℃。
  3. 根据权利要求1所述的多嵌段支化聚乙烯，其特征在于，所述硬段中各支链的摩尔百分含量占比是：52～100mol％为甲基支链，0～14.6mol％为乙基支链，0～4.8mol％为丙基支链，0～3.6mol％为丁基支链，0～13.6mol％为戊基支链，0～12.5mol％为碳数≥6的支链；所述软段中各支链的摩尔百分含量占比是：44.5～56mol％为甲基支链，3.5～11.7mol％为乙基支链，4.5～14.6mol％为丙基支链，2.5～6.6mol％为丁基支链，11.0～22.4mol％为戊基支链，6.5～15mol％为碳数≥6的支链。
  4. 根据权利要求1所述的多嵌段支化聚乙烯，其特征在于，该多嵌段支化聚乙烯的拉伸强度不低于10MPa，断裂伸长率不低于500％。
  5. 根据权利要求1所述的多嵌段支化聚乙烯，其特征在于，该多嵌段支化聚乙烯具备橡胶的特性，是一种热塑性弹性体：在18～29℃室温下被拉伸到原来的长度的2倍并保持1分钟后除掉外力，能在1分钟内恢复到原来长度的1.5倍以下。
  6. 根据权利要求1所述的多嵌段支化聚乙烯，其特征在于，该多嵌段支化聚乙烯是一种多组份的混合物，通过升温淋洗分级(TREF)的方法，以甲苯为溶剂至少可以分离出10～11种组份：其中，
    (1)在30℃下淋洗出来的组份含量为3.3～30wt％(重量百分含量)，该组份的重均分子量为3.0×104～21.4×104g/mol，分子量分布指数为2.4～3.8，支化度为110～220个支链/1000个碳，支链中48～62.8mol％为甲基支链，3～4mol％为乙基支链，10～12mol％为丙基支链，4.7～6.1mol％为丁基支链，10～14mol％为戊基支链，6.3～18.9mol％为碳数≥6的支链，玻璃化转变温度为–64.6℃～–61℃，有两个熔点，熔点一为50～60℃，熔点二为110～115℃，结晶度为0.3～2.5％，结晶温度为70～80℃；
    (2)在40℃下淋洗出来的组份含量为5.8～10wt％，该组份的重均分子量为10×104～26×104g/mol，分子量分布指数为2.4～3.8，支化度为120～180个支链/1000个碳，支链中45～60mol％为甲基支链，2～3.5mol％为乙基支链，11～15mol％为丙基支链，1～3mol％为丁基支链，9～13mol％为戊基支链，12.5～20.5mol％为碳数≥6的支链，玻璃化转变温度为–64℃～–61℃，有两个熔点，熔点一为65～80℃，熔点二为110～116℃，结晶度为1.5～3.5％，有两个结晶温度，结晶温度一为45～60℃，结晶温度二为80～95℃；
    (3)在50℃下淋洗出来的组份含量为3.4～6.5wt％，该组份的重均分子量为12.8×104～30×104g/mol，分子量分布指数为2.6～3.6，支化度为90～150个支链/1000个碳，支链中58～67mol％为甲基支链，3～5.5mol％为乙基支链，7.9～11mol％为丙基支链，0～3mol％为丁基支链，7～13mol％为戊基支链，7.5～15mol％为碳数≥6的支链，玻璃化转变温度为–69℃～–64℃，有两个熔点，熔点一为80～90℃，熔点二为110～120℃，结晶度为3～6％，有两个结晶温度，结晶温度一为55～70℃，结晶温度二为80～95℃；
    (4)在60℃下淋洗出来的组份含量为3.4～6.5wt％，该组份的重均分子量为14×104～34×104g/mol，分子量分布指数为3.2～3.8，支化度为46～100个支链/1000个碳，支链中75～90mol％为甲基支链，0～2.5mol％为乙基支链，0～2mol％为丙基支链，0～3mol％为丁基支链，6～15mol％为戊基支链，4～9mol％为碳数≥6的支链，玻璃化转变温度为–72℃～–68℃，熔点为90～100℃，结晶度为10～16％，结晶温度为75～85℃；
    (5)在70℃下淋洗出来的组份含量为5.5～8wt％，该组份的重均分子量为17×104～40×104g/mol，分子量分布指数为3.5～4.0，支化度为26～70个支链/1000个碳，支链中80～95mol％为甲基支链，0～2mol％为乙基支链，0～2mol％为丙基支链，0～3mol％为丁基支链，3～17mol％为戊基支链，1～5mol％为碳数≥6的支链，玻璃化转变温度为–72℃～–68℃，熔点为95～110℃，结晶度为15～25％，结晶温度为80～95℃；
    (6)在80℃下淋洗出来的组份含量为5.5～9wt％，该组份的重均分子量为20×104～48×104g/mol，分子量分布指数为2.7～3.2，支化度为17～60个支链/1000个碳，支链中70～85mol％为甲基支链，10～18mol％为乙基支链，0～2mol％为丙基支链，0～3mol％为丁基支链，0～3mol％为戊基支链，5～12mol％为碳数≥6的支链，玻璃化转变温度为–74℃～–69℃，熔点为105～115℃，结晶度为20～30％，结晶温度为90～100℃；
    (7)在90℃下淋洗出来的组份含量为11.5～20wt％，该组份的重均分子量为23×104～60×104g/mol，分子量分布指数为2.5～3.2，支化度为10～40个支链/1000个碳，支链中88～98mol％为甲基支链，0～2mol％为 乙基支链，0～2mol％为丙基支链，0～3mol％为丁基支链，0～3mol％为戊基支链，2～6mol％为碳数≥6的支链，玻璃化转变温度为–68℃～–60℃，熔点为110～120℃，结晶度为25～35％，结晶温度为95～105℃；
    (8)在100℃下淋洗出来的组份含量为9～16wt％，该组份的重均分子量为24×104～60×104g/mol，分子量分布指数为2.2～3.0，支化度为10～30个支链/1000个碳，支链中90～100mol％为甲基支链，0～2mol％为乙基支链，0～2mol％为丙基支链，0～2mol％为丁基支链，0～2mol％为戊基支链，0～2mol％为碳数≥6的支链，玻璃化转变温度为–70℃～–64℃，熔点为115～125℃，结晶度为25～33％，结晶温度为100～110℃；
    (9)在110℃下淋洗出来的组份含量为7～14wt％，该组份的重均分子量为20×104～60×104g/mol，分子量分布指数为2.2～3.0，支化度为8～25个支链/1000个碳，支链中70～80mol％为甲基支链，0～2mol％为乙基支链，0～2mol％为丙基支链，0～2mol％为丁基支链，0～2mol％为戊基支链，20～30mol％为碳数≥6的支链，玻璃化转变温度为–68℃～–62℃，熔点为120～130℃，结晶度为30～38％，结晶温度为105～115℃；
    (10)在120℃下淋洗出来的组份含量为2.5～7wt％，该组份的重均分子量为20×104～60×104g/mol，分子量分布指数为2.5～3.0，支化度为5～20个支链/1000个碳，支链中95～100mol％为甲基支链，0～1mol％为乙基支链，0～1mol％为丙基支链，0～1mol％为丁基支链，0～1mol％为戊基支链，0～1mol％为碳数≥6的支链，玻璃化转变温度为–71℃～–67℃，熔点为120～130℃，结晶度为36～40％，结晶温度为105～115℃；
    (11)淋洗温度高于120℃的组份含量为0～5wt％，该组份的重均分子量为15×104～40×104g/mol，分子量分布指数为2.5～3.0，支化度为0～10个支链/1000个碳，支链中100mol％为甲基支链，玻璃化转变温度为–63.8℃～–61℃，熔点为122～130℃，结晶度为35～40％，结晶温度为108～115℃。
  7. 一种多嵌段支化聚乙烯的制备方法，其特征在于，是以双核苊(α-二亚胺)镍催化剂为主催化剂、烷基铝为助催化剂，再加以链穿梭剂二乙基锌催化乙烯进行均聚，通过链穿梭聚合反应获得所述多嵌段支化聚乙烯；
    Figure PCTCN2016109278-appb-100002
    所述双核苊(α-二亚胺)镍催化剂的化学结构如式I所示，其中R为甲基或异丙基；
    所述烷基铝为一氯二乙基铝、倍半乙基氯化铝或二氯乙基铝中的一种。
  8. 根据权利要求7所述的方法，其特征在于，该制备方法的具体步骤为：
    将烷基铝、链穿梭剂二乙基锌和双核苊(α-二亚胺)镍催化剂溶于溶剂中，通入压力为0.4～2.0MPa的乙烯后进行链穿梭聚合反应，控制聚合温度为25～40℃，聚合时间为30～60分钟；聚合结束后，加入酸化乙醇终止聚合反应；将聚合产物沉淀出来，经过滤、洗涤，得到多嵌段支化聚乙烯；
    在聚合体系中，双核苊(α-二亚胺)镍催化剂的浓度为2.5～45.5μmol/L，烷基铝中的铝与双核苊(α-二亚胺)镍催化剂中的镍的摩尔比(Al/Ni比)为50～200，链穿梭剂二乙基锌中的锌与双核苊(α-二亚胺)镍催化剂中的镍的摩尔比为10～100。
  9. 根据权利要求8所述的方法，其特征在于，所用的溶剂为正己烷、正庚烷中的一种；或者是正庚烷与甲苯的混合物，混合物中正庚烷与甲苯的体积比为99:1～10:1。
  10. 多嵌段支化聚乙烯或包含该多嵌段支化聚乙烯聚合物的组合物作为下述任一产品的应用，或在制造下述任一产品中的应用：薄膜、多层膜的至少一层、层压制品的至少一层、发泡制品、聚丙烯冲击改性剂、纤维、无纺布、注射成型制品、吹塑制品、旋转模塑制品或粘合剂。
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