WO2017181424A1 - 一种聚乙烯材料及其应用 - Google Patents

一种聚乙烯材料及其应用 Download PDF

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WO2017181424A1
WO2017181424A1 PCT/CN2016/080041 CN2016080041W WO2017181424A1 WO 2017181424 A1 WO2017181424 A1 WO 2017181424A1 CN 2016080041 W CN2016080041 W CN 2016080041W WO 2017181424 A1 WO2017181424 A1 WO 2017181424A1
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polyethylene material
ethylene
polyethylene
reaction
reactor
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PCT/CN2016/080041
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English (en)
French (fr)
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王靖岱
吴文清
阳永荣
韩国栋
蒋斌波
孙洪霞
黄正梁
崔宇辉
廖祖维
胡晓波
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中国石油化工股份有限公司
浙江大学
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Priority to KR1020187033791A priority Critical patent/KR102321154B1/ko
Priority to PCT/CN2016/080041 priority patent/WO2017181424A1/zh
Priority to US16/095,670 priority patent/US10899858B2/en
Publication of WO2017181424A1 publication Critical patent/WO2017181424A1/zh

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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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • 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
    • C08F2/00—Processes of polymerisation
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/01—Hydrocarbons
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/01—High molecular weight, e.g. >800,000 Da.
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    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
    • C—CHEMISTRY; METALLURGY
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    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/08—Low density, i.e. < 0.91 g/cm3
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio
    • C—CHEMISTRY; METALLURGY
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    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/18—Bulk density
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C08L2203/162—Applications used for films sealable films

Definitions

  • the invention relates to the technical field of polyethylene, in particular to a new polyethylene polymer and its application.
  • Polyethylene is the most widely used and most abundant olefin polymer in the world. It is a thermoplastic general-purpose plastic with various structures and characteristics, and is one of the main varieties of synthetic resin. Polyethylene has a wide range of products, such as high density polyethylene (HDPE, density 0.940-0.960g/cm 3 ), medium density polyethylene (MDPE, 0.926-0.940g/cm 3 ), low density polyethylene (LDPE, 0.88-0.926 g/cm 3 ), linear low density polyethylene (LLDPE, 0.915-0.926 g/cm 3 ) and very low density polyethylene (VLDPE, 0.890-0.915 g/cm 3 ).
  • HDPE high density polyethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • the polyethylene is classified according to the polymerization method mainly: a slurry polymerization method, a solution polymerization method, and a gas phase polymerization method.
  • the production capacity of the gas phase polymerization fluidized bed process accounts for about 1/3 of the world's total polyethylene production capacity, and the proportion in China is nearly 1/2.
  • gas phase polymerization has the advantages of simple process, short process, flexible operation, mild reaction conditions, solvent recovery and convenient switching of grades.
  • the molecular weight and its distribution have a large impact on the performance of its products.
  • High molecular weight polyethylene has good physical and mechanical properties, but has the disadvantage of being difficult to process.
  • Low molecular weight polyethylene has good processing rheological properties but poor physical and mechanical properties.
  • a common method for adjusting the molecular weight and molecular weight distribution of polyethylene was to change the partial pressure of hydrogen in the reaction system. At present, the regulation of polyethylene production is no longer limited to this method.
  • the addition of ⁇ -olefin comonomer will also change the molecular weight and distribution of polyethylene.
  • the ⁇ -olefin comonomer will also change the branch of polyethylene.
  • the chain structure is capable of regulating the physical properties and processing properties of the polyethylene.
  • the properties of the meta-copolymer facilitate the manufacture of the film.
  • Patent application WO 2006/002778 relates to a piping system comprising a terpolymer of propylene/ethylene and an alpha-olefin, wherein the ethylene content is between 0 and 9 mol%, preferably between 1 and 7 mol%, and The hexene content is from 0.2 mol% to 5 mol%. Selection is made within these ranges to obtain a polymer having improved properties which can be used for the film.
  • Chinese patent application CN1384844 relates to a copolymer of ethylene and a C 3 -C 12 ⁇ -olefin having a molar mass distribution Mw/Mn ⁇ 10 and a density of from 0.85 g/cm 3 to 0.95 g/cm 3 .
  • the monomer content is from 1 to 40% by weight, and the molar mass Mn is greater than 150,000 g/mol, and the composition index of the comonomer has a width index of more than 70%.
  • the polymer can be used in fibers, moldings, foils or polymer blends.
  • Polyethylene HDPE is a full-density polyethylene product with high molecular weight content, high degree of branching, and good physical properties such as ductility.
  • a polyethylene material having a density distribution in the range of 0.880 to 0.960 g/cm 3 ; a content of 40 ° C fraction obtained by subjecting the polyethylene material to temperature rising and leaching classification In the range of 9.0 to 40.0 wt%, preferably in the range of 10.0 to 25.0 wt%, more preferably in the range of 9.9 to 20.0 wt%; and the melting temperature of the polyethylene material is in the range of 110 to 135 ° C, preferably 116 A range of -130 ° C, more preferably at 119-128 ° C.
  • the content of the fraction at 40 ° C is, for example, 9.0, 9.5, 9.9, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 18.0, 20.0, 22.0 or 24.0% by weight or the like.
  • the melting temperature of the polyethylene material is, for example, 116, 118, 120, 121, 122, 123, 125 or 128 ° C or the like.
  • the content of the polyethylene material at 50 ° C is in the range of 9.0 to 40.0% by weight, preferably in the range of 10.0 to 25.0% by weight, more preferably in the range of 10.2-16.0% by weight.
  • the low molecular weight fraction (especially the fraction of 40 ° C) therein has a content relative to conventional conventional polyethylene, for example polyethylene prepared by conventional gas phase processes. Significantly increased, and the degree of branching is high. It is well known that the lower the molecular weight of polyethylene, the higher the degree of branching and the lower the degree of crystallinity. Therefore, it will be understood by those skilled in the art that when the content of the low molecular weight fraction is high, the melting temperature of the polyethylene material is lowered. However, the inventors have unexpectedly discovered that the polyethylene material provided by the present invention still has a relatively high melting temperature in the case of a high content of low molecular weight fraction. And further discovering that the polyethylene material provided by the present invention having this feature is It has good bidirectional ductility and is a material which is especially suitable for film formation with good processing and use properties.
  • the polyethylene material has a fraction content at 110 ° C in the range of 8.0 to 30.0 wt%, preferably in the range of 9.0-18.0 wt%, such as 9.0, 10.0, 11.0, 12.0, 13.0. , 14.0, 15.0 or 16.0 wt%.
  • the content of the high molecular weight fraction (especially the fraction of 110 ° C) of the polyethylene material provided according to the present invention is also relatively high, and the degree of branching of this portion is increased relative to conventional polyethylene. Therefore, the branches in the polyethylene polymer provided by the present invention have a relatively wide distribution between molecular chains, and a plurality of branched portions are distributed in the high molecular weight fraction.
  • the standard deviation of the content of the fraction of the polyethylene material at intervals of 10 ° C in the range of 40-100 ° C as determined by the temperature rising elution fraction ranges from 0 to 6.0%, preferably at 0.5- 3.0; Further, it is preferred that the standard deviation of the content of the fraction of the polyethylene material at intervals of 10 ° C in 40-110 ° C is in the range of 0-6.0%, preferably 0.5-3.5%.
  • the content between the individual fractions of the polyethylene material is relatively average and also reflects the relatively high content of the high molecular weight and low molecular weight fractions of the invention.
  • the polyethylene material has a number average crystallite thickness of 6-18 nm, a weight average platelet thickness of 8-20 nm, preferably a platelet thickness distribution system (number of weight average platelet thickness/number)
  • the average crystal grain thickness is 1-1.333.
  • the platelet thickness can be determined using continuous self-nucleation annealing thermal grading techniques well known in the art.
  • the polyethylene material has a weight average molecular weight of from 5,000 to 350,000, preferably from 10,000 to 250,000; a molecular weight distribution coefficient (PDI) of from 2.0 to 15.0, preferably from 2.5 to 6.0.
  • PDI molecular weight distribution coefficient
  • the polyethylene material has a melt flow index (230 ° C, 2.16 kg) of 0.8 to 2.0 g/10 min; and/or a tensile yield strength of 15 to 25 MPa; and/or The elongation at break is 450-700%; and/or the dart impact strength is 200-260 g.
  • the polyethylene material provided according to the present invention preferably has a haze of 6-18%.
  • the polyethylene material provided by the present invention has good ductility and other excellent mechanical properties.
  • the present invention provides a novel polyethylene material having the unique features (or combination of features) as above, having good mechanical properties and processability.
  • the polyethylene material is prepared in a single reactor.
  • the polyethylene material is prepared by alternating between an ethylene homopolymerization reaction and an ethylene copolymerization reaction in a single reactor, or between different copolymerization reactions.
  • the polyethylene material provided according to the present invention is not physically mixed by ethylene homopolymer and/or ethylene copolymer of different molecular weights, or further melt-blended.
  • the polyethylene material provided by the invention is chemically blended at various levels, and is a molecular chain level mixing.
  • the polyethylene material is prepared by a method comprising the following steps (gas-liquid olefin polymerization process): passing a reaction raw material containing ethylene into a single reactor for polymerization, intermittently A condensate comprising comonomer is introduced to control switching between ethylene homopolymerization and copolymerization, or between different copolymerization reactions in the reactor.
  • Whether or not the condensate containing the comonomer is introduced can be determined according to a predetermined ethylene copolymerization or homopolymerization in the reactor. For example, if the next reaction is scheduled to be a homopolymerization reaction, the passage of the comonomer is stopped; conversely, if the next reaction is predetermined to be a copolymerization reaction, a suitable comonomer is selected and passed as needed. Therefore, the term "intermittently pass" means selectively introduced, for example, according to the need for copolymerization or homopolymerization in the reactor, the type of copolymerization reaction, etc., at intervals, or every other period. Time does not pass.
  • the condensate comprising different types of comonomers can be separately charged in separate storage tanks and passed into the reactor at the appropriate times as needed.
  • the ethylene copolymerization reaction it is preferred to carry out the ethylene copolymerization reaction first, followed by the reaction between the ethylene homopolymerization reaction and the ethylene copolymerization reaction, or the switching mode between the different copolymerization reactions. That is, the initial reaction is an ethylene copolymerization reaction, and then switched to an ethylene homopolymerization reaction, followed by continuing the reaction in accordance with a predetermined reaction switching procedure.
  • An advantage of this preferred embodiment is that the initially formed copolymerized polyethylene particles are loose and the active centers within the particles are not embedded, ensuring late polymerization activity.
  • the reaction pressure in the polymerization in the reactor is from 0.5 to 10 MPa, preferably from 1.5 to 5 MPa; the reaction temperature is from 40 to 150 ° C, preferably from 50 to 120 ° C, more preferably from 50 to 110 ° C.
  • the gaseous material in the reactor is withdrawn from the top of the reactor and can be separated into a gas phase stream and a liquid phase stream by compression, condensation, and gas-liquid separation.
  • the liquid phase stream is primarily a comonomer and a condensing agent that can be stored in a storage tank;
  • the gas phase stream is primarily ethylene and hydrogen which are returned to the reactor from the lower portion of the fluidized bed reactor along with other feedstock.
  • the fluidized bed reactor mainly has an atmosphere of ethylene and hydrogen, and the content of the comonomer and the condensing agent is extremely small, and homopolymerization of ethylene occurs to form HDPE having a low degree of branching and high density.
  • the comonomer and the condensing agent are injected into the reactor from the storage tank, and can be introduced from the bottom of the reactor or the side wall of the distribution plate at a single point or multiple points, and the lower temperature reaction is carried out.
  • the zone produces low density, high molecular weight polyethylene
  • the upper high temperature zone produces high density, low molecular weight polyethylene.
  • the unreacted raw materials are discharged from the upper portion of the reactor and subjected to compression, condensation, and gas-liquid separation, and both the gas phase stream and the liquid phase stream are returned to the fluidized bed to continue to participate in the reaction.
  • the switching to the homopolymerization of the olefin is continued, and the operation is alternated continuously, and the total polymerization time is preferably 2-4 hours to finally obtain the desired high performance polyethylene product.
  • the low/high density polyethylene is prepared by ethylene copolymerization
  • ethylene, comonomer, hydrogen, catalyst, cocatalyst and condensing agent are contained in the reaction system.
  • the reactor is divided into a gas-liquid solid phase reaction zone and a gas-solid phase reaction zone.
  • the gas-solid phase reaction zone is a high temperature reaction zone, and the comonomer content thereof is relatively low, and the temperature is preferably between 80 and 110 ° C, preferably between 80 and 104 ° C; the reaction zone is reacted to obtain a relatively high density low molecular weight poly Ethylene.
  • the gas-liquid solid phase reaction zone is a low temperature reaction
  • the zone has a higher comonomer content, preferably between 50 and 77 ° C, preferably between 60 and 77 ° C; this reaction zone is reacted to give a relatively low density high molecular weight polyethylene.
  • the polymerization temperature is between 80 and 110 ° C, preferably between 85 and 110 ° C.
  • the switching frequency between ethylene homopolymerization and copolymerization is at least 1 time/hour, preferably greater than or equal to 3 times/hour.
  • the switching frequency between different copolymerization reactions is at least 1 time/hour, preferably greater than or equal to 3 times/hour.
  • the operation time of each homopolymerization phase lasts from 3 to 60 minutes, preferably from 8 to 20 minutes; the operation time of each copolymerization phase lasts from 5 to 60 minutes, preferably from 8 to 20 minutes.
  • the molar ratio of comonomer to ethylene in the reactor during the ethylene copolymerization process is from 0 to 0.1.
  • the molar ratio of hydrogen to ethylene in the reactor during the olefin homopolymerization and olefin copolymerization is from 0.01 to 1.0.
  • reaction feed gas flow rate is from 1 to 500 tons per hour.
  • the comonomer is selected from olefins of 18 carbon atoms or less, especially alpha-olefins, preferably selected from butene, hexene and octene, especially preferably from alpha-butene, ⁇ -hexene and ⁇ -octene, preferably 1-hexene.
  • the polyethylene material provided by the present invention is preferably a random copolymer of ethylene and at least one of butene, hexene and octene.
  • the polyethylene material is an ethylene/1-hexene copolymer, an ethylene/1-butene/1-hexene random copolymer or an ethylene/1-hexene/1-octane Alkene random copolymer.
  • the polyethylene material is an ethylene/1-butene/1-hexene random copolymer by first copolymerizing ethylene, 1-butene and 1-hexene, and then It is cut into the ethylene homopolymerization reaction stage, and then cut into a copolymerization reaction stage of ethylene, 1-butene and 1-hexene, and the reaction is cyclically prepared.
  • the time of copolymerization and homopolymerization is as defined above.
  • the polyethylene material is an ethylene/1-hexene/1-octene random copolymer by first copolymerizing ethylene and 1-octene, and then cutting into ethylene homopolymerization. In the stage, the ethylene and 1-hexene copolymerization reaction stage is further cut, and then cut into the ethylene homopolymerization reaction stage, and then cut into a copolymerization reaction stage of ethylene and 1-octene to carry out a cyclic reaction to prepare.
  • the time of copolymerization and homopolymerization is as defined above.
  • Suitable condensing agents are preferably selected from the group consisting of C4-C7 saturated linear or branched alkanes, and at least one of C4-C7 cycloalkanes; preferably at least one of n-pentane, isopentane, hexane and heptane. One; most preferred is isopentane and/or hexane.
  • At least one of a cocatalyst, an antistatic agent, a chain transfer agent, a molecular regulator, a condensing agent and an inert gas is introduced into the reactor during the polymerization reaction.
  • the condensing agent in this preferred embodiment is an additional condensing agent, i.e., a condensing agent free of comonomer.
  • the antistatic agent is a conventional antistatic agent, for example, one or more selected from the group consisting of aluminum distearate, an ethoxylated amine, a polysulfone copolymer, a polymeric polyamine, and an oil-soluble sulfonic acid. combination.
  • the chain transfer agent is a conventional chain transfer agent comprising hydrogen and an alkyl metal, preferably hydrogen.
  • the inert gas may be a conventionally used inert gas such as nitrogen.
  • the catalyst used in the preparation of the polyethylene material of the present invention may be at least one of the following: a Ziegler-Natta catalyst, a metallocene catalyst, a transition metal catalyst, an inorganic chromium catalyst, an organic chromium catalyst, or a composite catalyst of two catalysts.
  • a titanocene catalyst capable of polymerizing polyethylene is preferred, and a titanocene catalyst supported on a support is more preferred.
  • the cocatalyst is selected from at least one of the following: modified aluminoxane, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, diisobutylaluminum, dichloroethylaluminum , trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum, monohydrogen diethyl aluminum and monohydrogen isobutyl aluminum, preferably triethyl aluminum or triisobutyl aluminum.
  • the reactor used to prepare the polyethylene material of the invention is preferably a fluidized bed reactor.
  • the invention also provides for the use of a polyethylene material provided according to the invention, for example in the preparation of a film (or film article); the film (film article) preferably comprises a packaging material and/or a product label, more preferably a cooked film , high transparent film, barrier protective film, heat sealing film or label film.
  • the polyethylene material provided according to the present invention has specific characteristics, such as a low molecular weight, a high degree of branching fraction, a relatively high content, a relatively high molecular weight fraction, and a high degree of branching. At the same time, the polyethylene material also has a relatively high melting temperature. At the same time, the polyethylene material is a full density polyethylene having a suitable molecular weight size and molecular weight distribution. Therefore, the polyethylene material provided by the invention has improved mechanical properties and processing properties, such as good ductility and impact resistance, and is a material with objective application prospects.
  • Fig. 1 shows the results of analysis of the degree of branching analysis of the polyethylene prepared in Example 1 and the polyethylene in Comparative Example 3.
  • the characterization means employed in the present invention are as follows.
  • Melting temperature Measured using a differential scanning calorimeter (TA Corporation, USA Model TA Q200). The specific method is: weigh the sample about 6mg, heat to about 220 ° C at a rate of 20 ° C / min, and keep it in a nitrogen stream for 2 min, then cool it to about 40 ° C at a rate of 20 ° C / min, at this temperature Hold for 2 min under to crystallize the sample. The sample was then heated to 220 ° C at a temperature increase rate of 20 ° C / min to melt again. The melt scanning process was recorded, a thermogram was obtained, and the melting temperature was read therefrom.
  • melt flow index MFR The melt flow index MFR was measured according to GB/T 3682-83 and measured at 230 ° C, 2.16 kg.
  • Density Determined according to GB/T1033-70.
  • Tensile yield strength and elongation at break determined according to GB/T1040-79.
  • Weight average molecular weight and molecular weight distribution coefficient determined by gel permeation chromatography Polymer Laboratories PL-220 instrument. The column and the rotating cell were operated at 140 °C. The solvent was 1,2,4-trichlorobenzene and the polymer concentration was 3 Torr. The injection volume was 100 microliters and the flow rate was 1.0 ml/min.
  • the temperature rising and leaching grading technique classifies the polyethylene molecules according to the crystallinity according to the influence of the chain structure parameters on the crystallization process and crystallinity of the polyethylene molecules, and separates them into a plurality of narrowly distributed fractions.
  • the temperature rise and wash grading includes two processes of crystal precipitation and temperature rising and leaching:
  • the polyethylene dissolves at a high temperature to form a stable dilute solution.
  • Slowly lowering the temperature causes the polyethylene crystal to deposit on the surface of the carrier material (inert particles such as quartz sand); the polyethylene molecules with different chain structures form a gradient of crystallinity.
  • the crystal layer such as polyethylene molecules with different short-branched content, will form a gradient distribution from the inside to the outside according to the degree of crystallinity due to the different crystallinity.
  • the carrier material deposited with the polyethylene crystal layer is loaded in the rinsing column, and the carrier is leached by using a good solvent of polyethylene in a continuous or intermittent heating environment to fractionate the crystals of different crystallinity.
  • Ethylene Ethylene
  • the temperature rising and leaching classification test used in the present invention is a routine operation process in the art, and the specific operations are as follows:
  • the rinse bottle was filled with quartz sand and rinsed thoroughly with water to remove impurities, and 50 mesh was selected.
  • the washed quartz sand was baked at 800 ° C for 4 hours, and the treated quartz sand was filled into the rinse bottle to a specified height.
  • the procedure for starting the oil bath was cooled and lowered from 130 ° C to room temperature (30 ° C) at a rate of 1.5 ° C / h.
  • the high crystallization temperature polymer component is first precipitated and wrapped in the quartz sand surface layer, and then the fraction having a low crystallization temperature is precipitated.
  • the flask containing the pure xylene solvent is placed in a temperature-controlled oil bath, and a circulating pump is used to inject xylene from the high-end to the rinse bottle, and the polymer solution of different elution temperatures is extruded out by the liquid level difference. Go to a collection bottle.
  • the present invention collects and measures a fraction of the eluent at a temperature ranging from 40 ° C to 110 ° C, and collects a corresponding eluent sample at intervals of 10 ° C.
  • Continuous self-nucleation annealing thermal classification generally includes the following steps:
  • the sample is cooled to a preset minimum temperature at a certain cooling rate (this minimum temperature ensures that the sample can crystallize at this temperature) and is kept at a minimum temperature for a period of time;
  • the sample is heated to a next set self-nucleation temperature TS at a certain temperature increase rate (relative to the previous self-nucleation temperature T S , the next self-nucleation temperature T S is decreased by 2.5 or 5 ° C), and Constant temperature for a period of time, such a cycle (the temperature range of the entire heat classification process is similar to the melting range of the sample);
  • the continuous self-nucleation annealing thermal classification test used in the present invention is a routine operation step in the art, and the specific method is as follows:
  • the polyethylene sample was heated from room temperature to 160 ° C at 10 ° C / min under a nitrogen atmosphere, and the heat history was eliminated at a constant temperature of 3 min; the temperature was lowered at 10 ° C / min. To 0 ° C, stay for 5 min; heat to 10 ° C / min to nucleation temperature T S , stay 5 min; 10 ° C / min to 0 ° C, stay 5 min, complete a self-nucleation process.
  • T S nucleation temperature
  • the polyethylene material of the present invention is prepared by conducting ethylene homopolymerization and ethylene/1-hexene copolymerization in a fluidized bed reactor.
  • a catalytic system of Ziegler-Natta catalyst and triethylaluminum was charged in the fluidized bed reactor.
  • the reaction feed gas including nitrogen, hydrogen, ethylene, methane, ethane, 1-hexene and a small amount of isopentane
  • the condensate isopentane containing 1-hexene
  • the temperature was 58 ° C, and the ethylene/1-hexene copolymerization reaction was first carried out.
  • the remaining gas after the reaction is taken as a recycle gas from the top outlet of the reactor, and the recycle gas is subjected to compression, condensation, and gas-liquid separation.
  • the liquid stream is stored in a 1-hexene storage tank while the remaining gas is recycled to the reactor as a recycle gas through the reactor feed port to continue the reaction.
  • the circulating gas is passed into the bottom of the reactor bed, it is a gas-liquid mixture.
  • the liquid mass fraction in the fluidized bed is 24 wt%, and the apparent fluidizing gas velocity is 0.63 m/s.
  • the temperature at the bottom of the bed (gas-liquid-solid reaction zone) was 68 ° C, and the temperature in the upper layer of the bed (gas-solid reaction zone) was 85 ° C.
  • the dew point temperature of the liquid isopentane in the recycle gas is between the bottom temperature of the bed and the upper temperature.
  • the copolymerization polymerization time was 15 minutes.
  • the reaction is cut into an ethylene homopolymerization stage.
  • the recycle gas to the bottom inlet of the reactor included hydrogen, nitrogen, methane, ethane, ethylene, 1-hexene and a small amount of isopentane at a pressure of 3.1 MPa and a temperature of 100 °C.
  • the circulating gas stream from the heat exchanger does not contain condensate, the gas phase density is 28.0kg/m 3 , and the ⁇ -olefin and isopentane after gas-liquid separation (accounting for 80% of the circulating gas flow) %) is injected into the storage tank, and a small amount of unseparated condensate and ⁇ -olefin are injected into the fluidized bed reactor along with the recycle gas.
  • Gas phase polymerization time (including process switching operation time) 8 minutes.
  • the polymerization time was 3 hours, and polyethylene a was obtained.
  • the polyethylene a was subjected to temperature rising leaching grading test, continuous self-nucleating annealing hot grading test and other performance tests.
  • the fractions of each temperature are shown in Table 1.
  • the results of continuous self-nucleation annealing thermal grading test are shown in Table 2. Show, other performance test results are shown in Table 3.
  • the polyethylene material of the present invention is prepared by conducting ethylene homopolymerization and ethylene/1-hexene copolymerization in a fluidized bed reactor.
  • a catalytic system of Ziegler-Natta catalyst and triethylaluminum was charged in the fluidized bed reactor.
  • the reaction feed gas including hydrogen, nitrogen, methane, ethane, ethylene, 1-hexene and a small amount of isopentane
  • the condensate isopentane containing 1-hexene
  • the temperature was 60 ° C, and the ethylene/1-hexene copolymerization reaction was first carried out.
  • the remaining gas after the reaction is taken as a recycle gas from the top outlet of the reactor, and the recycle gas is subjected to compression, condensation, and gas-liquid separation.
  • the liquid stream is stored in a 1-hexene storage tank while the remaining gas is recycled to the reactor as a recycle gas through the reactor feed port to continue the reaction.
  • the circulating gas is introduced into the bottom of the reactor bed, it is a gas-liquid mixture.
  • the liquid mass fraction in the fluidized bed is 26 wt%, and the apparent fluidizing gas velocity is 0.68 m/s.
  • the temperature at the bottom of the bed (gas-liquid-solid reaction zone) was 75 ° C, and the temperature of the upper bed polymerization (gas-solid reaction zone) was 92 °C.
  • the dew point temperature of the liquid isopentane in the recycle gas is between the bottom temperature of the bed and the upper temperature.
  • the copolymerization polymerization time was 20 minutes.
  • the reaction is cut into an ethylene homopolymerization stage.
  • the recycle gas fed to the bottom inlet of the reactor included hydrogen, nitrogen, methane, ethane, ethylene, 1-hexene and a small amount of isopentane at a pressure of 3.6 MPa and a temperature of 96 °C.
  • the circulating gas stream from the heat exchanger does not contain condensate, the gas phase density is 27.2kg/m 3 , and the ⁇ -olefin and isopentane after gas-liquid separation (accounting for 80% of the circulating gas flow) %) is injected into the storage tank, and a small amount of unseparated condensate and ⁇ -olefin are injected into the fluidized bed reactor along with the recycle gas.
  • Gas phase polymerization time (including process switching operation time) was 12 minutes.
  • the polymerization time was 3 hours, and polyethylene b was obtained.
  • the polyethylene b was subjected to temperature rising leaching grading test, continuous self-nucleating annealing hot grading test and other performance tests.
  • the fractions of each temperature are shown in Table 1.
  • the results of continuous self-nucleation annealing thermal grading test are shown in Table 2. Show, other performance test results are shown in Table 3.
  • the polyethylene material of the present invention is prepared by conducting ethylene homopolymerization and ethylene/1-hexene copolymerization in a fluidized bed reactor.
  • a catalytic system of Ziegler-Natta catalyst and triethylaluminum was charged in the fluidized bed reactor.
  • the reaction feed gas containing hydrogen, nitrogen, methane, ethane, ethylene, 1-hexene and a small amount of isopentane
  • the condensate isopentane containing 1-hexene
  • the temperature was 56 ° C, and the ethylene/1-hexene copolymerization reaction was first carried out.
  • the remaining gas after the reaction is taken as a recycle gas from the top outlet of the reactor, and the recycle gas is subjected to compression, condensation, and gas-liquid separation.
  • the liquid stream is stored in a 1-hexene storage tank while the remaining gas is recycled to the reactor as a recycle gas through the reactor feed port to continue the reaction.
  • the circulating gas is passed into the bottom of the reactor bed, it is a gas-liquid mixture, the liquid mass fraction in the fluidized bed is 30 wt%, and the apparent fluidizing gas velocity is 0.62 m/s.
  • the temperature at the bottom of the bed (gas-liquid-solid reaction zone) was 70 ° C, and the temperature of the upper bed polymerization (gas-solid reaction zone) was 84 °C.
  • the dew point temperature of the liquid isopentane in the recycle gas is between the bottom temperature of the bed and the upper temperature.
  • the copolymerization polymerization time was 8 minutes.
  • the reaction is cut into an ethylene homopolymerization stage.
  • the recycle gas fed to the bottom inlet of the reactor included hydrogen, nitrogen, methane, ethane, ethylene, 1-hexene and a small amount of isopentane at a pressure of 2.6 MPa and a temperature of 88 °C.
  • the circulating gas stream from the heat exchanger does not contain condensate, the gas phase density is 28.2 kg/m 3 , and 1-hexene and isopentane after gas-liquid separation (accounting for circulating gas flow) 80%) is injected into the storage tank, and a small amount of unseparated condensate and 1-hexene are injected into the fluidized bed reactor along with the recycle gas.
  • Gas phase polymerization time (including process switching operation time) 8 minutes.
  • ethylene was homopolymerized and cut into ethylene/1-hexene copolymerization, and 1-hexene and isopentane condensate was introduced from the upper portion of the fluidized bed distribution through a feed pump, and the lower polymerization temperature was gradually lowered to 70 °C.
  • the copolymerization reaction was carried out at this stage for 12 minutes.
  • the polymerization time was 2.5 hours, and polyethylene c was obtained.
  • the polyethylene c was subjected to temperature rising leaching grading test, continuous self-nucleating annealing hot grading test and other performance tests.
  • the fractions of each temperature are shown in Table 1.
  • the results of continuous self-nucleation annealing thermal grading test are shown in Table 2. Show, other performance test results are shown in Table 3.
  • the polyethylene material of the present invention is prepared by conducting ethylene homopolymerization and ethylene/1-butene/1-hexene copolymerization in a fluidized bed reactor.
  • a catalytic system of Ziegler-Natta catalyst and triethylaluminum was charged in the fluidized bed reactor.
  • the reaction feed gas containing hydrogen, nitrogen, methane, ethane, ethylene, 1-butene, 1-hexene and a small amount of isopentane
  • the condensate isopentane containing 1-hexene
  • the remaining gas after the reaction is taken as a recycle gas from the top outlet of the reactor, and the recycle gas is subjected to compression, condensation, and gas-liquid separation.
  • the liquid stream is stored in a 1-hexene storage tank while the remaining gas is recycled to the reactor as a recycle gas through the reactor feed port to continue the reaction.
  • the circulating gas is introduced into the bottom of the reactor bed, it is a gas-liquid mixture.
  • the liquid mass fraction in the fluidized bed is 26 wt%, and the apparent fluidizing gas velocity is 0.58 m/s.
  • the temperature at the bottom of the bed (gas-liquid-solid reaction zone) was 70 ° C, and the temperature of the upper bed polymerization (gas-solid reaction zone) was 86 °C.
  • the dew point temperature of the liquid isopentane in the recycle gas is between the bottom temperature of the bed and the upper temperature.
  • the copolymerization polymerization time was 8 minutes.
  • the reaction is cut into an ethylene homopolymerization stage.
  • the recycle gas to the bottom inlet of the reactor included hydrogen, nitrogen, methane, ethane, ethylene, 1-butene and a small amount of isopentane at a pressure of 2.6 MPa and a temperature of 78 °C.
  • the circulating gas stream from the heat exchanger does not contain condensate, the gas phase density is 26.2kg/m 3 , and the ⁇ -olefin and isopentane after gas-liquid separation (accounting for 80% of the circulating gas flow) %)
  • the ⁇ -olefin and isopentane after gas-liquid separation (accounting for 80% of the circulating gas flow) %)
  • Gas phase polymerization time was 16 minutes.
  • the polymerization time was 3.5 hours, and polyethylene d was obtained.
  • the polyethylene d was subjected to temperature rising leaching grading test, continuous self-nucleating annealing hot grading test and other performance tests.
  • the fractions of each temperature are shown in Table 1.
  • the results of continuous self-nucleation annealing thermal grading test are shown in Table 2. Show, other performance test results are shown in Table 3.
  • the polyethylene material of the present invention is prepared by conducting ethylene homopolymerization and ethylene/1-hexene/1-octene copolymerization in a fluidized bed reactor.
  • a catalytic system of Ziegler-Natta catalyst and triethylaluminum was charged in the fluidized bed reactor.
  • the reaction feed gas containing hydrogen, nitrogen, methane, ethane, ethylene, 1-octene and a small amount of isopentane
  • the condensate isopentane containing 1-octene
  • the temperature was 62 ° C, and the ethylene/1-octene copolymerization reaction was first carried out.
  • the remaining gas after the reaction is taken as a recycle gas from the top outlet of the reactor, and the recycle gas is subjected to compression, condensation, and gas-liquid separation.
  • the liquid stream is stored in a 1-octene storage tank while the remaining gas is recycled to the reactor as a recycle gas through the reactor feed port to continue the reaction.
  • the circulating gas is passed into the bottom of the reactor bed, it is a gas-liquid mixture.
  • the liquid mass fraction in the fluidized bed is 26 wt%, and the apparent fluidizing gas velocity is 0.66 m/s.
  • the temperature at the bottom of the bed (gas-liquid-solid reaction zone) was 66 ° C, and the temperature in the upper layer of the bed (gas-solid reaction zone) was 90 °C.
  • the dew point temperature of the liquid isopentane in the recycle gas is between the bottom temperature of the bed and the upper temperature.
  • the copolymerization polymerization time was 10 minutes.
  • the reaction is cut into the ethylene homopolymerization stage.
  • the recycle gas fed to the bottom inlet of the reactor included hydrogen, nitrogen, methane, ethane, ethylene, 1-octene and a small amount of isopentane at a pressure of 2.6 MPa and a temperature of 96 °C.
  • the circulating gas stream from the heat exchanger does not contain condensate, the gas phase density is 26.2kg/m 3 , and the ⁇ -olefin and isopentane after gas-liquid separation (accounting for 80% of the circulating gas flow) %)
  • the ⁇ -olefin and isopentane after gas-liquid separation (accounting for 80% of the circulating gas flow) %)
  • Gas phase polymerization time was 10 minutes.
  • the reaction was then switched to an ethylene/1-hexene copolymerization reaction.
  • the above recycle gas is passed from the feed port at the bottom of the reactor to continue the reaction while introducing 1-hexene and condensate.
  • the remaining gas after the reaction is taken as a recycle gas from the top outlet of the reactor, and the recycle gas is subjected to compression, condensation, and gas-liquid separation.
  • the liquid stream is stored in a 1-hexene storage tank while the remaining gas is recycled to the reactor as a recycle gas through the reactor feed port to continue the reaction.
  • the circulating gas is passed into the bottom of the reactor bed, it is a gas-liquid mixture.
  • the liquid mass fraction in the fluidized bed is 29 wt%, and the apparent fluidizing gas velocity is 0.72 m/s.
  • the temperature at the bottom of the bed was 70 ° C, and the temperature of the upper bed polymerization (gas-solid reaction zone) was 88 °C.
  • the dew point temperature of the liquid isopentane in the recycle gas is between the bottom temperature of the bed and the upper temperature.
  • the copolymerization polymerization time was 8 minutes.
  • the reaction is cut into an ethylene homopolymerization stage.
  • the recycle gas to the bottom inlet of the reactor included hydrogen, nitrogen, methane, ethane, ethylene, 1-hexene and a small amount of isopentane at a pressure of 2.8 MPa and a temperature of 96 °C.
  • the circulating gas stream from the heat exchanger does not contain condensate, the gas phase density is 26.8kg/m 3 , and the ⁇ -olefin and isopentane after gas-liquid separation (accounting for 80% of the circulating gas flow) %) is injected into the storage tank, and a small amount of unseparated condensate and 1-hexene are injected into the fluidized bed reactor along with the recycle gas.
  • Gas phase polymerization time (including process switching operation time) 8 minutes.
  • ethylene was homopolymerized and cut into ethylene/1-octene copolymerization, and 1-octene and isopentane condensate was introduced from the fluidized bed distribution plate through a feed pump, and the lower polymerization temperature was gradually lowered to 66 °C.
  • the copolymerization reaction was carried out at this stage for 10 minutes.
  • the polymerization time was 4.5 hours, and polyethylene e was obtained.
  • the polyethylene e was subjected to temperature rising leaching grading test, continuous self-nucleating annealing hot grading test and other performance tests.
  • the fractions of each temperature are shown in Table 1.
  • the results of continuous self-nucleation annealing thermal grading test are shown in Table 2. Show, other performance test results are shown in Table 3.
  • the bimodal polyethylene resin product was prepared in a single reactor system using a gas phase polymerization using a spray dried catalyst system in accordance with the process described in the patent application "CN200580027288".
  • the spray dried catalyst composition was suspended in a mixture of mineral oil and hexane to obtain a catalyst slurry for injection into a fluidized bed reactor.
  • Typical reactor conditions are: a polymerization temperature of 85-100 ° C, a hexene comonomer content of about 0.007 (C6: C2 molar ratio), and a H2: C2 molar ratio of 0.0035.
  • a bimodal polyethylene f having a density of about 0.946 and a broadening of up to 95 can be obtained.
  • the polyethylene f was subjected to temperature rising leaching grading test, continuous self-nucleating annealing hot grading test and other performance tests.
  • the fractions of each temperature are shown in Table 1.
  • the results of continuous self-nucleation annealing thermal grading test are shown in Table 2. Show, other performance test results are shown in Table 3.
  • 1-butene is used as a comonomer, and the composition of the reactants is: 30.12% by volume of ethylene and 6.98% by volume of 1-butene. Hydrogen was 6.30% by volume. A 300 ppm concentration of cocatalyst methylaluminoxane was added to the reactor, followed by initiation of a catalyst charging apparatus to charge the metallocene catalyst to the fluidized bed reactor at a flow rate of 1.0 kg/hr. Metallocene polyethylene g can be obtained according to the gas phase polymerization method.
  • the polyethylene g was subjected to temperature rising leaching grading test, continuous self-nucleating annealing hot grading test and other performance tests.
  • the fractions of each temperature are shown in Table 1.
  • the results of continuous self-nucleation annealing thermal grading test are shown in Table 2. Show, other performance test results are shown in Table 3.
  • the branching degree analysis of the 1820 grade polyethylene prepared by the traditional gas phase method of Shandong Qilu Petrochemical was carried out in the same manner as the branching degree analysis method used in Example 1.
  • the polyethylene is passed through a gas phase polymerization technique, using ethylene as a raw material, and 1-butene is a total
  • the polymonomer, hydrogen is a chain transfer agent, is prepared by polymerization in a gas phase fluidized bed reactor.
  • Tm is the melting temperature
  • f i is the relative content of each fraction
  • l is the number average crystallite thickness
  • MSL is the length of the methylene sequence.
  • the polyethylene ae produced by the method of the present invention all meet the temperature rise elution fraction of 40 ° C in the range of 9.0% - 40.0%, and 40 ° - 110 ° C every 10 ° C intervals
  • the standard deviation of the fraction ranges from 0% to 6.0%.
  • the polyethylene f prepared in Comparative Example 1 had a temperature rise and elution fraction of 40 ° C fraction not in the range of 9.0% to 40.0%.
  • the standard deviation of 35.1% of each component of °C is not within the reasonable protection range described in the present invention.
  • the platelet thickness distribution of the polyethylene ae produced by the method of the present invention is similar, and the platelet thickness of the P7 fraction (high molecular weight fraction) is 14-15 nm, which is lower than
  • the platelet thickness of polyethylene f and g indicates that the polyethylene branch obtained by the method of the invention has a wider distribution and a significantly higher branching content in the high molecular weight portion, thereby significantly improving the mechanical properties of the product.
  • the main feature of the method for producing polyethylene of the present invention is that the content of the low molecular weight portion is remarkably improved, and the branching content of the high molecular weight portion is remarkably increased.
  • the mechanical strength of polyethylene depends mainly on its high molecular weight fraction, and the branching of the high molecular weight fraction enhances the entanglement between the lanyard molecules, thereby increasing the tensile strength of the product.
  • Fig. 1 the branching of the conventional vapor-phase polyethylene is distributed on a molecular chain having a molecular weight of 110,000 or less, and the polyethylene molecular chain of 110,000 or more has almost no branched structure, and the branched chain distribution of the polyethylene provided by the present invention is obtained.
  • the molecular chain having a molecular weight of 150,000 is reached, the distribution of the branches between the molecular chains is wide, and the branching content of the high molecular weight portion is remarkably increased.
  • the low molecular weight and high degree of branching of the polyethylene produced by the method of the invention plays a nucleating role in the crystallization of the polymer, so the spherulite crystal grains of the whole polymer are more, and the grain size smaller.
  • the effect of spherulite size on performance is significant. In general, the spherulite size decreases, the haze of the polyethylene decreases, that is, the transparency increases; the spherulite size decreases, and the impact strength of the polyethylene increases.

Abstract

本发明提供了一种聚乙烯材料及其应用，所述聚乙烯材料的密度分布在0.880-0.960g/cm3的范围；对所述聚乙烯材料进行升温淋洗分级得到的40℃级分的含量在9.0-40.0wt％的范围，优选在10.0-25.0wt％的范围，更优选在9.9-20.0wt％的范围；且所述聚乙烯材料的熔融温度熔点在110-135℃的范围，优选在116-130℃的范围。根据本发明提供的聚乙烯材料中低分子、高支化度的级分含量明显高，同时高分子量级分含量也相对较高，且所述高分子量级分具有高支化度。在此情况下，所述聚乙烯材料具有相对较高的熔融温度。

Description

一种聚乙烯材料及其应用 技术领域
本发明涉及聚乙烯技术领域，具体涉及一种新的聚乙烯聚合物及其应用。
背景技术
聚乙烯是目前世界上应用最为广泛、产量最大的烯烃聚合物，是一种具有多种结构和特性的热塑性通用塑料，是合成树脂的主要品种之一。聚乙烯的产品分类众多，例如有高密度聚乙烯(HDPE，密度为0.940-0.960g/cm3)、中密度聚乙烯(MDPE，0.926-0.940g/cm3)、低密度聚乙烯(LDPE，0.88-0.926g/cm3)、线性低密度聚乙烯(LLDPE，0.915-0.926g/cm3)和极低密度聚乙烯(VLDPE，0.890-0.915g/cm3)。聚乙烯按照聚合方法分类主要有：淤浆聚合法、溶液聚合法和气相聚合法。其中气相聚合流化床工艺的生产能力约占世界聚乙烯总生产能力的1/3，在中国的比例更是接近1/2。相对于其他几种聚合方法，气相聚合有工艺简单、流程短、操作灵活方便、反应条件温和、溶剂回收处理以及牌号切换方便等优点。
对于聚乙烯，分子量及其分布对其产品性能有很大影响。高分子量的聚乙烯其物理机械性能较好，但是存在着加工难度大的缺点。低分子量的聚乙烯其加工流变性能良好，但是物理机械性能较差。过去，用于调节聚乙烯分子量和分子量分布的常用方法是改变反应体系中氢气的分压。目前，对聚乙烯生产的调控已不再局限于此方法，α-烯烃共聚单体的加入同样会改变聚乙烯的分子量及其分布，同时，α-烯烃共聚单体还会改变聚乙烯的支链结构，故而能够调控聚乙烯的物理性能和加工性能。
EP0038119的欧洲专利涉及一种三元共聚物，其中乙烯和α-烯烃符合以下关系：乙烯％+Aα-烯烃％＝3.0至5.0，其中对于1-己烯，A为0.455；此范围外的三元共聚物的特性有利于制造薄膜。专利申请WO 2006/002778涉及一种包括丙烯/乙烯和α-烯烃的三元共聚物的管道系统，其中所述乙烯含量介于0至9mol％，优选介于1mol％至7mol％，且1-己烯含量介于0.2mol％至5mol％。在这些范围内进行选择，获得可用于薄膜的具有改良性质的聚合物。
中国专利申请CN1384844涉及一种乙烯与C3-C12 α-烯烃的共聚物，该共聚物的摩尔 质量分布Mw/Mn<10，其密度是0.85g/cm3至0.95g/cm3，共聚单体含量为1至40wt％，以及摩尔质量Mn大于150000g/mol，并且共聚单体的组成分布的宽度指数大于70％。该聚合物可以用于纤维、模制品、箔或聚合物混合物。
尽管通过采用α-烯烃作为共聚单体来合成乙烯共聚物已经产生了多种多样的聚乙烯产品，但是在世界范围内仍然有许多国家并未具备大规模生产乙烯/α-烯烃共聚物的设备和能力。因此，一方面目前以及未来市场上均存在对具有优良性能的聚乙烯产品的进一步需求，尤其在α-烯烃资源稀缺地区；另一方面，更重要的是，仍然存在对具有特殊结构和组成特征的聚乙烯产品的不断的需求。因此，加快烯烃共聚聚乙烯产品的研究开发和生产十分重要。
发明内容
本发明的目的在于提供一种新型的聚乙烯聚合物，该聚乙烯聚合物可通过在单一反应器中进行烯烃共聚和烯烃均聚交替操作生产，可以是从极低密度聚乙烯VLDPE到高密度聚乙烯HDPE的全密度覆盖聚乙烯产品，其低分子量部分含量高、支化度高，具有良好的延展性等物理性能。
根据本发明，提供了一种聚乙烯材料，所述聚乙烯材料的密度分布在0.880-0.960g/cm3的范围；对所述聚乙烯材料进行升温淋洗分级得到的40℃级分的含量在9.0-40.0wt％的范围，优选在10.0-25.0wt％的范围，更优选在9.9-20.0wt％的范围；且所述聚乙烯材料的熔融温度在110-135 ℃的范围，优选在116-130℃的范围，更优选在119-128℃。
所述40℃的级分含量例如为9.0、9.5、9.9、10.0、11.0、12.0、13.0、14.0、15.0、16.0、18.0、20.0、22.0或24.0wt％等。
所述聚乙烯材料的熔融温度例如为116、118、120、121、122、123、125或128℃等。
在本发明的优选实施方式中，所述聚乙烯材料在50℃的级分含量在9.0-40.0wt％的范围，优选在10.0-25.0wt％的范围，更优选在10.2-16.0wt％的范围；如9.5、9.9、10.2、11.0、12.0、13.0、14.0或15.0等。
根据本发明提供的聚乙烯聚合物的一个突出的特点是，其中的低分子量级分(尤其是40℃的级分)含量相对于现有的常规聚乙烯、例如通过传统气相法制备的聚乙烯显著增高，且支化度高。公知的是，聚乙烯的分子量越低，支化度越高,结晶度就越低。所以，本领域技术人员可以理解的是，当低分子量级分含量高时，聚乙烯材料的熔融温度会有所下降。然而，本发明人意外地发现，本发明提供的所述聚乙烯材料在低分子量级分含量高的情况下却仍然具有较高的熔融温度。并进一步发现，具有此特征的本发明提供的聚乙烯材料尤 其具有良好的双向延展性，是一种具有良好加工和使用性能的尤其适用于制成膜的材料。
在本发明的优选实施方式中，所述聚乙烯材料在110℃的级分含量在8.0-30.0wt％的范围，优选在9.0-18.0wt％的范围，例如9.0、10.0、11.0、12.0、13.0、14.0、15.0或16.0wt％。
根据本发明提供的聚乙烯材料的高分子量级分(尤指110℃的级分)的含量也相对较高，且这部分的支化度相对于常规聚乙烯而言有所提高。因此，本发明提供的聚乙烯聚合物中的支链在分子链间的分布相对较宽，且较多的支链部分分布在高分子量级分部分。
在本发明的优选实施方式，由升温淋洗分级测定的、所述聚乙烯材料在40-100℃中每间隔10℃的级分的含量的标准偏差范围在0-6.0％，优选在0.5-3.0；进一步地，优选所述聚乙烯材料在40-110℃中每间隔10℃的级分的含量的标准偏差范围在0-6.0％，优选0.5-3.5％。根据本发明的该优选实施方式，聚乙烯材料的各个级分之间的含量是相对平均的，也体现了本发明的高分子量和低分子量级分部分的含量相对较高。
根据本发明的优选实施方式，所述聚乙烯材料的数均片晶厚度为6-18nm，重均片晶厚度为8 -20nm，优选片晶厚度的分布系(数重均片晶厚度/数均片晶厚度)为1-1.333。所述片晶厚度可采用本领域公知的连续自成核退火热分级技术来测定。
根据本发明的优选实施方式，所述聚乙烯材料的重均分子量为5000-350000，优选10000 -250000；分子量分布系数(PDI)为2.0-15.0，优选2.5-6.0。
根据本发明的优选实施方式，所述聚乙烯材料的熔体流动指数(230℃，2.16kg)为0.8-2.0g/10min；和/或，拉伸屈服强度为15-25MPa；和/或，断裂伸长率为450-700％；和/或，落镖冲击强度为200-260g。根据本发明提供的聚乙烯材料的雾度优选为6-18％。由此可见，本发明提供的聚乙烯材料具有良好的延展性和其他优良的力学性能。
由上文可知，本发明提供了一种具有如上独特的特征(或特征组合)的新的聚乙烯材料，具有良好的力学性能和加工性能。
在本发明的优选实施方式中，所述聚乙烯材料在单一反应器中制备。
在本发明的进一步优选实施方式中，所述聚乙烯材料通过在单一反应器中的乙烯均聚反应和乙烯共聚反应之间、或者不同共聚反应之间的交替进行来制备。
即，根据本发明提供的聚乙烯材料，并非由不同分子量的乙烯均聚物和/或乙烯共聚物物理混合，或者进一步经熔融共混而成。本发明提供的聚乙烯材料各级分间为化学共混，为分子链级的混合。
在本发明的进一步优选实施方式中，所述聚乙烯材料通过包括以下步骤的方法(气液法烯烃聚合工艺)制备：将包含乙烯的反应原料通入单一反应器进行聚合反应中，间歇地 通入包含共聚单体的冷凝液，以控制所述反应器中实现乙烯均聚和共聚之间、或者不同共聚反应之间的切换。
是否通入包含共聚单体的冷凝液，可根据预定的在反应器中进行乙烯共聚还是均聚来决定。例如，若预定接下来的反应为均聚反应，则停止通入共聚单体；反过来，若预定接下来的反应为共聚反应，则按需要选择并通入合适的共聚单体。因此，所述“间歇地通入”是指选择性地通入，例如根据对反应器中进行共聚或是均聚反应、共聚反应类型的需要等，每隔一段时间通入，或每隔一段时间不通入。
在优选的实施方式中，包含不同种类的共聚单体的冷凝液可分别装在不同的储罐中，根据需要在适当的时间通入所述反应器中。
在本发明的一个优选实施方式中，优选首先进行乙烯共聚反应，然后再进行乙烯均聚反应和乙烯共聚反应之间、或者不同共聚反应之间的切换模式的反应。即，初始反应是乙烯共聚反应，然后再切换成乙烯均聚反应，接着按照预定的反应切换程序继续进行反应。此优选实施方式的优势是初始生成的共聚聚乙烯颗粒疏松，颗粒内的活性中心不会被包埋，保证了后期的聚合活性。
根据本发明的优选实施方式，反应器中的聚合反应的反应压力为0.5-10MPa，优选1.5-5MPa；反应温度为40-150℃，优选50-120℃，还优选50-110℃。
在一个具体的实施方式中，当施行乙烯均聚时，反应器中的气体物料从反应器顶部排出，可经过压缩、冷凝和气液分离，分为气相物流和液相物流。液相物流主要为共聚单体和冷凝剂，可储存于储罐中；气相物流主要为乙烯和氢气，其从流化床反应器下部和其他原料一起返回反应器。此时，流化床反应器内主要为乙烯和氢气氛围，共聚单体和冷凝剂的含量极少，发生乙烯的均聚生长，生成支化度低密度大的HDPE。按照设定时间聚合后，切换到乙烯共聚模式，共聚单体和冷凝剂从储料罐中注入反应器，可以从反应器底部或其分布板上部侧壁单点或多点引入，下部低温反应区生成低密度高分子量的聚乙烯，上部高温区生成高密度低分子量的聚乙烯。未反应的原料从反应器上部排出并经过压缩、冷凝、和气液分离，气相物流和液相物流均返回流化床继续参与反应。按照设计的聚合时间反应结束后，继续切换到烯烃均聚，依此不断交替操作，总聚合时间优选为2-4小时，最终得到所需的高性能聚乙烯产品。
采用乙烯共聚制备低/高密度聚乙烯时，反应体系内有乙烯、共聚单体、氢气、催化剂、助催化剂和冷凝剂等。反应器内分为气液固相的反应区和气固相反应区。所述气固相反应区为高温反应区，其共聚单体含量较低，温度优选在80-110℃之间，优选为80-104℃之间；这个反应区反应得到相对高密度低分子量聚乙烯。所述气液固相反应区为低温反应 区，其共聚单体含量较高，温度优选在50-77℃之间，优选为60-77℃之间；这个反应区反应得到相对低密度高分子量聚乙烯。
进一步优选地，气固相反应区和气液固相反应区两个区域间存在至少10℃以上的温差，优选温差至少为15℃。
在优选的实施方式中，在乙烯均聚阶段中，聚合温度为80-110℃之间，优选为85-110℃之间。
在本发明的优选实施方式中，乙烯均聚和共聚之间的切换频率至少为1次/小时，优选大于或等于3次/小时。
在本发明的优选实施方式中，不同共聚反应之间的切换频率至少为1次/小时，优选大于或等于3次/小时。
根据本发明的优选实施方式，每个均聚阶段的操作时间持续3-60分钟，优选8-20分钟；每个共聚阶段的操作时间持续5-60分钟，优选8-20分钟。
在本发明的优选实施方式中，在乙烯共聚过程中，反应器内共聚单体与乙烯的摩尔比为0-0.1。
在本发明的优选实施方式中，在烯烃均聚和烯烃共聚过程中，反应器内氢气与乙烯的摩尔比为0.01-1.0。
在本发明优选的实施方式中，反应原料气流量为1-500吨/小时。
根据本发明的优选实施方式，所述共聚单体选自18个碳原子以下的烯烃，尤其是α-烯烃，优选选自丁烯、己烯和辛烯，尤其是优选自α-丁烯、α-己烯和α-辛烯，最好是1-己烯。本发明提供的聚乙烯材料优选为乙烯与丁烯、己烯和辛烯中的至少一种的无规共聚物。
根据本发明尤其优选的实施方式，所述聚乙烯材料为乙烯/1-己烯共聚物、乙烯/1-丁烯/1-己烯无规共聚物或乙烯/1-己烯/1-辛烯无规共聚物。
在一个具体的实施方式中，所述聚乙烯材料为乙烯/1-丁烯/1-己烯无规共聚物，其通过首先使乙烯、1-丁烯和1-己烯发生共聚反应，然后切入乙烯均聚反应阶段，再切入乙烯、1-丁烯和1-己烯的共聚反应阶段，如此循环反应来制备。其中，共聚、均聚反应的时间如上所限定。
在一个具体的实施方式中，所述聚乙烯材料为乙烯/1-己烯/1-辛烯无规共聚物，其通过首先使乙烯和1-辛烯进行共聚反应，然后切入乙烯均聚反应阶段，再切入乙烯和1-己烯共聚反应阶段，接着切入乙烯均聚反应阶段，再切入乙烯和1-辛烯的共聚反应阶段进行循环反应来制备。其中，共聚、均聚反应的时间如上所限定。
适用的冷凝剂优选选自C4-C7的饱和直链或支链的烷烃，以及C4-C7的环烷烃中的至少一种；优选正戊烷、异戊烷、己烷和庚烷中的至少一种；最优选异戊烷和/或己烷。
根据本发明的优选实施方式，在聚合反应过程中，将助催化剂、抗静电剂、链转移剂、分子调节剂、冷凝剂和惰性气体中的至少一种通入反应器中。该优选实施方式中所述冷凝剂为额外的冷凝剂，即可不含共聚单体的冷凝剂。
所述抗静电剂是常规的抗静电剂，例如选自双硬脂酸铝、乙氧基化的胺、聚砜共聚物、聚合多胺和油溶性磺酸等中的一种或多种的组合物。
所述链转移剂是常规的链转移剂，包括氢和烷基金属，优选氢气。
所述惰性气体可以使常规使用的惰性气体，例如氮气。
在本发明聚乙烯材料的制备过程中使用的催化剂可以采用以下至少一种：Ziegler-Natta催化剂、茂金属催化剂、过渡金属催化剂、无机铬催化剂、有机铬催化剂，或者两种催化剂的复合催化剂。优选能聚合聚乙烯的茂钛催化剂，更优选负载于载体上的茂钛催化剂。助催化剂选自以下至少一种：改性铝氧烷、一氯二乙基铝、一氯二异丁基铝、倍半乙基氯化铝、二异丁基铝、二氯一乙基铝、三甲基铝、三乙基铝、三异丁基铝、三辛基铝、一氢二乙基铝和一氢二异丁基铝，优选三乙基铝或三异丁基铝。
根据本发明，用于制备本发明聚乙烯材料的所述反应器优选为流化床反应器。
本发明还提供根据本发明提供的聚乙烯材料的应用，例如在薄膜(或薄膜制品)的制备中的应用；所述薄膜(薄膜制品)优选包括包装材料和/或商品标签，更优选蒸煮膜、高透明膜、阻隔保护膜、热封膜或标签膜。
根据本发明提供的聚乙烯材料具有特异的特征，如低分子、高支化度的级分含量明显高，高分子量级分含量也相对较高，且所述高分子量级分具有高支化度，同时所述聚乙烯材料还具有相对较高的熔融温度。同时，所述聚乙烯材料是全密度型聚乙烯，具有合适的分子量大小和分子量分布。由此，本发明提供的聚乙烯材料具有提高的力学性能和加工性能，例如良好的延展性、抗冲击性，是一种具备客观应用前景的材料。
附图说明
以下结合附图来对本发明进行详细地描述。应当理解，附图的提供仅是为了更好地理解本发明，其不应当被理解成对本发明的限制。
图1显示了实施例1制备的聚乙烯和对比例3的聚乙烯的支化度分析对比结果。
具体实施方式
以下结合实施例和附图对本发明进行详细描述，但需要理解的是，所述实施例和附图仅用于对本发明进行示例性的描述，而并不能对本发明的保护范围构成任何限制。所有包含在本发明的发明宗旨范围内的合理的变换和组合均落入本发明的保护范围。
本发明所采用的表征手段如下。
熔融温度：使用差示扫描量热仪(美国TA公司，型号TA Q200)测定。具体方法为：称量样品6mg左右，以20℃/min的速率加热至220℃左右，并在氮气流中保持2min，然后将其以20℃/min的速率冷却至40℃左右，在此温度下保持2min以结晶样品。然后将该样品以20℃/min的升温速率升温至220℃再次熔化。记录熔融扫描过程，获得热分析图，并由此读出熔融温度。
熔体流动指数MFR：根据GB/T3682-83测定熔体流动指数MFR，在230℃，2.16kg下测定。
密度：根据GB/T1033-70 测定。
拉伸屈服强度、断裂伸长率：根据GB/T1040-79测定。
雾度：根据GB/T2410-80测定。
落镖冲击强度：根据GB/T9639-88测定。
重均分子量及分子量分布系数：采用凝胶渗透色谱Polymer Laboratories PL-220仪器测定。管柱及旋转格室在140℃操作。溶剂是1,2,4-三氯苯，聚合物浓度为3‰。注射体积100微升，流速1.0毫升/分钟。
升温淋洗分级试验
升温淋洗分级技术(TREF)是根据链结构参数对聚乙烯分子的结晶过程和结晶度大小的影响不同而对聚乙烯分子按结晶度大小进行分级，分离成多个分布较窄的级分。
升温淋洗分级包括结晶沉析和升温淋洗两个过程：
结晶沉析阶段，聚乙烯高温下溶解形成稳定的稀溶液，缓慢降温会使聚乙烯晶体沉积在载体物质(石英沙等惰性微粒)的表面；链结构不同的聚乙烯分子形成结晶度成梯度分布的结晶层，如短支链含量不同的聚乙烯分子由于结晶能力不同，会按照结晶度从大到小形成从里到外的梯度分布。
升温淋洗阶段，将沉积有聚乙烯结晶层的载体物质装载在淋洗柱中，在连续或间歇升温环境下，采用聚乙烯良溶剂对载体进行淋洗，即可分级出不同结晶度的聚乙烯。
本发明所采用的升温淋洗分级试验为本领域常规操作过程，具体操作如下：
(1)石英沙处理
淋洗瓶填充石英沙用水充分冲洗，除去杂质，选取50目。将洗后石英沙在800℃下烘烤4小时，往淋洗瓶中填充处理后石英沙到指定高度。
(2)聚合物溶液配制
将1.2g聚合物样品(并加0.1g BHT抗氧剂)溶于250ml二甲苯中，容器采用磁力搅拌。待溶到肉眼看不出固体后，再搅拌2个小时，保证聚合物样品充分溶解。将溶解好的样品从三口瓶的小口径管小心迅速地倒入沙瓶中，再用60ml二甲苯溶液分两次倒入沙瓶洗涤。保证洗后总液面高度低于沙面高度，以低于沙面1-2cm为佳。
(3)程序降温(结晶沉析阶段)
样品溶液加入淋洗瓶后，启动油浴的程序降温，以1.5℃/h的速率从130℃降到室温(30℃)。此过程中，高结晶温度聚合物成分首先析出并包裹在石英沙表层，之后低结晶温度的级份析出。
(4)程序升温(升温淋洗阶段)
将装有纯二甲苯溶剂的烧瓶置于程序升温控制的油浴中，通过一个循环泵，从高端向淋洗瓶中注入二甲苯，利用液位差将不同淋洗温度的聚合物溶液压出到一个收集瓶中。其中，本发明收集并测定了在40℃-110℃淋洗温度范围的级分淋洗液，每间隔10℃收集一个相应级分的淋洗液样品。
(5)淋洗液处理
所得各级份淋洗液通过旋转蒸发仪减压浓缩后，用异丙醇沉淀、过滤、烘干、称重、计算含量。
连续自成核退火热分级试验
连续自成核退火热分级技术(SSA)一般包括以下几步：
(1)将样品升温至熔融温度以上(至少高于熔融温度25℃)，恒温一定时间以消除热历史；
(2)将样品以一定的降温速率降温至预先设定的最低温度(此最低温度保证样品能在此温度下结晶)，并在最低温度下恒温一段时间；
(3)将样品以一定的升温速率升至第一个设定好的自成核温度TS(一般高于熔融温度25℃)，并恒温一段时间；
(4)重复步骤(2)；
(5)将样品以一定的升温速率升温至下一个设定的自成核温度TS(相对于前一个自成核温度TS，下一个自成核温度TS下降2.5或5℃)，并恒温一段时间，如此循环(整个热分级处理的温度范围与样品的熔程相似)；
(6)将样品以一定的升温速率升温至步骤(1)设定的熔融温度，记录升温熔融曲线。
本发明所采用的连续自成核退火热分级试验为本领域常规操作步骤，具体方法如下：
使用差示扫描量热仪(美国TA公司，型号TA Q200)，在氮气气氛下，将聚乙烯样品以10℃/min从室温升温至160℃，恒温3min消除热历史；以10℃/min降温至0℃，停留5min；以10℃/min升温至成核温度TS，停留5min；以10℃/min降温至0℃，停留5min，完成一个自成核过程。记录聚乙烯在127、122、117、112、107、102、97℃进行自成核退火的分级结果，依次以P1、P2、P3、P4、P5、P6、P7表示前述温度下的级分。分级结束后，最后以10℃/min的速率升温至160℃，记录最终的熔融曲线。
实施例1
在流化床反应器中进行乙烯均聚和乙烯/1-己烯共聚反应来制备本发明的聚乙烯材料。在所述流化床反应器中装填齐格勒纳塔催化剂和三乙基铝的催化体系。将反应原料气(包含氮气、氢气、乙烯、甲烷、乙烷、1-己烯和少量异戊烷)和冷凝液异戊烷(包含有1-己烯)从反应器底部入口通入，入口的温度为58℃，首先进行乙烯/1-己烯共聚反应。将反应后的剩余气体作为循环气体从所述反应器的顶部出口导出，对所述循环气体经压缩、冷凝和气液分离。将液体料流储存至1-己烯储罐中，同时将剩余气体作为循环气体经反应器进料口循环至反应器中继续进行反应。循环气通入反应器床层底部时是气液混合物，流化床内的液体质量分数24wt％，表观流化气速为0.63m/s。床层底部聚合(气液固反应区)温度为68℃，而床层上部聚合(气固反应区)温度为85℃。循环气中液体异戊烷的露点温度介于床层底部温度与上部温度之间。共聚聚合时间为15分钟。
经过预定时间的共聚聚合反应之后，将反应切入乙烯均聚阶段。通入反应器底部入口的循环气包括氢气、氮气、甲烷、乙烷、乙烯、1-己烯和少量异戊烷，压力为3.1MPa，温度为100℃。循环气经多次循环后，从换热器出来的循环气流中不含冷凝液，气相密度为28.0kg/m3，经气液分离后的α-烯烃和异戊烷(占循环气流的80％)注入储料罐，未分离的少量冷凝液和α-烯烃随同循环气注入流化床反应器。气相聚合时间(包含工艺切换操作时间)8分钟。
然后，从乙烯均聚又切入乙烯/1-己烯共聚，1-己烯和异戊烷冷凝液通过进料泵从流化 床分布板上部引入，下部聚合温度逐步降低至68℃。此阶段共聚反应进行时间为15分钟。
依此循环交替操作，聚合时间为3小时，得到聚乙烯a。
对聚乙烯a分别进行升温淋洗分级测试、连续自成核退火热分级测试和其他性能测试，各温度的级分含量如表1所示，连续自成核退火热分级测试结果如表2所示，其他各项性能测试结果见表3。
此外，使用核磁共振仪(美国瓦里安公司，型号NMK/300MHZ)对聚乙烯a进行支化度分析，并与传统气相法聚乙烯的相应测试结果进行比较，结果见图1。
结合表2，引入统计学参数来定量表达片晶厚度的多分散性。利用式(1)和式(2)分别计算出样品的数均片晶厚度(ln)和重均片晶厚度(lw)，利用式(3)计算片晶厚度的分布系数(I)，结果见表4。I越大，样品的片晶厚度分布越宽，即可结晶序列长度分布越宽，对应于分子结构上，短链支化的分布更加无规。
ln＝(n1l1+n2l2+…+nili)/(n1+n2+…+ni)＝∑fili      (1)
lw＝(n1l1 2+n2l2 2+…+nili 2)/(n1l1+n2l2+…+nili)＝∑fili 2/∑fili    (2)
I＝lw/ln         (3)
式中，ni为每个级分的峰面积；li为每个级分的数均片晶厚度；fi为每个级分的相对含量。
实施例2
在流化床反应器中进行乙烯均聚和乙烯/1-己烯共聚反应来制备本发明的聚乙烯材料。在所述流化床反应器中装填齐格勒纳塔催化剂和三乙基铝的催化体系。将反应原料气(包括氢气、氮气、甲烷、乙烷、乙烯、1-己烯和少量异戊烷)和冷凝液异戊烷(含有1-己烯)从反应器底部入口通入，入口的温度为60℃，首先进行乙烯/1-己烯共聚反应。将反应后的剩余气体作为循环气体从所述反应器的顶部出口导出，对所述循环气体经压缩、冷凝和气液分离。将液体料流储存至1-己烯储罐中，同时将剩余气体作为循环气体经反应器进料口循环至反应器中继续进行反应。循环气通入反应器床层底部时是气液混合物，流化床内的液体质量分数26wt％，表观流化气速为0.68m/s。床层底部聚合(气液固反应区)温度为75℃，而床层上部聚合(气固反应区)温度为92℃。循环气中液体异戊烷的露点温度介于床层底部温度与上部温度之间。共聚聚合时间为20分钟。
经过预定时间的共聚聚合反应之后，将反应切入乙烯均聚阶段。通入反应器底部入口 的循环气包括氢气、氮气、甲烷、乙烷、乙烯、1-己烯和少量异戊烷，压力为3.6MPa，温度为96℃。循环气经多次循环后，从换热器出来的循环气流中不含冷凝液，气相密度为27.2kg/m3，经气液分离后的α-烯烃和异戊烷(占循环气流的80％)注入储料罐，未分离的少量冷凝液和α-烯烃随同循环气注入流化床反应器。气相聚合时间(包含工艺切换操作时间)12分钟。
然后，从乙烯均聚又切入乙烯/1-己烯共聚，1-己烯和异戊烷冷凝液通过进料泵从流化床分布板上部引入，下部聚合温度逐步降低至75℃。此阶段共聚反应进行时间为8分钟。
依此循环交替操作，聚合时间为3小时，得到聚乙烯b。
对聚乙烯b分别进行升温淋洗分级测试、连续自成核退火热分级测试和其他性能测试，各温度的级分含量如表1所示，连续自成核退火热分级测试结果如表2所示，其他各项性能测试结果见表3。
实施例3
在流化床反应器中进行乙烯均聚和乙烯/1-己烯共聚反应来制备本发明的聚乙烯材料。在所述流化床反应器中装填齐格勒纳塔催化剂和三乙基铝的催化体系。将反应原料气(包含氢气、氮气、甲烷、乙烷、乙烯、1-己烯和少量异戊烷)和冷凝液异戊烷(包含有1-己烯)从反应器底部入口通入，入口的温度为56℃，首先进行乙烯/1-己烯共聚反应。将反应后的剩余气体作为循环气体从所述反应器的顶部出口导出，对所述循环气体经压缩、冷凝和气液分离。将液体料流储存至1-己烯储罐中，同时将剩余气体作为循环气体经反应器进料口循环至反应器中继续进行反应。循环气通入反应器床层底部时是气液混合物，流化床内的液体质量分数30wt％，表观流化气速为0.62m/s。床层底部聚合(气液固反应区)温度为70℃，而床层上部聚合(气固反应区)温度为84℃。循环气中液体异戊烷的露点温度介于床层底部温度与上部温度之间。共聚聚合时间为8分钟。
经过预定时间的共聚聚合反应之后，将反应切入乙烯均聚阶段。通入反应器底部入口的循环气包括氢气、氮气、甲烷、乙烷、乙烯、1-己烯和少量异戊烷，压力为2.6MPa，温度为88℃。循环气经多次循环后，从换热器出来的循环气流中不含冷凝液，气相密度为28.2kg/m3，经气液分离后的1-己烯和异戊烷(占循环气流的80％)注入储料罐，未分离的少量冷凝液和1-己烯随同循环气注入流化床反应器。气相聚合时间(包含工艺切换操作时间)8分钟。
然后，从乙烯均聚又切入乙烯/1-己烯共聚，1-己烯和异戊烷冷凝液通过进料泵从流化床分布板上部引入，下部聚合温度逐步降低至70℃。此阶段共聚反应进行时间为12分钟。
依此循环交替操作，聚合时间为2.5小时，得到聚乙烯c。
对聚乙烯c分别进行升温淋洗分级测试、连续自成核退火热分级测试和其他性能测试，各温度的级分含量如表1所示，连续自成核退火热分级测试结果如表2所示，其他各项性能测试结果见表3。
实施例4
在流化床反应器中进行乙烯均聚和乙烯/1-丁烯/1-己烯共聚反应来制备本发明的聚乙烯材料。在所述流化床反应器中装填齐格勒纳塔催化剂和三乙基铝的催化体系。将反应原料气(包含氢气、氮气、甲烷、乙烷、乙烯、1-丁烯、1-己烯和少量异戊烷)和冷凝液异戊烷(包含有1-己烯)从反应器底部入口通入，入口的温度为56℃，首先进行乙烯/1-丁烯/1-己烯共聚反应。将反应后的剩余气体作为循环气体从所述反应器的顶部出口导出，对所述循环气体经压缩、冷凝和气液分离。将液体料流储存至1-己烯储罐中，同时将剩余气体作为循环气体经反应器进料口循环至反应器中继续进行反应。循环气通入反应器床层底部时是气液混合物，流化床内的液体质量分数26wt％，表观流化气速为0.58m/s。床层底部聚合(气液固反应区)温度为70℃，而床层上部聚合(气固反应区)温度为86℃。循环气中液体异戊烷的露点温度介于床层底部温度与上部温度之间。共聚聚合时间为8分钟。
经过预定时间的共聚聚合反应之后，将反应切入乙烯均聚阶段。通入反应器底部入口的循环气包括氢气、氮气、甲烷、乙烷、乙烯、1-丁烯和少量异戊烷，压力为2.6MPa，温度为78℃。循环气经多次循环后，从换热器出来的循环气流中不含冷凝液，气相密度为26.2kg/m3，经气液分离后的α-烯烃和异戊烷(占循环气流的80％)注入储料罐，未分离的少量冷凝液和1-丁烯随同循环气注入流化床反应器。气相聚合时间(包含工艺切换操作时间)16分钟。
然后，从乙烯均聚又切入乙烯/1-丁烯/1-己烯共聚，1-己烯和异戊烷冷凝液通过进料泵从流化床分布板上部引入，下部聚合温度逐步降低至70℃。此阶段共聚反应进行时间为12分钟。
依此循环交替操作，聚合时间为3.5小时，得到聚乙烯d。
对聚乙烯d分别进行升温淋洗分级测试、连续自成核退火热分级测试和其他性能测试，各温度的级分含量如表1所示，连续自成核退火热分级测试结果如表2所示，其他各项性能测试结果见表3。
实施例5
在流化床反应器中进行乙烯均聚和乙烯/1-己烯/1-辛烯共聚反应来制备本发明的聚乙烯材料。在所述流化床反应器中装填齐格勒纳塔催化剂和三乙基铝的催化体系。将反应原料气(包含氢气、氮气、甲烷、乙烷、乙烯、1-辛烯和少量异戊烷)和冷凝液异戊烷(含有1-辛烯)从反应器底部入口通入，入口的温度为62℃，首先进行乙烯/1-辛烯共聚反应。将反应后的剩余气体作为循环气体从所述反应器的顶部出口导出，对所述循环气体经压缩、冷凝和气液分离。将液体料流储存至1-辛烯储罐中，同时将剩余气体作为循环气体经反应器进料口循环至反应器中继续进行反应。循环气通入反应器床层底部时是气液混合物，流化床内的液体质量分数26wt％，表观流化气速为0.66m/s。床层底部聚合(气液固反应区)温度为66℃，而床层上部聚合(气固反应区)温度为90℃。循环气中液体异戊烷的露点温度介于床层底部温度与上部温度之间。共聚聚合时间为10分钟。
经过预定时间的乙烯/1-辛烯共聚聚合反应之后，将反应切入乙烯均聚阶段。通入反应器底部入口的循环气包括氢气、氮气、甲烷、乙烷、乙烯、1-辛烯和少量异戊烷，压力为2.6MPa，温度为96℃。循环气经多次循环后，从换热器出来的循环气流中不含冷凝液，气相密度为26.2kg/m3，经气液分离后的α-烯烃和异戊烷(占循环气流的80％)注入储料罐，未分离的少量冷凝液和1-辛烯随同循环气注入流化床反应器。气相聚合时间(包含工艺切换操作时间)10分钟。
接着将反应切换至乙烯/1-己烯共聚反应。上述循环气从反应器底部进料口通入继续用于反应，同时通入1-己烯和冷凝液。将反应后的剩余气体作为循环气体从所述反应器的顶部出口导出，对所述循环气体经压缩、冷凝和气液分离。将液体料流储存至1-己烯储罐中，同时将剩余气体作为循环气体经反应器进料口循环至反应器中继续进行反应。循环气通入反应器床层底部时是气液混合物，流化床内的液体质量分数29wt％，表观流化气速为0.72m/s。床层底部聚合(气液固反应区)温度为70℃，而床层上部聚合(气固反应区)温度为88℃。循环气中液体异戊烷的露点温度介于床层底部温度与上部温度之间。共聚聚合时间为8分钟。
经过预定时间的乙烯/1-己烯共聚聚合反应之后，将反应切入乙烯均聚阶段。通入反应器底部入口的循环气包括氢气、氮气、甲烷、乙烷、乙烯、1-己烯和少量异戊烷，压力为2.8MPa，温度为96℃。循环气经多次循环后，从换热器出来的循环气流中不含冷凝液，气相密度为26.8kg/m3，经气液分离后的α-烯烃和异戊烷(占循环气流的80％)注入储料罐，未分离的少量冷凝液和1-己烯随同循环气注入流化床反应器。气相聚合时间(包含工艺切换操作时间)8分钟。
然后，从乙烯均聚又切入乙烯/1-辛烯共聚，1-辛烯和异戊烷冷凝液通过进料泵从流化床分布板上部引入，下部聚合温度逐步降低至66℃。此阶段共聚反应进行时间为10分钟。
依此循环交替操作，聚合时间为4.5小时，得到聚乙烯e。
对聚乙烯e分别进行升温淋洗分级测试、连续自成核退火热分级测试和其他性能测试，各温度的级分含量如表1所示，连续自成核退火热分级测试结果如表2所示，其他各项性能测试结果见表3。
对比例1
根据专利申请“CN200580027288”实施例中所述的方法，在单反应器系统中，使用气相聚合，采用喷雾干燥的催化剂系统来制备双峰聚乙烯树脂产物。在本对比例中，经喷雾干燥的催化剂组合物被悬浮于矿物油与己烷的混合物中得到催化剂淤浆，用于注射进入流化床反应器。典型的反应器条件是：聚合温度为85-100℃，己烯共聚单体的含量约为0.007(C6：C2摩尔比)，H2：C2摩尔比为0.0035。按照这个方法可以制得密度为0.946左右，展宽高达95的双峰聚乙烯f。
对聚乙烯f分别进行升温淋洗分级测试、连续自成核退火热分级测试和其他性能测试，各温度的级分含量如表1所示，连续自成核退火热分级测试结果如表2所示，其他各项性能测试结果见表3。
对比例2
在一个直径为3米、直筒高度12米的工业流化床烯烃聚合反应器中，以1-丁烯为共聚单体，反应物组成为：乙烯30.12体积％、1-丁烯6.98体积％、氢气6.30体积％。向反应器内加入300ppm浓度的助催化剂甲基铝氧烷，接着启动催化剂加料设备将茂金属催化剂按1.0kg/hr的流率加入流化床反应器。按照该气相聚合方法可以制得茂金属聚乙烯g。
对聚乙烯g分别进行升温淋洗分级测试、连续自成核退火热分级测试和其他性能测试，各温度的级分含量如表1所示，连续自成核退火热分级测试结果如表2所示，其他各项性能测试结果见表3。
对比例3
对山东齐鲁石化传统气相法制备的1820牌号聚乙烯进行支化度分析，方法同实施例1中采用的支化度分析方法。该聚乙烯通过气相法聚合技术，以乙烯为原料，1-丁烯为共 聚单体，氢气为链转移剂，在气相流化床反应器中聚合来制备。
表1 聚乙烯的升温淋洗分级测试结果
Figure PCTCN2016080041-appb-000001
表2 聚乙烯的连续自成核退火热分级测试结果
Figure PCTCN2016080041-appb-000002
Figure PCTCN2016080041-appb-000003
注：Tm为熔融温度；fi为各级分的相对含量；l为数均片晶厚度；MSL为亚甲基序列长度。
表3 聚乙烯的各项物性指标
Figure PCTCN2016080041-appb-000004
表4
Figure PCTCN2016080041-appb-000005
从表1中我们可知，用本发明所述方法生产得到的聚乙烯a-e均满足40℃的升温淋洗分级级分含量在9.0％-40.0％，且40-110℃每间隔10℃的各级分的标准差范围在0％-6.0％之间。对比例1制备的聚乙烯f其升温淋洗分级40℃级分含量不在9.0％-40.0％的范围内。对比例2中所述方法得到的聚乙烯g是利用茂金属催化剂制得的，其分子量分布系数很小(PDI＝1.1)，其升温淋洗分级40℃的级分含量0.0％和40-110℃各级分含量的标准差35.1％均不在本发明所述的合理保护范围之内。
从表格2中的数据我们可以发现，用本发明所述方法生产得到的聚乙烯a-e的片晶厚度分布相近，且P7级份(高分子量级份)的片晶厚度在14-15nm，低于聚乙烯f、g的片晶厚度，说明本发明所述方法生产得到的聚乙烯支链分布更宽，在高分子量部分的支链含量明显提高，从而显著提高了产品的力学性能。
同时，从表格2中还可以发现，本发明所述方法生产得到的聚乙烯a-e的P1级份(低分子量级份)的含量高于聚乙烯f、g，这与表格1的升温淋洗分级数据是相一致的。低分 子量级份的增加提高了产品的加工性能，使得本发明的聚乙烯产品有利于应用成型加工。
对照表1和表3中的数据我们可以发现，用本发明所述方法生产得到的聚乙烯a、b、c、d和e相较于用对比例1方法得到的聚乙烯f和对比例2得到的茂金属聚乙烯g在熔体流动指数、拉伸屈服强度、断裂伸长率和落镖冲击强度上都有明显的性能优势。
从链结构角度分析，本发明方法生产聚乙烯的主要特点是低分子量部分含量明显提高，且高分子量部分的支链含量显著增加。聚乙烯的力学强度主要取决于其高分子量部分，高分子量部分的支链增强了系带分子之间的缠结作用，从而提高了产品的拉伸强度。
从图1可以看出，传统气相法聚乙烯的支链分布在分子量110000以下的分子链上，110000以上的聚乙烯分子链几乎不含有支链结构，而本发明提供的聚乙烯的支链分布到达分子量150000的分子链，支链在分子链间的分布宽，高分子量部分的支链含量显著增加。
从晶态结构角度分析，本发明方法生产聚乙烯的低分子量、高支化度部分在聚合物结晶过程中起到了成核作用，所以整个聚合物的球晶晶粒数目更多，晶粒尺寸更小。对于聚乙烯来说，球晶尺寸对性能的影响很显著。一般来说，球晶尺寸下降，聚乙烯的雾度下降，即透明度提高；球晶尺寸下降，聚乙烯的冲击强度提高。
虽然本发明已作了详细描述，但对本领域技术人员来说，在本发明精神和范围内的修改将是显而易见的。此外，应当理解的是，本发明记载的各方面、不同具体实施方式的各部分、和列举的各种特征可被组合或全部或部分互换。在上述的各个具体实施方式中，那些参考另一个具体实施方式的实施方式可适当地与其它实施方式组合，这是将由本领域技术人员所能理解的。此外，本领域技术人员将会理解，前面的描述仅是示例的方式，并不旨在限制本发明。

Claims (17)

  1. 一种聚乙烯材料，所述聚乙烯材料的密度分布在0.880-0.960g/cm3的范围；对所述聚乙烯材料进行升温淋洗分级得到的40℃级分的含量在9.0-40.0wt％的范围，优选在10.0-25.0wt％的范围，更优选在9.9-20.0wt％的范围；且所述聚乙烯材料的熔融温度在110-135℃的范围，优选在116-130℃的范围。
  2. 根据权利要求1所述的聚乙烯材料，其特征在于，所述聚乙烯材料在110℃的级分含量在8.0-30.0wt％的范围，优选在9.0-18.0wt％的范围。
  3. 根据权利要求1或2所述的聚乙烯材料，其特征在于，由升温淋洗分级测定的、所述聚乙烯材料在40-100℃中每间隔10℃的级分的含量的标准偏差范围在0-6.0％，优选所述聚乙烯材料在40-110℃中每间隔10℃的级分的含量的标准偏差范围在0-6.0％，优选0.5-3.5％。
  4. 根据权利要求1-3中任一项所述的聚乙烯材料，其特征在于，所述聚乙烯材料的数均片晶厚度为6-18nm，重均片晶厚度为8-20nm，优选片晶厚度的分布系数为1-1.333。
  5. 根据权利要求1-4中任一项所述的聚乙烯材料，其特征在于，所述聚乙烯材料的重均分子量为5000-350000，优选10000-250000；分子量分布系数为2.0-15.0，优选2.5-6.0。
  6. 根据权利要求1-5中任一项所述的聚乙烯材料，其特征在于，所述聚乙烯材料的熔体流动指数(230℃，2.16kg)为0.8-2.0g/10min；拉伸屈服强度为15-25MPa；断裂伸长率为450-700％；落镖冲击强度为200-260g；和/或，雾度为6-18％。
  7. 根据权利要求1-6中任一项所述的聚乙烯材料，其特征在于，所述聚乙烯材料在单一反应器中制备，优选所述反应器为流化床反应器。
  8. 根据权利要求7所述的聚乙烯材料，其特征在于，所述聚乙烯材料通过在单一反应器中的乙烯均聚反应和乙烯共聚反应之间、或者不同共聚反应之间的交替进行来制备；优选首先进行乙烯共聚反应，然后再进行乙烯均聚反应和乙烯共聚反应之间、或者不同共聚反应之间的切换模式的反应。
  9. 根据权利要求1-8中任一项所述的聚乙烯材料，其特征在于，所述聚乙烯材料通过包括以下步骤的方法制备：将包含乙烯的反应原料通入单一反应器进行聚合反应中，间 歇地通入包含共聚单体的冷凝液，以控制所述反应器中实现乙烯均聚和共聚之间、或者不同共聚反应之间的切换。
  10. 根据权利要求9所述的聚乙烯材料，其特征在于，乙烯均聚和共聚之间的切换频率至少为1次/小时，优选大于或等于3次/小时；和/或
    不同共聚反应之间的切换频率至少为1次/小时，优选大于或等于3次/小时。
  11. 根据权利要求9或10所述的聚乙烯材料，其特征在于，每个均聚阶段的操作时间持续3-60分钟，优选8-20分钟；每个共聚阶段的操作时间持续5-60分钟，优选8-20分钟。
  12. 根据权利要求9-11任一项所述的聚乙烯材料，其特征在于，所述共聚单体选自18个碳原子以下的烯烃，优选选自丁烯、己烯和辛烯，更优选1-己烯。
  13. 根据权利要求9-12任一项所述的聚乙烯材料，其特征在于，所述冷凝剂选自C4-C7的饱和直链或支链的烷烃，以及C4-C7的环烷烃中的至少一种；优选正戊烷、异戊烷、己烷和庚烷中的至少一种；最优选异戊烷和/或己烷。
  14. 根据权利要求9-13任一项所述的聚乙烯材料，其特征在于，在聚合反应过程中，将助催化剂、抗静电剂、链转移剂、分子调节剂、冷凝剂和惰性气体中的至少一种通入反应器中。
  15. 根据权利要求9-14任一项所述的聚乙烯材料，其特征在于，反应器中的聚合反应的反应压力为0.5-10MPa，优选1.5-5MPa；反应温度为40-150℃，优选50-120℃。
  16. 根据权利要求1-15任一项所述的聚乙烯材料，其特征在于，所述聚乙烯材料为乙烯/1-己烯共聚物、乙烯/1-丁烯/1-己烯无规共聚物或乙烯/1-己烯/1-辛烯无规共聚物。
  17. 根据权利要求1-16中任一项所述的聚乙烯材料的应用，尤其在制备薄膜中的应用，所述薄膜优选包括包装材料和/或商品标签，更优选蒸煮膜、高透明膜、阻隔保护膜、热封膜、标签膜或医用包装膜。
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