WO2023051580A1 - 乙烯-α-烯烃共聚物及其制备方法和应用以及组合物 - Google Patents

乙烯-α-烯烃共聚物及其制备方法和应用以及组合物 Download PDF

Info

Publication number
WO2023051580A1
WO2023051580A1 PCT/CN2022/122018 CN2022122018W WO2023051580A1 WO 2023051580 A1 WO2023051580 A1 WO 2023051580A1 CN 2022122018 W CN2022122018 W CN 2022122018W WO 2023051580 A1 WO2023051580 A1 WO 2023051580A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethylene
olefin
olefin copolymer
mol
structural units
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2022/122018
Other languages
English (en)
French (fr)
Inventor
吴长江
李娟�
侯莉萍
王伟
张韬毅
罗春霞
张龙贵
郑俊鹏
郑刚
杜文杰
盛建昉
郜菲菲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to US18/697,054 priority Critical patent/US20240400732A1/en
Priority to JP2024519643A priority patent/JP2024534672A/ja
Priority to KR1020247012344A priority patent/KR20240055131A/ko
Priority to EP22874965.1A priority patent/EP4400522A4/en
Publication of WO2023051580A1 publication Critical patent/WO2023051580A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/09—Cyclic bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is part of a cyclic group
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/27—Amount of comonomer in wt% or mol%
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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

Definitions

  • the invention relates to the field of ethylene copolymers, in particular to an ethylene-copolymerized olefin copolymer with a high comonomer dispersion index, its preparation method and application, and a composition containing the ethylene- ⁇ -olefin copolymer.
  • Polyethylene is one of the most widely used materials commercially.
  • Ethylene polymers prepared using coordination polymerization technology include high-density polyethylene, medium-density polyethylene, linear low-density polyethylene, polyolefin plastic/elastomer, etc.
  • Polymerization techniques known in the art include slurry polymerization techniques, gas phase polymerization techniques and solution polymerization techniques, and the catalysts used are classified into titanium-based Z-N catalysts, chromium-based catalysts and metallocene catalysts.
  • the ethylene copolymer developed by using metallocene catalyst is one of the high-performance varieties of polyethylene. ene) transformation. With the increase of comonomer, the density of polyethylene decreases gradually, from high, medium and low density linear polyethylene to polyolefin plastic/elastomer in turn. Different from low-density polyethylene obtained by free radical polymerization, this type of low-density ethylene copolymer elastomer only contains short-chain branched structures formed by comonomers. The type, content and distribution of these short-chain branches directly affect the mechanical properties of the copolymer .
  • the purpose of the present invention is to provide a kind of ethylene-alpha-olefin copolymer with high comonomer dispersion index in order to overcome the problem that the dispersity of the existing ethylene-alpha-olefin copolymer comonomer existing in the prior art is not high enough and its preparation method and application as well as compositions comprising the ethylene-alpha-olefin copolymer.
  • the first aspect of the present invention provides an ethylene- ⁇ -olefin copolymer, wherein the ethylene- ⁇ -olefin copolymer contains 70-95 mol% of structural units derived from ethylene and 5-30 mol% of Structural units derived from ⁇ -olefins, the ⁇ -olefins are olefins with 5-10 carbon atoms, and the dispersion index RMD of the structural units of the ⁇ -olefins in the molecular chain is greater than 102%.
  • the ethylene- ⁇ -olefin copolymer contains 80-95 mol% of structural units derived from ethylene and 5-20 mol% of structural units derived from ⁇ -olefins, and the ⁇ -olefins have 5-10 carbon atoms olefin, and the dispersion index RMD of the structural unit of the ⁇ -olefin in the molecular chain is greater than 103%.
  • the ethylene- ⁇ -olefin copolymer contains 82-89mol% of structural units derived from ethylene and 11-18mol% of structural units derived from ⁇ -olefin; more preferably, the ethylene- ⁇ -olefin copolymer Containing 84-89mol% of structural units derived from ethylene and more than 11mol% and less than 17mol% of structural units derived from ⁇ -olefins; more preferably, the ethylene- ⁇ -olefin copolymer contains 84-89mol% of structural units derived from ethylene Structural units and 11-16 mol% of structural units derived from ⁇ -olefins.
  • the molecular chain dispersion index RMD of the structural units of the ⁇ -olefin is above 104%, more preferably 104-108%.
  • the molecular weight distribution Mw/Mn of the ethylene- ⁇ -olefin copolymer is 1.5-3, more preferably 1.5-2.5, even more preferably 1.5-2.3.
  • the melt index MFRC of the ethylene- ⁇ -olefin copolymer at a temperature of 190°C and a load of 2.16 kg is 1.0-50 g/10 min, more preferably 1-15 g/10 min.
  • the semi-melting enthalpy temperature T 1/2 of the ethylene- ⁇ -olefin copolymer is 5-80°C, more preferably 10-70°C, even more preferably 15-60°C.
  • the ⁇ -olefin is an olefin with 5-8 carbon atoms.
  • the ⁇ -olefin is one or more of 1-pentene, 1-hexene, 1-octene and 4-methyl-1 pentene, more preferably 1-octene alkene.
  • a method for preparing ethylene- ⁇ -olefin copolymer comprising: under the condition of olefin solution copolymerization, in the presence of catalyst, co-catalyst and phenol, make ethylene and ⁇ -olefin carry out copolymerization , to obtain ethylene- ⁇ -olefin copolymer,
  • the catalyst contains diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride and/or diphenylmethylene (cyclopentadienyl) (2,7-di-tert Butyl-fluorenyl) zirconium dichloride, the cocatalyst is an organoaluminum compound, and the phenol is 2,4-dihalo-1-naphthol,
  • the amount of ethylene and ⁇ -olefin is such that the molar ratio of the structural unit derived from ethylene to the structural unit derived from ⁇ -olefin in the ethylene- ⁇ -olefin copolymer is (80-95):(5-20), and the
  • the ⁇ -olefin is an olefin having 5 to 10 carbon atoms.
  • the amount of ethylene and ⁇ -olefin is such that the molar ratio of the structural units derived from ethylene to the structural units derived from ⁇ -olefin in the ethylene- ⁇ -olefin copolymer is (82-89):(11-18), More preferred are (84-89): (11-16).
  • the catalyst is used in an amount of 0.01-10 ⁇ 10 -6 mol in terms of active metal.
  • the organoaluminum compound is aluminoxane and/or hydrocarbyl aluminum represented by formula 1,
  • R 1 , R 2 and R 3 are the same or different, each independently selected from alkyl (including cycloalkyl), alkoxy, aryl, alkaryl, aralkyl and hydrogen, and R 1 , R 2 and R 3 are not hydrogen atoms at the same time.
  • the organoaluminum compound is preferably methylaluminoxane.
  • the molar ratio of the organoaluminum compound calculated as aluminum to the catalyst calculated as active metal is 50-5000:1.
  • the molar ratio of 2,4-dihalo-1-naphthol to the catalyst calculated as active metal is 1-500:1.
  • the 2,4-dihalo-1-naphthol is 2,4-dichloro-1-naphthol and/or 2,4-dibromo-1-naphthol, more preferably 2,4- Dichloro-1-naphthol.
  • the ⁇ -olefin is an olefin with 5-8 carbon atoms.
  • the ⁇ -olefin is one or more of 1-pentene, 1-hexene, 1-octene and 4-methyl-1 pentene, more preferably 1-octene alkene.
  • the olefin solution copolymerization conditions include: the copolymerization temperature is -40 to 200°C, preferably 25 to 120°C, more preferably 50 to 70°C; the partial pressure of ethylene during polymerization is 0.05-5MPa, preferably 0.1-2MPa , more preferably 0.8-1.2MPa.
  • the solvent used for olefin solution copolymerization is one or more of benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane and cyclohexane.
  • an ethylene- ⁇ -olefin copolymer composition wherein the composition contains the ethylene- ⁇ -olefin copolymer described in the present invention or the ethylene- ⁇ -olefin copolymer prepared by the preparation method of the present invention.
  • - olefin copolymers, and solvents are provided.
  • the solvent is the residual preparation solvent from the preparation of the ethylene- ⁇ -olefin copolymer.
  • the application of the ethylene- ⁇ -olefin copolymer of the present invention in the preparation of packaging films is provided.
  • the present invention can provide an ethylene- ⁇ -olefin copolymer with a high comonomer dispersion index, its preparation method and application, and a composition containing the ethylene- ⁇ -olefin copolymer.
  • the ethylene- ⁇ -olefin copolymer of the present invention has a high comonomer dispersion index, when compared with the existing ethylene- ⁇ -olefin copolymer, when the ⁇ -olefin comonomer molar percentage content is the same, the present invention
  • the ethylene-alpha-olefin copolymers of the invention have a lower half-melting enthalpy temperature.
  • the ethylene- ⁇ -olefin copolymer of the present invention has a high comonomer dispersion index, when compared with the existing ethylene- ⁇ -olefin copolymer, when the same crystallinity and melting temperature are achieved, the The ethylene- ⁇ -olefin copolymers have a smaller amount of ⁇ -olefin comonomer, which can reduce the cost.
  • an ethylene- ⁇ -olefin copolymer wherein the ethylene- ⁇ -olefin copolymer contains 70-95 mol% of structural units derived from ethylene and 5-30 mol% of ⁇ -olefin-derived
  • the structural unit of the ⁇ -olefin is an olefin with 5-10 carbon atoms, and the dispersion index RMD of the structural unit of the ⁇ -olefin in the molecular chain is greater than 102%.
  • the structural units of the comonomers are dispersed in the molecular chain in a "super random" state, which means that the ⁇ -olefins in which the structural units of ethylene are copolymerized
  • the structural units are dispersed very uniformly and efficiently, so that polymer-specific melting points and densities can be achieved with relatively small amounts of comonomers. This means that the raw material cost of the polymer can be effectively reduced.
  • the so-called "super random" dispersion state means that in the ethylene- ⁇ -olefin copolymer of the present invention, the comonomer structural units are arranged separately, rather than forming a row or block structure, That is to say, the comonomer structural units are discontinuous and randomly dispersed in the polymer molecular chain.
  • the degree of dispersion of the comonomers on the polymer chains is higher than the ideal random distribution.
  • the ethylene- ⁇ -olefin copolymer contains 80-95 mol% of structural units derived from ethylene and 5-20 mol% of structural units derived from ⁇ -olefin; more preferably, the ethylene- ⁇ - The olefin copolymer contains 82-89mol% of structural units derived from ethylene and 11-18mol% of structural units derived from ⁇ -olefins; further preferably, the ethylene- ⁇ -olefin copolymer contains 80-88mol% of structural units derived from ethylene Structural unit observations 12-20 mol% of structural units derived from ⁇ -olefins.
  • the specific content of structural units derived from ethylene in the ethylene- ⁇ -olefin copolymer can be, for example: 80mol%, 81mol%, 82mol%, 83mol%, 84mol%, 85mol%, 86mol%, 87mol%, 88mol% %, 89mol%, 90mol%, 91mol%, 92mol%, 93mol%, 94mol%, 95mol%, etc., and the range formed by any two of the above values. .
  • the specific content of structural units derived from ⁇ -olefin in the ethylene- ⁇ -olefin copolymer can be, for example, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, 10 mol%, 11 mol%, 12 mol% , 13mol%, 14mol%, 15mol%, 16mol%, 17mol%, 18mol%, 19mol%, 20mol%, etc., and the range formed by any two of the above values. .
  • the dispersion index RMD of the structural unit of the ⁇ -olefin in the molecular chain is 103% or more; more preferably, the dispersion index RMD of the structural unit of the ⁇ -olefin in the molecular chain is 104% or more More preferably, the dispersion index RMD of the structural unit of the ⁇ -olefin in the molecular chain is 104-108%; further preferably, the dispersion index RMD of the structural unit of the ⁇ -olefin in the molecular chain is 104-107% .
  • the dispersion index RMD of the structural unit of the ⁇ -olefin in the molecular chain can be, for example: 103.1%, 103.6%, 103.7%, 103.8%, 103.9%, 104%, 104.1%, 104.2%, 104.3%, 104.4 %, 104.5%, 104.6%, 104.7%, 104.8%, 104.9%, 105%, 105.1%, 105.2%, 105.3%, 105.4%, 105.5%, 105.6%, 105.7%, 105.8%, 105.9%, 106%, 106.1%, 106.2%, 106.3%, 106.4%, 106.5%, 106.6%, 106.7%, 106.8%, 106.9%, 107%, 107.1%, 107.2%, 107.3%, 107.4%, 107.5%, 107.6%, 107.7% , 107.8%, 107.9%, 108%
  • the dispersion index RMD of the structural unit of the ⁇ -olefin in the molecular chain is defined by the following formula, and is measured as follows:
  • AMD absolute comonomer dispersion
  • BMD complete random comonomer dispersion or Bernoulli dispersion
  • the monomer absolute dispersity AMD is determined by the following procedure. Absolute monomer dispersion is defined as the ratio of the number of comonomer clusters in the average molecule (N) divided by the number of monomer units in the average chain (X). If n 1 represents the number of isolated comonomer units and n 2 represents adjacent clusters of comonomer units up to ...n x clusters of x adjacent comonomer units in the copolymer, X and N are defined as follows:
  • the absolute comonomer dispersion AMD is thus defined as:
  • AMD would be 100 if only isolated comonomer units were present in the polymer molecule. Conversely, if all comonomer units are clustered together, AMD is 0.
  • the ideal random or Bernoulli distributed BMD is determined by the following formula:
  • MC concentration (mole percent) of comonomer in the polymer.
  • EXE, EXX, and XXX were determined based on NMR peak height or peak area.
  • X is O, representing 1-octene copolymerized units.
  • the relative monomer dispersion RMD can be determined according to the above formula. In the following description, the measured comonomer relative and absolute monomer dispersions are calculated from the above formulas.
  • the molecular weight distribution Mw/Mn of the ethylene- ⁇ -olefin copolymer may be 1.5-3, preferably 1.5-2.5, more preferably 1.5-2.3.
  • examples of the molecular weight distribution Mw/Mn of the ethylene- ⁇ -olefin copolymer include: 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8 , 2.9, 3.0, etc.
  • the melt index MFRC of the ethylene- ⁇ -olefin copolymer at a temperature of 190° C. and a load of 2.16 kg may be 1.0-50 g/10 min, preferably 1-15 g/10 min.
  • the melt index MFRC of the ethylene- ⁇ -olefin copolymer at a temperature of 190°C and a load of 2.16 kg can be, for example, 1.0 g/10 min, 2.0 g/10 min, 3.0 g/10 min, 4.0 g/ 10min, 5.0g/10min, 6.0g/10min, 7.0g/10min, 8.0g/10min, 9.0g/10min, 10.0g/10min, 11.0g/10min, 12.0g/10min, 13.0g/10min, 14.0g/ 10min, 15.0g/10min, 16.0g/10min, 17.0g/10min, 18.0g/10min, 19.0g/10min, 20.0g/10min, 21.0g/10min, 22.0g/10min, 23.0g/10min, 24.0g/ 10min, 25.0g/10min, 26.0g/10min, 27.0g/10min, 28.0g/10min, 29.0g/10min, 30.0g/10min, 31.0g/10min, 32.0g/10min, 33.0g/10min, 3
  • the semi-melting enthalpy temperature T 1/2 of the ethylene- ⁇ -olefin copolymer may be 5-80°C, preferably 10-70°C, more preferably 15-60°C.
  • T 1/2 is defined to indicate the corresponding melting temperature when the melting enthalpy is half of the total melting enthalpy.
  • a higher T 1/2 means a higher melting point, and conversely, a lower T 1/2 means a lower melting point.
  • the semi-melting enthalpy temperature T 1/2 of the ethylene- ⁇ -olefin copolymer includes, for example: 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, 11°C, 12°C, 13°C, 14°C, 15°C, 16°C, 17°C, 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C , 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, 36°C, 37°C, 38°C, 39°C, 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C °C, 47°C, 48°C, 49°C, 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58
  • the ⁇ -olefin is an olefin with 5-10 carbon atoms; preferably, the ⁇ -olefin is an olefin with 5-8 carbon atoms; more preferably, the ⁇ -olefin is Alkenes with 6-8 carbon atoms.
  • the ⁇ -olefin for example, one or more of 1-pentene, 1-hexene, 1-octene and 4-methyl-1 pentene can be mentioned; preferably, the ⁇ -olefin is 1-octene.
  • the ethylene- ⁇ -olefin copolymer is an ethylene/-octene copolymer, because the ethylene/1-octene copolymer of the present invention has a high comonomer dispersion index, therefore, Compared with the existing ethylene/1-octene copolymer, when the 1-octene comonomer molar percentage is the same, the ethylene/1-octene copolymer of the present invention has lower semi-melting enthalpy
  • the temperature for example, can be lowered by 2°C-8°C, preferably by 3°C-6°C, more preferably by 4°C-5°C.
  • the ethylene- ⁇ -olefin copolymer is an ethylene/-octene copolymer, because the ethylene/1-octene copolymer of the present invention has a high comonomer dispersion index, therefore .
  • the ethylene/1-octene copolymer of the present invention has a smaller amount of 1-octene copolymerized monomer Comonomers can be reduced by 0.3-1.2 mol%, preferably by 0.5-1.0 mol%, more preferably by 0.6-0.8 mol%.
  • the preparation method of the ethylene- ⁇ -olefin copolymer of the present invention comprises: the method comprises: under the condition of olefin solution copolymerization, in the presence of catalyst, co-catalyst and phenol , so that ethylene and ⁇ -olefins are copolymerized to obtain ethylene- ⁇ -olefin copolymers,
  • the catalyst contains diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride and/or diphenylmethylene (cyclopentadienyl) (2,7-di-tert Butyl-fluorenyl) zirconium dichloride, the cocatalyst is an organoaluminum compound, and the phenol is 2,4-dihalo-1-naphthol,
  • the amount of ethylene and ⁇ -olefin is such that the molar ratio of the structural unit derived from ethylene to the structural unit derived from ⁇ -olefin in the ethylene- ⁇ -olefin copolymer is (80-95):(5-20), and the
  • the ⁇ -olefin is an olefin having 5 to 10 carbon atoms.
  • the amount of ethylene and ⁇ -olefin is such that the molar ratio of the structural unit derived from ethylene to the structural unit derived from ⁇ -olefin in the ethylene- ⁇ -olefin copolymer is (82-89) : (11-18); More preferably, the consumption of ethylene and ⁇ -olefin makes the molar ratio of the structural unit from ethylene and the structural unit from ⁇ -olefin in the ethylene- ⁇ -olefin copolymer be (84-89 ): (11-16).
  • the amount of the catalyst used can be selected according to the amount of ethylene used, preferably, relative to 1 mol of the ethylene, the amount of the catalyst used in terms of active metal is 0.01-10 ⁇ 10 -6 mol ; More preferably, relative to 1 mol of the ethylene, the catalyst is used in an amount of 0.1-5 ⁇ 10 -6 mol in terms of active metal.
  • the organoaluminum compound may be aluminoxane and/or hydrocarbyl aluminum.
  • the organoaluminum compound aluminoxane, preferably methylaluminoxane (MAO).
  • the organoaluminum compound is hydrocarbylaluminum represented by formula 1,
  • R 1 , R 2 and R 3 are the same or different, each independently selected from alkyl (including cycloalkyl), alkoxy, aryl, alkaryl, aralkyl and hydrogen, and R 1 , R 2 and R 3 are not hydrogen atoms at the same time;
  • alkylaluminum compound may include, but are not limited to: diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diphenylaluminum hydride, di-p- Tolyl aluminum hydride, dibenzyl aluminum hydride, phenylethyl aluminum hydride, phenyl n-propyl aluminum hydride, p-tolyl ethyl aluminum hydride, p-tolyl n-propyl aluminum hydride, p-tolyl isopropyl aluminum hydride Aluminum, benzyl ethyl aluminum hydride, benzyl n-propyl aluminum hydride, benzyl isopropyl aluminum hydride, ethyl ethyl aluminum hydride, butyl aluminum hydride, isobutyl aluminum hydride,
  • R 1 , R 2 and R 3 are methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl. More preferably, in Formula 11, R 1 , R 2 and R 3 are all isobutyl.
  • the organoaluminum compound is preferably methylaluminoxane.
  • the molar ratio of the organoaluminum compound in terms of aluminum to the catalyst in terms of active metal is 50-5000:1, more preferably 200-3000:1, even more preferably 500-2000 :1.
  • the molar ratio of 2,4-dihalo-1-naphthol to the catalyst in terms of active metal is 1-500:1, more preferably 5-300:1, even more preferably 10- 200:1, more preferably 50-150:1.
  • 2,4-dihalo-1-naphthol examples include 2,4-dichloro-1-naphthol and/or 2,4-dibromo-1-naphthol, preferably 2,4-dichloro-1-naphthol. Chloro-1-naphthol.
  • the ⁇ -olefin is an ⁇ -olefin with 5-10 carbon atoms; preferably, the ⁇ -olefin is an olefin with 5-8 carbon atoms; more preferably, the The ⁇ -olefin is an olefin having 6 to 8 carbon atoms.
  • the ⁇ -olefin for example, one or more of 1-pentene, 1-hexene, 1-octene and 4-methyl-1 pentene can be mentioned; preferably, the ⁇ -olefin is 1-octene.
  • the olefin solution copolymerization conditions may include: the copolymerization temperature is -40 to 200°C, preferably 25 to 120°C, more preferably 50-70°C; the partial pressure of ethylene during polymerization is 0.05-5MPa, It is preferably 0.1-2 MPa, more preferably 0.8-1.2 MPa.
  • the polymerization process of the present invention can be carried out in a batch or continuous manner.
  • the polymerization process of the present invention is a solution polymerization process, and those skilled in the art should obviously understand that the solvent used therein should be in a liquid state under the polymerization reaction conditions, not react with the catalyst system, and will not participate in the polymerization The reaction will not react with the polymer obtained by the reaction, that is, the solvent is inert.
  • solvents will be apparent to those of ordinary skill in the coordination polymerization art and can be readily selected.
  • non-polar hydrocarbon solvents may be used, non-limiting examples of which are aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, one or more saturated Aliphatic hydrocarbons or alicyclic hydrocarbons such as butane, pentane, hexane, heptane, octane, cyclohexane, or any combination of two or more of the aforementioned solvents, preferably using hexane, octane Alkanes or heptanes, more preferably hexanes are used as solvents in the polymerization process of the present invention.
  • aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene
  • one or more saturated Aliphatic hydrocarbons or alicyclic hydrocarbons such as butane, pentane, hexane, heptane, octane, cycl
  • the consumption of non-polar hydrocarbon solvent is conventional, determined with polymer dispersibility and system heat dissipation, for example, the consumption of solvent can be controlled so that the monomer concentration is at 5-30wt%, Preferably in the range of 8-10 wt%.
  • the copolymer obtained in the polymerization process of the present invention usually has a very high average molecular weight, and those skilled in the art can use well-known methods to adjust the molecular weight.
  • molecular chain transfer agents such as diethyl zinc and hydrogen can be used as molecular weight regulators to control the molecular weight of the copolymer, preferably hydrogen is used to achieve this.
  • a very small amount of hydrogen can adjust the molecular weight of the copolymer in a wide range. Based on the total volume of the monomer mixed gas, the amount of hydrogen added is 0.01-10% by volume, more preferably 0.02-5% by volume.
  • a terminator may be used to terminate the polymerization reaction after the polymerization reaction is completed.
  • the terminators used in this step are conventional to those skilled in the art. Common terminators that can be used include deionized water, alcohols, acids, and the like. Here, preferably used terminators are acidified ethanol or acidified methanol.
  • an ethylene- ⁇ -olefin copolymer composition wherein the composition contains the ethylene- ⁇ -olefin copolymer of the present invention or the ethylene- ⁇ -olefin copolymer prepared by the method of the present invention.
  • - olefin copolymers, and solvents are provided.
  • the solvent is the residual preparation solvent from the preparation of the ethylene- ⁇ -olefin copolymer.
  • the preparation solvent may be, for example, the solvents mentioned in the above preparation method.
  • the composition is a product prepared by the preparation method of the present invention without removing the solvent or removing part of the solvent, which can directly function as a toughening modifier.
  • the application of the ethylene- ⁇ -olefin copolymer of the present invention in the preparation of packaging films is provided.
  • the ethylene- ⁇ -olefin copolymer of the present invention has low crystallinity and excellent transparency, it is particularly suitable for preparing packaging films.
  • the ethylene- ⁇ -olefin copolymer of the present invention has a lower glass transition temperature and excellent low-temperature toughness, it is particularly suitable for use as a toughening modifier.
  • test methods are as follows.
  • the molecular weight and molecular weight distribution of the samples were determined by PL-GPC 220 GPC from Polymer Laboratories, UK, and the chromatographic columns were three Plgel 10 ⁇ m MIXED-B columns connected in series.
  • the solvent and mobile phase are both 1,2,4-trichlorobenzene (containing 0.025% antioxidant 2,6-dibutyl-p-cresol), the column temperature is 150°C, the flow rate is 1.0ml/min, and the sample concentration is 1mg/ml , equipped with IR5 infrared concentration detector, using narrow distribution polystyrene standard sample for universal calibration.
  • the molecular weight and molecular weight distribution of the samples were determined by PL-GPC 220 GPC from Polymer Laboratories, UK, and the chromatographic columns were three Plgel 10 ⁇ m MIXED-B columns connected in series.
  • the solvent and mobile phase are both 1,2,4-trichlorobenzene (containing 0.025% antioxidant 2,6-dibutyl-p-cresol), the column temperature is 150°C, the flow rate is 1.0ml/min, and the sample concentration is 2mg/ml , using narrow distribution polystyrene standard samples for universal calibration.
  • the AVANCE III 400MHz nuclear magnetic resonance spectrometer produced by Bruker Company was used to study the comonomer content of the samples.
  • the solvent is deuterated o-dichlorobenzene.
  • Using a 10mm PASEX 13C-1H/D Z-GRD probe dissolve the sample with a mass concentration of 10% at 130°C.
  • the test temperature is 125°C
  • the rotation speed is 20 Hz
  • 90° Pulse 120ppm spectral width, sampling time 5 seconds, delay time 10 seconds, scan 6000 times.
  • the comonomer content was calculated by the methods recorded in the literature (such as Macromolecules 2000, 33, 8931-8944; Macromolecules 2001, 34, 5770-5777).
  • T 1/2 is defined to indicate the corresponding melting temperature when the melting enthalpy is half of the total melting enthalpy. A higher T 1/2 means a higher melting point, and conversely, a lower T 1/2 means a lower melting point.
  • Comparative examples 1-3 Commercial ethylene/1-octene copolymer samples, the grades are DOW engage8150, engage8137 and engage8842 respectively.
  • the difference is that no 2,4-dichloro-1-naphthol solution was added to obtain the polymer.
  • the comonomer content was 15.3 mol%
  • the RMD was 99.4%
  • the polymer molecular weight was 5.0 ⁇ 10 4
  • the polymer molecular weight distribution was 2.5.
  • Example 1-6 By comparing Examples 1-6 and Comparative Examples 1-3, it can be seen that the ethylene- ⁇ -olefin copolymer of the present invention has a high comonomer dispersion index.
  • Example 3 By comparing Example 3 with Comparative Example 1, it can be seen that the comonomer content of Example 3 and Comparative Example 1 is approximately the same, but the ethylene- ⁇ -olefin copolymer of Example 3 has a lower half-melting enthalpy temperature.
  • Example 1-3 By comparing Examples 1-3 with Comparative Example 1, it can be known that the copolymer of the present invention has lower copolymer content and higher RMD. In addition, by comparing Example 4 with Comparative Example 3, it can also be seen that the copolymer of the present invention has a lower copolymer content and a higher RMD.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

本发明涉及乙烯共聚物领域，公开了一种具有高共聚单体分散指数的乙烯-共聚烯烃共聚物及其制备方法和应用以及包含该乙烯-α-烯烃共聚物的组合物。所述乙烯-α-烯烃共聚物含有70-95mol％的来自乙烯的结构单元以及5-30mol％的来自α-烯烃的结构单元，所述α-烯烃为碳原子数为5-10的烯烃，且所述α-烯烃的结构单元在分子链的分散指数RMD大于102％。本发明的乙烯-α-烯烃共聚物具有高共聚单体分散指数。

Description

乙烯-α-烯烃共聚物及其制备方法和应用以及组合物
相关申请的交叉引用
本申请要求2021年09月30日提交的中国专利申请202111156978.3的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及乙烯共聚物领域，具体地，涉及一种具有高共聚单体分散指数的乙烯-共聚烯烃共聚物及其制备方法和应用以及包含该乙烯-α-烯烃共聚物的组合物。
背景技术
聚乙烯是商业化应用最广泛的材料之一。使用配位聚合技术制备的乙烯聚合物包括高密度聚乙烯、中密度聚乙烯、线型低密度聚乙烯、聚烯烃塑/弹性体等。本领域公知的聚合工艺有淤浆聚合工艺、气相聚合工艺和溶液聚合工艺，所用催化剂分为钛系Z-N催化剂、铬系催化剂和茂金属催化剂等。
采用茂金属催化剂开发的乙烯共聚物是聚乙烯高性能品种之一，共聚单体从1-丁烯向高级α-烯烃(1-己烯、1-辛烯和4-甲基-1-戊烯)转变。随着共聚单体的增加，聚乙烯密度逐渐降低，从高、中、低密度的线型聚乙烯到聚烯烃塑/弹性体依次转变。与自由基聚合得到的低密度聚乙烯不同，此类低密度乙烯共聚物弹性体只含有共聚单体形成的短支链结构，这些短支链的类型、含量及分布直接影响共聚物的机械性能。共聚单体在聚合物主链上分布均匀时，可以充分发挥共单体的效率，以最少量的共单体最大程度地降低共聚物的熔点和密度。所以如何实现高共聚单体含量共聚同时使共聚单体的更加有效均匀地分布在分子链上，是催化剂和聚合工艺研究领域都非常关注的问题，也是制备高性能乙烯与α-烯烃共聚物的重要挑战。
发明内容
本发明的目的是为了克服现有技术存在的现有乙烯-α-烯烃共聚物共聚单体的分散度还不够高的问题，提供一种具有高共聚单体分散指数的乙烯-α-烯烃共 聚物及其制备方法和应用以及包含该乙烯-α-烯烃共聚物的组合物。
为了实现上述目的，本发明的第一方面提供一种乙烯-α-烯烃共聚物，其中，所述乙烯-α-烯烃共聚物含有70-95mol％的来自乙烯的结构单元以及5-30mol％的来自α-烯烃的结构单元，所述α-烯烃为碳原子数为5-10的烯烃，且所述α-烯烃的结构单元在分子链的分散指数RMD大于102％。
优选地，所述乙烯-α-烯烃共聚物含有80-95mol％的来自乙烯的结构单元以及5-20mol％的来自α-烯烃的结构单元，所述α-烯烃为碳原子数为5-10的烯烃，且所述α-烯烃的结构单元在分子链的分散指数RMD大于103％。
优选地，所述乙烯-α-烯烃共聚物含有82-89mol％的来自乙烯的结构单元以及11-18mol％的来自α-烯烃的结构单元；更优选地，所述乙烯-α-烯烃共聚物含有84-89mol％的来自乙烯的结构单元以及11mol％以上且小于17mol％的来自α-烯烃的结构单元；进一步优选地，所述乙烯-α-烯烃共聚物含有84-89mol％的来自乙烯的结构单元以及11-16mol％的来自α-烯烃的结构单元。
优选地，所述α-烯烃的结构单元在分子链的分散指数RMD为104％以上，更优选为104-108％。
优选地，所述乙烯-α-烯烃共聚物的分子量分布Mw/Mn为1.5-3，更优选为1.5-2.5，进一步优选为1.5-2.3。
优选地，所述乙烯-α-烯烃共聚物在温度为190℃、载荷为2.16kg下的熔融指数MFRC为1.0-50g/10min，更优选为1-15g/10min。
优选地，所述乙烯-α-烯烃共聚物的半熔融焓温度T 1/2为5-80℃，更优选为10-70℃，进一步优选为15-60℃。
优选地，所述α-烯烃为碳原子数为5-8的烯烃。
优选地，所述α-烯烃为碳原子数为1-戊烯、1-己烯、1-辛烯和4-甲基-1戊烯中的一种或多种，更优选为1-辛烯。
根据本发明第二方面，提供一种乙烯-α-烯烃共聚物的制备方法，该方法包括：在烯烃溶液共聚条件下，在催化剂、助催化剂和酚存在下，使乙烯和α-烯烃进行共聚，得到乙烯-α-烯烃共聚物，
其中，所述催化剂含有二苯基亚甲基(环戊二烯基)(芴基)二氯化锆和/或二苯基亚甲基(环戊二烯基)(2,7-二叔丁基-芴基)二氯化锆，所述助催化剂为有机铝化 合物，所述酚为2,4-二卤-1-萘酚，
乙烯与α-烯烃的用量使得所述乙烯-α-烯烃共聚物中来自乙烯的结构单元与来自α-烯烃的结构单元的摩尔比为(80-95)：(5-20)，且所述α-烯烃为碳原子数5-10的烯烃。
优选地，乙烯与α-烯烃的用量使得所述乙烯-α-烯烃共聚物中来自乙烯的结构单元与来自α-烯烃的结构单元的摩尔比为(82-89)：(11-18)，更优选为(84-89)：(11-16)。
优选地，相对于1mol的所述乙烯，以活性金属计的所述催化剂的用量为0.01-10×10 -6mol。
优选地，所述有机铝化合物为铝氧烷和/或式1所示的烃基铝，
Figure PCTCN2022122018-appb-000001
式1中，R 1、R 2和R 3相同或不同，各自独立地选自烷基(包括环烷基)、烷氧基、芳基、烷芳基、芳烷基和氢，且R 1、R 2和R 3不同时为氢原子。
优选地，所述有机铝化合物优选为甲基铝氧烷。
优选地，以铝计的有机铝化合物与以活性金属计的催化剂的摩尔比为50-5000：1。
优选地，2,4-二卤-1-萘酚与以活性金属计的催化剂的摩尔比为1-500：1。
优选地，所述2,4-二卤-1-萘酚为2,4-二氯-1-萘酚和/或2,4-二溴-1-萘酚，更优选为2,4-二氯-1-萘酚。
优选地，所述α-烯烃为碳原子数为5-8的烯烃。
优选地，所述α-烯烃为碳原子数为1-戊烯、1-己烯、1-辛烯和4-甲基-1戊烯中的一种或多种，进一步优选为1-辛烯。
优选地，所述烯烃溶液共聚条件包括：共聚温度为-40至200℃，优选为25至120℃，更优选为50至70℃；聚合时乙烯分压为0.05-5MPa，优选为0.1-2MPa，更优选为0.8-1.2MPa。
优选地，烯烃溶液共聚所使用的溶剂为苯、甲苯、乙苯、二甲苯、戊烷、己烷、庚烷、辛烷和环己烷中的一种或多种。
根据本发明第三方面，提供一种乙烯-α-烯烃共聚物组合物，其中，该组合 物含有本发明所述的乙烯-α-烯烃共聚物或者本发明的制备方法制备得到的乙烯-α-烯烃共聚物、以及溶剂。
优选地，所述溶剂为乙烯-α-烯烃共聚物制备所残留的制备溶剂。
根据本发明第四方面，提供本发明的乙烯-α-烯烃共聚物在制备封装膜中的应用。
根据本发明第五方面，提供本发明的乙烯-α-烯烃共聚物或者本发明的乙烯-α-烯烃共聚物组合物作为增韧改性剂的应用。
通过上述技术方案，本发明能够提供一种具有高共聚单体分散指数的乙烯-α-烯烃共聚物及其制备方法和应用以及包含该乙烯-α-烯烃共聚物的组合物。
由于本发明的乙烯-α-烯烃共聚物具有高共聚单体分散指数，在与现有的乙烯-α-烯烃共聚物相比时，在α-烯烃共聚单体摩尔百分含量相同时，本发明所述的乙烯-α-烯烃共聚物具有更低的半熔融焓温度。
由于本发明的乙烯-α-烯烃共聚物具有高共聚单体分散指数，在与现有的乙烯-α-烯烃共聚物相比时，在达到相同的结晶度和熔点温度时，本发明所述的乙烯-α-烯烃共聚物具有更少量的α-烯烃共聚单体，从而能够降低成本。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
根据本发明第一方面，提供一种乙烯-α-烯烃共聚物，其中，所述乙烯-α-烯烃共聚物含有70-95mol％的来自乙烯的结构单元以及5-30mol％的来自α-烯烃的结构单元，所述α-烯烃为碳原子数为5-10的烯烃，且所述α-烯烃的结构单元在分子链的分散指数RMD大于102％。
本发明所提供的乙烯-α-烯烃的共聚物中，共聚单体的结构单元呈现一种“超级无规”的状态分散于分子链，也即说明乙烯的结构单元被共聚的α-烯烃的结构单元非常均匀、有效地分散开，因此，可以以较少量的共聚单体的量达成聚合物 特定的熔点和密度。这意味着可以有效降低聚合物的原材料成本。
在本发明中，所谓“超级无规”分散状态是指，在本发明的乙烯-α-烯烃的共聚物中，共聚单体结构单元是分离排列的，而非形成联排或嵌段结构，也即共聚单体结构单元在聚合物分子链上是非连续，无规分散排列的。在本发明的乙烯-α-烯烃的共聚物中，发现共聚单体在聚合物分子链上的分散程度高于理想的无规分布。
根据本发明，优选地，所述乙烯-α-烯烃共聚物含有80-95mol％的来自乙烯的结构单元以及5-20mol％的来自α-烯烃的结构单元；更优选地，所述乙烯-α-烯烃共聚物含有82-89mol％的来自乙烯的结构单元以及11-18mol％的来自α-烯烃的结构单元；进一步优选地，所述乙烯-α-烯烃共聚物含有80-88mol％的来自乙烯的结构单元意见12-20mol％的来自α-烯烃的结构单元。
具体地，来自乙烯的结构单元在所述乙烯-α-烯烃共聚物具体的含量例如可以为：80mol％、81mol％、82mol％、83mol％、84mol％、85mol％、86mol％、87mol％、88mol％、89mol％、90mol％、91mol％、92mol％、93mol％、94mol％、95mol％等，以及上述中任意两个数值所构成的范围。。
具体地，来自α-烯烃的结构单元在所述乙烯-α-烯烃共聚物具体的含量例如可以为：5mol％、6mol％、7mol％、8mol％、9mol％、10mol％、11mol％、12mol％、13mol％、14mol％、15mol％、16mol％、17mol％、18mol％、19mol％、20mol％等，以及上述中任意两个数值所构成的范围。。
根据本发明，优选地，所述α-烯烃的结构单元在分子链的分散指数RMD为103％以上；更优选地，所述α-烯烃的结构单元在分子链的分散指数RMD为104％以上；更优选地，所述α-烯烃的结构单元在分子链的分散指数RMD为104-108％；进一步优选地，所述α-烯烃的结构单元在分子链的分散指数RMD为104-107％。
具体地，所述α-烯烃的结构单元在分子链的分散指数RMD例如可以为：103.1％、103.6％、103.7％、103.8％、103.9％、104％、104.1％、104.2％、104.3％、104.4％、104.5％、104.6％、104.7％、104.8％、104.9％、105％、105.1％、105.2％、105.3％、105.4％、105.5％、105.6％、105.7％、105.8％、105.9％、106％、106.1％、106.2％、106.3％、106.4％、106.5％、106.6％、106.7％、106.8％、106.9％、107％、 107.1％、107.2％、107.3％、107.4％、107.5％、107.6％、107.7％、107.8％、107.9％、108％等，以及上述中任意两个数值所构成的范围。
在本发明中，所述α-烯烃的结构单元在分子链的分散指数RMD由以下公式定义，并按如下所述进行测定：
Figure PCTCN2022122018-appb-000002
其中AMD表示绝对共单体分散度，BMD表示完全随机共单体分散度或伯努利分散度。
单体绝对分散度AMD按以下步骤测定。单体绝对分散度定义为平均分子中的共聚单体簇数(N)除以平均链上的单体单元数(X)的比值。如果n 1代表孤立共聚单体单元的数量，n 2代表共聚单体单元的相邻簇，直至共聚物中x个相邻共聚单体单元的…n x簇，X和N的定义如下：
Figure PCTCN2022122018-appb-000003
Figure PCTCN2022122018-appb-000004
由此绝对共聚单体分散度AMD定义为：
Figure PCTCN2022122018-appb-000005
因此，如果聚合物分子中只存在孤立的共聚单体单元，AMD将为100。相反，如果所有的共单体单元都集中在一起，AMD为0。
理想的随机或伯努利分布BMD由以下公式确定：
Figure PCTCN2022122018-appb-000006
其中MC是聚合物中共聚单体的浓度(摩尔百分比)。因此，如果聚合物由95％乙烯和5％1-辛烯组成，BMD为95。
通过核磁共振NMR计算得到的绝对共聚单体分散度AMD的方法描述如下：
对聚合物进行核磁共振波谱分析，其核磁共振的峰可以通过相对于四甲基硅烷的位置(ppm)来确定和表征。鉴于较高的工作温度，实际的“校准”是相对于六甲基硅氧烷进行的。以E表示乙烯单元，X表示共聚单元，目前的计算方法大多倾向于用三元组分布来确定共聚单体的绝对分散性。所以支链所连接的碳原 子只能是这三种类型之一，即EXE、EXX和XXX。
由于两个或多个X单元组成的每个簇都将贡献两个EXX单元，因此存在以下关系：
EXE＝n 1
EXX＝2(n 2+n 3+…n i+…)
也即：
Figure PCTCN2022122018-appb-000007
同样地，由于三元组XXX在XXX中发现一次，在XXXX中发现两次，在XXXXX中发现三次，依此类推:
XXX＝n 3+2n 4+3n 5+…(n-2)n i+…
结合上述三个公式我们发现：
EXE+EXX+XXX＝n 1+2n 2+3n 3+…+in i+…＝X
因此，由核磁共振确定的绝对单体分散度为：
Figure PCTCN2022122018-appb-000008
根据核磁共振峰高或峰面积测定EXE、EXX和XXX。在本发明中实施例中X为O，代表1-辛烯共聚单元。
根据上述公式可以确定相对单体分散度RMD。在后述中，所述测定的共聚单体相对和绝对单体分散度由上述公式计算。
根据本发明，所述乙烯-α-烯烃共聚物的分子量分布Mw/Mn可以为1.5-3，优选为1.5-2.5，更优选为1.5-2.3。
具体地，所述乙烯-α-烯烃共聚物的分子量分布Mw/Mn例如可以举出：1.5、1.6、1.7、1.8、1.9、2.0、2.1、2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9、3.0等。
根据本发明，所述乙烯-α-烯烃共聚物在温度为190℃、载荷为2.16kg下的熔融指数MFRC可以为1.0-50g/10min，优选为1-15g/10min。
具体地，所述乙烯-α-烯烃共聚物在温度为190℃、载荷为2.16kg下的熔融指数MFRC例如可以举出：1.0g/10min、2.0g/10min、3.0g/10min、4.0g/10min、5.0g/10min、6.0g/10min、7.0g/10min、8.0g/10min、9.0g/10min、10.0g/10min、 11.0g/10min、12.0g/10min、13.0g/10min、14.0g/10min、15.0g/10min、16.0g/10min、17.0g/10min、18.0g/10min、19.0g/10min、20.0g/10min、21.0g/10min、22.0g/10min、23.0g/10min、24.0g/10min、25.0g/10min、26.0g/10min、27.0g/10min、28.0g/10min、29.0g/10min、30.0g/10min、31.0g/10min、32.0g/10min、33.0g/10min、34.0g/10min、35.0g/10min、36.0g/10min、37.0g/10min、38.0g/10min、39.0g/10min、40.0g/10min、41.0g/10min、42.0g/10min、43.0g/10min、44.0g/10min、45.0g/10min、46.0g/10min、47.0g/10min、48.0g/10min、49.0g/10min、50.0g/10min等。
根据本发明，所述乙烯-α-烯烃共聚物的半熔融焓温度T 1/2可以为5-80℃，优选10-70℃，更优选15-60℃。这里定义T 1/2表示当熔融焓为总熔融焓的一半时对应的熔融温度。T 1/2越高意味着熔点越高，反之，T 1/2越低意味着熔点越低。
具体地，所述乙烯-α-烯烃共聚物的半熔融焓温度T 1/2例如可以举出：5℃、6℃、7℃、8℃、9℃、10℃、11℃、12℃、13℃、14℃、15℃、16℃、17℃、18℃、19℃、20℃、21℃、22℃、23℃、24℃、25℃、26℃、27℃、28℃、29℃、30℃、31℃、32℃、33℃、34℃、35℃、36℃、37℃、38℃、39℃、40℃、41℃、42℃、43℃、44℃、45℃、46℃、47℃、48℃、49℃、50℃、51℃、52℃、53℃、54℃、55℃、56℃、57℃、58℃、59℃、60℃、61℃、62℃、63℃、64℃、65℃、66℃、67℃、68℃、69℃、70℃、71℃、72℃、73℃、74℃、75℃、76℃、77℃、78℃、79℃、80℃等
在本发明中，所述α-烯烃为碳原子数为5-10的烯烃；优选地，所述α-烯烃为碳原子数为5-8的烯烃；更优选地，所述α-烯烃为碳原子数为6-8的烯烃。
作为所述α-烯烃例如可以举出1-戊烯、1-己烯、1-辛烯和4-甲基-1戊烯中的一种或多种；优选地，所述α-烯烃为1-辛烯。
在本发明一个优选的实施方式中，所述乙烯-α-烯烃共聚物为乙烯/-辛烯共聚物，由于本发明的乙烯/1-辛烯共聚物具有高共聚单体分散指数，因此，与现有的乙烯/1-辛烯共聚物相比，在1-辛烯共聚单体摩尔百分含量相同时，本发明所述的乙烯/1-辛烯共聚物具有更低的半熔融焓温度，例如可降低2℃-8℃，优选降低3℃-6℃，更优选降低4℃-5℃。
在本发明另一个优选的实施方式中，所述乙烯-α-烯烃共聚物为乙烯/-辛烯共聚物，由于本发明的乙烯/1-辛烯共聚物具有高共聚单体分散指数，因此， 与现有的乙烯/1-辛烯共聚物相比，在达到相同的结晶度和熔点温度时，本发明所述的乙烯/1-辛烯共聚物具有更少量的1-辛烯共聚单体，共聚单体可降低0.3-1.2mol％，优选降低0.5-1.0mol％，更优降低0.6-0.8mol％。
根据本发明第二方面，提供本发明所述的乙烯-α-烯烃共聚物的制备方法，其中，该方法包括：该方法包括：在烯烃溶液共聚条件下，在催化剂、助催化剂和酚存在下，使乙烯和α-烯烃进行共聚，得到乙烯-α-烯烃共聚物，
其中，所述催化剂含有二苯基亚甲基(环戊二烯基)(芴基)二氯化锆和/或二苯基亚甲基(环戊二烯基)(2,7-二叔丁基-芴基)二氯化锆，所述助催化剂为有机铝化合物，所述酚为2,4-二卤-1-萘酚，
乙烯与α-烯烃的用量使得所述乙烯-α-烯烃共聚物中来自乙烯的结构单元与来自α-烯烃的结构单元的摩尔比为(80-95)：(5-20)，且所述α-烯烃为碳原子数5-10的烯烃。
根据本发明的制备方法，优选地，乙烯与α-烯烃的用量使得所述乙烯-α-烯烃共聚物中来自乙烯的结构单元与来自α-烯烃的结构单元的摩尔比为(82-89)：(11-18)；更优选地，乙烯与α-烯烃的用量使得所述乙烯-α-烯烃共聚物中来自乙烯的结构单元与来自α-烯烃的结构单元的摩尔比为(84-89)：(11-16)。
根据本发明的制备方法，所述催化剂的用量可以根据乙烯的用量来选择，优选地，相对于1mol的所述乙烯，以活性金属计的所述催化剂的用量为0.01-10×10 -6mol；更优选地，相对于1mol的所述乙烯，以活性金属计的所述催化剂的用量为0.1-5×10 -6mol。
根据本发明的制备方法，所述有机铝化合物可以为铝氧烷和/或烃基铝。
在一种实施方式中，所述有机铝化合物铝氧烷，优选为甲基铝氧烷(MAO)。
在另一种实施方式中，所述有机铝化合物为式1所示的烃基铝，
Figure PCTCN2022122018-appb-000009
式1中，R 1、R 2和R 3相同或不同，各自独立地选自烷基(包括环烷基)、烷氧基、芳基、烷芳基、芳烷基和氢，且R 1、R 2和R 3不同时为氢原子；
所述烷基铝化合物的具体实例可以包括但不限于：二乙基氢化铝、二正丙基氢化铝、二正丁基氢化铝、二异丁基氢化铝、二苯基氢化铝、二对甲苯基氢化 铝、二苄基氢化铝、苯基乙基氢化铝、苯基正丙基氢化铝、对甲苯基乙基氢化铝、对甲苯基正丙基氢化铝、对甲苯基异丙基氢化铝、苄基乙基氢化铝、苄基正丙基氢化铝、苄基异丙基氢化铝、乙基二氢化铝、丁基二氢化铝、异丁基二氢化铝、辛基二氢化铝、戊基二氢化铝、二乙基乙醇铝、二丙基乙醇铝、三甲基铝、三乙基铝、三正丙基铝、三异丙基铝、三正丁基铝、三异丁基铝、三戊基铝、三己基铝、三环己基铝、三辛基铝、三苯基铝、三对甲苯基铝、三苄基铝、乙基二苯基铝、乙基二对甲苯基铝、乙基二苄基铝、二乙基苯基铝、二乙基对甲苯基铝和二乙基苄基铝。
在一个优选的实例中，式1中，R 1、R 2和R 3为甲基、乙基、正丙基、异丙基、正丁基或者异丁基。更优选地，式11中，R 1、R 2和R 3均为异丁基。
根据本发明的制备方法，所述有机铝化合物优选为甲基铝氧烷。
根据本发明的制备方法，优选地，以铝计的有机铝化合物与以活性金属计的催化剂的摩尔比为50-5000：1，更优选为200-3000：1，更进一步优选为500-2000：1。
根据本发明的制备方法，2,4-二卤-1-萘酚与以活性金属计的催化剂的摩尔比为1-500：1，更优选为5-300：1，更进一步优选为10-200：1，更进一步优选为50-150：1。
作为上述2,4-二卤-1-萘酚例如可以举出2,4-二氯-1-萘酚和/或2,4-二溴-1-萘酚，优选为2,4-二氯-1-萘酚。
根据本发明的制备方法，所述α-烯烃为碳原子数为5-10的α-烯烃；优选地，所述α-烯烃为碳原子数为5-8的烯烃；更优选地，所述α-烯烃为碳原子数为6-8的烯烃。
作为所述α-烯烃例如可以举出1-戊烯、1-己烯、1-辛烯和4-甲基-1戊烯中的一种或多种；优选地，所述α-烯烃为1-辛烯。
根据本发明的制备方法，所述烯烃溶液共聚条件可以包括：共聚温度为-40至200℃，优选为25至120℃，更优选为50-70℃；聚合时乙烯分压为0.05-5MPa，优选为0.1-2MPa，更优选为0.8-1.2MPa。本发明的聚合工艺可以采用间歇或连续方式进行。
根据本发明的制备方法，本发明的聚合工艺为溶液聚合工艺，本领域技术 人员显然应当理解，其中使用的溶剂在聚合反应条件下应当呈液态，不与催化剂体系进行反应，并且不会参与聚合反应，也不会与反应得到的聚合物发生反应，即该溶剂是惰性的。这类溶剂对于配位聚合领域的普通技术人员而言是显而易见的，并且可以容易地进行选择。尽管如此，对本发明而言，可使用非极性烃类溶剂，该非极性烃类溶剂的非限制性实例为芳族烃如苯、甲苯、乙苯、二甲苯，一种或多种饱和的脂族烃或脂环族烃如丁烷、戊烷、己烷、庚烷、辛烷、环己烷、或者前述溶剂中的两种或更多种的任意组合，优选使用己烷、辛烷或庚烷，更优选使用己烷作为本发明聚合工艺中的溶剂。对于本发明的聚合工艺而言，非极性烃类溶剂的用量是常规的，以聚合物分散性和体系散热情况来确定，例如可控制溶剂的用量以使单体浓度在5-30wt％，优选为8-10wt％的范围内。
在本发明的聚合工艺中得到的共聚物通常具有很高的平均分子量，本领域的技术人员可以采用熟知的方法来调节分子量。尤其可以采用分子链转移剂如二乙基锌和氢气作为分子量调节剂控制共聚物的分子量，优选采用氢气来实现。非常小量的氢气就能在很大范围内调节共聚物的分子量，以单体混合气体的总体积为基准，氢气的加入量为0.01-10体积％，更优选为0.02-5体积％。
在本发明的制备方法中，在聚合反应完成后可以使用终止剂终止聚合反应。用于此步骤的终止剂对于本领域技术人员而言是常规的。通常可以使用的终止剂包括去离子水、醇、酸等。在此，优选使用的终止剂为酸化乙醇或酸化甲醇。
根据本发明的第三方面，提供一种乙烯-α-烯烃共聚物组合物，其中，该组合物含有本发明的乙烯-α-烯烃共聚物或者本发明所述的方法制备得到的乙烯-α-烯烃共聚物、以及溶剂。
根据本发明的组合物，优选地，所述溶剂为乙烯-α-烯烃共聚物制备所残留的制备溶剂。所述制备溶剂例如可以为上述制备方法中所举出的溶剂。
在本发明一个优选的实施方式中，所述组合物为本发明的制备方法制备得到的未去除溶剂或除去部分溶剂后的产物，其可以直接作为增韧改性剂发挥作用。
根据本发明第四方面，提供本发明的乙烯-α-烯烃共聚物在制备封装膜中的应用。
由于本发明的乙烯-α-烯烃共聚物结晶度低且透明性优异，特别适合制备封装膜。
根据本发明的第五方面，提供本发明的乙烯-α-烯烃共聚物或者本发明的乙烯-α-烯烃共聚物组合物作为增韧改性剂的应用。
由于本发明的乙烯-α-烯烃共聚物具有较低的玻璃化转温度且低温韧性优异，特别适合作为增韧改性剂使用。
以下结合实施例对本发明进行详细描述，但并不因此限制本发明的范围。
以下实施例和对比例中，测试方法如下。
(1)重均分子量及分子量分布测试
采用英国Polymer Laboratories公司的PL-GPC 220型GPC测定样品的分子量及分子量分布，色谱柱为3根串联Plgel 10μmMIXED-B柱。溶剂及流动相均为1,2,4-三氯苯(含0.025％抗氧剂2,6-二丁基对甲酚)，柱温150℃，流速1.0ml/min，样品浓度1mg/ml，配备IR5红外浓度检测器，采用窄分布聚苯乙烯标样进行普适标定。
(2)组成分布测试
采用英国Polymer Laboratories公司的PL-GPC 220型GPC测定样品的分子量及分子量分布，色谱柱为3根串联Plgel 10μmMIXED-B柱。溶剂及流动相均为1,2,4-三氯苯(含0.025％抗氧剂2,6-二丁基对甲酚)，柱温150℃，流速1.0ml/min，样品浓度2mg/ml，采用窄分布聚苯乙烯标样进行普适标定。
(3)共聚单体含量及分散度测试
采用Bruker公司生产的AVANCE III 400MHz型核磁共振谱仪研究试样的共单体含量。溶剂为氘代邻二氯苯，使用10毫米PASEX 13C-1H/D Z-GRD探头，于130℃将质量浓度为10％的试样溶解均匀，测试温度125℃，旋转速度20赫兹，90°脉冲，120ppm谱宽，采样时间5秒，延迟时间10秒，扫描6000次。根据13C-NMR谱图，以文献记载的方法(如Macromolecules 2000,33,8931-8944；Macromolecules 2001,34,5770-5777)计算共聚单体的含量。
共聚单体分散度AMD的具体测试方法见上述说明书中的记载。
(4)热分析测试
采用TA 100差示扫描量热仪，扫描温度-80℃～200℃，升降温速率10℃/min。去除热历史，得到二次升温熔融曲线，并进行归一化积分处理。这里定义T 1/2表示当熔融焓为总熔融焓的一半时对应的熔融温度。T 1/2越高意味着熔点越高， 反之，T 1/2越低意味着熔点越低。
对比例1-3：商业化乙烯/1-辛烯共聚物样品，牌号分别为DOW engage8150，engage8137和engage8842。
实施例1
对已经充分烘干的250毫升的聚合装置进行抽真空，氮气冲洗，反复三次。然后再进行抽真空，电磁阀控制，充入1个标准大气压乙烯，室温下加入25毫升反应溶剂甲苯、1毫升2,4-二氯-1-萘酚溶液(含有2,4-二氯-1-萘酚0.5毫摩尔)、0.8毫升1-辛烯，再加入3毫升甲基铝氧烷(MAO)溶液(含甲基铝氧烷5.0毫摩尔)，升温至50摄氏度，加入1毫升含有5.0微摩尔二苯基亚甲基(环戊二烯基)(芴基)二氯化锆甲苯溶液，开始计时。20分钟后，关闭乙烯，在反应液中加入酸化乙醇，搅拌6小时，过滤得到的聚合物，真空干燥24小时，称重得到1.47克聚合物。其测试结果如表1所示。
实施例2
对已经充分烘干的250毫升的聚合装置进行抽真空，氮气冲洗，反复三次。然后再进行抽真空，电磁阀控制，充入1个标准大气压乙烯，室温下加入25毫升反应溶剂甲苯、1毫升2,4-二氯-1-萘酚溶液(含有2,4-二氯-1-萘酚0.5毫摩尔)、0.9毫升1-辛烯，再加入3毫升甲基铝氧烷(MAO)溶液(含甲基铝氧烷5.0毫摩尔)，升温至70摄氏度，加入1毫升含有5.0微摩尔二苯基亚甲基(环戊二烯基)(芴基)二氯化锆甲苯溶液，开始计时。20分钟后，关闭乙烯，在反应液中加入酸化乙醇，搅拌6小时，过滤得到的聚合物，真空干燥24小时，称重得到1.58克聚合物。其测试结果如表1所示。
实施例3
对已经充分烘干的250毫升的聚合装置进行抽真空，氮气冲洗，反复三次。然后再进行抽真空，电磁阀控制，充入1个标准大气压乙烯，室温下加入25毫升反应溶剂甲苯、1毫升2,4-二氯-1-萘酚溶液(含有2,4-二氯-1-萘酚0.5毫摩尔)、1.0毫升1-辛烯，再加入3毫升甲基铝氧烷(MAO)溶液(含甲基铝氧烷5.0毫 摩尔)，升温至55摄氏度，加入1毫升含有5.0微摩尔二苯基亚甲基(环戊二烯基)(芴基)二氯化锆甲苯溶液，开始计时。20分钟后，关闭乙烯，在反应液中加入酸化乙醇，搅拌6小时，过滤得到的聚合物，真空干燥24小时，称重得到1.51克聚合物。其测试结果如表1所示。
实施例4
对已经充分烘干的250毫升的聚合装置进行抽真空，氮气冲洗，反复三次。然后再进行抽真空，电磁阀控制，充入1个标准大气压乙烯，室温下加入25毫升反应溶剂甲苯、1毫升2,4-二氯-1-萘酚溶液(含有2,4-二氯-1-萘酚0.5毫摩尔)、1.1毫升1-辛烯，再加入3毫升甲基铝氧烷(MAO)溶液(含甲基铝氧烷5.0毫摩尔)，升温至70摄氏度，加入1毫升含有5.0微摩尔二苯基亚甲基(环戊二烯基)(芴基)二氯化锆甲苯溶液，开始计时。20分钟后，关闭乙烯，在反应液中加入酸化乙醇，搅拌6小时，过滤得到的聚合物，真空干燥24小时，称重得到1.61克聚合物。其测试结果如表1所示。
实施例5
对已经充分烘干的250毫升的聚合装置进行抽真空，氮气冲洗，反复三次。然后再进行抽真空，电磁阀控制，充入1个标准大气压乙烯，室温下加入25毫升反应溶剂甲苯、1毫升2,4-二氯-1-萘酚溶液(含有2,4-二氯-1-萘酚0.5毫摩尔)、1.3毫升1-辛烯，再加入3毫升甲基铝氧烷(MAO)溶液(含甲基铝氧烷5.0毫摩尔)，升温至70摄氏度，加入1毫升含有5.0微摩尔二苯基亚甲基(环戊二烯基)(芴基)二氯化锆甲苯溶液，开始计时。20分钟后，关闭乙烯，在反应液中加入酸化乙醇，搅拌6小时，过滤得到的聚合物，真空干燥24小时，称重得到1.65克聚合物。其测试结果如表1所示。
实施例6
对已经充分烘干的250毫升的聚合装置进行抽真空，氮气冲洗，反复三次。然后再进行抽真空，电磁阀控制，充入1个标准大气压乙烯，室温下加入25毫升反应溶剂甲苯、1毫升2,4-二氯-1-萘酚溶液(含有2,4-二氯-1-萘酚0.5毫摩尔)、 1.3毫升1-己烯，再加入3毫升甲基铝氧烷(MAO)溶液(含甲基铝氧烷5.0毫摩尔)，升温至70摄氏度，加入1毫升含有5.0微摩尔二苯基亚甲基(环戊二烯基)(芴基)二氯化锆甲苯溶液，开始计时。20分钟后，关闭乙烯，在反应液中加入酸化乙醇，搅拌6小时，过滤得到的聚合物，真空干燥24小时，称重得到1.65克聚合物。其测试结果如表1所示。
对比例4
按照实施例3的方法进行，不同的是，未添加2,4-二氯-1-萘酚溶液，得到的聚合物。得到的聚合物中，共聚单体含量为15.3mol％，RMD为99.4％，聚合物分子量为5.0×10 4，聚合物分子量分布为2.5。
表1
Figure PCTCN2022122018-appb-000010
通过将实施例1-6和对比例1-3对比可知，本发明的乙烯-α-烯烃共聚物具有高共聚单体分散指数。通过将实施例3与对比例1进行对比可知，实施例3与对比例1的共聚单体含量大致相同，但实施例3的乙烯-α-烯烃共聚物具有更低的半熔融焓温度。
通过将实施例1-3与对比例1对比可知，本发明的共聚物具有更低的共聚含量，且具有更高的RMD。此外，通过将实施例4与对比例3进行对比同样可知，本发明的共聚物具有更低的共聚含量，且具有更高的RMD。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本 发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (18)

  1. 一种乙烯-α-烯烃共聚物，其特征在于，所述乙烯-α-烯烃共聚物含有70-95mol％的来自乙烯的结构单元以及5-30mol％的来自α-烯烃的结构单元，所述α-烯烃为碳原子数为5-10的烯烃，且所述α-烯烃的结构单元在分子链的分散指数RMD大于102％。
  2. 根据权利要求1所述的乙烯-α-烯烃共聚物，其中，所述乙烯-α-烯烃共聚物含有80-95mol％的来自乙烯的结构单元以及5-20mol％的来自α-烯烃的结构单元；
    所述乙烯-α-烯烃共聚物含有82-89mol％的来自乙烯的结构单元以及11-18mol％的来自α-烯烃的结构单元；
    优选地，所述乙烯-α-烯烃共聚物含有大于83mol％且为89mol％以下的来自乙烯的结构单元以及11mol％以上且小于17mol％的来自α-烯烃的结构单元；
    优选地，所述乙烯-α-烯烃共聚物含有84-89mol％的来自乙烯的结构单元以及11-16mol％的来自α-烯烃的结构单元。
  3. 根据权利要求1所述的乙烯-α-烯烃共聚物，其中，所述α-烯烃的结构单元在分子链的分散指数RMD为103％以上，优选为104％以上，更优选为104-108％。
  4. 根据权利要求1-3中任意一项所述的乙烯-α-烯烃共聚物，其中，所述乙烯-α-烯烃共聚物的分子量分布Mw/Mn为1.5-3，优选为1.5-2.5，更优选为1.5-2.3。
  5. 根据权利要求1-3中任意一项所述的乙烯-α-烯烃共聚物，其中，所述乙烯-α-烯烃共聚物在温度为190℃、载荷为2.16kg下的熔融指数MFRC为1.0-50g/10min，优选为1-15g/10min；
    优选地，所述乙烯-α-烯烃共聚物的半熔融焓温度T 1/2为5-80℃，优选为10-70℃，更优选为15-60℃。
  6. 根据权利要求1-3中任意一项所述的乙烯-α-烯烃共聚物，其中，所述α-烯烃为碳原子数为5-8的烯烃，优选为1-戊烯、1-己烯、1-辛烯和4-甲基-1戊烯中的一种或多种，更优选为1-辛烯。
  7. 一种乙烯-α-烯烃共聚物的制备方法，其特征在于，该方法包括：在烯烃溶液共聚条件下，在催化剂、助催化剂和酚存在下，使乙烯和α-烯烃进行共聚，得到乙烯-α-烯烃共聚物，
    其中，所述催化剂含有二苯基亚甲基(环戊二烯基)(芴基)二氯化锆和/或二苯基亚甲基(环戊二烯基)(2,7-二叔丁基-芴基)二氯化锆，所述助催化剂为有机铝化合物，所述酚为2,4-二卤-1-萘酚，
    乙烯与α-烯烃的用量使得所述乙烯-α-烯烃共聚物中来自乙烯的结构单元与来自α-烯烃的结构单元的摩尔比为(80-95)：(5-20)，且所述α-烯烃为碳原子数5-10的烯烃。
  8. 根据权利要求7所述的方法，其中，乙烯与α-烯烃的用量使得所述乙烯-α-烯烃共聚物中来自乙烯的结构单元与来自α-烯烃的结构单元的摩尔比为(82-89)：(11-18)，更优选为(84-89)：(11-16)。
  9. 根据权利要求7所述的方法，其中，相对于1mol的所述乙烯，以活性金属计的所述催化剂的用量为0.01-10×10 -6mol。
  10. 根据权利要求7-9中任意一项所述的方法，其中，所述有机铝化合物为铝氧烷和/或式1所示的烃基铝，
    Figure PCTCN2022122018-appb-100001
    式1中，R 1、R 2和R 3相同或不同，各自独立地选自烷基(包括环烷基)、烷氧基、芳基、烷芳基、芳烷基和氢，且R 1、R 2和R 3不同时为氢原子；
    优选地，所述有机铝化合物优选为甲基铝氧烷；
    优选地，以铝计的有机铝化合物与以活性金属计的催化剂的摩尔比为 50-5000：1。
  11. 根据权利要求7-9中任意一项所述的方法，其中，2,4-二卤-1-萘酚与以活性金属计的催化剂的摩尔比为1-500：1；
    优选地，所述2,4-二卤-1-萘酚为2,4-二氯-1-萘酚和/或2,4-二溴-1-萘酚，更优选为2,4-二氯-1-萘酚。
  12. 根据权利要求7-9中任意一项所述的方法，其中，所述α-烯烃为碳原子数为5-8的烯烃，更优选为1-戊烯、1-己烯、1-辛烯和4-甲基-1戊烯中的一种或多种，进一步优选为1-辛烯。
  13. 根据权利要求7-9中任意一项所述的方法，其中，所述烯烃溶液共聚条件包括：共聚温度为-40至200℃，优选为25至120℃，更优选为50至70℃；聚合时乙烯分压为0.05-5MPa，优选为0.1-2MPa，更优选为0.8-1.2MPa。
  14. 根据权利要求7-9中任意一项所述的方法，其中，烯烃溶液共聚所使用的溶剂为苯、甲苯、乙苯、二甲苯、戊烷、己烷、庚烷、辛烷和环己烷中的一种或多种。
  15. 一种乙烯-α-烯烃共聚物组合物，其特征在于，该组合物含有权利要求1-7中任意一项所述的乙烯-α-烯烃共聚物或者权利要求8-14中任意一项所述的方法制备得到的乙烯-α-烯烃共聚物、以及溶剂。
  16. 根据权利要求15所述的组合物，其中，所述溶剂为乙烯-α-烯烃共聚物制备所残留的制备溶剂。
  17. 权利要求1-6中任意一项所述的乙烯-α-烯烃共聚物在制备封装膜中的应用。
  18. 权利要求1-6中任意一项所述的乙烯-α-烯烃共聚物或者权利要求15或16所述的乙烯-α-烯烃共聚物组合物作为增韧改性剂的应用。
PCT/CN2022/122018 2021-09-30 2022-09-28 乙烯-α-烯烃共聚物及其制备方法和应用以及组合物 Ceased WO2023051580A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US18/697,054 US20240400732A1 (en) 2021-09-30 2022-09-28 ETHYLENE-Alpha-OLEFIN COPOLYMER, PREPARATION METHOD THEREFOR, APPLICATION AND COMPOSITION THEREOF
JP2024519643A JP2024534672A (ja) 2021-09-30 2022-09-28 エチレン－α－オレフィンコポリマー、その製造方法、及び使用、並びに組成物
KR1020247012344A KR20240055131A (ko) 2021-09-30 2022-09-28 에틸렌-α-올레핀 공중합체, 이의 제조 방법과 응용 및 조성물
EP22874965.1A EP4400522A4 (en) 2021-09-30 2022-09-28 ETHYLENE-ALPHA-OLEFIN COPOLYMER, PREPARATION METHOD, APPLICATION AND COMPOSITION BASED THEREON

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111156978.3A CN115894759B (zh) 2021-09-30 2021-09-30 乙烯-α-烯烃共聚物及其制备方法和应用以及组合物
CN202111156978.3 2021-09-30

Publications (1)

Publication Number Publication Date
WO2023051580A1 true WO2023051580A1 (zh) 2023-04-06

Family

ID=85733882

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/122018 Ceased WO2023051580A1 (zh) 2021-09-30 2022-09-28 乙烯-α-烯烃共聚物及其制备方法和应用以及组合物

Country Status (6)

Country Link
US (1) US20240400732A1 (zh)
EP (1) EP4400522A4 (zh)
JP (1) JP2024534672A (zh)
KR (1) KR20240055131A (zh)
CN (1) CN115894759B (zh)
WO (1) WO2023051580A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117700593A (zh) * 2023-12-13 2024-03-15 海南贝欧亿科技有限公司 一种生物基高极性热塑性聚烯烃弹性体及其制备方法及光伏封装胶膜

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023051575A1 (zh) * 2021-09-30 2023-04-06 中国石油化工股份有限公司 催化剂组合物及其应用
CN119955040B (zh) * 2024-12-20 2025-10-17 浙江大学 一种共聚单体含量梯级分布的嵌段共聚物制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4522987A (en) * 1982-07-09 1985-06-11 Phillips Petroleum Company Low density polyethylene
US5436305A (en) * 1991-05-09 1995-07-25 Phillips Petroleum Company Organometallic fluorenyl compounds, preparation, and use
JPH08198909A (ja) * 1995-01-26 1996-08-06 Tosoh Corp オレフィン重合体製造用触媒、その製造方法及びそれを用いたオレフィン重合体の製造方法
CN102356098A (zh) * 2009-03-17 2012-02-15 切弗朗菲利浦化学公司 制备聚合催化剂的方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5571880A (en) * 1991-05-09 1996-11-05 Phillips Petroleum Company Organometallic fluorenyl compounds and use thereof in an alpha-olefin polymerization process
DE69632678T2 (de) * 1995-09-11 2005-06-09 Mitsui Chemicals, Inc. Harzzusammensetzung und deren verwendung
JPH1053619A (ja) * 1996-08-12 1998-02-24 Sumitomo Chem Co Ltd ポリオレフィン系樹脂組成物の製造方法
WO1998034986A1 (en) * 1997-02-07 1998-08-13 Exxon Chemical Patents Inc. Improved processing olefin copolymers
JP2000234046A (ja) * 1998-12-18 2000-08-29 Mitsui Chemicals Inc 樹脂分散物、その調製方法、それを用いた樹脂塗工金属板及び積層板の製造方法
KR100753478B1 (ko) * 2005-02-15 2007-08-31 주식회사 엘지화학 혼성 담지 메탈로센 촉매 및 이를 이용한 폴리에틸렌 공중합체의 제조방법
US8153243B2 (en) * 2005-12-09 2012-04-10 Dow Global Technologies Llc Interpolymers suitable for multilayer films
KR20120024815A (ko) * 2009-05-29 2012-03-14 스미또모 가가꾸 가부시끼가이샤 에틸렌-α-올레핀 공중합체, 성형품, 공중합용 촉매 및 에틸렌-α-올레핀 공중합체의 제조 방법
CN102639573A (zh) * 2009-12-15 2012-08-15 住友化学株式会社 乙烯-α-烯烃共聚物
EP3127958B1 (en) * 2015-08-04 2021-09-01 FUJIFILM Business Innovation Corp. Resin composition, resin molded article, and method of preparing resin composition
KR102013170B1 (ko) * 2018-04-05 2019-08-22 대림산업 주식회사 폴리올레핀 수지 조성물 및 이의 제조방법
CN112661785B (zh) * 2019-10-15 2022-10-21 中国石油化工股份有限公司 一种萘氧基单茂过渡金属化合物、包含其的催化剂组合物与应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4522987A (en) * 1982-07-09 1985-06-11 Phillips Petroleum Company Low density polyethylene
US5436305A (en) * 1991-05-09 1995-07-25 Phillips Petroleum Company Organometallic fluorenyl compounds, preparation, and use
JPH08198909A (ja) * 1995-01-26 1996-08-06 Tosoh Corp オレフィン重合体製造用触媒、その製造方法及びそれを用いたオレフィン重合体の製造方法
CN102356098A (zh) * 2009-03-17 2012-02-15 切弗朗菲利浦化学公司 制备聚合催化剂的方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MACROMOLECULES, vol. 33, 2000, pages 8931 - 8944
MACROMOLECULES, vol. 34, 2001, pages 5770 - 5777
See also references of EP4400522A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117700593A (zh) * 2023-12-13 2024-03-15 海南贝欧亿科技有限公司 一种生物基高极性热塑性聚烯烃弹性体及其制备方法及光伏封装胶膜

Also Published As

Publication number Publication date
JP2024534672A (ja) 2024-09-20
EP4400522A1 (en) 2024-07-17
KR20240055131A (ko) 2024-04-26
CN115894759A (zh) 2023-04-04
US20240400732A1 (en) 2024-12-05
CN115894759B (zh) 2024-07-02
EP4400522A4 (en) 2025-04-23

Similar Documents

Publication Publication Date Title
WO2023051580A1 (zh) 乙烯-α-烯烃共聚物及其制备方法和应用以及组合物
JP7238135B2 (ja) オレフィン重合用触媒およびこれを用いて調製されたオレフィン系重合体
CN106232638B (zh) 具有优异耐环境应力开裂性的聚烯烃
RU2668075C2 (ru) Гетерофазный сополимер
KR102198772B1 (ko) 다중모드 폴리에틸렌 폴리머 및 상기 폴리머의 제조 방법
JP2021500449A (ja) オレフィン−オレフィンアルコール共重合体及びその製造方法
CN105899553A (zh) 多相聚丙烯聚合物
CN109384885B (zh) 一种梳状乙烯基聚烯烃热塑性弹性体的制备方法
CN109983040B (zh) 聚烯烃催化剂和使用其制备聚烯烃的方法
US20090270580A1 (en) Ethylene Polymer, and Thermoplastic Resin Composition Comprising the Same, and Molded Product Obtained Therefrom
CN114539478A (zh) 基于进料策略调控的梳状聚烯烃热塑性弹性体的制备方法
CN109535323A (zh) 一种新型梳状丙烯基聚烯烃热塑性弹性体的制备方法
WO2019080877A1 (zh) 烯烃与不饱和羧酸或不饱和羧酸衍生物的共聚物
KR20260026089A (ko) 에틸렌/α-올레핀 공중합체 및 이의 응용
KR102559050B1 (ko) 프로필렌-1-부텐 공중합체 및 그 제조방법
JP5776603B2 (ja) ポリエチレン系樹脂組成物およびその成形体
JP2015172210A (ja) ポリエチレン系樹脂組成物およびその成形体
CN106103502B (zh) 包含金属茂络合物和助催化剂的催化剂
KR102821274B1 (ko) 혼성 담지 촉매
CN114507311B (zh) 乙烯聚合物及其制备方法
JP5303264B2 (ja) １−ブテン系重合体およびその製造方法
JP2002534538A (ja) 狭い組成分布と高融点を有するエチレンコポリマーおよびその製法
CN108290971B (zh) 金属茂负载型催化剂及使用该催化剂制备聚烯烃的方法
CN116162195B (zh) 一种高分子量的烯烃聚合物及其制备方法
CN116589619A (zh) 聚乙烯醇/乙烯/1-辛烯三元共聚物及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22874965

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2024519643

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2022874965

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2022874965

Country of ref document: EP

Effective date: 20240408

ENP Entry into the national phase

Ref document number: 20247012344

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE