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
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  • 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.

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• 2021
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