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
  • 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
  • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
  • C08F4/652—Pretreating with metals or metal-containing compounds
  • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
• • 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
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • 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
  • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene
• • 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

Definitions

• the coordination atoms of the non-metallocene catalysts are oxygen, nitrogen, Sulfur and phosphorus, which do not contain a cyclopentadienyl group or a derivative group thereof, such as a fluorenyl group and a fluorenyl group, etc., characterized in that the central ion has strong electrophilicity and has a cis-alkyl or halogen metal central structure.
• d is selected from 0 or 1;
• B is selected from a nitrogen-containing group, a phosphorus-containing group or a C!-Cso hydrocarbon group
• inorganic materials having a hydroxyl group on the surface are preferable, and examples thereof include silica, alumina, magnesia, and titania. a molecular sieve and montmorillonite, or a mixed oxide of silicon dioxide and a metal oxide selected from the group consisting of lanthanum or lanthanum, such as a silica-magnesia mixed oxide, a silica-alumina mixed oxide, Silica is particularly preferred.
• the magnesium compound may be selected, for example, from magnesium, magnesium alkoxide, magnesium alkoxide, magnesium alkyl, alkyl magnesium, alkyl alkyl or any one thereof. Mixture of species or mixtures,
• the alkyl magnesium may, for example, be selected from the group consisting of methyl magnesium (Mg(CH 3 ) 2 ), ethyl magnesium (Mg(C 2 H 5 ) 2 ), propyl magnesium (Mg(C 3 H 7 ) 2 ), n-butyl Magnesium (Mg(C 4 H 9 ) 2 ) and isobutyl magnesium (Mg(iC 4 H 9 ) 2 ) and the like, among which ethyl magnesium and n-butyl magnesium are preferred, :
• n is an integer from 1 to 50, preferably from 10 to 30.
• the ratio of the auxiliary chemical treatment agent to the porous carrier in terms of the A1 element if the porous carrier is treated with a magnesium treated porous body at this time, the magnesium is treated with the magnesium
• the ratio of the treated porous carrier is 0.25 to 4 mmol: 1 g, preferably 0.5 to 2 mmol: 1 g,
• the following method can be mentioned. First, prepare a solution of the auxiliary chemical treatment agent, and then add a prescribed amount of the chemical treatment to the porous carrier at a temperature below the boiling point of the solution at room temperature to the solution, and the reaction is 0.5 - 6h (if necessary, by stirring) Thereby obtaining the porous carrier subjected to the pretreatment.
• the obtained pretreated porous carrier can be separated from the mixed solution by filtration and washing (1 to 6 times, preferably 1 to 3 times). It is finally dried, but it can also be used directly for the processing steps as described below without separation.
• a solution of the chemical treatment agent is first prepared, and then a predetermined amount of the chemical treatment agent is added (preferably dropwise) to the porous carrier;
• a treatment agent such as titanium tetrachloride
• a specified amount of the chemical treatment can be directly added (but after being prepared as a solution) to the porous carrier (preferably dropwise) to make a contact reaction (required)
• stirring 0.5 to 24 hours, preferably 1 to 8 hours, more preferably 2 to 6 hours, and most preferably 2 to 4 times, followed by filtration and washing, followed by drying, thereby obtaining a modified porous carrier.
• aluminoxane and the aluminum alkyl those previously mentioned as a co-chemical treating agent can be used, of which methylaluminoxane and tri-aluminum are preferable.
• the amount of the olefin polymerization activity can be obtained, and the polymer such as polyethylene thus obtained has an excellent polymer form and a high polymer bulk density.
• the non-metallocene ligand was dissolved in hexane, and then the modified porous carrier was added. After stirring for 4 hours, the mixture was filtered, washed twice with hexane, 25 ml per hexane, and then dried at 25 t! for 6 h to obtain a supported non-metallocene. catalyst.
• the ligand concentration was 0.045 g/ml, and the ratio of the non-metallocene ligand to the porous carrier was: 0.193 ⁇ mol: 1 gram.
• the porous carrier is selected from the group consisting of polypropylene, the surface functional group is a hydroxyl group, and the heat activation condition is 200 ⁇ , 1 2 atmosphere for 2 hours.
• the non-metallocene ligand is dissolved in hexane, and then the above modified porous carrier is added, stirred for 4 hours, filtered, washed twice with hexane, 25 ml per hexane, and then dried at 251 C for 2 h to obtain a negative type.
• Metallocene catalyst The concentration of the ligand is 0.045 g/ml, and the ratio of the non-metallocene ligand to the porous carrier is: 0.193 mmol: 1 g.
• Non-metallocene ligands changed to , wherein the ligand concentration is 0.28 g/ml, and the ratio of the non-metallocene ligand to the porous carrier is: 0.02 mmol: 1 g, and the solvent for dissolving the non-metallocene ligand is changed to dichloromethane.
• the chemical treatment agent was changed to tetramethyl zirconium.
• the ratio of ethylmagnesium chloride to tetrahydrofuran is 1:12; the molar ratio of ethylmagnesium chloride to trichloromethane is 1:1; the ratio of shield of ethylmagnesium chloride to porous carrier is 1:3.4; tetramethoxy
• the molar ratio of titanium to non-metallocene ligand is 1:0.5; the mass concentration of non-metallocene ligand is 0.28 g/ ⁇ l; the mass ratio of non-metallocene ligand to magnesium treated porous carrier is 0.05:1 .
• Non-metallocene ligands changed to The solvent for dissolving the non-metallocene ligand was changed to cyclohexane.
• the catalytic charge is CAT-II-B,
• Non-metallocene ligands changed to .
• the solvent in which the non-metallocene ligand is dissolved is changed to chlorohexane.
• the ratio is that the molar ratio of antimony tetrachloride to non-metallocene ligand is 1:0.6; the ratio of methyl aluminoxane to magnesium treated porous carrier is 3 mmol: 1 g.
• the chemical treatment agent uses a mixture of zirconium tetrachloride and triethylaluminum. First, a solution of triethylaluminum in hexane is added. After 1.5 hours of reaction, it is filtered, washed once with chlorohexane, and then zirconium tetrachloride is added dropwise. Toluene solution.
• the ratio is that the molar ratio of titanium tetrachloride to non-metallocene ligand is 1:0.5; the mass concentration of non-metallocene ligand is 0.05 g/ml; the mass ratio of non-metallocene ligand to magnesium treated porous carrier Is 0.15: 1.
• the molar ratio of titanium tetrabromide to non-metallocene ligand is 1:0.3; the concentration of non-metallocene ligand is 0.11 g / liter; the non-metallocene ligand and magnesium treated porous carrier The mass ratio is 0.22: 1.
• the preparation process of the magnesium-treated porous carrier was the same as in Example 11-1.
• the chemical treatment agent uses a combination of titanium tetrachloride and isobutyl aluminoxane. a solution of butyl aluminoxane in benzene,
• Non-metallocene ligands changed to The solvent in which the non-metallocene ligand is dissolved is changed to xylene.
• the chemical treatment agent uses a composite treatment agent of zirconium tetrachloride and triethylaluminum.
• a solution of triethylaluminum in hexane was added, and after 1.5 h of reaction, it was filtered, washed once with chlorohexane, and dried under vacuum for 2 h.
• the porous carrier is selected from the silica prepared by the high temperature hydrolysis process of silicon tetrachloride, and the heat activated nano member is 600*C, and dried under a dry nitrogen atmosphere for 8 hours.
• Ethanol is changed to heptanol.
• Ethanol was changed to phenylpropanol.
• Non-metallocene ligands changed to
• the porous carrier was made of silica gel, model ES757 of Ineos Co., Ltd., and it was continuously calcined in a 600 ⁇ , ⁇ 2 atmosphere for 4 hours.
• the ratio of triethyl aluminum to magnesium treated porous carrier was 0.25 mmol: 1 g.
• Magnesium chloride was changed to magnesium oxyhydroxide.
• the porous support is selected from the silica prepared by the high temperature hydrolysis process of silicon tetrachloride, and the heat activation condition is 600, and the drying is continued for 8 hours under a dry nitrogen atmosphere.
• anhydrous magnesium chloride was dissolved in a mixture of tetrahydrofuran and ethanol, heated to 60, stirred for 1.5 hours to form a solution, and then heat activated silica gel was added to the solution, at 60 Stir for 2 h to form a transparent system. Then, hexane is added to precipitate the magnesium compound, followed by filtration.
• triisobutylaluminoxane was added dropwise, followed by dropwise addition of titanium tetrachloride.

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• 2008
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