WO2010133081A1 - 一种烯烃聚合用催化剂载体及其制备方法和应用 - Google Patents
一种烯烃聚合用催化剂载体及其制备方法和应用 Download PDFInfo
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- WO2010133081A1 WO2010133081A1 PCT/CN2010/000502 CN2010000502W WO2010133081A1 WO 2010133081 A1 WO2010133081 A1 WO 2010133081A1 CN 2010000502 W CN2010000502 W CN 2010000502W WO 2010133081 A1 WO2010133081 A1 WO 2010133081A1
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- Prior art keywords
- inorganic
- catalyst
- organic composite
- polar solvent
- organic
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B01J35/58—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0202—Alcohols or phenols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0209—Esters of carboxylic or carbonic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- 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 present invention relates to the field of olefin polymerization catalysts, and in particular to a catalyst for olefin polymerization and a preparation method and application thereof. Background technique
- the Ziegler-Nat ta polyolefin catalyst originated in the 1950s, it is still the main catalyst for olefin polymerization.
- TiCl 3 /AlEt 2 Cl-based developed into a highly efficient catalytic system consisting mainly of IVB ⁇ VB metal compounds (such as titanium compounds or vanadium compounds), magnesium halides and at least one electron donor, in industrial applications and research and development. Occupy an important position. Whether used for ethylene polymerization or propylene polymerization, the catalytic productivity and performance of the catalyst are constantly being improved to produce a polymer resin having higher performance while reducing consumption.
- the carrier is not only a dispersing agent for dispersing the active center of the catalyst, but also for maximally increasing the activity of the catalyst, or a template for polymer growth. Many production practices and studies have demonstrated that the particle morphology, size, particle distribution, and strength of the carrier determine the stability and continuity of the polymer production process, especially for gas phase and slurry processes.
- the method for dispersing the active center of the catalyst generally has the following methods: (1) a carrier method, that is, a catalyst component is physically or chemically supported on a formed carrier, and the shaped carrier is usually An inert inorganic material such as magnesium chloride, silica gel, alumina or diatomaceous earth, or an organic substance such as crosslinked polystyrene; (2) a method of coprecipitating the catalyst component with magnesium chloride to disperse the active center
- the magnesium chloride support such as the olefin polymerization catalyst prepared in U.S. Patent No.
- Inorganic/organic composite supported polyolefin catalysts are an important direction in the development of novel carriers. Utilizing the diversity of functional groups on the organic support, the activity, selectivity and performance of the supported catalyst can be regulated.
- Existing inorganic/organic composite carrier research has focused on improving the activity of the catalyst and improving the properties and morphology of the polymer by adjusting the properties of the support. Sukhdeep Kaur et al. reacted Mg(OEt) 2 with benzoyl chloride to obtain a MgCl 2 ⁇ ⁇ solid, which was poured into a homogeneous solution of methacrylic acid and 1-octene copolymer in chlorobenzene to obtain MgCl 2 ⁇ xEB/Poly (methyl
- the invention provides an inorganic/organic composite carrier, load
- the Ziegler-Nat ter catalyst can be used to catalyze the polymerization of olefins to obtain a polymerization product having a high melt flow ratio and a broad molecular weight distribution.
- An inorganic/organic composite carrier comprising an inert inorganic material, a complex of a polyol and a magnesium halide, and an organic polymer containing a polar functional group, wherein a complex of a polyol and a magnesium halide is deposited on an inert inorganic material and The organic polymer of the functional group is supported on the complex.
- the complex has the following formula:
- R (0H) n ⁇ MgX 2 ] m
- R is dC 2 .
- the inert inorganic material is preferably one or more of magnesium chloride, silica gel, alumina, diatomaceous earth, and most preferably silica gel.
- the silica gel is divided into two types: a porous silica gel and a non-porous silica gel.
- the fumed silica is preferably used.
- the average particle diameter of the fumed silica is preferably not more than 1.0 ⁇ m, particularly preferably 2 ⁇ m ⁇ It is not more than 0. 5 ⁇ ⁇ , most preferably 0. 2 ⁇ m.
- BET preferably more than 1. 0 cc / g, most preferably greater than 2. 0 cc / g
- BET when the pore size of the silica gel is selected, the pore volume of the silica gel is determined to be greater than 1. 6 cc / g, particularly preferably greater than 1. 8 cc / g
- the specific surface area is preferably greater than 100 m7g, more preferably at least 200 m 2 /g, most preferably at least 350 m 2 /g.
- the average particle diameter is preferably less than 20 ⁇ , more preferably less than 10 ⁇ , most preferably less than 5 ⁇ .
- the polar functional group in the organic polymer may be -0 ⁇ , -C00H, -NH 2 , -CO-, -CN, -X, -0-, -NH -, -C00-, -CO-NH - One or more of -CO-NH-C0-, -SO-, -SO-, -0-CO-O-.
- These polar functional groups are complexed with a titanium compound or a vanadium compound to adsorb and disperse the active component of the catalyst.
- the organic polymer is preferably regenerated cellulose, nitrocellulose, cellulose acetate, ethyl cellulose, bisphenol type polysulfone, polyaryl ether sulfone, phenolphthalein type polyether sulfone, polyether ketone, aliphatic polyamide.
- polysulfone amide polysulfone amide, aliphatic diacid polyimide, wholly aromatic polyimide, polystyrene, styrene copolymer, fluorine-containing polyimide, polyester, polyethylene copolymer, polypropylene copolymer, Poly 4-methyl-1-pentene copolymer, polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polydimethylsiloxane, polytrimethylsilylpropyne, polytetrafluoroethylene One or more of polyvinylidene fluoride.
- These organic polymers are readily soluble in polar solvents to form polymer homogeneous solutions and contain the polar functional groups required by the present invention.
- Per The content of the functional group in the organic polymer having a polar functional group is not less than 1. Ommol, preferably not less than 2 mmol, more preferably not less than 3 mmol.
- the polar functional group has a positive effect on the activity of the catalyst and can increase the activity of the catalyst to some extent.
- the polyol is preferably a fatty alcohol, more preferably a dibasic saturated fatty alcohol, most preferably ethylene glycol, 1, 3-propanediol, 1,4-butanediol, 1, 5-pentanediol and 1,6
- magnesium hydride is preferably magnesium chloride.
- the invention also provides a preparation method of the above inorganic/organic composite carrier, which comprises the following steps:
- the non-polar solvent is introduced into the slurry prepared in the step (5), or the slurry prepared in the step (5) is formed into a catalyst carrier by a spray drying method, and the catalyst carrier is washed with a non-polar solvent.
- step (1) the polyol and the inert inorganic material are stirred in a polar solvent, and the polyol is adsorbed on the inert inorganic material
- step (3) After the addition of the magnesium halide solution, a complex complexation reaction occurs between the polyol and the magnesium halide, and the formed complex is rapidly precipitated from the solution and deposited on the inert inorganic material.
- the organic polymer is precipitated from the solution by a phase inversion method and deposited on the surface of the complex, or by spray drying to obtain a complex comprising an inert inorganic material, a polyol and a magnesium halide. And an inorganic/organic composite carrier of a polar functional group-containing organic polymer.
- the polyol in the step (1) and the inert inorganic material are stirred for 1 hour in a polar solvent of about 50 X, and after the magnesium halide solution is added, the reaction is at least 30 minutes, and then the mixture is cooled to room temperature or below, for example, 0. After C, it is mixed with the organic polymer solution and introduced into a non-polar solvent until the required volume of non-polar solvent is added.
- the inorganic inert material is made of silica gel
- the purchased silica gel needs to be activated.
- the specific activation method is as follows:
- the silica was added to the activation furnace at a flow rate of 200 to 1000 under a nitrogen stream.
- C preferably SOO S OO C is more preferably 500 to 750 ° C, particularly preferably 600 to 700 ° C for 2 to 10 hours, preferably 3 to 7 hours, more preferably 4 to 5 hours, to surface the silica particles.
- the hydroxyl content is reduced to 0.5 to 0.7 ol / g, and then cooled to ambient temperature to become dehydrated silica gel.
- the surface of the silica gel may be modified with an alkyl magnesium to remove residual hydroxyl groups on the surface of the silica gel.
- the specific operation method is as follows:
- the dehydrated silica gel and an appropriate amount of a non-polar solvent are added to a vessel with agitation, and the non-polar solvent includes ethane, propane, butane, isobutane, pentane, isopentane, hexane, cyclohexane. And heptane or the like is preferably pentane, isopentane, hexane or cyclohexane.
- each mole of silica gel is added 0.5 to 0.7 mmol of alkyl magnesium, and the magnesium alkyl includes diethyl magnesium, dipropyl magnesium, dibutyl magnesium, dihexyl magnesium, dipentyl magnesium, monochloroethyl.
- the molar ratio of the magnesium halide to the polyol is preferably 0.02 to 50, the weight ratio of the magnesium halide to the inert inorganic material is preferably 0.01 to 1, and the weight ratio of the organic polymer to the inert inorganic material is preferably 0.01 to 3. .
- the polar solvent is preferably tetrahydrofuran; the non-polar solvent is a saturated alkane, preferably a saturated alkane of 1 to 12 carbon atoms, and most preferably a saturated alkane having 5 to 7 carbon atoms.
- the stirring speed in the step (4) is preferably 500 rpm or less, more preferably 100 to 300 rpm.
- the non-polar solvent is preferably passed into the slurry in a gaseous phase.
- the method of obtaining the inorganic/organic composite carrier may be carried out by a phase conversion method in which an anti-solvent is introduced or a spray drying method.
- the volume ratio of the nonpolar solvent to the polar solvent is preferably from 0.05 to 20, more preferably from 0.1 to 10, most preferably from 0.3 to 5.
- the non-polar solvent is slowly introduced into the slurry prepared in the step (5) in the form of steam, and the introduction time is in the range of 1 to 20 h, preferably 2 to 5 h. After the end of the anti-solvent addition, the mixture was stopped and allowed to stand for stratification, and the supernatant was filtered or decanted to separate the precipitate.
- the precipitate is washed a plurality of times with a non-polar solvent, and the number of washings is preferably 2 to 6 times, more preferably 3 to 4 times, and the washing temperature is preferably 50 to 90 ° C, more preferably 60 to 70 ° (.
- the process primarily removes excess polar solvent and polyol. After washing, it is purged with nitrogen until it is free flowing.
- the drying temperature is preferably from 50 to 90 °C.
- the precipitate is preferably separated and washed with a non-polar solvent such as an alkane; the number of washings is preferably 2 to 6 times, more preferably 3 to 4 times, and the washing temperature is preferably 50 to 90 ° C, more preferably 60 to 70. °C.
- This process primarily removes excess polar solvents and polyols.
- the crucible was purged with nitrogen until it was free flowing.
- the invention also provides a method for preparing a polyolefin catalyst by using the above inorganic/organic composite carrier, comprising the following steps:
- the catalyst carrier is dispersed in a non-polar solvent, a compound containing a group IVB to V Group B and an electron donor are added, and after stirring, the precipitate is separated, washed, and dried to obtain a catalyst.
- the catalyst carrier is subjected to dehydroxylation treatment, and the dehydroxylation reagent is aluminum alkyl, titanium tetrachloride, silicon tetrachloride or the like.
- the compound containing the IVB to V B group metal is preferably a titanium-containing compound or a vanadium-containing compound. More preferably, it is titanium tetrachloride, titanium tetrabutoxide, titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium dichlorodiethoxylate, titanium trichloroethoxylate, two At least one of titanium chlorobutoxide, titanium trichloroquinoline, and vanadium tetrachloride.
- the electron donor is preferably at least one of ethyl benzoate, dialkyl phthalate, phenyltriethoxysilane, diether and succinate.
- the temperature is controlled at 0 to 10 ° C at the beginning of the reaction, and the reaction time is more than 2 h, preferably 2-8 h;
- the reaction is further carried out by gradually increasing the temperature to 60 to 80 ° C for a duration of more than 2 h, preferably 2-8 h.
- the molar ratio of the electron donor to the catalyst carrier is preferably 0. 1 ⁇
- the reaction pressure is 0. 5-5 MPa, preferably 1-3 MPa; and the reaction temperature is 30-150. C, preferably 60-120 ° C, more preferably 90-110. C.
- the slurry polymerization process is generally from 0.1 to about 5. OMPa or higher, preferably from about 0. 5MPa to about 2. OMPa pressure and 0 ° C - about 120 ° C, preferably from about 30 to about 110 ° C, more It is preferably operated at a temperature of from about 60 to about 100 °C.
- a typical gas phase fluidized bed reactor system consists of a recycle gas compressor, a cooler, a polymerization reactor in which solid particles are held in a fluidized state by a passing recycle gas.
- the solid ZN catalyst prepared by the invention is mixed with mineral oil to form a slurry and then added to the reactor intermittently or continuously by a transfer pump, or the prepared solid ZN catalyst is directly or continuously added by using nitrogen as a carrier.
- a molecular weight regulator preferably hydrogen
- the solid Z-N catalyst prepared by the present invention may be used as a cocatalyst and/or scavenger when used in the polymerization of ethylene.
- the alkyl metal compound include: an alkyl aluminum compound, an alkyl lithium compound, an alkyl zinc compound, an alkyl boron compound, preferably an alkyl aluminum compound, more preferably triethyl aluminum, triisobutyl Base aluminum or tri-n-hexyl aluminum.
- the molar ratio of the alkyl metal compound to the titanium compound may be in the range of 5:1 to 300:1, preferably in the range of 20:1 to 250:1, more preferably in the range of 40:1 to 200:1.
- the solid Z-N catalyst of the present invention can be used for homopolymerization of ethylene or copolymerization of ethylene and ct-olefin.
- Suitable a - Examples of olefin comonomers include dC 2.
- A-olefin such as but not limited to: propylene, butene-1, pentene-1, hexene-1, octene-1 or higher a-olefin, preferably butene-1, hexene- 1 and octene-1. 1-0. 2 ⁇ The ot - olefin.
- hydrogen gas can be used as the molecular weight modifier. 5 ⁇
- the molar ratio of the hydrogen and the ethylene may be 0. 01-1. 0, preferably 0. 1-0.
- the range of the range of 0. 915-0. 930 g/cm 3 is preferably in the range of 0. 915-0. 960 g/cm 3 , preferably in the range of 0. 915-0. 930 g/cm 3 .
- the polymerization process of the present invention can produce broad molecular weight distribution of polyethylene, the polyethylene may have from about 30-- 200 melt flow ratio MFR (FI / MI) 0
- a typical loop bulk polymerization process consists of a catalyst prepolymerized small loop reactor and a large polymerization loop reactor; propylene, hydrogen, the cocatalyst, external electron donor continuously added to the loop reaction ⁇
- the polymer and liquid propylene are continuously circulated in the loop, the heat of polymerization is removed by the jacketed cooling water; the operating pressure of the reactor is 1. 0 - - 5.
- OMpa preferably 3. 0 - - 4.
- operating temperature is 50--90 °C, preferably 65--75 °C
- mediating molecular weight of hydrogen is 100--8000 ppm, preferably 500--5000 ppm, the ratio of cocatalyst to electron donor is 1 --- 100, preferably 2 - 40
- the external electron donor includes: ethyl benzoate, dialkyl phthalate, phenyl triethoxysilane, diether, and the like.
- the density can be in the range of from 0.915 to 960 g/cm 3 , preferably in the range of from 0.95 to 930 g/cm 3 , high load.
- the flow index (FI) is from about 1 to about 200 g ocO., preferably from about 2 to about 100 g/10 min.
- the polymerization process of the present invention can produce a broad molecular weight distribution of polypropylene which can have a molecular weight distribution of from about 5 to about 15 for Mw/Mn.
- ASTM D1928 was used to test the density of the polymer resin (DE);
- ASTM D1238 was used to test the melt index (Ml, 190 at 2.16 kg load) and flow index (FI, 190" C at 21.6 kg load);
- ASTM D638 is used to test the tensile strength of polymer resins.
- the molecular weight distribution of the polymer was measured by gel chromatography (GPC).
- melt flow ratio (MFR) of the polymerization product can be adjusted by changing the hydrogen content
- the catalyst provided by the present invention is characterized by high activity when it is used for the polymerization of ethylene or propylene.
- step (3) Slowly add all the magnesium chloride solution in step (3) to the TS-610/butanediol/THF solution in step (2) and keep it under rapid stirring at 45 ⁇ 50 ° (: stirring for 2 hours) Forming a slurry carrier and then cooling to 0";
- the catalyst carrier is prepared by using styrene-acrylamide copolymer as organic material, wherein the weight ratio of silica gel TS-610, magnesium chloride and styrene-acrylamide copolymer is 50:20:30, and the total amount of titanium tetrachloride is 8ml. The rest of the operation was the same as in Example 1, and a catalyst carrier and a supported ZN catalyst were prepared.
- the catalyst carrier prepared by using styrene-acrylamide copolymer as organic material, the weight ratio of silica gel TS-610, magnesium chloride and styrene-acrylamide copolymer is 30:20:50, and the total amount of titanium tetrachloride is 10ml, the rest Operation is the same as in Example 1, preparation of catalysis Agent carrier and supported ZN catalyst.
- the surface hydroxyl group content of the activated silica gel is 0. 5 ⁇ 0. 7 mmol / g, stored under nitrogen protection;
- step (2) The activated silica gel of step (1) and tetrahydrofuran are stirred at room temperature. According to the addition of 0.2 ml of propylene glycol per gram of silica gel, 70 ml of propylene glycol is added and stirred at room temperature for 1 h, then the temperature is raised to 40 C. , preparing a silica gel HHV-4/propylene glycol/THF mixture;
- the weight ratio of the silica gel HHV-4, the magnesium chloride to the styrene-acrylic acid copolymer is 30: 20: 50, the total amount of titanium tetrachloride is 0. 08 mol, the electron donor is changed to 0. 06 mol dioxane
- the phthalic acid ester was used in the same manner as in Example 5 to prepare a catalyst carrier and a supported ZN catalyst.
- a 200 g of a porous silica gel HHV-3 (Tianjin Chemical Research Institute) having an average particle size of 10 ⁇ m is placed in an activation furnace having a diameter of 50 mm in a nitrogen flow having a flow rate of 0.10 m/s.
- the temperature of the activation furnace is raised to 120 °C, after 2 hours of constant temperature, the temperature is raised to 600 °C at a rate of 50 °C / h, the temperature is kept for 4 h, and then the temperature is lowered to room temperature to obtain activated silica gel.
- the surface hydroxyl group content of the activated silica gel is 0. 5 ⁇ 0. 7 mmo l /g, stored under nitrogen protection;
- step (2) The activated silica gel of step (1) is stirred with isopentane at room temperature, and is calculated by adding 0.25 ml of 1, 4-butanediol per gram of silica gel, and then adding 50 ml of 1, 4-but The diol was stirred at 20 ° C for 1 h and then heated to 40 ° C to prepare a silica gel HHV-3/butanediol solution;
- the catalyst carrier and the support were prepared in the same manner as in Example 7 except that the weight ratio of the silica gel HHV-3, the magnesium chloride to the styrene-acrylamide copolymer was 30:20:50, and the total amount of titanium tetrachloride was 5 ml.
- Type ZN catalyst Type ZN catalyst.
- step (2) Stir the activated silica gel of step (1) with isopentane at room temperature, add 0.058 kg of TEA per kg of silica gel, add 80 ml of 1 mol/L TEA and stir at room temperature. After h, the isopentane was removed by purging with nitrogen. Chemically activated silica gel.
- step (2) Stir the activated silica gel of step (1) with isopentane at room temperature, add 0.058 kg of TEA per kg of silica gel, add 120 ml of 1 mol/L TEA and stir at room temperature. After h, the isopentane was removed by purging with nitrogen to obtain a chemically activated silica gel.
- Ps in the A and B catalysts are styrene-acrylic acid copolymers; Ps in the C and D catalysts are styrene-acrylamide copolymers; Ts refers to TS-610 gas phase non-porous silica gel; Mg refers to magnesium chloride.
- the particle diameters are the equivalent diameters (average particle diameters) of the largest particles having a cumulative distribution of 90%, 50%, and 10% in the particle size distribution curve, respectively.
- Span represents the dispersion index of the particle size and is the ratio of the volume average particle diameter to the number average particle diameter.
- the ZN catalysts with different component contents prepared in Examples 5 to 8 were numbered as catalysts F, G, H, and I, and compared with the conventional catalyst prepared in Comparative Example 2, and the test results of each catalyst are shown in Table 2.
- Ps is a styrene-acrylic acid copolymer in F and G catalysts; Ps is a styrene-acrylamide copolymer in H and I catalysts; S i refers to HHV-3/4 silica gel; Mg Means magnesium chloride; ED is an electron donor.
- the particle diameters are the equivalent diameters (average particle diameters) of the largest particles having a cumulative distribution of 90%, 50%, and 10% in the particle size distribution curve, respectively.
- Span represents the dispersion index of the particle size and is the ratio of the volume average particle diameter to the number average particle diameter.
- the small pilot fluidized bed polymerization reactor of ⁇ 80 ⁇ 900 was flow-exchanged with nitrogen for 1 h, and the circulating reaction gas of the industrial reactor was used (molar composition: ethylene 37.6%, 1-butene 15.5%, hydrogen 4.7%, Nitrogen 35.5% and isopentane 6.7%; triethylaluminum concentration 320 ppm; flow replacement for about 3 h, small reactor reaction temperature of 81 ° C, reaction pressure of 2.09 Mpa, keeping the reaction gas flowing, respectively
- the solid ZN catalysts A, B, C, and D prepared in the above Examples 1 to 4 were each 0.10 g, and were purged with a high-pressure nitrogen gas (pressure of 3.
- Ps is a styrene-acrylic acid copolymer in A and B catalysts; Ps is a styrene-acrylamide copolymer in C and D catalysts; Ts refers to TS-610 vapor phase nonporous silica gel; Mg refers to magnesium chloride; H 2 / C 2 is the molar ratio of hydrogen to ethylene; C 4 /C 2 represents the molar ratio of 1-butene to ethylene; Cat. refers to the catalyst; MFR is the melt ratio FI/ML
- the M1 of the polymer produced by the catalyst of the present invention is lower than the M1 of the polymer produced by the conventional catalyst E', and the MFR is higher than the MFR of the polymer produced by the conventional catalyst E'. It is shown that the processing properties of the polymer produced by the catalyst of the present invention are improved and the mechanical properties of the polymer are also improved.
- the flow rate of the ⁇ 80 ⁇ 900 leg small pilot fluidized bed polymerization reactor was replaced by nitrogen for 1 hour, and the circulating reaction gas of the industrial reactor was used (molar composition: ethylene 38.1% 1-butene 16.5%, hydrogen 7.8%, nitrogen) 31.4% and inert alkane isopentane 2%, triethylaluminum concentration is 320 ppm; keep flow replacement for about 3 hours, small test reactor reaction temperature is: 81 °C, reaction pressure: 2.09 Mpa, keep the reaction gas
- Ps in the AB catalyst is styrene-acrylic acid copolymer; Ps is styrene-acrylamide copolymer in CD catalyst; Ts refers to TS-610 gas phase non-porous silica gel; Mg refers to magnesium chloride; H 2 /C 2 is hydrogen Mole ratio to ethylene; C 4 /C 2 The table is the molar ratio of 1-butene to ethylene; Cat. refers to the catalyst; MFR is the melt ratio, ie FI/ML
- the MFR of the polymerization level can be increased with the increase of the hydrogen concentration, that is, the catalyst can be used for the polymerization of ethylene to increase the concentration of hydrogen by increasing the concentration of hydrogen.
- the MFR of ethylene improves the processing properties of polyethylene.
- the flow rate of the ⁇ 80 ⁇ 900 mm small pilot fluidized bed polymerization reactor was replaced by nitrogen for 1 h, and the circulating reaction gas of the industrial reactor was used (molar composition: ethylene 38.0%, 1-butene 16.5%, hydrogen 5.0%, nitrogen 34.5). % and isopentane 6.0%, triethyl aluminum concentration is 320 ppm; the small test reactor reaction temperature is: 81 ° C, the reaction pressure is: 2.09 Mpa, the reaction gas flow is maintained, and the above examples 5-8 are respectively prepared.
- the solid catalysts F, G, H, and I each were 0.10 g, and were purged into a reactor with a high-pressure nitrogen gas (pressure of 3.
- Ps in the F and G catalysts are styrene-acrylic acid copolymers
- Ps in the H and I catalysts are styrene-acrylamide copolymers
- Si refers to HHV-3/4 silica gel
- Mg refers to magnesium chloride
- H 2 /C 2 is a molar ratio of hydrogen to ethylene
- C 4 /C 2 represents a molar ratio of 1-butene to ethylene
- Cat. refers to a catalyst
- MFR is a melt ratio, ie, FI/MI.
- the M1 of the polymer produced by the catalyst of the present invention is lower than the M1 of the polymer produced by the conventional catalyst, and the MFR is higher than the MFR of the polymer produced by the conventional catalyst E'. It is demonstrated that the processability of the polymer produced by the catalyst of the present invention is improved and the mechanical properties of the polymer are also improved.
- the flow rate of the ⁇ 80 ⁇ 900 mm small pilot fluidized bed polymerization reactor was replaced by nitrogen for 1 h, and the circulating reaction gas of the industrial reactor was used (molar composition: ethylene 37.5%, 1-butene 16.5%, hydrogen 7.6%, nitrogen). 32.4% and isopentane 6.0%, the concentration of triethylaluminum is 320ppm and the flow replacement is about 3 h.
- the reaction temperature of the pilot reactor is 81 °C
- the reaction pressure is 2.09 Mpa
- the reaction gas flow is maintained, respectively.
- Ps in the F and G catalysts are styrene-acrylic acid copolymers
- Ps in the H and I catalysts are styrene-acrylamide copolymers
- S i refers to HHV-3/4 silica gel
- Mg refers to magnesium chloride
- H 2 / C 2 is a molar ratio of hydrogen to ethylene
- C 4 /C 2 represents a molar ratio of 1-butene to ethylene
- Ca t. refers to a catalyst
- MFR is a melt ratio, ie, FI/MI.
- the solid ZN catalysts A, B, C, and D prepared in Examples 1 to 4 and the conventional ZN catalyst E' prepared in Comparative Example 1 were each 0.1 g, respectively, and 10 ml of hexane and 7.5 ml of cocatalyst were added.
- Base aluminum (10% by weight concentration) 1. 0 ml of electron donating isobutyltriethyloxysilane (6% by weight concentration) is uniformly mixed, that is, a load type Z which can be used for propylene polymerization is obtained.
- - N catalyst, a, b, c, d, e*, spare is uniformly mixed, that is, a load type Z which can be used for propylene polymerization.
- the hydrogen in the metering bottle A was fed to the reactor, and then 2.3 L of liquid propylene and the supported ZN catalyst prepared above were metered in, the internal temperature of the reactor was raised to 70 ° C, and the reactor clamp was adjusted when the polymerization reaction started.
- the water is set to control the polymerization temperature at 70 ⁇ 0.5. C, pressure 3. 2 Mpa, polymerization 1 h, unreacted propylene was discharged to a torch under reduced pressure, and the reactor was replaced with nitrogen 2 to 3 times to remove hydrocarbons to obtain a propylene polymer.
- the prepared propylene polymer physical property data of the prepared negative-type Z-N catalysts a, b, c, d and comparative example e' are shown in Table 7:
- A, b catalyst PSA is harmless ethylene-acrylic acid copolymer; c, d catalyst PSA is styrene-acrylamide copolymer; Ts refers to TS-610 gas phase non-porous silica gel; H 2 / C 3 is hydrogen and The molar ratio of propylene, the molar ratio of A1 /ED triethylaluminum to the electron donor; Ca t. refers to the catalyst, and Mw/Mn is the molecular weight distribution.
Description
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US13/321,054 US9120089B2 (en) | 2009-05-18 | 2010-04-15 | Catalyst support used for olefin polymerization and preparing method and application thereof |
SG2011085354A SG176162A1 (en) | 2009-05-18 | 2010-04-15 | Catalyst support used for olefinic polymerization and preparing method and application thereof |
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CN (1) | CN101554595B (zh) |
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CN115960279A (zh) * | 2021-10-08 | 2023-04-14 | 中国石油化工股份有限公司 | 一种催化剂载体及其制备方法和应用 |
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CN101554595B (zh) * | 2009-05-18 | 2011-02-02 | 中国石油化工股份有限公司 | 一种烯烃聚合用催化剂载体及其制备方法和应用 |
CN101940958B (zh) * | 2009-07-09 | 2012-07-18 | 中国石油化工股份有限公司 | 负载型铁基合成气制低碳烯烃催化剂的制备方法 |
CN102432710A (zh) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | 一种用于乙烯聚合催化剂载体的制备方法、催化剂组分及催化剂 |
CN103524642B (zh) * | 2012-07-04 | 2015-08-19 | 中国石油天然气股份有限公司 | 一种改性载体硅胶的制备方法 |
US10407518B2 (en) * | 2013-12-18 | 2019-09-10 | Braskem S.A. | Catalyst support and related processes |
WO2015089615A2 (en) * | 2013-12-18 | 2015-06-25 | Braskem S.A. | Catalyst support and related processes |
CN105482003B (zh) * | 2014-10-10 | 2018-01-23 | 中国石油化工股份有限公司 | 一种乙烯聚合催化剂所用的载体及其催化剂 |
CN105622790B (zh) * | 2014-11-06 | 2018-01-19 | 中国石油化工股份有限公司 | 一种乙烯均聚合或共聚合催化剂所用的载体及其催化剂 |
WO2016086837A1 (zh) * | 2014-12-05 | 2016-06-09 | 中国石油天然气股份有限公司 | 一种二元磺酸酯化合物及其应用与烯烃聚合催化剂组分和烯烃聚合催化剂 |
CN105801729B (zh) * | 2016-05-30 | 2018-01-05 | 宁波大学 | 聚乙烯的制备方法 |
CN116003655A (zh) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | 一种烯烃聚合用催化剂载体及其制法和应用 |
CN116063593A (zh) * | 2021-10-30 | 2023-05-05 | 中国石油化工股份有限公司 | 一种用于烯烃聚合的催化剂组分、含其的催化剂及其制备方法和应用 |
CN115785308A (zh) * | 2022-11-30 | 2023-03-14 | 上海化工研究院有限公司 | 一种用于生产增强聚烯烃的催化剂及其制备和应用 |
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