CN102408504A - Methods of ethylene homopolymerization and copolymerization of ethylene and butylene-1 under action of vanadium catalyst - Google Patents
Methods of ethylene homopolymerization and copolymerization of ethylene and butylene-1 under action of vanadium catalyst Download PDFInfo
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- CN102408504A CN102408504A CN2011103596253A CN201110359625A CN102408504A CN 102408504 A CN102408504 A CN 102408504A CN 2011103596253 A CN2011103596253 A CN 2011103596253A CN 201110359625 A CN201110359625 A CN 201110359625A CN 102408504 A CN102408504 A CN 102408504A
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Abstract
The invention relates to a method of ethylene homopolymerization and copolymerization of ethylene and butylene-1 under the action of a vanadium catalyst and aims to solve the following problems: in a method of producing a polyolefine product by utilizing the existing catalyst, the molecular weight distribution of the polyolefine product is narrower, the stacking density of a polymerization product is lower and the control difficulty of the production process is high. The method of copolymerization of ethylene and butylene-1comprises the following steps: preparing the vanadium catalyst; utilizing nitrogen gas to blow a polymerizing pot, adding a solvent, stirring, dissolving a cocatalyst in the solvent to obtain a solution, adding the solution into the polymerizing pot and then heating the polymerizing pot; adding the hydrogen gas and the vanadium catalyst, continuing heating, and introducing ethylene for polymerization reaction; after reacting for 1-4 hours, stopping introducing ethylene or ethylene and butylene-1; and cooling, performing decompression discharge and drying products. The prepared olefin polymer has the characteristics of high molecular weight, wide molecular weight distribution, high stacking density and narrow and controllable particle size distribution.
Description
Technical field
The present invention relates to ethylene homo method and ethene and butene-1 copolymerization process under the vanadium series catalyst effect.
Background technology
Catalyzer is the core of polyolefin industry development; In recent years; In the world wide each big factory commercial city through the development of new polyolefin catalyst, improve Catalytic processes to satisfy the market demand growing to high performance polyethylene products; Not only quicken the update of catalyzer, but also constantly widened the Application Areas of polyethylene product.
In the past during slurry method explained hereafter polyolefin products; Used catalyzer mainly is a Ti/Mg carrier model Z-N catalyzer, the MWD of this Catalyst Production polyolefin products (MWD) relative narrower, and when producing the higher molecular weight polyolefin products; The processing characteristics of product is relatively poor; As expect the polyolefin products of HMW, wide molecular weight distribution, and need take dual reactor process or complex catalyst system, bring problems such as the increase of controlling of production process difficulty, production cost increase.In addition, adopt Ti/Mg carrier model Z-N catalyst system, the tap density of polymerisate is relatively low, has limited the raising of plant capacity.
Among the preparation method of existing preparation wide molecular weight distribution polyolefin product, there is the problem that cost is high, influence product performance because of resinous blending is inhomogeneous in two kinds of polymer blending methods; Though big through grading reactor stage feeding polymerization operation adjustment handiness, production efficiency is low, production cost is high; And in single reaction vessel, adopt bimetal or many metal active constituents catalyzer, though be rationally feasible theoretically, in fact wanting the comprehensive poly behavior of closing is one, realizes that industrial difficulty is bigger.
Summary of the invention
The present invention is the MWD relative narrower that will solve polyolefin products in the method for utilizing existing Catalyst Production polyolefin products; The tap density of polymerisate is relatively low; The problem that the controlling of production process difficulty is big provides ethylene homo method and ethene and butene-1 copolymerization process under the vanadium series catalyst effect.
Ethylene homo method under the vanadium series catalyst effect of the present invention, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.1～10; Two, blow row 2L polymeric kettle with nitrogen, add the 1L solvent, start stirring, promotor is dissolved in the solvent, obtain the solution of 1～10mmol/L, solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.03～0.05MPa and the vanadium series catalyst of step 1 preparation, after temperature of reaction system reaches 75～100 ℃, begin to feed ethene and carry out polyreaction, reaction pressure is 0.5～3.0MPa; Four, reaction stopped logical ethene after 1～4 hour, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect; Wherein in the promotor in aluminium and the vanadium series catalyst mol ratio of vanadium be 10～8000: 1; Solvent described in the step 2 is a kind of in propane, butane, Trimethylmethane, pentane, hexane, heptane, octane, hexanaphthene, methylcyclohexane, toluene, the YLENE or several kinds mixture wherein; Promotor described in the step 2 is a kind of in a chloro-di-isobutyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, dichloro one aluminium triethyl, triethyl aluminum, aluminium diethyl monochloride, the tri-n-hexyl aluminum or several kinds mixture wherein.
Ethene under the vanadium series catalyst effect of the present invention and butene-1 copolymerization process, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.1～10; Two, blow row 2L polymeric kettle with nitrogen, add the 1L solvent, start stirring, promotor is dissolved in the solvent, obtain the solution of 1～10mmol/L, solution is added polymeric kettle, polymeric kettle is heated up; Three,, temperature of reaction system adds the hydrogen of 0.03～0.05MPa and the vanadium series catalyst of step 1 preparation when rising to 70 ℃; After temperature of reaction system reaches 75～100 ℃; Begin to feed ethene and butene-1 and carry out polyreaction, reaction pressure is 0.5～3.0MPa; Four, reaction stopped logical ethene after 1～4 hour, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect; Wherein in the promotor in aluminium and the vanadium series catalyst mol ratio of vanadium be 10～8000: 1; Solvent described in the step 2 is a kind of in propane, butane, Trimethylmethane, pentane, hexane, heptane, octane, hexanaphthene, methylcyclohexane, toluene, the YLENE or several kinds mixture wherein; Promotor described in the step 2 is a kind of in a chloro-di-isobutyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, dichloro one aluminium triethyl, triethyl aluminum, aluminium diethyl monochloride, the tri-n-hexyl aluminum or several kinds mixture wherein; The molar content that the butene-1 that feeds in the step 3 accounts for ethene is 1%～10%.
The present invention uses a kind of vanadium catalyst system of composite carrier loadization, through kind, ratio and the adding mode of adjustment promotor and the polyethylene product that hydrogen usage is produced different molecular weight and MWD width.
Vanadium compound among the present invention; Can cooperate with suitable promotor and be used for ethene, propylene, iso-butylene, 1-butylene, 1-hexene, 1-octene, 1-decene, end alkene, conjugation or unconjugated diene or polyenoid, vinylbenzene, norbornylene or tetrahydrobenzene monomer and carry out polymerization greater than 10 carbon; Ethene or propylene and iso-butylene, 1-butylene, 1-hexene, 1-octene, 1-decene, greater than the end alkene of 10 carbon, the copolymerization of conjugation or unconjugated diene or polyenoid, vinylbenzene, norbornylene or cyclopentenes.Polymerization activity reaches 1.0 * 10
7GPE (molVh)
-1More than, the weight-average molecular weight of measuring polymkeric substance with the GPC appearance is greater than 350,000, and the MWD width is greater than 15.
In the preparation process of olefinic polymerization, the activation method of vanadium compound is very crucial, comprises the kind and the consumption of activation temperature and promotor.At first vanadium compound is mixed with the organoaluminum promotor and carry out alkylated reaction; Detrimental impurity in the effect part removing system of organoaluminum promotor; Like water, alcohol etc., complex reaction further takes place in another part and vanadium compound, forms the active site of different valence state.The ratio in different valence state active site has determined the molecular weight and the MWD width of polyolefin products.
Advantage of the present invention is: the present invention utilizes single reactor to produce on original aq slurry process production equipment, need not to change polymerization technique.Prepared olefin polymer has the molecular weight height, MWD is wide, tap density is high, the pattern of polymkeric substance is rule spheroidal particle, polymerisate do not have fine powder, no oligopolymer, narrow grain size distribution of polymers and controlled characteristics.This olefin polymer can be used for the production of pressure resistant pipe material, high-strength membrane and big hollow container, can improve the throughput of full scale plant effectively.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the ethylene homo method under the effect of this embodiment vanadium series catalyst, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.1～10; Two, blow row 2L polymeric kettle with nitrogen, add the 1L solvent, start stirring, promotor is dissolved in the solvent, obtain the solution of 1～10mmol/L, solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.03～0.05MPa and the vanadium series catalyst of step 1 preparation, after temperature of reaction system reaches 75～100 ℃, begin to feed ethene and carry out polyreaction, reaction pressure is 0.5～3.0MPa; Four, reaction stopped logical ethene after 1～4 hour, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect; Wherein in the promotor in aluminium and the vanadium series catalyst mol ratio of vanadium be 10～8000: 1; Solvent described in the step 2 is a kind of in propane, butane, Trimethylmethane, pentane, hexane, heptane, octane, hexanaphthene, methylcyclohexane, toluene, the YLENE or several kinds mixture wherein; Promotor described in the step 2 is a kind of in a chloro-di-isobutyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, dichloro one aluminium triethyl, triethyl aluminum, aluminium diethyl monochloride, the tri-n-hexyl aluminum or several kinds mixture wherein.
When solvent is mixture described in this embodiment step 2, press between each component arbitrarily than mixing; When promotor described in the step 2 is mixture, press between each component arbitrarily than mixing.
This embodiment utilizes single reactor to produce on original aq slurry process production equipment, need not to change polymerization technique.Prepared olefin polymer has the molecular weight height, MWD is wide, tap density is high, the pattern of polymkeric substance is rule spheroidal particle, polymerisate do not have fine powder, no oligopolymer, narrow grain size distribution of polymers and controlled characteristics.This olefin polymer can be used for the production of pressure resistant pipe material, high-strength membrane and big hollow container, can improve the throughput of full scale plant effectively.
Embodiment two: what this embodiment and embodiment one were different is: the concrete grammar of preparation vanadium series catalyst is in the step 1: a, in ether and aromatic hydrocarbon mixture, add the Mg powder with iodo activation; Be to react under 0～160 ℃ the condition in temperature, obtain organo-magnesium compound; Wherein the mol ratio of Mg, ether and aromatic hydrocarbon is 1: 0.1～10.0: 1.0～15; B, organo-magnesium compound and aromatic ester, aromatic hydrocarbon, organoaluminum that step a is obtained react, and temperature of reaction is-20～100 ℃, obtains magnesium, aluminum compound complex carrier; Wherein the mol ratio of Mg in the organo-magnesium compound and aromatic ester, aromatic hydrocarbon and organoaluminum is 1: 0.1～5.0: 1.0～15: 1.0～15; C, magnesium, aluminum compound complex carrier and vanadium compound that step b is obtained react, and temperature of reaction is 20～120 ℃, obtains vanadium series catalyst, and the structural formula of vanadium series catalyst is VMgnAl, and n is 0.1～10; Wherein the mol ratio of Mg in magnesium, the aluminum compound complex carrier and vanadium compound is 1: 0.001～0.01; Wherein the ether in said ether of step a and the aromatic hydrocarbon mixture is a kind of in n-butyl ether, di-n-butyl ether, ether, the isoamyl oxide or several kinds mixture wherein, and aromatic hydrocarbon is a kind of in benzene,toluene,xylene, chlorobenzene, the trichlorotoluene zotrichloride or several kinds mixture wherein; The described aromatic ester of step b is a kind of in oil of Niobe, ethyl benzoate, Witcizer 300, the diethyl phthalate or several kinds mixture wherein; Said aromatic hydrocarbon is a kind of in benzene,toluene,xylene, chlorobenzene, the trichlorotoluene zotrichloride or several kinds mixture wherein, and said organoaluminum is a kind of in a chloro-di-isobutyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, dichloro one aluminium triethyl, aluminium diethyl monochloride, the tri-n-hexyl aluminum or several kinds mixture wherein; The described vanadium compound of step c is any one in three halogenation vanadyl, alkoxyl group halogenation vanadyl, pure vanadyl, methyl ethyl diketone vanadyl, four halogenation vanadium, alkoxyl group halogenation vanadium, the vanadium acetylacetonate.Other is identical with embodiment one.
When the said ether of this embodiment step a is mixture, press between each component arbitrarily than mixing; When the said aromatic hydrocarbon of step a is mixture, press between each component arbitrarily than mixing; When the described aromatic ester of step b is mixture, press between each component arbitrarily than mixing; When the described aromatic hydrocarbon of step b is mixture, press between each component arbitrarily than mixing; When the described organoaluminum of step b is mixture, press between each component arbitrarily than mixing.
Embodiment three: what this embodiment was different with embodiment one or two is: structural formula is VMgnAl in the step 1, and wherein n is 0.8～1.0.Other is identical with embodiment one or two.
Embodiment four: what this embodiment was different with one of embodiment one to three is: the solution that obtains 2～6mmol/L in the step 2.Other is identical with one of embodiment one to three.
Embodiment five: what this embodiment was different with one of embodiment one to four is: in the promotor in aluminium and the vanadium series catalyst mol ratio of vanadium be 80～300: 1.Other is identical with one of embodiment one to four.
Embodiment six: the ethylene homo method under the effect of this embodiment vanadium series catalyst, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.9; Two, blow row 2L polymeric kettle with nitrogen, add the 1L hexane, start stirring, triisobutyl aluminium is dissolved in the hexane, obtain the solution of 4mmol/L, 4mmol solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.05MPa and the vanadium series catalyst of 37mg step 1 preparation, after temperature of reaction system reaches 80 ℃, begin to feed ethene and carry out polyreaction, reaction pressure is 0.74MPa; Four, reaction stopped logical ethene after 2 hours, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect.
The polymerization activity of catalyzer reaches 1.6 * 10
7GPE (molVh)
-1, polymer bulk density 0.38g/cm
3, the MWD of polymkeric substance is 21, the weight-average molecular weight of polymkeric substance is 450000.
Embodiment seven: the ethylene homo method under the effect of this embodiment vanadium series catalyst, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.9; Two, blow row 2L polymeric kettle with nitrogen, add the 1L hexane, start stirring, triisobutyl aluminium is dissolved in the hexane, obtain the solution of 2mmol/L, 2mmol solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.05MPa and the vanadium series catalyst of 37mg step 1 preparation, after temperature of reaction system reaches 80 ℃, begin to feed ethene and carry out polyreaction, reaction pressure is 0.74MPa; Four, reaction stopped logical ethene after 2 hours, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect.
The polymerization activity of catalyzer reaches 0.5 * 10
7GPE (molVh)
-1, polymer bulk density 0.38g/cm
3, the MWD of polymkeric substance is 18, the weight-average molecular weight of polymkeric substance is 320000.
Embodiment eight: the ethylene homo method under the effect of this embodiment vanadium series catalyst, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.9; Two, blow row 2L polymeric kettle with nitrogen, add the 1L hexane, start stirring, triisobutyl aluminium is dissolved in the hexane, obtain the solution of 6mmol/L, 6mmol solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.05MPa and the vanadium series catalyst of 37mg step 1 preparation, after temperature of reaction system reaches 80 ℃, begin to feed ethene and carry out polyreaction, reaction pressure is 0.74MPa; Four, reaction stopped logical ethene after 2 hours, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect.
The polymerization activity of catalyzer reaches 2.1 * 10
7GPE (molVh)
-1, polymer bulk density 0.40g/cm
3, the MWD of polymkeric substance is 22, the weight-average molecular weight of polymkeric substance is 510000.
Embodiment nine: the ethylene homo method under the effect of this embodiment vanadium series catalyst, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.9; Two, blow row 2L polymeric kettle with nitrogen, add the 1L hexane, start stirring, triethyl aluminum is dissolved in the hexane, obtain the solution of 4mmol/L, 4mmol solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.05MPa and the vanadium series catalyst of 37mg step 1 preparation, after temperature of reaction system reaches 80 ℃, begin to feed ethene and carry out polyreaction, reaction pressure is 0.74MPa; Four, reaction stopped logical ethene after 2 hours, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect.
The polymerization activity of catalyzer reaches 1.1 * 10
7GPE (molVh)
-1, polymer bulk density 0.36g/cm
3, the MWD of polymkeric substance is 16, the weight-average molecular weight of polymkeric substance is 405000.
Embodiment ten: the ethylene homo method under the effect of this embodiment vanadium series catalyst, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.9; Two, blow row 2L polymeric kettle with nitrogen, add the 1L hexane, start stirring, triisobutyl aluminium is dissolved in the hexane, obtain the solution of 4mmol/L, 4mmol solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.05MPa and the vanadium series catalyst of 37mg step 1 preparation, after temperature of reaction system reaches 75 ℃, begin to feed ethene and carry out polyreaction, reaction pressure is 0.74MPa; Four, reaction stopped logical ethene after 2 hours, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect.
The polymerization activity of catalyzer reaches 1.2 * 10
7GPE (molVh)
-1, polymer bulk density 0.34g/cm
3, the MWD of polymkeric substance is 15, the weight-average molecular weight of polymkeric substance is 310000.
Embodiment 11: the ethylene homo method under the effect of this embodiment vanadium series catalyst, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.9; Two, blow row 2L polymeric kettle with nitrogen, add the 1L hexane, start stirring, triisobutyl aluminium is dissolved in the hexane, obtain the solution of 4mmol/L, 4mmol solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.05MPa and the vanadium series catalyst of 37mg step 1 preparation, after temperature of reaction system reaches 90 ℃, begin to feed ethene and carry out polyreaction, reaction pressure is 0.74MPa; Four, reaction stopped logical ethene after 2 hours, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect.
The polymerization activity of catalyzer reaches 3.5 * 10
7GPE (molVh)
-1, polymer bulk density 0.41g/cm
3, the MWD of polymkeric substance is 24, the weight-average molecular weight of polymkeric substance is 580000.
Embodiment 12: the ethylene homo method under the effect of this embodiment vanadium series catalyst, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.9; Two, blow row 2L polymeric kettle with nitrogen, add the 1L hexane, start stirring, triisobutyl aluminium is dissolved in the hexane, obtain the solution of 4mmol/L, 4mmol solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.05MPa and the vanadium series catalyst of 37mg step 1 preparation, after temperature of reaction system reaches 100 ℃, begin to feed ethene and carry out polyreaction, reaction pressure is 0.74MPa; Four, reaction stopped logical ethene after 2 hours, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect.
The polymerization activity of catalyzer reaches 3.2 * 10
7GPE (molVh)
-1, polymer bulk density 0.42g/cm
3, the MWD of polymkeric substance is 23, the weight-average molecular weight of polymkeric substance is 550000.
Embodiment 13: the ethylene homo method under the effect of this embodiment vanadium series catalyst, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.9; Two, blow row 2L polymeric kettle with nitrogen, add the 1L hexane, start stirring, triisobutyl aluminium is dissolved in the hexane, obtain the solution of 4mmol/L, 4mmol solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.05MPa and the vanadium series catalyst of 37mg step 1 preparation, after temperature of reaction system reaches 80 ℃, begin to feed ethene and carry out polyreaction, reaction pressure is 1.9MPa; Four, reaction stopped logical ethene after 2 hours, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect.
The polymerization activity of catalyzer reaches 4.7 * 10
7GPE (molVh)
-1, polymer bulk density 0.44g/cm
3, the MWD of polymkeric substance is 22, the weight-average molecular weight of polymkeric substance is 480000.
Embodiment 14: the ethylene homo method under the effect of this embodiment vanadium series catalyst, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 6.5; Two, blow row 2L polymeric kettle with nitrogen, add the 1L hexane, start stirring, triisobutyl aluminium is dissolved in the hexane, obtain the solution of 4mmol/L, 4mmol solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.05MPa and the vanadium series catalyst of 37mg step 1 preparation, after temperature of reaction system reaches 80 ℃, begin to feed ethene and carry out polyreaction, reaction pressure is 0.74MPa; Four, reaction stopped logical ethene after 2 hours, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect.
The polymerization activity of catalyzer reaches 0.6 * 10
7GPE (molVh)
-1, polymer bulk density 0.41g/cm
3, the MWD of polymkeric substance is 16, the weight-average molecular weight of polymkeric substance is 564400.
Embodiment 15: ethene under the effect of this embodiment vanadium series catalyst and butene-1 copolymerization process, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.1～10; Two, blow row 2L polymeric kettle with nitrogen, add the 1L solvent, start stirring, promotor is dissolved in the solvent, obtain the solution of 1～10mmol/L, solution is added polymeric kettle, polymeric kettle is heated up; Three,, temperature of reaction system adds the hydrogen of 0.03～0.05MPa and the vanadium series catalyst of step 1 preparation when rising to 70 ℃; After temperature of reaction system reaches 75～100 ℃; Begin to feed ethene and butene-1 and carry out polyreaction, reaction pressure is 0.5～3.0MPa; Four, reaction stopped logical ethene after 1～4 hour, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect; Wherein in the promotor in aluminium and the vanadium series catalyst mol ratio of vanadium be 10～8000: 1; Solvent described in the step 2 is a kind of in propane, butane, Trimethylmethane, pentane, hexane, heptane, octane, hexanaphthene, methylcyclohexane, toluene, the YLENE or several kinds mixture wherein; Promotor described in the step 2 is a kind of in a chloro-di-isobutyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, dichloro one aluminium triethyl, triethyl aluminum, aluminium diethyl monochloride, the tri-n-hexyl aluminum or several kinds mixture wherein; The molar content that the butene-1 that feeds in the step 3 accounts for ethene is 1%～10%.
When solvent is mixture described in this embodiment step 2, press between each component arbitrarily than mixing; When promotor described in the step 2 is mixture, press between each component arbitrarily than mixing.
Embodiment 16: what this embodiment and embodiment 15 were different is: the concrete grammar of preparation vanadium series catalyst is in the step 1: a, in ether and aromatic hydrocarbon mixture, add the Mg powder with iodo activation; Be to react under 0～160 ℃ the condition in temperature, obtain organo-magnesium compound; Wherein the mol ratio of Mg, ether and aromatic hydrocarbon is 1: 0.1～10.0: 1.0～15; B, organo-magnesium compound and aromatic ester, aromatic hydrocarbon, organoaluminum that step a is obtained react, and temperature of reaction is-20～100 ℃, obtains magnesium, aluminum compound complex carrier; Wherein the mol ratio of Mg in the organo-magnesium compound and aromatic ester, aromatic hydrocarbon and organoaluminum is 1: 0.1～5.0: 1.0～15: 1.0～15; C, magnesium, aluminum compound complex carrier and vanadium compound that step b is obtained react, and temperature of reaction is 20～120 ℃, obtains vanadium series catalyst, and the structural formula of vanadium series catalyst is VMgnAl, and n is 0.1～10; Wherein the mol ratio of Mg in magnesium, the aluminum compound complex carrier and vanadium compound is 1: 0.001～0.01; Wherein the ether in said ether of step a and the aromatic hydrocarbon mixture is a kind of in n-butyl ether, di-n-butyl ether, ether, the isoamyl oxide or several kinds mixture wherein, and aromatic hydrocarbon is a kind of in benzene,toluene,xylene, chlorobenzene, the trichlorotoluene zotrichloride or several kinds mixture wherein; The described aromatic ester of step b is a kind of in oil of Niobe, ethyl benzoate, Witcizer 300, the diethyl phthalate or several kinds mixture wherein; Said aromatic hydrocarbon is a kind of in benzene,toluene,xylene, chlorobenzene, the trichlorotoluene zotrichloride or several kinds mixture wherein, and said organoaluminum is a kind of in a chloro-di-isobutyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, dichloro one aluminium triethyl, aluminium diethyl monochloride, the tri-n-hexyl aluminum or several kinds mixture wherein; The described vanadium compound of step c is any one in three halogenation vanadyl, alkoxyl group halogenation vanadyl, pure vanadyl, methyl ethyl diketone vanadyl, four halogenation vanadium, alkoxyl group halogenation vanadium, the vanadium acetylacetonate.Other is identical with embodiment 15.
When the said ether of this embodiment step a is mixture, press between each component arbitrarily than mixing; When the said aromatic hydrocarbon of step a is mixture, press between each component arbitrarily than mixing; When the described aromatic ester of step b is mixture, press between each component arbitrarily than mixing; When the described aromatic hydrocarbon of step b is mixture, press between each component arbitrarily than mixing; When the described organoaluminum of step b is mixture, press between each component arbitrarily than mixing.
Embodiment 17: what this embodiment was different with embodiment 15 or 16 is: structural formula is VMgnAl in the step 1, and wherein n is 0.8～1.0.Other and embodiment 15 or ten six phases with.
Embodiment 18: what this embodiment was different with one of embodiment 15 to 17 is: the solution that obtains 2～6mmol/L in the step 2.Other is identical with one of embodiment 15 to 17.
Embodiment 19: what this embodiment was different with one of embodiment 15 to 18 is: the molar content that the butene-1 that feeds in the step 3 accounts for ethene is 3%～7%.Other is identical with one of embodiment 15 to 18.
Embodiment 20: ethene under the effect of this embodiment vanadium series catalyst and butene-1 copolymerization process, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.9; Two, blow row 2L polymeric kettle with nitrogen, add the 1L hexane, start stirring, triisobutyl aluminium is dissolved in the hexane, obtain the solution of 4mmol/L, 4mmol solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.03MPa and the vanadium series catalyst of step 1 preparation, after temperature of reaction system reaches 80 ℃, begin to feed ethene and butene-1 and carry out polyreaction, reaction pressure is 1.9MPa; Four, reaction stopped logical ethene after 2 hours, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect; The molar content that the butene-1 that feeds in the step 3 accounts for ethene is 7%.
The polymerization activity of catalyzer is 4.3KgPE/gCat.h, and polymer stacks density is 0.38g/ml, and the MWD of polymkeric substance is 22, and the weight-average molecular weight of polymkeric substance is 331313, and the degree of branching is 6.29/1000C.
Embodiment 21: ethene under the effect of this embodiment vanadium series catalyst and butene-1 copolymerization process, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.9; Two, blow row 2L polymeric kettle with nitrogen, add the 1L hexane, start stirring, triisobutyl aluminium is dissolved in the hexane, obtain the solution of 4mmol/L, 4mmol solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.03MPa and the vanadium series catalyst of step 1 preparation, after temperature of reaction system reaches 80 ℃, begin to feed ethene and butene-1 and carry out polyreaction, reaction pressure is 1.9MPa; Four, reaction stopped logical ethene after 2 hours, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect; The molar content that the butene-1 that feeds in the step 3 accounts for ethene is 5%.
The polymerization activity of catalyzer is 2.9KgPE/gCat.h, and polymer stacks density is 0.38g/ml.
Embodiment 22: ethene under the effect of this embodiment vanadium series catalyst and butene-1 copolymerization process, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.9; Two, blow row 2L polymeric kettle with nitrogen, add the 1L hexane, start stirring, triisobutyl aluminium is dissolved in the hexane, obtain the solution of 4mmol/L, 4mmol solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.03MPa and the vanadium series catalyst of step 1 preparation, after temperature of reaction system reaches 80 ℃, begin to feed ethene and butene-1 and carry out polyreaction, reaction pressure is 1.9MPa; Four, reaction stopped logical ethene after 2 hours, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect; The molar content that the butene-1 that feeds in the step 3 accounts for ethene is 3%.
The polymerization activity of catalyzer is 2.7KgPE/g Cat.h, and the bulk density of polymkeric substance is 0.39g/ml, and density is 0.9418g/ml.The polymkeric substance weight-average molecular weight is 271769, and MWD is 18.The degree of branching is 4.77/1000C.
Embodiment 23: ethene under the effect of this embodiment vanadium series catalyst and butene-1 copolymerization process, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.9; Two, blow row 2L polymeric kettle with nitrogen, add the 1L hexane, start stirring, triisobutyl aluminium is dissolved in the hexane, obtain the solution of 4mmol/L, 4mmol solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.03MPa and the vanadium series catalyst of step 1 preparation, after temperature of reaction system reaches 80 ℃, begin to feed ethene and butene-1 and carry out polyreaction, reaction pressure is 1.9MPa; Four, reaction stopped logical ethene after 2 hours, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect; The molar content that the butene-1 that feeds in the step 3 accounts for ethene is 3%.
The polymerization activity of catalyzer is 2.3KgPE/gCat.h, and the bulk density of polymkeric substance is 0.41g/ml.
Claims (10)
1. the ethylene homo method under the vanadium series catalyst effect is characterized in that the ethylene homo method under the vanadium series catalyst effect, carries out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.1～10; Two, blow row 2L polymeric kettle with nitrogen, add the 1L solvent, start stirring, promotor is dissolved in the solvent, obtain the solution of 1～10mmol/L, solution is added polymeric kettle, polymeric kettle is heated up; Three, when temperature of reaction system rises to 70 ℃, add the hydrogen of 0.03～0.05MPa and the vanadium series catalyst of step 1 preparation, after temperature of reaction system reaches 75～100 ℃, begin to feed ethene and carry out polyreaction, reaction pressure is 0.5～3.0MPa; Four, reaction stopped logical ethene after 1～4 hour, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect; Wherein in the promotor in aluminium and the vanadium series catalyst mol ratio of vanadium be 10～8000: 1; Solvent described in the step 2 is a kind of in propane, butane, Trimethylmethane, pentane, hexane, heptane, octane, hexanaphthene, methylcyclohexane, toluene, the YLENE or several kinds mixture wherein; Promotor described in the step 2 is a kind of in a chloro-di-isobutyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, dichloro one aluminium triethyl, triethyl aluminum, aluminium diethyl monochloride, the tri-n-hexyl aluminum or several kinds mixture wherein.
2. the ethylene homo method under the vanadium series catalyst effect according to claim 1; The concrete grammar that it is characterized in that in the step 1 preparation vanadium series catalyst is: a, in ether and aromatic hydrocarbon mixture, add the Mg powder with iodo activation; Be to react under 0～160 ℃ the condition in temperature, obtain organo-magnesium compound; Wherein the mol ratio of Mg, ether and aromatic hydrocarbon is 1: 0.1～10.0: 1.0～15; B, organo-magnesium compound and aromatic ester, aromatic hydrocarbon, organoaluminum that step a is obtained react, and temperature of reaction is-20～100 ℃, obtains magnesium, aluminum compound complex carrier; Wherein the mol ratio of Mg in the organo-magnesium compound and aromatic ester, aromatic hydrocarbon and organoaluminum is 1: 0.1～5.0: 1.0～15: 1.0～15; C, magnesium, aluminum compound complex carrier and vanadium compound that step b is obtained react, and temperature of reaction is 20～120 ℃, obtains vanadium series catalyst, and the structural formula of vanadium series catalyst is VMgnAl, and n is 0.1～10; Wherein the mol ratio of Mg in magnesium, the aluminum compound complex carrier and vanadium compound is 1: 0.001～0.01; Wherein the ether in said ether of step a and the aromatic hydrocarbon mixture is a kind of in n-butyl ether, di-n-butyl ether, ether, the isoamyl oxide or several kinds mixture wherein, and aromatic hydrocarbon is a kind of in benzene,toluene,xylene, chlorobenzene, the trichlorotoluene zotrichloride or several kinds mixture wherein; The described aromatic ester of step b is a kind of in oil of Niobe, ethyl benzoate, Witcizer 300, the diethyl phthalate or several kinds mixture wherein; Said aromatic hydrocarbon is a kind of in benzene,toluene,xylene, chlorobenzene, the trichlorotoluene zotrichloride or several kinds mixture wherein, and said organoaluminum is a kind of in a chloro-di-isobutyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, dichloro one aluminium triethyl, aluminium diethyl monochloride, the tri-n-hexyl aluminum or several kinds mixture wherein; The described vanadium compound of step c is any one in three halogenation vanadyl, alkoxyl group halogenation vanadyl, pure vanadyl, methyl ethyl diketone vanadyl, four halogenation vanadium, alkoxyl group halogenation vanadium, the vanadium acetylacetonate.
3. the ethylene homo method under the vanadium series catalyst effect according to claim 1 and 2 is characterized in that structural formula is VMgnAl in the step 1, and wherein n is 0.8～1.0.
4. the ethylene homo method under the vanadium series catalyst effect according to claim 3 is characterized in that obtaining in the step 2 solution of 2～6mmol/L.
5. the ethylene homo method under the vanadium series catalyst effect according to claim 4 is characterized in that in the promotor that the mol ratio of vanadium is 80～300: 1 in the aluminium and vanadium series catalyst.
6. ethene under the vanadium series catalyst effect and butene-1 copolymerization process is characterized in that ethene and butene-1 copolymerization process under the vanadium series catalyst effect, carry out according to the following steps:
One, preparation vanadium series catalyst, its structural formula is VMgnAl, wherein n is 0.1～10; Two, blow row 2L polymeric kettle with nitrogen, add the 1L solvent, start stirring, promotor is dissolved in the solvent, obtain the solution of 1～10mmol/L, solution is added polymeric kettle, polymeric kettle is heated up; Three,, temperature of reaction system adds the hydrogen of 0.03～0.05MPa and the vanadium series catalyst of step 1 preparation when rising to 70 ℃; After temperature of reaction system reaches 75～100 ℃; Begin to feed ethene and butene-1 and carry out polyreaction, reaction pressure is 0.5～3.0MPa; Four, reaction stopped logical ethene after 1～4 hour, began cooling, the pressure release discharging, and desciccate is promptly accomplished the ethylene homo method under the vanadium series catalyst effect; Wherein in the promotor in aluminium and the vanadium series catalyst mol ratio of vanadium be 10～8000: 1; Solvent described in the step 2 is a kind of in propane, butane, Trimethylmethane, pentane, hexane, heptane, octane, hexanaphthene, methylcyclohexane, toluene, the YLENE or several kinds mixture wherein; Promotor described in the step 2 is a kind of in a chloro-di-isobutyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, dichloro one aluminium triethyl, triethyl aluminum, aluminium diethyl monochloride, the tri-n-hexyl aluminum or several kinds mixture wherein; The molar content that the butene-1 that feeds in the step 3 accounts for ethene is 1%～10%.
7. ethene under the vanadium series catalyst effect according to claim 6 and butene-1 copolymerization process; The concrete grammar that it is characterized in that in the step 1 preparation vanadium series catalyst is: a, in ether and aromatic hydrocarbon mixture, add the Mg powder with iodo activation; Be to react under 0～160 ℃ the condition in temperature, obtain organo-magnesium compound; Wherein the mol ratio of Mg, ether and aromatic hydrocarbon is 1: 0.1～10.0: 1.0～15; B, organo-magnesium compound and aromatic ester, aromatic hydrocarbon, organoaluminum that step a is obtained react, and temperature of reaction is-20～100 ℃, obtains magnesium, aluminum compound complex carrier; Wherein the mol ratio of Mg in the organo-magnesium compound and aromatic ester, aromatic hydrocarbon and organoaluminum is 1: 0.1～5.0: 1.0～15: 1.0～15; C, magnesium, aluminum compound complex carrier and vanadium compound that step b is obtained react, and temperature of reaction is 20～120 ℃, obtains vanadium series catalyst, and the structural formula of vanadium series catalyst is VMgnAl, and n is 0.1～10; Wherein the mol ratio of Mg in magnesium, the aluminum compound complex carrier and vanadium compound is 1: 0.001～0.01; Wherein the ether in said ether of step a and the aromatic hydrocarbon mixture is a kind of in n-butyl ether, di-n-butyl ether, ether, the isoamyl oxide or several kinds mixture wherein, and aromatic hydrocarbon is a kind of in benzene,toluene,xylene, chlorobenzene, the trichlorotoluene zotrichloride or several kinds mixture wherein; The described aromatic ester of step b is a kind of in oil of Niobe, ethyl benzoate, Witcizer 300, the diethyl phthalate or several kinds mixture wherein; Said aromatic hydrocarbon is a kind of in benzene,toluene,xylene, chlorobenzene, the trichlorotoluene zotrichloride or several kinds mixture wherein, and said organoaluminum is a kind of in a chloro-di-isobutyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, dichloro one aluminium triethyl, aluminium diethyl monochloride, the tri-n-hexyl aluminum or several kinds mixture wherein; The described vanadium compound of step c is any one in three halogenation vanadyl, alkoxyl group halogenation vanadyl, pure vanadyl, methyl ethyl diketone vanadyl, four halogenation vanadium, alkoxyl group halogenation vanadium, the vanadium acetylacetonate.
8. according to ethene and butene-1 copolymerization process under claim 6 or the 7 described vanadium series catalyst effects, it is characterized in that structural formula is VMgnAl in the step 1, wherein n is 0.8～1.0.
9. ethene under the vanadium series catalyst effect according to claim 8 and butene-1 copolymerization process is characterized in that obtaining in the step 2 solution of 2～6mmol/L.
10. ethene under the vanadium series catalyst effect according to claim 9 and butene-1 copolymerization process is characterized in that the molar content that the butene-1 that feeds in the step 3 accounts for ethene is 3%～7%.
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| CN105732853A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | A preparing method of a Z-N catalyst |
| CN105732852A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | A Z-N catalyst |
| CN112679641A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Polyethylene resin for hollow products, composition and preparation method thereof |
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| CN1675261A (en) * | 2002-08-09 | 2005-09-28 | 巴塞尔聚烯烃有限公司 | Modified ziegler catalyst, process for preparing it and process for preparing poly-1-olefins in its presence |
| WO2010097351A1 (en) * | 2009-02-24 | 2010-09-02 | Borealis Ag | Multi-stage process for producing multi-modal linear low density polyethylene |
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| CN1489604A (en) * | 2001-02-07 | 2004-04-14 | ɳ�ػ�����ҵ��˾ | Process for polymerization of olefins |
| CN1675261A (en) * | 2002-08-09 | 2005-09-28 | 巴塞尔聚烯烃有限公司 | Modified ziegler catalyst, process for preparing it and process for preparing poly-1-olefins in its presence |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105732853A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | A preparing method of a Z-N catalyst |
| CN105732852A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | A Z-N catalyst |
| CN105732852B (en) * | 2014-12-10 | 2018-08-10 | 中国石油天然气股份有限公司 | Z-N catalyst |
| CN105732853B (en) * | 2014-12-10 | 2019-04-09 | 中国石油天然气股份有限公司 | The preparation method of Z-N catalyst |
| CN112679641A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Polyethylene resin for hollow products, composition and preparation method thereof |
| CN112679641B (en) * | 2019-10-18 | 2023-01-20 | 中国石油化工股份有限公司 | Polyethylene resin for hollow products, composition and preparation method thereof |
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