CN1098282C - Carried chrome-contg. catalyst for polymerization of ethylene and preparing method thereof - Google Patents
Carried chrome-contg. catalyst for polymerization of ethylene and preparing method thereof Download PDFInfo
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- CN1098282C CN1098282C CN96111424A CN96111424A CN1098282C CN 1098282 C CN1098282 C CN 1098282C CN 96111424 A CN96111424 A CN 96111424A CN 96111424 A CN96111424 A CN 96111424A CN 1098282 C CN1098282 C CN 1098282C
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Abstract
The present invention relates to a carried chrome catalyst for ethylene homopolymerization or ethylene and alpha-olefin copolymerization, and a preparation method thereof. The catalyst has high activity and can produce an ethylene polymer with adjustable molecular weight and large molecular weight distribution. The catalyst of the present invention is prepared by that an organic chrome compound is used as a raw material to be carried on a carrier in a liquid hydrocarbon solvent; after a carried product carries out heat treatment at oxygen atmosphere, the carried product touches a metal organic compound in IIA, IIB or IIIA in a periodic table. The catalyst has the main advantages of low cost and high activity.
Description
The present invention relates to a kind of Catalysts and its preparation method that ethylene homo or ethene and alpha-olefin carry out copolymerization that is used for, particularly a kind of have high reactivity and a copolymerization performance preferably, can produce that molecular weight is adjustable, the polyvinyl carried chrome-contg catalyzer and the novel preparation method thereof of molecular weight distribution broad.
Vinyl polymerization carried chrome-contg catalyzer is this area development catalyzer early, and this class catalyzer generally consists of carrier, active ingredient, is with or without promotor; Wherein carrier is an inorganic oxide, and active ingredient is the organic or inorganic compound of chromium, and promotor is an organometallics, but each the concrete component concentration and the preparation method of catalyzer have nothing in common with each other, thereby the performance and price of gained catalyzer etc. differs greatly.USP3,709,853 disclosed carried chrome-contg catalyzer, its carrier is through the activatory inorganic oxide, this carrier has high surface area, and the active ingredient that is adsorbed on this carrier is bicyclic pentadiene chromium (II) compound, and this catalyst active center is more single, hydrogen response is very strong, can prepare the narrow molding graae polyethylene product of molecular weight distribution, need be but be unsuitable for made membrane, tubing etc. than the extrusion molding level product of wide molecular weight distribution.
USP3,324,095 disclosed loading type silane chromate ester catalysts, carrier is an inorganic oxide, and active ingredient is the silane chromate ester, and promotor is a kind ofly to have at least 1 or be no more than 2 organo-aluminium compounds that are connected in the-oxyl on the aluminium atom; Molecular weight is higher though this catalyzer can be used for preparing, molecular weight distribution is than the extrusion molding level product of broad, and the synthesis technique complexity of this catalyst activity component causes catalyzer to cost an arm and a leg.
USP2,825,721 disclosed loading type chromium oxide catalysts are chromium trioxide or at least can partial oxygen under the high temperature oxidation condition change into the compound of chromium trioxide, load to prepare on the silica gel in the aqueous solution.This catalyzer has overcome the shortcoming of active ingredient synthesis technique complexity, has reduced the catalyzer cost, but narrower with the product molecular weight distribution of this Preparation of Catalyst.
The purpose of this invention is to provide a kind of have high reactivity and better copolymerization performance, can produce that molecular weight is adjustable, the carried chrome-contg catalyzer and the novel preparation method thereof of the Alathon of molecular weight distribution broad or ethene and alpha-olefin copolymer.
For achieving the above object, catalyzer provided by the invention is to be carrier with the inorganic oxide, the organometallics that contains aluminium, boron or zinc is a promotor, active ingredient is the oxide compound of chromium, and the oxide compound of chromium derives from cyclopentadienyl or the thermal treatment of condensed ring (fused ring) cyclopentadienyl chromium cpd under oxygen-containing atmosphere that links to each other with the π key with chromium.By the support of the catalyst quality, chromium content is 0.05～3.0%, is preferably 0.07～0.5%; The mol ratio of chromium is 0.1～50 in metal in the promotor and the active ingredient, is preferably 1～20.
The basic preparation method of catalyzer of the present invention is the cyclopentadienyl or the condensed ring cyclopentadienyl chromium cpd that will link to each other with the π key with chromium, in the liquid hydrocarbon solvent, load on the carrier, the load product contacts with the organometallics that contains aluminium, boron or zinc and obtains under oxygen-containing atmosphere after the thermal treatment.May further comprise the steps:
(1) inorganic oxide carrier is dry down at 100 ℃～800 ℃;
(2) will with chromium with cyclopentadienyl or condensed ring cyclopentadienyl chromium cpd that the π key links to each other, in hydrocarbon solvent, load on the drying support that step (1) obtains;
(3) the load product that will remove behind the hydrocarbon solvent activates under 300 ℃～1000 ℃ oxygen-containing atmosphere;
(4) contact with product that step (3) obtains in hydrocarbon solvent with the organometallics that contains aluminium, boron or zinc, obtain containing the catalyzer of hydrocarbon solvent, if necessary catalyzer is made pulverous words, can remove hydrocarbon solvent.
Catalyzer of the present invention more specifically can prepare by following step:
(i), be preferably in 100 ℃～300 ℃ down dry 2～10hr with dry 0.5～20hr in the inert gas of inorganic oxide carrier under 100 ℃～800 ℃;
(ii) under nitrogen protection, the cyclopentadienyl or the condensed ring cyclopentadienyl chromium cpd that will link to each other with the π key with chromium are through loading in the hydrocarbon solvent of processed on the drying support that (i) obtain; Load time is 10min～10hr, make solvent evaporated after, by the carrier quality, chromium content is 0.05～3.0%, is preferably 0.07～0.5%;
(iii) remove hydrocarbon solvent, obtain the free-pouring dry powder of energy;
The dry powder that obtains in (iv) will be (iii) is in 300 ℃～1000 ℃ oxygen-containing atmosphere and activates 0.5～20hr under the fluidized state, is preferably in 400 ℃～800 ℃ activation 2～10hr down;
(v) under nitrogen protection, with the organometallics promotor that contains aluminium, boron or zinc, contacting with the product that (iv) obtains through in the hydrocarbon solvent of processed, catalytic temperature is 10 ℃～80 ℃, time is 10min～10hr, it is 0.1～50 that the consumption of reactant should make the mol ratio of chromium in metal in the promotor and the active ingredient, is preferably 1～20;
(vi) if necessary catalyzer is made pulverous words, can be removed hydrocarbon solvent, obtain the free-pouring powdered catalyst of energy that volatile content is no more than 1% (w/w).
As catalyst activity component raw material of the present invention be: the cyclopentadienyl or the condensed ring cyclopentadienyl chromium cpd that link to each other with the π key with chromium.Bicyclic pentadiene chromium (II) compound (two luxuriant chromium) that for example has following structural formula:
Here R and R ' are the alkyl with 1～20 left and right sides carbon atom, this alkyl can be saturated, also can be undersaturated, it both can comprise aliphatic group, as methyl, ethyl, propyl group, butyl, amyl group, allyl group or the like, also can comprise alicyclic hydrocarbon radical, as cyclopentyl, cyclohexyl, suberyl or the like, can also comprise aryl, as phenyl, naphthyl or the like; And n and n ' are 0～5 integer.The preparation method who can be used as two luxuriant chromium cpds of catalyst activity component raw material of the present invention can be referring to United States Patent (USP) 2,870, and 183 and 3,071,605.
And ring cyclopentadienyl chromium cpd, for example two indenyls and two fluorenyl chromium (II) compound, its preparation can be referring to United States Patent (USP) profit 4,015,059.These also encircle the cyclopentadienyl chromium cpd and have following structural formula: Ar-Cr (II) Ar ｀, and Ar can be identical with Ar ｀ here, also can be different.Can be indenyl with following structure:
Here Ra and Ra ' are the alkyl of identical or different C1～C10, and m is 0～4 integer, and x is 0,1,2 or 3.
Ar and Ar ' also can be the fluorenyls with following structure:
Here Rb and Rb ' are the alkyl of identical or different C1～C10, this alkyl can be saturated or unsaturated, they can comprise aliphatic group, alicyclic hydrocarbon radical and aryl, as methyl, ethyl, propyl group, butyl, amyl group, cyclopentyl, cyclohexyl, allyl group, phenyl and naphthyl: m ' and m " is identical or different 0～4 integer; Y is H, Rb or Rb ', and Z is 0 or 1 integer.
Add-on scope as for organo-chromium compound is not strict, usually by the carrier quality, chromium content is just can obtain rendeing a service catalyzer preferably at 0.05～3.0% o'clock, brings into play preferably for the catalytic effect that makes the active centre, and the optimum range of chromium content is 0.07～0.5%.
Inorganic oxide carrier is silica gel, aluminum oxide, Thorotrast, zirconium white, and its specific surface area is 50～1000m
2/ g, the aperture is 60～700 , and particle size is 50～200um, and the preferential specific surface area of selecting is 200～500m
2/ g, the aperture is 100～300 , particle size is 70～150um, as: density silica gel in the microballoon of W.R Grace ' sG-952 level and W.R.Grace ' s G-56 level.
Carrier is with before organo-chromium compound contacts in the Preparation of catalysts step of the present invention (i), the most handy rare gas element or dry air heat or are predrying, drying temperature can be between 100 ℃～800 ℃, be preferably in 100 ℃～300 ℃, have been found that drying temperature has remarkable influence to the molecular weight distribution and the melting index of production polymkeric substance.
Used liquid hydrocarbon solvent when preparing catalyzer of the present invention can be the aromatic hydrocarbons of aliphatic hydrocarbon, alicyclic hydrocarbon or the C6～C10 of C5-C10, preferably iso-pentane, pentane, normal hexane, hexanaphthene, benzene,toluene,xylene or the like.
The liquid hydrocarbon solvent should carry out pre-treatment before using, promptly make anhydrously by rectifying or other method, and did not contain any possible catalyzer poison.Use a kind of sorbent material, handle liquid hydrocarbon solvent as silica gel, aluminum oxide, molecular sieve or other materials similar of high surface area, to remove the impurity of trace, this way is effectively.
(iv) the activation of middle dry powder can be under any temperature near its sintering temperature for Preparation of catalysts step of the present invention, under oxygen-containing atmosphere, carry out, oxygen-containing gas can be dry air or oxygen, this reactivation process helps the water on the carrier is replaced, activation temperature can be at 300 ℃～1000 ℃, but do not allow too high, in order to avoid cause the sintering of carrier, preferably 400 ℃～800 ℃.If used air or oxygen is that thorough drying is crossed, soak time only needed 0.5～8 hour, otherwise needs the longer time, as 8～20 hours.Preferably carry out: first following dry 1 hour at 150 ℃ with nitrogen according to following operation steps, fully remove the organism that desolvates and decompose, in order to avoid catch fire, switch to dry air or oxygen then, drying is 1 hour under 300 ℃, is warming up to temperature required constant temperature subsequently and is activated to required time, stops heating at last, continue to feed dry air or oxygen, make product be cooled to room temperature.
Promotor of the present invention is the organometallics that belongs to II A in the periodictable, II B or III A family.Comprising organo-aluminium compound organoboron compound and organic zinc compound.
Adoptable organo-aluminium compound is the compound of alkylaluminium cpd and aluminum alkoxide, and alkylaluminium cpd has: trialkyl aluminium compound, aluminum alkyl halide and alkyl aluminum hydride.Alkyl in these compounds can contain 1～14 carbon atom, and halogen then is chlorine, bromine, fluorine or iodine.The example of concrete alkylaluminium cpd has trimethyl aluminium, triethyl aluminum, tri-butyl aluminum, three decyl aluminium, dotriacontyl aluminium, diethyl aluminum chloride, dibutyl aluminum chloride, dibutyl aluminum bromide, dibutyl aluminum iodide, dibutyl aluminum fluoride, dihexylaluminum chloride, dichloromethyl aluminium, dibromo aluminium triethyl, two chlorobutyl aluminium, dichloro amyl group aluminium and other similar compound, can be expressed as usually following structural formula: RyAlXz wherein R be the alkyl that contains 1～14 carbon atom; X is hydrogen or a kind of halogen; Y is 1～3 integer; Z is 0～2 integer; Y and z sum are 3.The alkoxy aluminum compound general formula is: RxAl (OR) w, wherein x and w are integer 1 or 2, itself and be 3; R is the alkyl that contains 1～14 carbon atom, and the alkyl of R is not strict, and this is any alkyl that can be selected from alkyl, aralkyl, aryl, alkaryl, alicyclic radical, two alicyclic radical and other classes such as alkyl.Concrete example is a methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, hexyl, cyclohexyl, the 2-methyl amyl, heptyl, octyl group, the 2-ethylhexyl, cyclohexyl methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, phenmethyl, styroyl, right-the methylbenzene methyl, phenyl, tolyl, xylyl, naphthyl, the ethylbenzene base, the first naphthyl, the diformazan naphthyl, norcamphyl, norborneol methyl or other class such as hydro carbons.With the R group that contains 1～8 carbon atom that the aluminium atom directly links to each other is the cheapest compound that is easy to obtain of price.Obviously each group of R can be identical or different.
Described organoboron compound is an alkyl boron compound, and its general formula is: BR
3Here R is the alkyl that contains 1～14 carbon atom of having an appointment, and concrete boron alkyl example has trimethylammonium borine, boron triethyl, triisobutyl borine, tri-n-butylbo-rane and other similar compounds.Wherein best is triethyl-boron.
The organometallics that an other class can independently be used or be used in combination with organo-aluminium compound, organoboron compound is organic zinc compound.This class organic zinc compound comprises zinc ethyl, di-isopropyl zinc and other similar compound.Organic zinc compound can also be as the reagent of impurity in the scavenge system except can be used as activator.
The present invention also comprises the mixture that uses organo-aluminium compound, the mixture of organoboron compound, and the mixture of organic zinc compound.
After metal-organic consumption and the load and to be oxidized into the amount of chromium cpd of chromic oxide relevant.Amount ranges is not strict, and only needing to be enough to becomes the active sites with catalytic performance with the chromic oxide reduction.Can adopt to hang down to every mole of chromium to reach 0.1 mole aluminium, boron or zinc, be preferably every mole of chromium is adopted about 1～20 mole aluminium, boron or zinc.As long as activity of such catalysts is not play a part bad, also can adopt the more organometallics of volume.Adopt above technical scheme, can be raw material with organo-chromium compound, with a kind of brand-new preparation method, obtain a kind of carried chrome-contg catalyzer, this catalyzer can be under gas phase, or in liquid phase, make vinyl polymerization or make ethene and alpha-olefin copolymer closes, the gas phase polymerization process of indication of the present invention is fluidized bed gas-phase polymerization method and agitated bed gas phase polymerization process; Indication liquid polymerization method of the present invention is slurry phase polymerisation process and solution polymerization process.
Once the present invention is further illustrated by embodiment:
Polymer performance used in the example is measured as follows:
Melt flow rate (MFR) I
2.16Test conditions is selected sequence number 3 in the GB3682 table for use
Load 2.160Kg, 190 ℃ of test temperatures
Melt flow rate (MFR) I5 test conditions is selected sequence number 4 load 5.00Kg in the GB3682 table, 190 ℃ of experimental temperatures for use
Melt flow rate (MFR) I
21.6Test conditions is selected sequence number 6 in the GB3682 table for use
Load 21.60Kg, 190 ℃ of experimental temperatures
Density d GB 1033
The material bar of extruding during with the test melt flow rate (MFR) is tested after boiling water boiled 30 minutes, and waited to naturally cool to room temperature as test sample.The evaluation method of catalyzer:
Catalyzer of the present invention is to adopt the agitated bed gas phase polymerization process at laboratory evaluation, and reactor is 1.5 liters the stainless steel polymeric kettle that has chuck.
Polyreaction is undertaken by following step: reactor is warming up to temperature required following 10 ℃; vacuumize repeatedly; inflated with nitrogen repeatedly; with air in the displacement still; after vacuumizing for the last time; charge into the ethylene gas of 0.1MPa; ball valve from the kettle cover adds 0.2～0.4g catalyzer under nitrogen protection then; close ball valve, start and stir, catalyzer is evenly distributed in the interior whole space of still; charge into hydrogen then on demand in succession; and with reactant gases (the monomeric gas mixture of ethylene gas or ethene and copolymerization) be pressurized to the reaction required pressure, pick up counting, and be calculated as follows rate of polymerization Wpoly:
Wherein Q is in polymerization time τ poly (min), and the yield of polymkeric substance (g), q are catalyzer add-on (g), and c is a chromium content (w/w) in the catalyzer.Example 1-reference example (promptly with 3,324,095 catalyzer)
Will about 15gDavison 952 (or Davison 955) silica gel put in the quartz glass tube that dry bottom portion has core, feeding drying nitrogen makes it be fluidized state, handled 1 hour down prior to 150 ℃, be warming up to again 600 ℃ following 2 hours, under nitrogen gas stream, be cooled to room temperature then.
In two mouthfuls of pipes of a 300ml, add 200ml exsiccant normal hexane and 0.305g pair-tri-phenyl-silane chromate in addition; under 45 ℃; make it be dissolved as orange solution; add the good silica gel of the above-mentioned drying of 10g; under nitrogen protection; stirred 1 hour; make two-tri-phenyl-silane chromate chemisorption on silica gel; cause solution to fade gradually; at this moment the hexane solution that adds 3.59ml 25% (w/w) diethylaluminum ethoxide again stirred under nitrogen protection after 1 hour, with drying nitrogen stripping solvent; make chromium content 0.25%, Al/Cr (moles/mole) is 10 free flowable catalyzer.Example 2
Place the bottom to have the quartz glass tube of core in about 15g Davison 952 (or Davison 955) silica gel, feed drying nitrogen and make it be fluidized state,, under nitrogen gas stream, be cooled to room temperature then in 200 ℃ of processing 2 hours.
In two mouthfuls of pipes of a 300ml, add 200ml exsiccant normal hexane in addition; with the above-mentioned dried silica gel of 10g; stirring makes it be paste-like; the toluene solution that under nitrogen protection, adds 2.023ml 5% (w/w) two luxuriant chromium again; under room temperature, stirred 1 hour; use drying nitrogen stripping solvent then, obtain containing the intermediate product of the free flowable catalyzer of organic chromium.
Above-mentioned catalyzer intermediate product is put into quartz glass tube again, feed drying nitrogen earlier, be under the fluidized state in 150 ℃ and handled 1 hour, switch to dry air again, handled 1 hour down in 300 ℃, be warming up to 800 ℃ of activation at last after 2 hours, stop heating, continue to feed dry air and make it be cooled to room temperature.
Get the above-mentioned product of 0.5g and put into the two-mouth bottle that contains the ml hexane solution; the hexane solution that under nitrogen protection, adds 0.179ml 25% diethylaluminum ethoxide again; at room temperature stirring reaction is 1 hour; use drying nitrogen stripping solvent then; make chromium content 0.25%, Al/Cr is 10 free flowable catalyzer.
Now use-case 1, example 2 made catalyzer are estimated (being above-mentioned meteorological agitated bed polyreaction) gained and be the results are shown in table 1 respectively:
Table 1.
Polymerizing condition: Tpoly=95 ℃ P
C2H4=1.1Mpa τ poly=60min
| Instance number | Catalyst formulation | Rate of polymerization | Melt flow rate (MFR) | Melt flow ratio | Molecular weight | Density | |||
| Cr content | AL/Cr | Wpoly | W′poly | I 2.16 | I 21.6 | I 21.6/I 2.16 | Mw | d | |
| ％(m/m) | mol/mol | gPE/gCat.h | kgPE/gCr.h | g/10min | g/10min | g/cm 3 | |||
| Example 1 | 0.25 | 10 | 237 | 95 | 0.51 | 67.12 | 131.6 | 164000 | 0.9672 |
| Example 2 | 0.25 | 10 | 298 | 119 | 0.31 | 37.25 | 120.2 | 226000 | 0.9600 |
The result shows: catalyst activity of the present invention is higher than loading type silane chromate ester catalyst, and the molecular weight distribution of prepared product is approaching with it.Example 3--6
The step of preparation catalyzer is similar to example 2, just adds the hexane solution of 25% diethylaluminum ethoxide of 5% 2 luxuriant chromium toluene solution of different volumes and different volumes.Make chromium content and be respectively 0.07%, 0.15%, 0.30%, 0.50% (w/w), and Al/Cr is 10 catalyzer than (mol/mol), then, estimates in above-mentioned gas phase agitated bed polymeric kettle, the results are shown in table 2:
Table 2:
Polymerizing condition: Tpoly=90 ℃, P
C2H4=1.1MPa τ poly=60min example 7--10
| Instance number | Catalyst formulation | Rate of polymerization | Melt flow rate (MFR) | |||
| Cr content | Al/Cr | Activation temperature | Wpoly | W′poly | I 21.6 | |
| ％(w/w) | mol/mol | ℃ | gPE/gCat.h | KgPE/gCr.h | g/10min | |
| Example 3 | 0.07 | 10 | 800 | 114 | 45.6 | 0.28 |
| Example 4 | 0.15 | 10 | 800 | 163 | 65.2 | 1.05 |
| Example 5 | 0.30 | 10 | 800 | 296 | 118.4 | 4.56 |
| Example 6 | 0.50 | 10 | 800 | 343 | 137.2 | 9.02 |
The step of preparation catalyzer is similar to example 2, just adds the hexane solution of 25% diethylaluminum ethoxide of different volumes, make the Al/Cr ratio and be respectively 3,6,8,10, and chromium content all is 0.25% catalyzer, lists in table 3 by the above-mentioned steps evaluation result:
Table 3:
Polymerizing condition: Tpoly=90 ℃ P
C2H4=1.1Mpa τ poly=60min example 11--13
| Instance number | Catalyst formulation | Rate of polymerization | Melt flow rate (MFR) | Melt flow ratio | Molecular weight | ||||
| Cr content | Al/Cr | Activation temperature | Wpoly | W′poly | I 2.16 | I 21.6/ | I 21.6/I 2.16 | Mw | |
| ％(w/w) | mol/mol | ℃ | gPE/gCat.h | kgPE/gCr.h | g/10min | g/10min | |||
| Example 7 | 0.25 | 3 | 800 | 271 | 108 | 0.04 | 8.061 | 201.5 | 304000 |
| Example 8 | 0.25 | 6 | 800 | 366 | 146 | 0.08 | 9.63 | 120.4 | 286000 |
| Example 9 | 0.25 | 8 | 800 | 333 | 133 | 0.13 | 12.86 | 98.9 | 270000 |
| Example 10 | 0.25 | 10 | 800 | 276 | 110 | 0.02 | 3.78 | 189 | 387000 |
The step of preparation catalyzer is similar to example 2, the carrier that just will be soaked with two luxuriant chromium activates under 400 ℃, 600 ℃ and 800 ℃ respectively, obtains chromium content 0.25%, and Al/Cr is than the catalyzer that is 10, and in gas phase agitated bed polymeric kettle, carry out the polymerization evaluation, the results are shown in table 4:
Table 4:
Polymerizing condition: Tpoly=90 ℃ P
C2H4=1.1Mpa τ poly=60min example 14--16
| Instance number | Catalyst formulation | Polymerization | Speed | Melt flow rate (MFR) | Melt flow ratio | Molecular weight | |||
| Cr content | Al/Cr | Activation temperature | Wpoly | W′poly | I 2.16 | I 21.6/ | I 21.6/I 2.16 | Mw | |
| ％(m/m) | mol/mol | ℃ | gPE/gCar.h | kgPE/gCr.h | g/10min | g/10min | |||
| Example 11 | 0.25 | 10 | 400 | 149 | 59.6 | 0.54 | 59.34 | 110 | 196000 |
| Example 12 | 0.25 | 10 | 600 | 144 | 57.6 | 0.14 | 21.94 | 157 | 238000 |
| Example 13 | 0.25 | 10 | 800 | 210 | 84 | 0.01 | 3.31 | 331 | 419000 |
The step of preparation catalyzer is similar to example 2, just selects for use different alkylaluminium cpds as reductive agent, and obtained catalyst chromium content is 0.25%, and the Al/Cr ratio is 10, estimates in gas phase agitated bed polymerization Fu again.The results are shown in table 5: table 5:
Polymerizing condition: Tpoly=90 ℃ P
C2H4=1.1MPa τ poly=60min example 17--26
| Instance number | The reductive agent title | Rate of polymerization | Melt flow rate (MFR) | Melt flow ratio | Molecular weight | ||
| Wpoly | W′poly | I 2.16 | I 21.6/ | I 21.6/I 2.16 | Mw | ||
| gPE/gCat.h | kgPE/gCr.h | g/10min | g/10min | ||||
| Example 14 | Diethylaluminum ethoxide | 210 | 84 | 0.01 | 3.31 | 311 | 419000 |
| Example 15 | Triethyl aluminum | 124 | 49.6 | 0.02 | 7.03 | 351.5 | 592000 |
| Example 16 | Triisobutyl aluminium | 217 | 86.8 | 0.05 | 10.31 | 206.2 | 297000 |
In order to investigate the copolymerization performance of catalyzer of the present invention, adopt example 2 steps to make catalyzer, and carry out the polymerization evaluation by above-mentioned steps, just unstripped gas changes the gas mixture of ethene and propylene or ethene and butylene into, the results are shown in table 6 table 6
Catalyzer: Cr content=0.25% AL/Cr=10 Ta=800 ℃ polymerizing condition: Tpoly=90 ℃ of P be total=1.1MPa τ poly=180min
| Instance number | The % of copolymerization unit (mole) | Polymerization rate | Melt flow rate (MFR) | Density | |||
| Type | Raw mix | Reaction mixture | Wpoly | W′poly | I 5 | d | |
| gPE/gCat.h | kgPE/gCr.h | g/10min | g/cm 3 | ||||
| Example 17 | Propylene | 0 | 0 | 226 | 90.4 | 0.22 | 0.960 |
| Example 18 | Propylene | 0.8 | 3.8 | 155 | 62 | 0.81 | 0.956 |
| Example 19 | Propylene | 2.0 | 9.1 | 140 | 56 | 3.53 | 0.951 |
| Example 20 | Propylene | 3.2 | 13.9 | 106 | 42.4 | 6.42 | 0.948 |
| Example 21 | Propylene | 5.2 | 24.6 | 99 | 39.5 | 12.45 | 0.934 |
| Example 22 | Propylene | 9.8 | 40.1 | 34 | 13.6 | ||
| Example 23 | Butylene | 0 | 0 | 206 | 82.4 | 0.72 | 0.960 |
| Example 24 | Butylene | 1.5 | 6.9 | 147 | 58.8 | 5.40 | 0.956 |
| Example 25 | Butylene | 3.9 | 15.5 | 79 | 31.6 | 11.40 | 0.941 |
| Example 26 | Butylene | 6.2 | 56.2 | 26 | 10.4 | ||
The advantage of Catalysts and its preparation method of the present invention is: activity is high, cost is low, can produce the polymer that molecular weight is adjustable, molecular weight distribution is wider.
Claims (12)
1. one kind is used for the catalyzer that ethylene homo or ethene and alpha-olefin carry out copolymerization, carrier is an inorganic oxide, active ingredient is the oxide compound of chromium, promotor is an organometallics, it is characterized in that: the oxide compound of (1) active ingredient chromium derives from cyclopentadienyl or the thermal treatment of condensed ring cyclopentadienyl chromium cpd under oxygen-containing atmosphere that links to each other with the π key with chromium, by the support of the catalyst quality, chromium content is 0.05～3.0%;
(2) promotor is organo-aluminium compound, organoboron compound or organic zinc compound, and wherein the mol ratio of chromium is 0.1～50 in this element of aluminium, boron or zinc and the active ingredient.
2. by the described catalyzer of claim 1, wherein inorganic oxide carrier is silica gel, aluminum oxide, Thorotrast or zirconium white.
3. by claim 1 or 2 described catalyzer, wherein the specific surface area of inorganic oxide carrier is 50～1000m
2/ g, the aperture is 60～700 , particle size is 50～200um.
4. by the described catalyzer of claim 3, wherein the specific surface area of inorganic oxide carrier is 200～500m
2/ g, the aperture is 100～300 , particle size is 70～150um.
5. by the described catalyzer of claim 1, wherein the oxide compound of active ingredient chromium derives from bicyclic pentadiene chromium (II) compound with following structural formula:
Here R and R ' are for having the saturated or unsaturated alkyl of 1～20 carbon atom, and n and n ' are 0～5 integer.
6. by claim 1 or 5 described catalyzer, it is characterized in that by the support of the catalyst quality chromium content is 0.07～0.5%.
7. by the described catalyzer of claim 1, wherein organo-aluminium compound, organoboron compound or organic zinc compound are alkylaluminium cpd, alkoxy aluminum compound, alkyl boron compound, alkyl zinc compound or its blend.
8. by claim 1 or 7 described catalyzer, wherein the mol ratio of chromium is 1～20 in aluminium, boron or zinc element in organo-aluminium compound, organoboron compound or the organic zinc compound and the active ingredient.
9. described Preparation of catalysts method of claim 1, it is characterized in that: in the liquid hydrocarbon solvent, will load on the carrier with cyclopentadienyl or the condensed ring cyclopentadienyl chromium cpd that the π key links to each other with chromium, the load product makes after contacting with it with organo-aluminium compound, organoboron compound or organic zinc compound under oxygen-containing atmosphere after the thermal treatment.
10. by the described method for preparing catalyst of claim 9, may further comprise the steps:
(1) the dry 0.5～20hr in 100 ℃～800 ℃ inert gas of the inorganic oxide carrier with high surface area;
(2) drying support that obtains in a certain amount of step (1) is scattered in through in the hydrocarbon solvent of processed, be paste-like, then under nitrogen protection, to wherein adding a certain amount of cyclopentadienyl or condensed ring cyclopentadienyl chromium cpd that links to each other with the π key with chromium, stir dipping 10min～10hr; After making solvent evaporated, by the carrier quality, chromium content is 0.05～3.0%;
(3) remove hydrocarbon solvent, obtain the free-pouring dry powder of energy;
(4) dry powder that obtains in the step (3) is under the fluidized state in 300 ℃～1000 ℃ oxygen-containing atmosphere activates 0.5～20hr;
(5) product that a certain amount of step (4) is obtained is scattered in through in the hydrocarbon solvent of processed, under nitrogen protection, with organo-aluminium compound, organoboron compound or organic zinc compound, 10min～the 10hr that under 10 ℃～80 ℃, contacts with it, make wherein this element of aluminium, boron or zinc and the mol ratio of chromium be 0.1～50;
(6) if necessary catalyzer is made pulverous words, can under nitrogen protection, be removed hydrocarbon solvent, obtain the free-pouring powdered catalyst of energy that volatile content is no more than 1 (weight) %.
11. by the described method for preparing catalyst of claim 10, the drying temperature of inorganic oxide carrier is 100 ℃～300 ℃ in the step (1).
12. by the described method for preparing catalyst of claim 10, the activation temperature of load product is 400 ℃～800 ℃ in the step (4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96111424A CN1098282C (en) | 1996-08-31 | 1996-08-31 | Carried chrome-contg. catalyst for polymerization of ethylene and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96111424A CN1098282C (en) | 1996-08-31 | 1996-08-31 | Carried chrome-contg. catalyst for polymerization of ethylene and preparing method thereof |
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| Publication Number | Publication Date |
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| CN1175590A CN1175590A (en) | 1998-03-11 |
| CN1098282C true CN1098282C (en) | 2003-01-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7504463B2 (en) | 2002-12-27 | 2009-03-17 | Univation Technologies, Llc | Production of broad molecular weight polyethylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286123A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | catalyst component of ethylene polymerization and preparation method thereof |
| CN102952221A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Preparation method of chromium polyethylene catalyst |
| CN104004117A (en) * | 2013-02-27 | 2014-08-27 | 中国石油化工股份有限公司 | Polymerization method for high density polyethylene by using vapor phase method |
| CN104277157A (en) * | 2013-07-05 | 2015-01-14 | 中国石油天然气股份有限公司 | Load type titanium aluminum modified chromium series catalyst and preparation and application thereof |
| CN105294888B (en) * | 2014-06-06 | 2019-03-29 | 中国石油化工股份有限公司 | High-crystallinity broad peak polyvinyl resin and preparation method thereof |
| CN106467589B (en) * | 2015-08-21 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of catalytic component, preparation method and application for vinyl polymerization |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5849708A (en) * | 1981-09-09 | 1983-03-24 | Mitsubishi Chem Ind Ltd | Polymerizing method of ethylene |
| US5079317A (en) * | 1988-10-13 | 1992-01-07 | Nippon Oil Co., Ltd. | Process for producing polyethylenes |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5849708A (en) * | 1981-09-09 | 1983-03-24 | Mitsubishi Chem Ind Ltd | Polymerizing method of ethylene |
| US5079317A (en) * | 1988-10-13 | 1992-01-07 | Nippon Oil Co., Ltd. | Process for producing polyethylenes |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7504463B2 (en) | 2002-12-27 | 2009-03-17 | Univation Technologies, Llc | Production of broad molecular weight polyethylene |
| US7563851B2 (en) | 2002-12-27 | 2009-07-21 | Univation Technologies, Llc | Production of broad molecular weight polyethylene |
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| Publication number | Publication date |
|---|---|
| CN1175590A (en) | 1998-03-11 |
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