CN1218972C - Catalyst for ethylene polymerization or copolymerization and its preparing method - Google Patents
Catalyst for ethylene polymerization or copolymerization and its preparing method Download PDFInfo
- Publication number
- CN1218972C CN1218972C CN 03119634 CN03119634A CN1218972C CN 1218972 C CN1218972 C CN 1218972C CN 03119634 CN03119634 CN 03119634 CN 03119634 A CN03119634 A CN 03119634A CN 1218972 C CN1218972 C CN 1218972C
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- component
- vinyl polymerization
- copolymerization
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a composite supported catalyst for ethene polymerization or copolymerization and a preparation method thereof. The catalyst is prepared by dissolving magnesium halide in an organic epoxide, an organic phosphorus compound and an inert diluent, using an alcohol compound to process the magnesium halide solution, adding a porous inert carrier with a large specific surface area to the magnesium halide solution in the existence of an alkane separation assisting agent and adding the halide of the transitional metal of titanium for coprecipitation. When used for the ethene polymerization or copolymerization, the catalyst shows high catalytic activity and has the advantages of high hydrogen regulating sensitivity, good particle shape and less fine polymer powder.
Description
Technical field
The present invention relates to a kind ofly be used for that ethylene homo closes or the catalyst component of ethene and other a-alpha-olefinic copolymerizations and preparation method thereof, and the application in vinyl polymerization or copolymerization.
Background technology
Later 1970s, it is the titanium-magnesium high-effective carrier catalyst of carrier with the magnesium chloride that companies such as Mitsui petroleum chemistry company and U.S. Meng Ai have succeeded in developing, owing to adopted carrier to improve titanium atom active centre utilization ratio, simplified the polymerization technique flow process, therefore made world's polyolefin industry obtain fast development.Mitsui petroleum chemistry company Preparation of catalysts method of disclosed vinyl polymerization and copolymerization in JP49-51378 is: magnesium dichloride through grinding and ethanol synthesis generate MgCl in the mineral oil medium again
26C
2H
5OH alcohol adduct slurries remove most of ethanol with aluminium diethyl monochloride generation esterification again, carry the titanium reaction with titanium tetrachloride at last, obtain Ti/MgCl
2High-effective carrier catalyst.This method for preparing catalyst is simple, the reaction conditions gentleness, and activity is higher during the catalyst vinyl polymerization.But in the Preparation of catalysts process, the irregular platy shaped particle that produces when there be former grinding in the carrier magnesium chloride in the slurry reaction system causes the solid catalyst particle form that obtains relatively poor, and thickness is inhomogeneous, thereby polymer morphology is also bad, and fine powder is more.
This is that the catalyzer of preparing carriers is general mobile relatively poor with single magnesium chloride, has limited the application of catalyzer in industrial production, the particularly application on gas-phase fluidized-bed reactor.Therefore people by introducing a kind of effective carrier or weighting material, promptly adopt complex carrier type catalyzer to improve the particle form of catalyzer again.The common practice is that the halogenide with the halogenide of titanium and magnesium is dissolved in and forms homogeneous solution in the solvent, adds inert silica gel carrier or alumina load then, steams solvent at last and obtains efficient complex carrier type solid catalyst.As US4302565, CN1064870 discloses the halogenide with tetrahydrofuran (THF) dissolving magnesium dichloride and titanium, add silica gel then, more progressively excessive tetrahydrofuran (THF) evaporate to dryness, the halogenide of magnesium dichloride and titanium is separated out and loads on the silica gel last preparation catalyzer gradually.Though it is good that this catalyzer has a particle form, good fluidity, the advantage that the polymer beads form is good, the dissatisfactory shortcoming of activity when all there is the complicated and polymerization of preparation method in the catalyzer of this method preparation.
Known patent CN85100997 discloses a kind of catalyst system that is used for olefinic polymerization and copolymerization again, this catalyst system comprises: (first) contains the ingredient of solid catalyst of Ti, (second) alkylaluminium cpd, (the third) organosilicon, wherein (first) component is to be dissolved in organic epoxy compounds and organo phosphorous compounds forms homogeneous solution by magnesium halide, this solution mixes with the titanium tetrahalide or derivatives thereof, in the presence of compounds such as precipitation additive such as organic acid anhydrides, organic acid, ether, ketone, separates out solids; This solids is handled with the multi-carboxylate, and it is attached on the solids, handles with titanium tetrahalide and inert diluent and obtains.When this catalyst system was used for propylene polymerization, catalyst activity was higher, and the degree of isotacticity of resulting polymers is higher, and apparent density is big.But this catalyzer is when being used for vinyl polymerization, still there is the granules of catalyst poor morphology, be difficult on gas-phase fluidized-bed, use, and activity is lower, hydrogen is transferred shortcoming such as sensitivity inadequately, particularly this dissolution system need add relatively large titanium tetrachloride in the presence of as precipitation additive at organic acid anhydride and could come out the solid particulate precipitating, not only strengthen the treatment capacity of waste liquid, also easily equipment has been caused corrosion simultaneously, strengthened the cost of catalyzer.For example disclosed under 85 ℃, the condition of hydrogen pressure 0.25Mpa, ethylene pressure 0.75Mpa in embodiment 24, vinyl polymerization 2 hours, polymerization activity only are 537Kg polyethylene/gTi (about 7000gPE/gcat).
Patent CN1229092 has improved the method for preparing catalyst among the CN85100997, in the Preparation of catalysts process, add ethanol class accelerative activator, activity increases substantially when making the catalyst vinyl polymerization for preparing, but this system has still adopted the magnesium halide dissolution system among the CN85100997, thereby still need relatively large titanium tetrahalide to carry out precipitating, simultaneously this catalyzer still with single magnesium dichloride as carrier, so the particle form of catalyzer is still not very good, the easily broken fine polymer powder that easily produces of granules of catalyst.
Summary of the invention
The shortcoming that the objective of the invention is to overcome above-mentioned catalyst preparation technology provides a kind of new class spherical catalyst component that is used for vinyl polymerization or copolymerization employing complex carrier and preparation method thereof with not enough.Have advantages of high catalytic activity during the catalyst vinyl polymerization of this method preparation, good hydrogen response, the solid difficult fragmentation of granules of catalyst, particle form well is the class sphere, and size distribution is narrow, and median size is 40 μ m～50 μ m.Both be suitable for the ethene slurry polymerization and also be suitable for the vapour phase polymerization mode, and the polymer beads form is good, fine powder is few, and slurry polymerization is less than 0.3% less than 75 μ m fine powders.
The present invention is different with CN85100997 and CN1229022, though also adopted organic epoxy compounds
Organo phosphorous compounds and inert diluent dissolve magnesium halide, but above-mentioned patent all need add organic acid anhydride, organic ether or ketone compounds as precipitation additive with need relative a large amount of halogenated titanium that solids is separated out simultaneously, the present invention only need adopt alkane as precipitation additive, and gets final product with quite a spot of halogenated titanium.Thereby reduced the liquid waste disposal amount, reduced pollution.
Simultaneously, the present invention also adopts porous inert carrier as complex carrier, but different with US4302565, CN1064870, has adopted and the diverse magnesium halide dissolution system of above-mentioned patent.Above-mentioned patent all adopts THF to dissolve magnesium halide and halogenated titanium, and needs drying step to remove unnecessary THF, just can reach magnesium halide, halogenated titanium are deposited in purpose on the silica gel.Usually, need at first prepare parent, again with the parent secondary load on silica gel, so preparation method's complexity.
Another object of the present invention provides a kind of preparation method of composite carried catalyst component.Adopt magnesium halide and porous inert carrier as complex carrier, the porous inert carrier shape is spherical in shape, particle size range is at 0.1 μ m～150 μ m, preferable particle size is 5 μ m～50 μ m, select the porous inert carrier for use, help improving magnesium halide in its surperficial load, help improving the content of magnesium in the catalyzer, the irregular aggregate of magnesium halide occurs in the catalyzer when also helping preventing high Mg content and cause the bad phenomenon of granules of catalyst to occur.
The present invention is used for vinyl polymerization or copolymerization catalyst, comprises following component:
A, titaniferous ingredient of solid catalyst, it is by being dissolved in magnesium halide in organic epoxy compounds, organo phosphorous compounds and the inert diluent, form homogeneous solution, add alcohol compound again, add the porous inert carrier through dehydration in the presence of the alkane precipitation additive, the halogenide or derivatives thereof eutectoid that adds transition metals Ti again goes out to be prepared from;
B, organo-aluminium compound;
Ratio between B component and the component A is 5～1000 with aluminium titanium molar ratio computing.
Magnesium halide described in the catalyst component A of the present invention is a magnesium dihalide, the complex compound of the water of magnesium dihalide and alcohol, a kind of by in alkyl or the-oxyl institute metathetical derivative of one of them halogen atom in the magnesium dihalide molecular formula, or their mixture.Above-mentioned magnesium dihalide is specially: magnesium dichloride, dibrominated magnesium, two magnesium iodides, preferred magnesium dichloride.
The halogenide or derivatives thereof of the transition metals Ti described in the catalyst component A of the present invention is a titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, a kind of in trichlorine one ethanolato-titanium, or their mixture.
Organic epoxy compounds is an oxyethane in the catalyst A component of the present invention, propylene oxide, butylene oxide ring, epoxy chloropropane, a kind of in the methyl glycidyl ether, or their mixture.
Organo phosphorous compounds is the ortho-phosphoric acid trimethyl in the catalyst A component of the present invention, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, a kind of in the phosphorous acid benzene methyl or their mixture.
Inert diluent is benzene, toluene and derivative thereof in the catalyst A component of the present invention.
Used alkane precipitation additive is a kind of in straight-chain paraffin, branched paraffin or the naphthenic hydrocarbon of 3～20 carbon or their mixture in the catalyst A component of the present invention, as butane, and pentane, hexane, hexanaphthene, heptane etc.
The volume ratio of inert diluent and alkane precipitation additive is in the catalyst A component of the present invention: 1: 0.1～5, be preferably: 1: 0.5～1.5.
Alcohol compound described in the catalyst component A of the present invention is C
1～C
10Straight chain alcohol or a kind of or their mixture in the isomery alcohol, for example, a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, hexanol, n-Heptyl alcohol, 2-Ethylhexyl Alcohol, n-Octanol, decyl alcohol, hexalin, methyl-cyclohexanol, Bian alcohol, the methyl Bian alcohol etc. or their mixture, preferred fat alcohol is the best with ethanol, butanols, 2-Ethylhexyl Alcohol.
Porous inert carrier is a silicon-dioxide among the catalyst component A of the present invention, wherein a kind of or its mixture of aluminium sesquioxide, the shape of porous inert carrier is spherical in shape, particle diameter is 0.1 μ m～150 μ m, preferable particle size is 5 μ m～50 μ m, and pore volume is 1.4～1.8ml/g, handles through dehydration and aluminum alkyls before using, handle the employed aluminum alkyls of porous inert carrier and be a kind of in trimethyl aluminium, triethyl aluminum, the triisobutyl aluminium or their mixture, with triethyl aluminum for well.
Magnesium halide and inert support mol ratio among the catalyst component A of the present invention are: 1: 0.5～15.
The mol ratio that adds between described each component of catalyst component A of the present invention is in every mole of magnesium halide, 0.01～10 mole of organic epoxy compounds, with 0.02～4 mole for well; 0.01～10 mole of organo phosphorous compounds, with 0.02～4 mole for well; 0.005～10 mole of alcohol compound, with 0.05～5 mole for well; 3～30 moles of inert diluents, with 5～20 moles for well; 0.5～15 mole of inert support; 0.04～1 mole in the halogenide of transition metals Ti, preferred 0.06～0.5 mole; The volume ratio of inert diluent and alkane precipitation additive is 1: 0.1～5, be preferably 1: 0.5～and 1.5.
The described alkylaluminium cpd of catalyst component B of the present invention, its general formula is AlR
nX
3-n, R can be 1～20 alkyl, particularly alkyl, aralkyl, aryl for hydrogen, carbonatoms in the formula; X is halogen, particularly chlorine and bromine; N is the number of 0＜n≤3.Particular compound is as aluminum alkyl halides such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, two different aluminium triethyl, wherein with triethyl aluminum, triisobutyl aluminium for well.
In the catalyst system of the present invention, in the B component among aluminium and the component A mol ratio of titanium be 5～1000, be preferably 50～500.
The preparation method of catalyst component A of the present invention is as follows: under agitation magnesium halide is dissolved in organic epoxy compounds, organo phosphorous compounds and the inert diluent, temperature remains on 30 ℃～80 ℃, form homogeneous solution, add alcohol compound reaction 0.5～2 hour, in the presence of the alkane precipitation additive, add porous inert carrier, then system is cooled in-30～60 ℃ of scopes, temperature is preferably-20～5 ℃; Titanium compound is splashed in the above-mentioned magnesium halide homogeneous solution with inert support, reaction mixture is warming up to 60～100 ℃ again, suspension was stirred under this temperature 0.5～8 hour, stopping to stir the back solids separates out from mixture solution, decant or remove by filter mother liquor, use the hexane wash solids, make titaniferous solid catalytic ingredient.
The catalyzer that is used for vinyl polymerization or copolymerization of the present invention is applicable to slurry polymerization and vapour phase polymerization mode.
Catalyzer of the present invention can be used for the equal polymerization of ethene, also can be used for the copolymerization of ethene and other alpha-olefin, and comonomer can be propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene etc.
Polymerization or copolymerization that catalyzer of the present invention is used for ethene compared with prior art have following tangible advantage:
1, has advantages of high catalytic activity during the catalyst vinyl polymerization, this catalyzer has good hydrogen response simultaneously, the solid difficult fragmentation of granules of catalyst, particle form well becomes the class sphere, size distribution is narrow, promptly can be used for slurry polymerization and also be suitable for carrying out polymerization on gas phase process, and the polymer beads form is good, fine powder seldom.The slurry polymerization polymkeric substance is less than 0.3% less than 75 μ m fine powders.
2, magnesium compound of the present invention adopts organic epoxy compounds, organo phosphorous compounds, inert diluent dissolves and forms homogeneous solution, adopts alkane precipitation additive and porous large specific surface inert support, only needs the halogenide of more a spot of titanium that solid particulate is separated out.
3, the add-on of titanium tetrachloride significantly reduces in the catalyst preparation process, does not need to carry out secondary and carries titanium, and carrying the titanium amount but increases greatly, and the synthesis technique of catalyzer is simplified greatly, has reduced the cost of catalyzer, has also reduced pollution.Be generally 1.0～3.0% as titanium content in the patent CN85100997 catalyzer, the highest also have only 4.14%, is generally 4.0～7.0% though titanium content is higher in the CN1229092 catalyzer.And the add-on of titanium tetrachloride is 1/6～1/5 of CN8510097 in the Preparation of catalysts of the present invention, CN1229092 1/5～1/4 but in the catalyzer titanium content be generally 4.0～7.0%, reach as high as 8.0%, this has improved the utilization ratio of titanium tetrachloride greatly.
4, the present invention adopts magnesium halide and porous inert carrier as complex carrier, the porous inert carrier shape is spherical in shape, particle size range is at 0.1 μ m～150 μ m, preferable particle size is 5 μ m～50 μ m, select bigger serface porous inert carrier for use, help improving magnesium halide in its surperficial load, help improving the content of magnesium in the catalyzer, the irregular aggregate of magnesium halide occurs in the catalyzer when also helping preventing high Mg content and cause the bad phenomenon of granules of catalyst to occur.With embodiment the present invention is described below, but and unrestricted invention scope.
Embodiment 1
(1) catalyzer is synthetic
In the reactor of fully replacing through high pure nitrogen, add the 2.4g magnesium dichloride successively,, be warming up to 80 ℃ under stirring through toluene 40ml, epoxy chloropropane 3.9ml, the tributyl phosphate 4.1ml that molecular sieve was handled, reacted 2 hours, solid dissolves the solution that forms homogeneous fully.Add 0.56ml ethanol, reaction is 1 hour under 80 ℃ of conditions.The hexane 30ml that adding is crossed through processed, silica gel 2.3g (600 ℃ of activation are after 0.7mmol triethyl aluminum activation treatment) is cooled to-25 ℃ with this system, slowly drips the 8ml titanium tetrachloride, slowly is warming up to 80 ℃ then, reacts 2 hours.Stop to stir, leave standstill, the very fast layering of suspension extracts the upper strata stillness of night, hexane wash four times, and high pure nitrogen dries up, and obtains the solid catalyst of good fluidity, narrow diameter distribution.Titanium content is 4.95% (weight) in the catalyzer, and Mg content is 7.65% (weight).
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M adds the catalyzer 15mg of the above-mentioned preparation of accurate weighing with syringe, be warming up to 75 ℃, feed hydrogen and make the still internal pressure reach 0.28Mpa, feed ethene again and make the interior stagnation pressure of still reach 1.03Mpa (gauge pressure), polymerization is 2 hours under 85 ℃ of conditions, polymerization result sees Table 1, table 2.
Embodiment 2
(1) catalyzer is synthetic with embodiment 1.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M adds the catalyzer 15mg of the above-mentioned preparation of accurate weighing with syringe, is warming up to 75 ℃, feeding hydrogen makes the still internal pressure reach 0.48Mpa, feed ethene again and make the interior stagnation pressure of still reach 1.03Mpa (gauge pressure), polymerization is 2 hours under 85 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 3
(1) catalyzer is synthetic with embodiment 1.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M adds the catalyzer 15mg of the above-mentioned preparation of accurate weighing with syringe, is warming up to 75 ℃, feeding hydrogen makes the still internal pressure reach 0.68Mpa, feed ethene again and make the interior stagnation pressure of still reach 1.03Mpa (gauge pressure), polymerization is 2 hours under 85 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 4
(1) catalyzer is synthetic
In the reactor of fully replacing through high pure nitrogen, add the 2.4g magnesium dichloride successively, toluene 40ml, the epoxy chloropropane 3.9ml, the tributyl phosphate 4.1ml that handled through molecular sieve.Be warming up to 80 ℃ under stirring, reacted 2 hours, solid dissolves the solution that forms homogeneous fully.Add the 1.56ml isooctyl alcohol, reaction is 1 hour under 80 ℃ of conditions.The hexane 50ml that adding is crossed through processed, silica gel 2.3g (600 ℃ of activation are after 0.7mmol triethyl aluminum activation treatment) is cooled to-25 ℃ with this system, slowly drips the 8ml titanium tetrachloride, slowly is warming up to 80 ℃ then, reacts 2 hours.Stop to stir, leave standstill, the very fast layering of suspension extracts the upper strata stillness of night, hexane wash four times, and high pure nitrogen dries up, and obtains the solid catalyst of good fluidity, narrow diameter distribution.Titanium content is 3.96% (weight) in the catalyzer, and Mg content is 7.79% (weight).
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M adds the catalyzer 15mg of the above-mentioned preparation of accurate weighing with syringe, is warming up to 75 ℃, feeding hydrogen makes the still internal pressure reach 0.28Mpa, feed ethene again and make the interior stagnation pressure of still reach 1.03Mpa (gauge pressure), polymerization is 2 hours under 85 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 5
(1) catalyzer is synthetic with embodiment 4.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M adds the catalyzer 15mg of the above-mentioned preparation of accurate weighing with syringe, is warming up to 75 ℃, feeding hydrogen makes the still internal pressure reach 0.50Mpa, feed ethene again and make the interior stagnation pressure of still reach 1.03Mpa (gauge pressure), polymerization is 2 hours under 85 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 6
(1) catalyzer is synthetic with embodiment 4.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M adds the catalyzer 15mg of the above-mentioned preparation of accurate weighing with syringe, is warming up to 75 ℃, feeding hydrogen makes the still internal pressure reach 0.75Mpa, feed ethene again and make the interior stagnation pressure of still reach 1.03Mpa (gauge pressure), polymerization is 2 hours under 85 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 7
(1) catalyzer is synthetic
In the reactor of fully replacing through high pure nitrogen, add the 2.4g magnesium dichloride successively,, be warming up to 80 ℃ under stirring through toluene 40ml, epoxy chloropropane 3.9ml, the tributyl phosphate 4.1ml that molecular sieve was handled, reacted 2 hours, solid dissolves the solution that forms homogeneous fully.Add the 1.56ml isooctyl alcohol, reaction is 1 hour under 80 ℃ of conditions.The heptane 30ml that adding is crossed through processed, silica gel 2.3g (600 ℃ of activation are after 0.7mmol triethyl aluminum activation treatment) is cooled to-25 ℃ with this system, slowly drips the 8ml titanium tetrachloride, slowly is warming up to 80 ℃ then, reacts 2 hours.Stop to stir, leave standstill, the very fast layering of suspension extracts the upper strata stillness of night, hexane wash four times, and high pure nitrogen dries up, and obtains the solid catalyst of good fluidity, narrow diameter distribution.Titanium content is 5.10% (weight) in the catalyzer, and Mg content is 7.56% (weight).
(2) vinyl polymerization is with embodiment 4.Polymerization result sees Table 1.
Embodiment 8
(1) catalyzer is synthetic with embodiment 1.
(2) ethene slurry copolymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M, the catalyzer that adds the quantitative above-mentioned preparation of accurate weighing with syringe, be warming up to 75 ℃, add 1-hexene 20ml, feed hydrogen and make the still internal pressure reach 0.28Mpa, feeding ethene again makes the interior stagnation pressure of still reach 1.03Mpa (gauge pressure), polymerization under 85 ℃ of conditions when the ethene absorption reaches 160g, stops polymerization.Polymerization result sees Table 2.
Embodiment 9
(1) catalyzer is synthetic with embodiment 1.
(2) copolymerization of ethene slurry is with embodiment 8.Just 1-hexene add-on changes 30ml into.Polymerization result sees Table 2.
Embodiment 10
Synthesizing with embodiment 1 of catalyzer, just the add-on of hexane precipitation additive is 10ml, and catalyst Ti content is 3.38%, and Mg content is 5.56%.
Embodiment 11
Synthesizing with embodiment 1 of catalyzer, just the silica gel add-on is 5 grams, and the titanium content of catalyzer is 2.96%, and Mg content is 4.12%.
Vinyl polymerization is with embodiment 1, and polymerization result sees Table 1.
Comparative Examples 1
(1) the synthetic CN85100997 embodiment 1 described method of pressing of catalyzer prepares.
In through the abundant metathetical reactor of high pure nitrogen, add 0.05 mole of Magnesium Chloride Anhydrous successively, 75 milliliters of toluene, be warming up to 50 ℃ under 0.1 mole of epoxy chloropropane and 0.03 mole of stirring of tributyl phosphate, and kept 2 hours, solid dissolves fully, adds 0.008 mole of Tetra hydro Phthalic anhydride then, keeps 1 hour again.Solution is cooled to-25 ℃, in 1 hour, drips 55 milliliters of titanium tetrachlorides, slowly be warming up to 80 ℃, in temperature-rise period, progressively separate out solids.Add 0.0125 mole of diisobutyl phthalate, under 80 ℃, kept 1 hour, filter the back, obtain pale brown look solid sediment with 100 milliliters of washed twice of toluene.Add 60 milliliters of toluene then, 40 milliliters of titanium tetrachlorides were handled 2 hours down at 90 ℃, and after the venting filtrate, re-treatment once again.Add 100 milliliters of washings of ethylene dichloride once, after 100 milliliters of washings of hexane four times, obtain solid catalyst, titanium content (weight) 1.92%, Mg content 17.5%.
(3) the vinyl polymerization condition is with embodiment 1, and polymerization result sees Table 1.
Comparative Examples 2
(1) the synthetic CN1229092 embodiment 1 described method of pressing of catalyzer prepares.
In the abundant metathetical reactor of high pure nitrogen, add the anhydrous MgCl of 0.042mol successively
2(about 4g), 60ml toluene, 0.032mol epoxy chloropropane, 0.022mol tributyl phosphate, 0.017mol ethanol rise under stirring
Temperature is to 80 ℃, and keep 15 minutes solids and dissolve fully, form homogeneous solution, add Tetra hydro Phthalic anhydride 0.0074mol then, kept again 1 hour, this solution is cooled to-25 ℃, again 0.5mol titanium tetrachloride (about 55ml) is splashed in it, slowly be warming up to 80 ℃ then, reacted 3 hours, use toluene and hexane wash 6 times after the filtration respectively, vacuum-drying obtains solid catalyst.
(2) the vinyl polymerization condition is with embodiment 1, and polymerization result sees Table 1
Comparative Examples 3
(1) catalyzer is synthetic
In the reactor of fully replacing through high pure nitrogen, add the 2.4g magnesium dichloride successively,, be warming up to 80 ℃ under stirring through toluene 40ml, epoxy chloropropane 3.9ml, the tributyl phosphate 4.1ml that molecular sieve was handled, reacted 2 hours, solid dissolves the solution that forms homogeneous fully.Add the 1.56ml isooctyl alcohol, reaction is 1 hour under 80 ℃ of conditions.Do not add alkane, add silica gel 2.3g (through 0.7mmol triethyl aluminum activation treatment), this system is cooled to-25 ℃, slowly drip the 8ml titanium tetrachloride, slowly be warming up to 80 ℃ then, reacted 2 hours.Stop to stir, leave standstill, solution is not stratified, can't extract supernatant, filters, and has solid to occur but more sticking, and gelatin phenomenon is arranged, and is difficult to filter.Dry up with high pure nitrogen, obtain hard blocks of solid catalyzer, can't be used for catalyzed polymerization.
Table 1
| Numbering | Modifier | Hydrogen (MPa) | Ethene (MPa) | Active (gPE/gcat) | PE apparent density (g/ml) | MI 2.16 (g/10min) | The degree of branching (CH 3/1000C) | Polymkeric substance particle diameter distribution (%) | |||
| ＞850μm | ～150μm | ～75μm | ＜75μm | ||||||||
| Embodiment 1 | Ethanol | 0.28 | 0.75 | 28000 | 0.34 | 0.48 | 1.085 | 28.5 | 64.2 | 7.1 | 0.2 |
| Embodiment 2 | Ethanol | 0.48 | 0.55 | 11400 | 0.33 | 4.67 | 1.986 | 26.8 | 69.3 | 3.7 | 0.2 |
| Embodiment 3 | Ethanol | 0.68 | 0.35 | 5000 | 0.31 | 44.6 | 3.768 | 23.8 | 69.6 | 6.3 | 0.3 |
| Embodiment 4 | Isooctyl alcohol | 0.28 | 0.75 | 11650 | 0.35 | 0.52 | 1.187 | 33.8 | 62.7 | 3.3 | 0.2 |
| Embodiment 5 | Isooctyl alcohol | 0.50 | 0.53 | 5640 | 0.34 | 7.34 | 2.294 | 26.2 | 72.0 | 1.7 | ＜0.1 |
| Embodiment 6 | Isooctyl alcohol | 0.75 | 0.28 | 1000 | 0.32 | ＞50 | 5.994 | ||||
| Embodiment 7 | Isooctyl alcohol | 0.28 | 0.75 | 12300 | 0.34 | 0.55 | 28.0 | 67.8 | 4.1 | 0.1 | |
| Embodiment 10 | Ethanol | 0.28 | 0.75 | 23000 | 0.34 | 0.51 | |||||
| Embodiment 11 | Ethanol | 0.28 | 0.75 | 19800 | 0.35 | 0.48 | |||||
| Comparative Examples 1 | 0.28 | 0.75 | 8100 | 0.35 | 25.5 | 27.1 | 40.2 | 7.2 | |||
| Comparative Examples 2 | Ethanol | 0.28 | 0.75 | 28000 | 0.36 | 0.50 | 18.0 | 32.4 | 39.6 | 10.0 | |
Listed embodiment 1, the data catalyzer of the present invention as can be seen of comparative example 1 are used for the active higher of vinyl polymerization in the table 1.Distribute from the polymkeric substance particle diameter, implement 1 with comparative example 1, the comparative example 2 better size distribution of having compared, fine polymer powder is few.From comparative example 3 as can be seen, if do not add the solid catalyst particle that the hexane precipitation additive can not get, can not be used for vinyl polymerization.
Table 2
| Numbering | Hydrogen (MPa) | Ethene (MPa) | Hexene-1 (ml) | Density (g/cm 3) |
| Embodiment 1 | 0.28 | 0.75 | 0 | 0.9485 |
| Embodiment 8 | 0.28 | 0.75 | 20 | 0.9379 |
| Embodiment 9 | 0.28 | 0.75 | 30 | 0.9393 |
The ethene of the different hexene concentration of table 2 expression and the density polymer that hervene copolymer closes change.
Claims (18)
1, a kind of vinyl polymerization or copolymerization catalyst of being used for is characterized in that, comprises following component:
A, titaniferous ingredient of solid catalyst, it is by being dissolved in magnesium halide in organic epoxy compounds, organo phosphorous compounds and the inert diluent, form homogeneous solution, add alcohol compound again, add the porous inert carrier through dehydration in the presence of the alkane precipitation additive, the halogenide or derivatives thereof eutectoid that adds transition metals Ti again goes out to be prepared from;
B, organo-aluminium compound;
Ratio between B component and the component A is 5～1000 with aluminium titanium molar ratio computing.
2, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that the magnesium halide described in the component A is a magnesium dihalide, the complex compound of the water of magnesium dihalide and alcohol, a kind of by in alkyl or the-oxyl institute metathetical derivative of one of them halogen atom in the magnesium dihalide molecular formula, or their mixture.
3, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, the halogenide or derivatives thereof that it is characterized in that the transition metals Ti described in the component A is a titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, one chlorine triethoxy titanium, dichloro diethoxy titanium, a kind of in trichlorine one ethanolato-titanium, or their mixture.
According to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that 4, organic epoxy compounds is an oxyethane in the described A component, propylene oxide, butylene oxide ring, epoxy chloropropane, a kind of in the methyl glycidyl ether, or their mixture.
5, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that organo phosphorous compounds is the ortho-phosphoric acid trimethyl in the described A component, the ortho-phosphoric acid triethyl, the ortho-phosphoric acid tri-n-butyl, a kind of in the phosphorous acid benzene methyl or their mixture.
According to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that 6, inert diluent is benzene, toluene and derivative thereof in the described A component.
7, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that used alkane precipitation additive is a kind of in straight-chain paraffin, branched paraffin or the naphthenic hydrocarbon of 3～20 carbon atoms or their mixture in the described A component.
According to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that 8, used alkane precipitation additive is butane, pentane, hexane, hexanaphthene, heptane in the described A component.
According to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that 9, the volume ratio of inert diluent and alkane precipitation additive is in the described A component: 1: 0.1～5.
According to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that 10, the volume ratio of inert diluent and alkane precipitation additive is in the described A component: 1: 0.5～1.5.
11,, it is characterized in that the alcohol compound described in the component A is C according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1
1～C
10Straight chain alcohol or a kind of or their mixture in the isomery alcohol.
12,, it is characterized in that porous inert carrier is a silicon-dioxide among the component A, wherein a kind of or its mixture of aluminium sesquioxide according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1.
13, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that the shape of the porous inert carrier among the component A is spherical in shape, particle diameter is 0.1 μ m～150 μ m.
14, according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1, it is characterized in that the shape of the porous inert carrier among the component A is spherical in shape, particle diameter is 5 μ m～50 μ m.
15,, it is characterized in that the porous inert carrier among the component A uses preceding the need handle through aluminum alkyls according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1.
16,, it is characterized in that magnesium halide and the inert support mol ratio among the component A is: 1: 0.5～15 according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1.
17,, it is characterized in that being applicable to slurry polymerization and vapour phase polymerization mode according to the catalyzer that is used for vinyl polymerization or copolymerization described in the claim 1.
18, the preparation method of the catalyzer component A that is used for vinyl polymerization or copolymerization described in the claim 1～17 is as follows: under agitation magnesium halide is dissolved in organic epoxy compounds, in organo phosphorous compounds and the inert diluent, temperature remains on 30 ℃～80 ℃, form homogeneous solution, add alcohol compound reaction 0.5～2 hour, in the presence of the alkane precipitation additive, add porous inert carrier, then system is cooled in-30～60 ℃ of scopes, titanium compound is splashed in the above-mentioned magnesium halide homogeneous solution with inert support, reaction mixture is warming up to 60～100 ℃ again, suspension was stirred under this temperature 0.5～8 hour, stopping to stir the back solids separates out from mixture solution, decant or remove by filter mother liquor, use the hexane wash solids, make titaniferous solid catalytic ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03119634 CN1218972C (en) | 2003-03-18 | 2003-03-18 | Catalyst for ethylene polymerization or copolymerization and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03119634 CN1218972C (en) | 2003-03-18 | 2003-03-18 | Catalyst for ethylene polymerization or copolymerization and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1532211A CN1532211A (en) | 2004-09-29 |
| CN1218972C true CN1218972C (en) | 2005-09-14 |
Family
ID=34285191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03119634 Expired - Lifetime CN1218972C (en) | 2003-03-18 | 2003-03-18 | Catalyst for ethylene polymerization or copolymerization and its preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1218972C (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173014B (en) * | 2006-10-31 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst for polymerization of ethylene or combined polymerization, producing method and application of the same |
| CN100484970C (en) * | 2007-04-30 | 2009-05-06 | 中国石油化工股份有限公司 | Method for preparing solid catalyst in olefin polymerization catalyst |
| CN101633704B (en) * | 2008-07-24 | 2011-12-28 | 中国石油化工股份有限公司 | Catalyst component used for ethylene polymerization reaction and catalyst thereof |
| CN101519464B (en) * | 2009-03-27 | 2011-05-11 | 迈瑞尔实验设备（上海）有限公司 | Catalyst for vinyl polymerization or copolymerization as well as preparation and application thereof |
| CN103087229B (en) * | 2011-11-01 | 2015-02-11 | 中国石油化工股份有限公司 | Catalyst component and catalyst used in ethylene polymerization |
| CN103772549B (en) * | 2012-10-23 | 2016-07-06 | 中国石油化工股份有限公司 | A kind of catalytic component for vinyl polymerization or combined polymerization and catalyst |
| CN103772552B (en) * | 2012-10-23 | 2016-07-06 | 中国石油化工股份有限公司 | A kind of catalytic component for vinyl polymerization or combined polymerization and catalyst |
| CN103788249B (en) * | 2012-10-29 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of carrier for olefin polymerization catalyst and application thereof |
| CN103788244B (en) * | 2012-10-29 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of carrier for olefin polymerization catalyst and application thereof |
| CN103214722B (en) * | 2013-05-09 | 2015-10-14 | 九江学院 | A kind of easily and the preparation method of polyolefin powder that all mixes of crushed aggregate of plant |
| CN107522799B (en) * | 2016-06-20 | 2020-09-15 | 中国石油化工股份有限公司 | Spherical carrier, olefin polymerization catalyst, preparation method and application thereof, and olefin polymerization method |
| CN107522803A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | Ball type carrier and olefin polymerization catalysis and its preparation method and application and the method for olefinic polymerization |
| CN107840909B (en) * | 2016-09-21 | 2021-04-13 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization, catalyst system and prepolymerization catalyst |
| CN107840917B (en) * | 2016-09-21 | 2021-02-05 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization, catalyst system and prepolymerization catalyst |
| CN109206545B (en) * | 2017-07-01 | 2021-07-02 | 中国石油化工股份有限公司 | Propylene polymer microparticles, solid catalyst component for olefin polymerization, and olefin polymerization catalyst |
| CN111234069B (en) * | 2018-11-29 | 2022-10-21 | 中国石油化工股份有限公司 | Magnesium/titanium-containing solid catalyst component, preparation method thereof, olefin polymerization catalyst and application thereof |
| CN112707981A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, catalyst and application |
-
2003
- 2003-03-18 CN CN 03119634 patent/CN1218972C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1532211A (en) | 2004-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1218972C (en) | Catalyst for ethylene polymerization or copolymerization and its preparing method | |
| CN1086191C (en) | Catalyst used for vinyl polymerizing or copolymerizing and its making method | |
| CN1044481C (en) | Supported olefin polymerization catalyst, its preparation and use | |
| CN1098866C (en) | Gas-phase method total density polyvinyl high-efficiency catalyst | |
| CN1160377C (en) | Catalyst for ethylene homo-and co-polymerization | |
| CN85100997A (en) | The catalyst system that is used for olefinic polymerization and copolymerization | |
| CN1823095A (en) | Olefin polymerization with pyridine moiety-containing single-site catalysts | |
| CN1236372A (en) | Components and catalysts for the polymerization of olefines | |
| CN1194993C (en) | Solid catalyst component for ethylene polymerization and catalyst therefor | |
| CN101260166A (en) | Ethene homopolymerization and copolymerization catalyst and preparation method thereof | |
| CN1098867C (en) | Slurry process total density polyvinyl high-efficiency catalyst | |
| CN1274721C (en) | Catalyst for ethene polymerization or multipolymer, preparing method thereof | |
| CN1814627A (en) | Catalyst active constituent and catalyst containing same | |
| CN1359394A (en) | Magnesium/titanium alkoxid complexes and polymerization catalysts made therefrom | |
| CN102358761B (en) | Olefin polymerization catalyst and preparation method thereof | |
| CN1931885A (en) | Catalyst for polymerizing olefin and its prepn process | |
| CN1233671C (en) | Catalyt and its component for polymerization of ethylene | |
| CN101113182A (en) | Catalyst component, catalyst, preparation method and its application | |
| CN1297575C (en) | Catalyst component for ethylene polymerization or copolymerization and its catalyst | |
| CN1461756A (en) | Nonmetallocene polyolefine catalyst and its preparation method | |
| CN101633705A (en) | Catalyst component used for ethylene polymerization reaction and catalyst thereof | |
| CN1279069C (en) | Polyethylene catalyst and its preparation method | |
| CN100363389C (en) | Catalyst used for ethylene polymerization or copolymerization and its preparation method | |
| CN1282673C (en) | Catalyst for ethylene polymerization or copolymerization and its prepn and application | |
| CN101565476B (en) | Catalyst for ethylene polymerization or copolymerization through slurry method and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20050914 |