CN102040689B - Prepolymerization catalyst for olefin polymerization and preparation method thereof - Google Patents
Prepolymerization catalyst for olefin polymerization and preparation method thereof Download PDFInfo
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Abstract
The invention provides a prepolymerization catalyst for olefin polymerization and a preparation method thereof. The prepolymerization catalyst is highly active during the polymerization. At the prepolymerization stage, beside the pressure and the hydrogen additional proportion, the prepolymerization temperature, varieties of alkylaluminium, the additional proportion of the alkylaluminium and the additional speed of a monomer are also controlled, thus the prepolymerization seriflux concentration of the catalyst can reach 10g/100ml, the particles of the prepolymerization catalyst do not agglomerate and adhere to walls. The finally generated polymerization powders do not agglomerate, the content of the fine powders is reduced obviously, the bulk density is high, and the liquidity is good.
Description
Technical field
The present invention relates to a kind of pre-polymerized catalyst components and preparation method who is used for olefinic polymerization, belong to field of olefin polymerisation.
Technical background
Use high activated catalyst to produce in the process of polymkeric substance, tend to follow polymerization process to produce fine polymer powder and caking phenomenon.Because vinyl polymerization is compared propylene polymerization and is had higher initial polymerization speed, so vinyl polymerization tends to produce more fine polymer powder and caking than propylene polymerization.Apparent in view on the ethene slurry polymerization of widespread use and gas phase polymerization apparatus.The generation of fine powder has disadvantageous effect to the long-term operation of process unit, and a large amount of caking tends to cause powder in carrying granulation process, to stop up.
For solving the above-mentioned situation that in polymerization process, occurs, can adopt the prepolymerized mode of catalyzer, use through the catalyzer of pre-polymerized catalyst as olefinic polymerization.This method is known.
Because vinyl polymerization is compared propylene polymerization and is had higher initial polymerization speed; So when carrying out the ethene prepolymerization under the slurry system that a catalyzer that greater activity arranged is having solvent to exist, these pre-polymerized catalyst particles tend to form loose agglomerating particles or on the still wall of reaction kettle and stirring arm, form and lump.These reunite, the loose non-constant of prepolymerization mobility of particle, and tap density is very low.This granules of catalyst can't satisfy the olefinic polymerization requirement, and both the feed system of possible blocking catalyst formed polymer lumps in the time of might causing polymerization again, disagreed with the original intention of pre-polymerized catalyst.
For example, patent JP-A-59-30806 and JP-A-8-337611 have just invented a kind of pre-polymerized catalyst, and this pre-polymerized catalyst can catalyzed ethylene homopolymerization or ethene-butylene copolymerization.But the pre-polymerized catalyst of original patent has clustering phenomena, and tap density is lower, and it is not smooth to flow.
Under above-mentioned situation, just hope to prepare a kind of pre-polymerized catalyst, when prepolymerization, do not form the gathering of granules of catalyst, and good fluidity; When polymerization, have higher activity, and produce caking and fine powder hardly.
Patent WO9628479 finds, through the speed that control hydrogen additional proportion and monomer add, can make that pre-polymerized catalyst does not lump, adhesion.
Patent EP1138699 realizes the prepolymerization of this invention catalyst solid component through conditions such as control al-ti ratio, prepolymerization multiple, grain diameter, molecular weight of prepolymer.
Patent CN1074221 proof ethene slowly adds, and helps reducing fine polymer powder.But need after prepolymerization, add the titanium tetrachloride solution treating processes again one time.
Patent CN1400979 thinks; Because vinyl polymerization is compared propylene polymerization and is had higher initial polymerization speed; The prepolymerization of catalyst solid component and ethene can not address the above problem fully, with respect to non-pre-polymerized catalyst, uses pre-polymerized catalyst not have advantage.This invention uses propylene monomer to carry out prepolymerization through adding the mode of electron donor, and its degree of isotacticity of the Vestolen PP 7052 of generation is that xylene soluble part content remains on 10-15%.
In sum; The Ziegler-Natta catalyst solid constituent that is used for vinyl polymerization; Increase granule strength for reaching, reduce fine powder content, avoid purposes such as pre-polymerized catalyst gathering and caking, adopted control hydrogen add-on, monomer to add factors such as speed, aluminum alkyls and titanium compound mol ratio, prepolymerization multiple, prepolymerization temperature, prepolymerization pressure; Or adopt and to add electron donor and carry out methods such as propylene pre-polymerization.Yet; In invention in the past, owing to still can not keep gentle prepolymerization condition, the concentration of slurry of catalyzer before prepolymerization generally can only be in 0.005g～2g/100ml scope; Improve concentration of slurry; The situation that tends to cause having avoided in the aforementioned invention takes place once more, and promptly granules of catalyst sticks together and sticks on still wall and the stirring arm, and draining the catalyzer prepolymer flowability that obtains also can non-constant.
The pre-polymerized catalyst that the purpose of this invention is to provide a kind of olefinic polymerization or copolymerization, this pre-polymerized catalyst still show high reactivity when polymerization.In prepolymerisation stage, catalyst slurry concentration can reach 10g/100ml concentration, and granules of catalyst does not lump, not sticking wall.The final polymer powders that generates does not lump, and fine powder content obviously reduces, and tap density is high, good fluidity.
The present invention finds through a large amount of experiments: on the basis of solid catalyst particle, control certain prepolymerization temperature, except that the hydrogen additional proportion, especially will control the kind of aluminum alkyls.Main and the prepolymerization degree of the additional proportion of aluminum alkyls has direct relation.The adding of hydrogen then with pre-polymerization process in the reunion of granules of catalyst direct relation is arranged.A less relatively al-ti ratio, promptly relatively low pre-polymerization multiple can be realized the object of the invention.
Summary of the invention
A kind of pre-polymerized catalyst that is used for olefinic polymerization of the present invention comprises following component:
(1) solids containing titanium catalyst component:
A, on a kind of solids that contains magnesium/titanium, the ingredient of solid catalyst of at least a titanium compound of load and at least a electron donor;
B, the ingredient of solid catalyst that obtains by spherical magnesium alkoxide mixture and titanium compound, at least a organometallic compound and the reaction of electron donor compound;
(2) prepolymer of ethene and/or terminal olefin.
The solids containing titanium catalyst component described in component (1) A wherein, it is on a kind of solids that contains magnesium/titanium, obtains behind at least a inorganic titanium compound, at least a organic titanic compound, at least a electron donor and at least a acvator in the load.The catalyst component particulate median size of gained is less and be evenly distributed, and has high catalytic activity, high hydrogen response, is applicable to that ethylene homo closes or copolymerization.
Titanium compound general formula described in the component of the present invention (1) is Ti (OR)
aX
b, R is C in the formula
1～C
14Aliphatic group or aryl, X is a halogen, a is 0,1 or 2, b is 1 to 4 integer, a+b=3 or 4.
The described prepolymer of pre-polymerized catalyst components of the present invention is not limited only to Alathon, also comprises the multipolymer of alkene such as ethene and butene-1, hexene-1 or octene-1.
The preparation method who is used for the pre-polymerized catalyst of olefinic polymerization or copolymerization of the present invention; Adopt component (1) A or two kinds of solids containing titanium catalyst components of B; With at least a alkylaluminium cpd, hydrogen and ethene or ethene and alpha-olefin comonomer generation prepolymerization; A spot of alkene obtains pre-polymerized catalyst in the polymerization; Wherein the mol ratio of aluminium in the alkylaluminium cpd and the titanium in the catalyst component (Al/Ti mol/mol) is 1～11, and the prepolymerization temperature is-20～90 ℃, and the weight ratio of gained pre-polymerized catalyst and ingredient of solid catalyst is 1.05～20 (g/g).
The present invention finds through a large amount of experimental studies; Selection through aluminum alkyls; And the control monomer adds speed; Can effectively improve the dispersiveness of pre-polymerized catalyst, the concentration of slurry in the time of can making catalyzer carry out prepolymerization improves greatly, and the operability that makes catalyzer carry out the prepolymerization processing improves greatly.
The present invention selects the alkylaluminium cpd of weak reductive action to be used for the preparation of pre-polymerized catalyst component, realizes pre-polymerization process.Tri-n-hexyl aluminum, triisobutyl aluminium or aluminium diethyl monochloride are preferred especially as the promotor of the preparation of pre-polymerized catalyst component.Aluminium in the aluminum alkyls and the titanium mol ratio in the catalyst component (Al/Ti mol/mol) they are 1～11, preferred 2～8.The weight ratio of pre-polymerized catalyst and solid catalyst is 1.05～20 (g/g), preferred 2～10 (g/g).
The preparation of pre-polymerized catalyst component of the present invention is that also slower ethene adds speed and prepolymerization speed, and monomer adds speed control at 0.05～2.25g/g.cat.h, and preferably adding speed is 0.07～1.50g/g.cat.h.
The used alkene of pre-polymerization among the present invention can be a kind of alkene or two or more olefinic polymerizations.The optimal ethylene homopolymerization.
The polymerization method of preparation pre-polymerized catalyst is not specially limited.Can be the suspension polymerization process, gas-phase polymerization processes or other polymerization process.Preferred suspension polymerization process.Can use discontinuous method production, also can use semicontinuous or continuation method production.
Using suspension polymerization to prepare under the situation of pre-polymerized catalyst, solvent for use can be that propane is to representative examples of saturated aliphatic solvents such as heptane.Also can be the aromatic series saturated solvent, like toluene, hexanaphthene etc.Wherein, preferred normal butane, iso-pentane, hexane.More preferably normal butane and hexane.
Using suspension polymerization to prepare under the situation of pre-polymerized catalyst, the catalyzer stirring velocity is not specially limited.As long as make suspended particle in slurries, can keep levitated state, and can get final product by homodisperse.
Using suspension polymerization to prepare under the situation of pre-polymerized catalyst, catalyst slurry concentration is the highest can to reach 10g catalyzer/100ml hexane solution, and catalyzer is uniformly dispersed, and not conglomeration is not assembled, sticking wall.
Prepolymerized polymerization temperature is one of important factor of preparation pre-polymerized catalyst.The prepolymerization temperature can be controlled within the common polymerization temperature scope, and preferred temperature range is-20 ℃ to 90 ℃.Preferred TR is 0 ℃ to 50 ℃.Polymerization pressure is controlled at normal pressure usually to 1.0MPa.
Be the molecular weight of controlled polymerization speed of response and prepolymer, can add hydrogen and control.Preferable methods is with ethene and hydrogen proportional mixing, adds in the prepolymerization reaction kettle again.Hydrogen can ethene suppressing polymerization rate, reduce polymericular weight, if do not add hydrogen, be easy to cause granules of catalyst to form loose agglomerating particles or on the still wall of reaction kettle and stirring arm, form lump.These reunite, the loose non-constant of prepolymerization mobility of particle, and tap density is very low.This granules of catalyst can't satisfy the olefinic polymerization requirement, and both possible blocking catalyst feed system forms polymer lumps in the time of might causing polymerization again.
Aluminum alkyls is as the promotor component of Ziegler-Natta catalyst, extensively known together and uses.Being used for organometallic compound of the present invention comprises: triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, ethoxyquin diethyl aluminum, fourth oxidation dibutyl aluminium, sesquialter ethoxyquin aluminium triethyl, sesquialter ethoxyquin butyl aluminium; Ethylaluminium dichloride, dichloride propyl group aluminium, bromination butyl aluminium, diethyl aluminium hydride, hydrogenation dibutyl aluminium; Oxyethyl group ethylaluminium chloride, butoxy chlorinated butyl aluminium or oxyethyl group bromination aluminium triethyl etc.Preferred trialkylaluminium, more preferably tri-n-hexyl aluminum, triisobutyl aluminium or aluminium diethyl monochloride.
In the common polyreaction, select triethyl aluminum to do promotor, comprise and also all adopt triethyl aluminum in the prepolymerization related patent U.S. Patent No..Yet in pre-polymerized catalyst, controlled polymerization speed, the control active site forms speed, is prepolymerized committed step.Through contriver's lot of experiment validation,, adopt the aluminum alkyls of littler reducing power can access better prepolymerization effect to two types of catalyst components involved in the present invention.The prepolymerized concentration of slurry of catalyzer can reach 0.1g/ml, has more possessed the industrialized condition of realization catalyzer prepolymerization.
The final state of pre-polymerized catalyst is a dry powder.Drying process is similar with common Ziegler-Natta catalyst drying process, the method that can take nitrogen to dry up; Also can adopt the method that vacuumizes dry.
A kind of method for preparing solids containing titanium catalyst component of the present invention (1) A is disclosed among the CN1463991A; It is included on a kind of solids that contains magnesium/titanium, at least a inorganic titanium compound, at least a organic titanic compound, at least a electron donor and at least a acvator in the load.
The method for preparing solids containing titanium catalyst component of the present invention (1) B is reacted the ingredient of solid catalyst that obtains by spherical magnesium alkoxide mixture and titanium compound, at least a organometallic compound and electron donor compound;
This catalyst component can adopt the preparation of following method: (1) is dispersed in spherical magnesium alkoxide complexes carrier in the inert solvent, and dispersion medium comprises: Trimethylmethane, hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, aliphatic saturated hydrocarbon inert solvents such as hydrogenated gasoline, kerosene.(2),, above-mentioned reaction soln and organometallic compound are carried out contact reacts at-40 ℃～60 ℃ in the presence of the electron compound; And mixture slowly is warming up to 40～60 ℃, behind the reaction certain hour, remove unreacted reactant and solvent; And adopt the inert diluent washing, and then react with titanium compound, catalyst component of the present invention obtained; Wherein in every mole of magnesium halide, the add-on of titanium compound is 1.0～15.0mol.
The invention beneficial effect:
The present invention provides a kind of efficient, finely disseminated pre-polymerized catalyst solid ingredient; This pre-polymerized catalyst components has narrow relatively particle size dispersion; Catalyst activity is higher, and fine polymer powder is considerably less, is specially adapted to ethene slurry and gas-phase polymerization process.
Embodiment
Embodiment given below is for the present invention is described, rather than limits the invention.
Testing method:
1, melting index (MI) is to measure according to ASTM D1238-99;
2, flow index (FI) is to measure according to ASTM D1238-99;
3, molten stream is melting index and the ratio of flow index than (MFR);
4, density polymer is to measure according to GB-1033;
5, size-grade distribution: according to method, with " MalvernInstr.2600 " tester based on the optical diffraction principle of one-wavelength laser.
Embodiment 1
1, the preparation of solids containing titanium catalyst component A
4.8 gram magnesium chlorides, 93 milliliters of toluene, 4.0 milliliters of epoxy chloropropane, 12.5 milliliters of tributyl phosphates are joined in the reaction kettle, are under 55 ℃ the condition, to react two hours in mixing speed 450rpm, temperature; Add 0.8 gram Tetra hydro Phthalic anhydride, continue reaction one hour, be cooled to-28 ℃; Drip 40 milliliters of titanium tetrachlorides, be warming up to 80 ℃ gradually, constant temperature one hour; The elimination mother liquor repeatedly washs after drying through inert diluent toluene and organic solvent hexane, obtains containing the solids of magnesium/titanium.
10ml four titanium butoxide and 10ml THF are joined in the dissolution kettle, add 1 gram titanous chloride after stirring again, dissolving forms compound titanium solution under the condition of mixing speed 450rpm.
The solids that 11 grams is obtained containing magnesium/titanium joins in another reaction kettle, adds the 100ml iso-pentane, drips the above-mentioned compound titanium solution that obtains of 10ml under 10 ℃ the condition stirring 200rpm, temperature.Normal temperature reacted one hour down; Filter solution, and, add the 60ml iso-pentane again with hexane wash twice; 3.5 the aluminium diethyl monochloride solution reaction of ml volumes concentration 26.43% one hour obtains particulate state solids containing titanium catalyst component A 18.2 grams through evaporation drying.Wherein contain Ti 1.89wt%, Mg11.32wt%, aluminium 1.09wt%, THF 34.52wt%.
2, prepolymerization
Under 20 ℃ temperature, have in the glass reactor of whisking appliance to 200ml, add the 100ml hexane; Stir simultaneously; The solids containing titanium catalyst component A 10g that obtains above the adding keeps internal temperature constant, and the hexane solution of 3ml tri-n-hexyl aluminum is slowly joined in the reactor drum.Then, under identical temperature, ethene (12ml/min) is mixed behind gas meter respectively with hydrogen (48ml/min), feed reactor drum.Reaction was carried out 2 hours, stopped air inlet.After washing, drying, obtain pre-polymerized catalyst, the pre-polymerization multiple is 2.0g pre-polymerized catalyst/g catalyzer.
3, polymerization
Volume is 2 liters a stainless steel cauldron; After hydrogen gas is fully replaced, be pressed into about 0.5 liter of hexane with nitrogen, use the syringe implantation concentration to be 1mmol/ml triethyl aluminum-hexane solution 2ml; Add a certain amount of above-mentioned acquisition pre-polymerized catalyst under stirring again, replenish the hexane total amount and be about 1 liter.
Heat up and successively feed hydrogen and ethene, 4.8 * 10 in the reinforced back that finishes
5Pa H
2, 5.5 * 10
5Pa ethene, polymerization temperature are 85 ℃, react two hours, and overbottom pressure in the still of lowering the temperature, drain is emitted the polymer slurries material, and the elimination hexane with the polymkeric substance oven dry, obtains polyethylene powder, and the result sees table one.
Embodiment 2
1, the preparation of solids containing titanium catalyst component A
5ml four titanium butoxide and 10ml THF are joined in the dissolution kettle, add 1 gram titanous chloride after stirring again, dissolving forms compound titanium solution under the condition of mixing speed 450rpm.
In reaction kettle, add the solids that contains magnesium/titanium 11 grams of preparation among the embodiment 1, add the 100ml iso-pentane, drip the compound titanium solution that obtains above the 10ml under 10 ℃ the condition stirring 200rpm, temperature.Normal temperature reacted one hour down, filtered solution, and with hexane wash twice, obtained particulate state solids containing titanium catalyst component A 15.8 grams through evaporation drying, wherein contained Ti 1.63wt%, Mg 11.34wt%, aluminium 0.30wt%, THF 34.54wt%.
2, prepolymerization
Under 20 ℃ temperature, have in the glass reactor of whisking appliance to 200ml, add the 100ml hexane, stir simultaneously, add 10g solids containing titanium catalyst component A.Keep internal temperature constant, the solution of 3ml tri-n-hexyl aluminum in hexane is slowly joined in the reactor drum.Then, under identical temperature, ethene (12ml/min) is mixed behind gas meter respectively with hydrogen (48ml/min), feed reactor drum.Reaction was carried out 2 hours, stopped air inlet.After washing, drying, obtain pre-polymerized catalyst, the pre-polymerization multiple is 2.0g pre-polymerized catalyst/g catalyzer.
3, polymerization
The polymerization appreciation condition is with embodiment 1, and the result sees table one.
Embodiment 3
1, solids containing titanium catalyst component A preparation
3ml four titanium butoxide and 10ml THF are joined in the dissolution kettle, add 1 gram titanous chloride after stirring again, dissolving forms compound titanium solution under the condition of mixing speed 450rpm.
In reaction kettle, add the solids that contains magnesium/titanium 11 grams of preparation among the embodiment 1, add the 100ml iso-pentane, drip the compound titanium solution that obtains above the 10ml under 10 ℃ the condition stirring 200rpm, temperature.Down reaction one hour of normal temperature filters solution, and with twice of hexane wash; Add the 60ml iso-pentane again, the aluminium diethyl monochloride solution reaction of 3.5 ml volumes concentration 26.43% one hour obtains particulate state solids containing titanium catalyst component A 14.1 grams through evaporation drying; Wherein contain Ti 1.83wt%; Mg 11.84wt%, aluminium 0.77wt%, THF 32.28wt%.
2, prepolymerization
Under 20 ℃ temperature, have in the glass reactor of whisking appliance to 200ml, add the 100ml hexane, stir simultaneously, add 10g solids containing titanium catalyst component A.Keep internal temperature constant, the solution of 3ml tri-n-hexyl aluminum in hexane is slowly joined in the reactor drum.Then, under identical temperature, ethene (12ml/min) is mixed behind gas meter respectively with hydrogen (48ml/min), feed reactor drum.Reaction was carried out 2 hours, stopped air inlet.After washing, drying, obtain pre-polymerized catalyst, the pre-polymerization multiple is 2.0g pre-polymerized catalyst/g catalyzer.
3, polymerization
The polymerization appreciation condition is with embodiment 1, and the result sees table one.
Embodiment 4:
1, solids containing titanium catalyst component A preparation
With embodiment 1.
2, prepolymerization
Under 20 ℃ temperature, have in the glass reactor of whisking appliance to 200ml, add the 100ml hexane, stir simultaneously, add 8g solids containing titanium catalyst component A.Keep internal temperature constant, the solution of 3ml triisobutyl aluminium in hexane is slowly joined in the reactor drum.Then, under identical temperature, ethene (12ml/min) is mixed behind gas meter respectively with hydrogen (48ml/min), feed reactor drum.Reaction was carried out 2 hours, stopped air inlet.After washing, drying, obtain pre-polymerized catalyst, the pre-polymerization multiple is 2.0g pre-polymerized catalyst/g catalyzer.
3, polymerization
The polymerization appreciation condition is with embodiment 1, and the result sees table one.
Embodiment 5:
1, the preparation of solids containing titanium catalyst component A
With embodiment 1.
2, prepolymerization
Under 20 ℃ temperature, have in the glass reactor of whisking appliance to 200ml, add the 100ml hexane, stir simultaneously, add 10g solids containing titanium catalyst component A.Keep internal temperature constant, the solution of 3ml triethyl aluminum in hexane is slowly joined in the reactor drum.Then, under identical temperature, ethene (12ml/min) is mixed behind gas meter respectively with hydrogen (48ml/min), feed reactor drum.Reaction was carried out 2 hours, stopped air inlet.After washing, drying, obtain pre-polymerized catalyst, the pre-polymerization multiple is 2.0g pre-polymerized catalyst/g catalyzer.The catalyzer property extreme difference that flows, caking.Can't carry out the polymerization evaluation.
Embodiment 6
1, the preparation of solids containing titanium catalyst component B
In the reactor drum of fully replacing through high pure nitrogen, add 6.0g magnesium alkoxide complexes carrier (with reference to Chinese patent 93102795.0 preparations) (the magnesium alkoxide ratio is 1.4) successively, hexane 60ml is cooled to 0 ℃ under stirring, and drips 60mlTiCl
4, be warming up to 40 ℃, isothermal reaction 2 hours.Be cooled to 0 ℃, drip the hexane solution of triethyl aluminum and THF, be warming up to 40 ℃ then, and keep reaction 0.5 hour.This system is cooled to 0 ℃, repeats to drip TiCl
4Process is warming up to 40 ℃ again, and keeps reaction 0.5 hour.With system room temperature washing twice, be warming up to 60 ℃ afterwards, reacted 2 hours.Stop to stir, leave standstill, the very fast layering of suspension-s; Extract the upper strata stillness of night, hexane wash twice, high pure nitrogen dries up; Obtain solids containing titanium catalyst component B 5.1 grams of good fluidity, narrow diameter distribution, wherein contain Ti 3.80wt%, Mg11.32wt%; Aluminium 1.09wt%, THF 24.52wt%.
2, prepolymerization
Under 20 ℃ temperature, have in the glass reactor of whisking appliance to 200ml, add the 100ml hexane, stir simultaneously, add the above-mentioned solids containing titanium catalyst component B that obtains of 10g.Keep internal temperature constant, the solution of 3ml three n-hexyl base aluminium in hexane is slowly joined in the reactor drum.Then, under identical temperature, ethene (12ml/min) is mixed behind gas meter respectively with hydrogen (48ml/min), feed reactor drum.Reaction was carried out 2 hours, stopped air inlet.After washing, drying, obtain pre-polymerized catalyst, the pre-polymerization multiple is 2.0g pre-polymerized catalyst/g catalyzer.
3, vinyl polymerization is with embodiment 1.Polymerization result is seen table one.
Embodiment 7
1, the preparation of solids containing titanium catalyst component B
In the reactor drum of fully replacing through high pure nitrogen; Add 6.0g magnesium alkoxide complexes carrier (the magnesium alkoxide ratio is 2.4) successively; Hexane 150ml is cooled to 0 ℃ under stirring, and drips the hexane solution and the 15ml THF of 17ml triethyl aluminum respectively; Be warming up to 60 ℃ then, and keep reaction 0.5 hour.This system is cooled to 0 ℃, and repeats above-mentioned dropping process.System with hexane room temperature washing twice, is cooled to 0 ℃ then, slowly drips titanium tetrachloride 22ml, be warming up to 60 ℃ afterwards, reacted 2 hours.Stop to stir, leave standstill, the very fast layering of suspension-s; Extract the upper strata stillness of night, hexane wash twice, high pure nitrogen dries up; Obtain solids containing titanium catalyst component B 5.5 grams of good fluidity, narrow diameter distribution, wherein contain Ti 3.50wt%, Mg 11.32wt%; Aluminium 1.09wt%, THF 14.52wt%.
2, prepolymerization
Under 20 ℃ temperature, have in the glass reactor of whisking appliance to 200ml, add the 100ml hexane, stir simultaneously, add 10g solids containing titanium catalyst component B.Keep internal temperature constant, the solution of 3ml triethyl aluminum in hexane is slowly joined in the reactor drum.Then, under identical temperature, ethene (12ml/min) is mixed behind gas meter respectively with hydrogen (48ml/min), feed reactor drum.Reaction was carried out 2 hours, stopped air inlet.After washing, drying, obtain pre-polymerized catalyst, the pre-polymerization multiple is 2.0g pre-polymerized catalyst/g catalyzer.
3, vinyl polymerization
Vinyl polymerization is with embodiment 1.Polymerization result is seen table one.
Embodiment 8
1, the preparation of solids containing titanium catalyst component B
With embodiment 6.
2, prepolymerization
Pre-polymerization process just is replaced by triisobutyl aluminium to promotor by tri-n-hexyl aluminum with embodiment 6, and add-on is 3ml.
3, vinyl polymerization is with embodiment 1.The polymerization catalyst result sees table one.
Embodiment 9
1, the preparation of solids containing titanium catalyst component B
With embodiment 6.
2, prepolymerization
Pre-polymerization process just is replaced by triethyl aluminum to promotor by tri-n-hexyl aluminum with embodiment 6, and add-on is 3ml.
3, the mobile property extreme difference of catalyzer, caking.Can't carry out the polymerization evaluation.
Embodiment 10
1, the preparation of solids containing titanium catalyst component B
With embodiment 9.
2, prepolymerization
Pre-polymerization process is with embodiment 9, and just the catalyst solid constituent add-on is reduced to 4 grams.
3, vinyl polymerization is with embodiment 1.The polymerization catalyst result sees table one.
Comparative example 1～10
With embodiment 1～10, just do not add pre-polymerization process.
The polymerization result contrast of table one: embodiment and comparative example
| Embodiment | Active * (gPE/gcat) | BD (g/cm 3) | The content (wt%) of the following fine powder of 195 μ m | MI (g/10min) |
| Embodiment 1 | 6500 | 0.36 | 0.1 | 0.61 |
| Comparative example 1 | 6351 | 0.36 | 0.5 | 0.45 |
| Embodiment 2 | 5785 | 0.36 | 0.1 | 1.65 |
| Comparative example 2 | 5900 | 0.37 | 0.7 | 1.58 |
| Embodiment 3 | 8150 | 0.35 | 0.1 | 1.86 |
| Comparative example 3 | 7500 | 0.35 | 0.4 | 2.17 |
| Embodiment 4 | 6870 | 0.36 | 0.1 | 1.05 |
| Comparative example 4 | 6351 | 0.36 | 0.5 | 0.45 |
| Embodiment 6 | 17499 | 0.33 | 0.5 | 2.14 |
| Comparative example 6 | 17185 | 0.31 | 16.7 | 2.82 |
| Embodiment 7 | 19650 | 0.34 | 0.8 | 2.42 |
| Comparative example 7 | 18765 | 0.32 | 15.5 | 2.50 |
| Embodiment 8 | 18530 | 0.33 | 1.0 | 1.95 |
| Comparative example 8 | 17185 | 0.31 | 16.7 | 2.82 |
| Embodiment 10 | 17850 | 0.32 | 0.7 | 2.76 |
| Comparative example 10 | 17185 | 0.31 | 16.7 | 2.82 |
*: the pre-polymerized catalyst activity is calculated according to original catalyst weight.
Polymerization result contrast by embodiment and comparative example is obviously visible, adopts prepolymerization method of the present invention, obtains the slurry polymerization that pre-polymerized catalyst is applied to ethene; The polymerization catalyst activity is higher; The polymkeric substance apparent density is high, fine polymer powder seldom, industrial application is highly advantageous to.
Claims (7)
1. a pre-polymerized catalyst that is used for olefinic polymerization is characterized in that, comprises following component:
(1) solids containing titanium catalyst component:
A, on a kind of solids that contains magnesium/titanium, the ingredient of solid catalyst of at least a titanium compound of load and at least a electron donor;
B, the ingredient of solid catalyst that obtains by spherical magnesium alkoxide mixture and titanium compound, at least a organometallic compound and the reaction of electron donor compound;
(2) prepolymer of ethene and/or terminal olefin;
Said pre-polymerized catalyst prepares through following method: adopt component (1) A or two kinds of solids containing titanium catalyst components of B; In the presence of at least a alkylaluminium cpd and hydrogen; With ethene or ethene and alpha-olefin comonomer generation prepolymerization; A spot of alkene obtains pre-polymerized catalyst in the polymerization; Wherein the mol ratio of aluminium in the alkylaluminium cpd and the titanium in the catalyst component (Al/Ti mol/mol) is 1～11; The prepolymerization temperature is-20～90 ℃; The weight ratio of gained pre-polymerized catalyst and solids containing titanium catalyst component is 1.05～20 (g/g); Described alkylaluminium cpd is selected from tri-n-hexyl aluminum, triisobutyl aluminium or aluminium diethyl monochloride, and monomer adding speed is 0.05～2.25g/g.cat.h during prepolymerization.
2. the pre-polymerized catalyst that is used for olefinic polymerization according to claim 1; It is characterized in that; Solids containing titanium catalyst component described in component (1) A; It is on a kind of solids that contains magnesium/titanium, obtains behind at least a inorganic titanium compound, at least a organic titanic compound, at least a electron donor and at least a acvator in the load.
3. the pre-polymerized catalyst that is used for olefinic polymerization according to claim 1 is characterized in that, the titanium compound general formula described in the component (1) is Ti (OR)
aX
b, R is C in the formula
1～C
14Aliphatic group or aryl, X is a halogen, a is 0,1 or 2, b is 1 to 4 integer, a+b=3 or 4;
4. the pre-polymerized catalyst that is used for olefinic polymerization according to claim 1 is characterized in that, prepolymer described in the component (2) is the multipolymer of Alathon or ethene and propylene, butene-1, hexene-1 or octene-1.
5. the pre-polymerized catalyst that is used for olefinic polymerization according to claim 1 is characterized in that, in the preparation of pre-polymerized catalyst, wherein the mol ratio of aluminium in the alkylaluminium cpd and the titanium in the catalyst component (Al/Ti mol/mol) is 2～8.
6. the pre-polymerized catalyst that is used for olefinic polymerization according to claim 1 is characterized in that, in the preparation of pre-polymerized catalyst, wherein prepolymerization temperature is 0～50 ℃.
7. the pre-polymerized catalyst that is used for olefinic polymerization according to claim 1 is characterized in that, in the preparation of pre-polymerized catalyst, wherein monomer adding speed is 0.07～1.50g/g.cat.h.
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| CN104974283B (en) * | 2014-04-11 | 2017-03-22 | 中国石油化工股份有限公司 | Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof |
| CN104119463A (en) * | 2014-07-16 | 2014-10-29 | 任丘市利和科技发展有限公司 | Catalyst component for vinyl polymerization and preparation method and application of catalyst component |
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| CN1262693A (en) * | 1998-03-23 | 2000-08-09 | 蒙特尔技术有限公司 | Prepolymerized catalyst components for polymerization of olefins |
| CN1390235A (en) * | 1999-09-10 | 2003-01-08 | 巴塞尔技术有限公司 | Catalyst for the polymerization of olefins |
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| CN1262693A (en) * | 1998-03-23 | 2000-08-09 | 蒙特尔技术有限公司 | Prepolymerized catalyst components for polymerization of olefins |
| CN1390235A (en) * | 1999-09-10 | 2003-01-08 | 巴塞尔技术有限公司 | Catalyst for the polymerization of olefins |
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