CN1152063C - Solid catalyst for polymerization of olefin and its preparing process - Google Patents
Solid catalyst for polymerization of olefin and its preparing process Download PDFInfo
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- CN1152063C CN1152063C CNB991003608A CN99100360A CN1152063C CN 1152063 C CN1152063 C CN 1152063C CN B991003608 A CNB991003608 A CN B991003608A CN 99100360 A CN99100360 A CN 99100360A CN 1152063 C CN1152063 C CN 1152063C
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Abstract
The present invention relates to an olefinic polymerization solid catalyst which comprises clay, magnesium halide and a transition metal compound, wherein the content of the magnesium halide is from 5.0 wt% to 50.0 wt%, and the content of transition metal is from 0.2 wt% to 20.0 wt%. The catalyst can also contain an internal electron donor compound, and the clay is mainly selected from fibre bar stone group clay. The catalyst is formed by the method that the clay is suspended in a magnesium halide solution, reacts for 0.5 to 6 hours, and then is loaded with the transition metal compound. The catalyst is used for a polymerization reaction of ethene or propylene, and has favorable polymerization activity.
Description
The present invention is a kind of solid catalyst for olefin polymerization and preparation method thereof, specifically, is a kind of solid catalyst that contains transistion metal compound and clay that is used for olefinic polymerization and preparation method thereof.
As everyone knows, can prepare efficient polyolefin catalyst as the carrier of Ziegler-Natta catalyst with Magnesium Chloride Anhydrous, as USP4,298,718 and USP4,495,338 is described.But except that Magnesium Chloride Anhydrous, can also be materials such as silicon carbide, silicon-dioxide, magnesiumcarbonate, magnesium oxide, as EP43220A as the carrier substance of Ziegler-Natta catalyst
1Disclose a kind of catalyzer that is immersed on the silicon-dioxide, this catalyzer is made with the precursor components impregnation of silica, and described precursor components is made by titanium, magnesium compound and electron donor compound, and its source is respectively MgCl
2, TiCl
4And tetrahydrofuran (THF).
USP5,362,825 disclose a kind of preparation method of polyolefin catalyst, this method is with the reactant of cross-linked clay and metal dihalides and at least a transistion metal compound, contact generates solids in the presence of liquid diluent, and the weight of used clay is 0.1～30 heavy % of above-mentioned reactant.The gained solids contacts with the halogenation organoaluminum and obtains solid catalyst.Metal dihalides described in this method is a magnesium dichloride, and transistion metal compound is Ti (OR)
4Clay is polynite or wilkinite, used clay need could use through complicated crosslinking Treatment step, and after the reactant contact reacts of itself and above-mentioned metal dihalides and at least a transistion metal compound, the gained solids also needs to handle with organo-aluminium compound and just can be used for polymerization catalyzed reaction.
The purpose of this invention is to provide a kind of raw material and be easy to get, and the simple polyolefine solid catalyst of preparation method and preparation method thereof.
Solid catalyst of the present invention comprises clay, magnesium halide and transistion metal compound, and wherein the content of magnesium halide is 5.0～50.0 heavy %, is preferably 20.0～50.0 heavy %, and the content of transition metal is 0.2～20.0 heavy %, is preferably 1.0～10.0 heavy %.
The preferred magnesium chloride of described magnesium halide.
Described clay is selected from fiber rod stone kind clay, kaolinite or montmorillonite.
The fiber rod stone kind clay is the aqueous aluminium magensium silicate of a class, mainly comprises sepiolite, octopus Piao stone, Palygorskite and attapulgite, and its crystal layer is that every limit is the silicon-oxy tetrahedron of two or three two strandss, 5 or 8 alumina octahedrals of therebetween.Connecting into the crystalline structure of duct formula between the unit layer by oxygen, is the crystalline structure of a kind of chain to the stratiform transition.
Sepiolite and octopus Piao stone belong to subtribe mineral together, have identical chemical constitution and crystalline structure.Each unit layer of sepiolite is upper and lower respectively to be the double-stranded wafers of three silicon-oxy tetrahedrons, and eight alumina octahedral wafers of therebetween connect into the crystalline structure of duct formula by oxygen between unit layer.Sepiolite ideal chemical formula is Si
12Mg
8O
30(OH)
4(OH
2)
4(8H
2O).
Palygorskite has identical chemical constitution and crystalline structure with attapulgite, but difference to some extent in nature.The Palygorskite crystal property is good, and fiber is long, the outward appearance softness; The attapulgite crystallinity is poor, and fiber is very short, outward appearance densification, iron level height.So attapulgite is subspecies of Palygorskite.Each unit layer of Palygorskite is by the double-stranded wafer of upper and lower two silicon-oxy tetrahedrons, and five alumina octahedrals of therebetween constitute, and each unit layer connects into the crystalline structure of duct formula each other by oxygen.Its ideal chemical formula is Si
8Mg
5O
20(OH)
2(OH
2)
4(4H
2O).
Described transistion metal compound is selected from halogenide, oxyhalogenation thing, the C of one of Ti, Zr, Hf, V, Nb, Ta, Ni and Sc
1～C
12Alcoxyl halogenide or hydrohalogen, halogenide, oxyhalogenation thing, the C of preferred titanium
1～C
12Alcoxyl halogenide or hydrohalogen, the halogenide of titanium more preferably is as TiCl
4
Catalyzer of the present invention also can comprise the internal electron donor compound, and the mol ratio of internal electron donor compound and magnesium is 1: 4～14, be preferably 1: 6～and 10.When this catalyzer is used for alpha-olefin, during as the tactic polymerization of propylene, 1-butylene or 4-methyl-1-pentene, must contain internal electron donor.
Described internal electron donor is the ester of general formula (I) or the ether of general formula (II),
General formula (I) and (II) in, R
1～R
4Be C
1～C
18Alkyl, C
3～C
18Cycloalkyl, C
6～C
18Aryl, aralkyl or alkaryl.The comparatively preferred ester of catalyzer of the present invention is phthalic acid di-n-butyl ester, diisobutyl phthalate or phthalic acid di-n-octyl ester, and comparatively preferred ether is R in the general formula (II)
1, R
2Be C
1～C
6Alkyl, R
3, R
4For the ether of methyl, as 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2-methyl-2-isobutyl--1,3-Propanal dimethyl acetal or 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal.
The preparation method of solid catalyst of the present invention comprises:
(1) in the presence of unreactive hydrocarbons solvent, is dissolved in magnesium halide in the polar organic solvent or makes it and Ti (OR)
4Form MgX
2NTi (OR)
4Title complex, Ti (OR) wherein
4In R be C
2～C
8Alkyl, C
3～C
8Cycloalkyl or C
6～C
8Aryl, preferred C
2～C
8Alkyl, n is 1～3 number,
(2) be that the clay of 1～20 times of magnesium halide is suspended in and reacted in the above-mentioned solution 0.5～6.0 hour with weight,
(3) add transistion metal compound, wherein the mol ratio of transition metal and magnesium is 3～30,60～135 ℃ of reactions down, collects solid matter.
For increasing catalyst activity, can in (2) step reaction mixture, add alkylaluminium cpd, maybe can isolate the halogenating agent of hydroxyl, as SiCl
4In activator, the mol ratio of activator and magnesium halide is 2～20, and then carries out the reaction of (3) step, and described alkylaluminium cpd is selected from C
1～C
8Aluminum alkyls or chlorination aluminum alkyls, preferred alkylaluminium cpd is triethyl aluminum, triisobutyl aluminium or aluminium diethyl monochloride.
Described unreactive hydrocarbons solvent is C
5～C
10Alkane, C
6～C
18Aromatic hydrocarbons, preferred C
6～C
10Alkane or C
6～C
8Aromatic hydrocarbons, most preferably hexane, heptane, octane or decane.Its consumption should be 5～100 times of magnesium halide weight.
Described polar organic solvent is selected from C
2～C
8Alcohol, preferred butanols, its consumption should make the magnesium halide dissolving, suitable consumption should be 3～6 times of magnesium halide molar weight.
Described transistion metal compound is selected from halogenide, oxyhalogenation thing, the C of one of Ti, Zr, Hf, V, Nb, Ta, Ni and Sc
1～C
12Alcoxyl halogenide or hydrohalogen, halogenide, oxyhalogenation thing, the C of preferred titanium
1～C
12Alcoxyl halogenide or hydrohalogen, the halogenide of titanium more preferably is as TiCl
4
After the reaction of 60～135 ℃ of adding transistion metal compounds and collecting solid, using alkane solvent thorough washing solid matter in the described method (3), till no negatively charged ion exists in filtrate, is TiCl as used transistion metal compound
4, the repetat alkane solvent is washed till does not have Cl in the filtrate
-Till.Washing finishes, and the gained solid promptly gets solid catalyst of the present invention 30～90 ℃ of dryings.
Clay is selected from fiber rod stone kind clay, kaolin or montmorillonite described in the above-mentioned preparation method, preferred sepiolite, octopus Piao stone, Palygorskite or attapulgite, more preferably sepiolite or attapulgite.When selecting clay mineral for use, should whether carry out pre-treatment according to the purity decision of institute's argillaceous in the original soil ore deposit before use, pretreated purpose is to remove impurity, as quartz sand, lime carbonate etc., pre-treatment can adopt the described method of CN1044772A to carry out.Pretreated clay also will carry out roasting at 100～600 ℃ before use, to remove adsorption moisture and other objectionable impurities wherein.Clay after the roasting can be made into powdery, particulate state or sphere, and the diameter of ball is 20～80 microns.
When preparation solid catalyst of the present invention, also can add ester or the ether of formula (II) or the mixture of the two of formula (I), its adding can be carried out in (3) step, and add-on is 0.1～0.5 times of magnesium halide molar weight.
Solid catalyst of the present invention is applicable to the polyreaction of alpha-olefin, should use alkylaluminium cpd to be promotor during polymerization, and preferred alkylaluminium cpd is triethyl aluminum, triisobutyl aluminium or three n-butylaluminum.The mol ratio of aluminium and transition metal should be greater than 1 in the used aluminum alkyls, and the mol ratio of suitable aluminium/transition metal is 20～800, is preferably 20～300.
When catalyzer of the present invention is used for alpha-olefin, during as the tactic polymerization of propylene, 1-butylene, except that using aluminum alkyls as the promotor, also will be according to the internal electron donor compound that contains in the solid catalyst, whether decision re-uses electron donor compound (external electron donor), and this compound can be identical with the internal electron donor compound, is selected from the ester of formula (I) when the internal electron donor compound, particularly during bialkyl ortho phthalate, it is R that the external electron donor compound preferably is selected from general formula
1R
2Si (OR)
2Silicon compound, R in the formula
1, R
2Be alkyl, cycloalkyl or the aromatic hydrocarbons that contains 1～8 carbon atom, R is the alkyl that contains 1～4 carbon atom, and preferred silicon compound is methylcyclohexyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane.The mol ratio of used alkylaluminium cpd and silicon compound is 10～50.When the internal electron donor compound is selected from the ether of formula (II), then need not use the external electron donor compound during polymerization.
Solid catalyst of the present invention is applicable to olefinic polymerization production polyolefin products, and polyreaction can be carried out in gas phase or liquid phase, can select for use unreactive hydrocarbons as attenuant during polymerization, and unreactive hydrocarbons commonly used are hexane, heptane.Suitable polymeric reaction temperature is 20～150 ℃, and preferably 60～90 ℃, reaction can be carried out under normal pressure, also can under high pressure carry out, as carrying out under 0.6～3.0MPa pressure.
The clay that solid catalyst provided by the invention is selected for use is cheap and easy to get, be easy to make be evenly distributed, the particle of good fluidity, and method for preparing catalyst is simple, with USP5,362,825 compare, and used clay does not need crosslinking Treatment, only need simple process to make solid catalyst by the carrying transition metal element, and have good polymerization activity.
Further describe the present invention below by example, but the present invention is not limited to this.
Example 1
This example prepares solid catalyst with sepiolite, and carries out ethylene polymerization.
Get anhydrous MgCl
2Powder (Fushun No.3 Petroleum Factory) 0.6 gram is put into the flask that has reflux exchanger and magneton stirring, adds 20 milliliters of normal heptanes and 1.2 milliliters of propyl carbinols, is warming up to MgCl under stirring
2Dissolving fully, sepiolite 1.0 grams (the Anhui Quanjiang produces natural sepiolite) after the 200 ℃ of roastings of learning from else's experience were handled in 5 hours join in the flask, continue to reflux 2 hours, and reactant is reduced to room temperature, add 6 milliliters of TiCl
4(Beijing chemical reagent factory), be warming up to reflux temperature after, continue to stir 2 hours, filtered while hot joins the gained solid in the flask again, adds 20 milliliters of normal heptanes and 3 milliliters of TiCl
4, reaction is 1 hour under reflux temperature, filters, and the gained solid washs 6 times by each 30 milliliters hexane consumption down at 60 ℃, and 60 ℃ of dryings obtain 1.8 gram pulverulent solids catalyst A.It is 4.14 heavy % that inductance coupled plasma atomic emission spectrometry (ICP/AES) is measured in this solid catalyst Ti content, MgCl
2Content is 32.1 heavy %.
With 500 milliliters of there-necked flask N that agitator and constant temperature system are housed
2Pump drainage displacement three times, again once with the ethene displacement, add 30 milligrams of the hexane solution of triisobutyl aluminium of 100 milliliters of hexanes, 2 milliliter of 1.5 mol and solid catalyst A successively, start stirring, feed ethylene gas, reaction is 2 hours under 40 ℃, 0.1MPa condition, uses 2 milliliters of ethanol termination reactions then, obtain exsiccant polyethylene powders 12 grams, the catalyst activity that calculates is 402 gram PE/ gram catalyzer.
Example 2
This example adopts sepiolite and MgCl
2Ti (OC
4H
9)
4Title complex prepare solid catalyst, and carry out ethylene polymerization.
Get anhydrous MgCl
2Powder 0.6 gram is put into the flask that has reflux exchanger and magneton stirring, adds 20 milliliters of normal heptanes, 1.8 milliliters of Ti (OC
4H
9)
4(Great Wall, Beijing chemical reagent factory) is warming up to MgCl under stirring
2Dissolving is fully got by the sepiolite after the example 1 method calcination process 1.8 gram, joins in the flask, stirs 2 hours having under the situation of backflow, and reactant is reduced to room temperature, adds 6 milliliters of TiCl
4, be warming up to reflux temperature after, continue to stir 2 hours, filtered while hot joins the gained solid in the flask again, adds 20 milliliters of normal heptanes and 3 milliliters of TiCl
4, reaction is 1 hour under reflux temperature, filters, and the gained solid washs 6 times by each 30 milliliters hexane consumption down at 60 ℃, and 60 ℃ of dryings obtain 2.8 gram pulverulent solids catalyst B.It is 2.86 heavy % that inductance coupled plasma atomic emission spectrometry (ICP/AES) is measured in this solid catalyst Ti content, MgCl
2Content is 19.9 heavy %.
Method according to example 1 is carried out vinyl polymerization, obtains polyethylene powders 7.5 grams, and catalyst activity is 240 gram PE/ gram catalyzer.
Example 3
This example is handled MgCl with aluminium diethyl monochloride
2Make solid catalyst with the reaction mixture of sepiolite, and carry out ethylene polymerization.
Get anhydrous MgCl
2Powder 0.8 gram, put into the flask that has reflux exchanger and magneton stirring, after adding 60 milliliters of octanes, slowly splash into 1.8 milliliters of propyl carbinols, stirring also was warming up to 120 ℃ in 2 hours, sepiolite 1.2 grams after the example 1 method calcination process are pressed in adding, and under this temperature, stirred 2 hours, cool the temperature to 60 ℃, the hexane solution that slowly adds the aluminium diethyl monochloride (Beijing Yanshan Petrochemical Company) of 8 milliliter of 1.0 mol is warming up to 120 ℃ and continues to stir filtered while hot 2 hours, the gained solid is joined in the flask again, add 60 milliliters of octanes and 8 milliliters of TiCl
4Reacted 1 hour, and filtered, the gained solid washs 3 times by each 30 milliliters hexane consumption down at 60 ℃, 60 ℃ of dryings, obtain 2.4 gram pulverulent solids catalyzer C, inductance coupled plasma atomic emission spectrometry (ICP/AES) measures that Ti content is 1.60 heavy % in this solid catalyst, MgCl
2Content is 33.02 heavy %.
Method according to example 1 is carried out vinyl polymerization, obtains polyethylene powders 7.8 grams, and catalyst activity is 260 gram PE/ gram catalyzer.
Example 4
This example is handled MgCl with triisobutyl aluminium
2Make solid catalyst with the reaction mixture of sepiolite, and carry out ethylene polymerization.
Method by example 3 prepares solid catalyst, and different is the hexane solution that aluminium diethyl monochloride is changed into the triisobutyl aluminium of 2 milliliter of 3.0 mol, TiCl
4Add-on be 3 milliliters, obtain solid catalyst D2.2 gram, Ti content is 2.13 heavy % among the D, MgCl
2Content is 32.49 heavy %.
Method by example 1 is carried out polyreaction, and catalyst activity is 290 gram PE/ gram catalyzer.
Example 5
This example also adopts triisobutyl aluminium to handle MgCl
2Make solid catalyst with the reaction mixture of sepiolite, and carry out ethylene polymerization.
In example 1 described flask, add 0.6 gram MgCl successively
2, 20 milliliters of normal heptanes, 2 milliliters of Ti (OC
4H
9)
4, be warming up to MgCl under stirring
2Dissolving fully, add sepiolite 1.8 grams, reaction is 2 hours under reflux temperature, separate solidliquid mixture while hot, the hexane solution that in solid phase, adds the triisobutyl aluminium of 30 milliliters of normal heptanes and 6 milliliter of 0.5 mol, reaction is 1 hour under reflux temperature, and solid matter adds 20 milliliters of normal heptanes and 2 milliliters of TiCl after washing once with 20 milliliters of normal heptanes
4, reaction is 2 hours under reflux temperature, and solid washs 3 times by each 30 milliliters hexane consumption down at 60 ℃, and 60 ℃ of dryings get pulverulent solids catalyzer E 2.6 grams, and wherein Ti content is 2.07 heavy %, MgCl
2Content is 20.96 heavy %.
Method by example 1 is carried out vinyl polymerization, and catalyst activity is 120 gram PE/ gram catalyzer.
Example 6
This example prepares solid catalyst with attapulgite, and carries out ethylene polymerization.
To make 20～80 microns bead after the product attapulgite pulverizing of Jiashan, Anhui, and in 160 ℃ of following roastings 6 hours.
In example 1 described flask, add 0.4 gram MgCl
2, 25 milliliters of toluene, 1.2 milliliters of propyl carbinols, be warming up to MgCl under stirring
2Dissolving fully adds above-mentioned attapulgite bead 1.8 grams, and reaction is 2 hours under reflux temperature, cools the temperature to room temperature, adds 8 milliliters of TiCl
4, heat up and be stirred to backflow, and under reflux temperature, reacted 2 hours, the separate solid material and under 60 ℃ with the hexane consumption of 30 milliliters of each consumptions washing 6 times, 60 ℃ of dryings, mobile good pellet catalyst F2.4 gram, wherein Ti content is 12.93 heavy %, MgCl
2Content is 19.4 heavy %.
Method by example 1 is carried out vinyl polymerization, and catalyst activity is 854 gram PE/ gram catalyzer.
Example 7
This example prepares solid catalyst with kaolin, and carries out ethylene polymerization.
The Kang Long of Fujian Nanan is produced kaolin make 10～80 microns bead with the method for spray shaping.
In the flask of band stirring and reflux exchanger, add 0.6 gram MgCl
2, 30 milliliters of n-decanes, 1.8 milliliters of propyl carbinols, be warming up to MgCl under stirring
2Dissolving fully adds above-mentioned kaolin bead 1.3 grams, and reaction is 1 hour under reflux temperature, and separating solid substances also adds 30 milliliters of n-decanes and 12 milliliters of TiCl
4, stirring heats up down and 120 ℃ of reactions 2 hours, the separate solid material also added 30 milliliters of n-decanes and 6 milliliters of TiCl
4, 120 ℃ of reactions 2 hours, the gained solid matter is by each 30 milliliters hexane consumption washing 6 times, 60 ℃ of dryings, mobile good pellet catalyst G 2.0 grams, wherein Ti content is 3.68 heavy %, MgCl
2Content is 30.3 heavy %.
Method by example 1 is carried out vinyl polymerization, and catalyst activity is 244 gram PE/ gram catalyzer.
Example 8
Adopt the method for example 1 to prepare solid catalyst and carry out ethylene polymerization, different is to replace sepiolite with montmorillonite (Black Hills, Liaoning product), makes solid catalyst H2.1 gram, and wherein Ti content is 3.52 heavy %, MgCl
2Content is 28.3 heavy %, and catalyst activity is 360 gram PE/ gram catalyzer.
Example 9
This example prepares solid catalyst with attapulgite, and carries out the copolymerization of ethene-hexene.
Method according to example 6 prepares solid catalyst, and the consumption of different is attapulgite is 1.0 grams, and and MgCl
2The solution reaction after-filtration, add 40 milliliters of octanes and 8 milliliters of TiCl in the solid phase
4, 120 ℃ were reacted 2 hours, and added 30 milliliters of octanes and 4 milliliters of TiCl in the gained solid phase again
4, 120 ℃ of reactions 1 hour, solid is by each 30 milliliters hexane consumption washing 6 times, after the drying, mobile good spherical catalyst K1.9 gram, wherein Ti content is 4.71 heavy %, MgCl
2Content is 15.3 heavy %.
With 500 milliliters of there-necked flask N that agitator and constant temperature system are housed
2Pump drainage displacement three times, again once, add 10 milliliters of hexenes earlier, add 30 milligrams of the hexane solution of triisobutyl aluminium of 100 milliliters of hexanes, 2 milliliter of 1.5 mol and solid catalyst K more successively with ethene displacement, start stirring, feed ethylene gas, reaction is 2 hours under 40 ℃, 0.1MPa condition, uses 2 milliliters of ethanol termination reactions then, obtain exsiccant polyethylene powders 23 grams, the catalyst activity that calculates is 760 gram PE/ gram catalyzer, and the fusing point of multipolymer is 126 ℃, adopts C
13The content that-NMR records hexene in the multipolymer is 2.1 moles of %.
Example 10
This example carries out the pressure polymerization of ethene with solid catalyst provided by the invention.
With the withstand voltage still N of 1 liter glass
2Purge 3 times, purge once with ethene again, add the hexane solution of triisobutyl aluminium of 400 milliliters of hexanes, 5 milliliter of 1.3 mol and the solid catalyst C60 milligram of example 3 preparations successively, feed ethene to still pressure and be 0.7MPa, 70 ℃ of reactions 2 hours, obtain 288 gram polyethylene, catalyst activity is 4800 gram PE/ gram catalyzer.
Example 11
This examples preparation contains the solid catalyst of o-benzene butyl phthalate ester, and carries out propylene polymerization.
In flask, add MgCl
2Powder 1.0 grams, 20 milliliters of n-decanes, 3.3 milliliters of propyl carbinols are warming up to MgCl
2All dissolvings add 1.0 gram sepiolites, and 120 ℃ were reacted 2 hours, system temperature were reduced to-10 ℃, added 10 milliliters of TiCl
4, slowly be warming up to 60 ℃, add 0.36 milliliter of o-benzene butyl phthalate ester (Beijing chemical reagent factory), continue to be warming up to 120 ℃ after, react 2 hours after-filtration, in solid phase, add 20 milliliters of n-decanes, 8 milliliters of TiCl again
4, continuing to react 2 hours at 120 ℃, the gained solid phase is washed 6 times by each 30 milliliters hexane consumption down at 60 ℃, and 60 ℃ are dry that solid catalyst L2.4 restrains, and wherein Ti content is 3.11 heavy %, MgCl
2Content is 13.8 heavy %.
With 500 milliliters of there-necked flask N that agitator and constant temperature system are housed
2Pump drainage displacement three times, again once with the propylene displacement, add 40 milligrams of 3 milliliters of the dimethoxydiphenylsilanes of hexane solution, 0.1 mol of the triisobutyl aluminium of 100 milliliters of hexanes, 6 milliliter of 1.5 mol and solid catalyst L successively, start stirring, feed propylene gas, reaction is 2 hours under 40 ℃, 0.1MPa condition, use 2 milliliters of ethanol termination reactions then, obtain exsiccant polypropylene powder 2.6 grams, catalyst activity is 64 gram PP/ gram catalyzer, and measuring the polypropylene degree of isotacticity with the boiling n-heptane extraction process is 95.3%.
Example 12
Method with example 11 prepares solid catalyst, and different is with 0.2 milliliter 2,2-diisobutyl-1, and the 3-Propanal dimethyl acetal replaces o-benzene butyl phthalate ester, and Ti content is 2.64 heavy % in the gained solid catalyst, MgCl
2Content is 6.7 heavy %.
Method by example 11 is carried out propylene polymerization, but does not add dimethoxydiphenylsilane in the polymerization process, gets polypropylene 5.6 grams, and catalyst activity is 140 gram PP/ gram catalyzer, and the polypropylene degree of isotacticity is 94.8%.
Claims (18)
1, a kind of olefin polymerization solid catalyst comprises clay, magnesium halide and transistion metal compound, and wherein the content of magnesium halide is 5.0～50.0 heavy %, and the content of transition metal is 0.2～20.0 heavy %, and described clay is fiber rod stone kind clay or kaolinite.
2,, it is characterized in that described magnesium halide is a magnesium chloride according to the described catalyzer of claim 1.
3,, it is characterized in that described transistion metal compound is selected from the halogenide of one of Ti, Zr, Hf, V, Nb, Ta, Ni and Sc, oxyhalogenation thing, C according to the described catalyzer of claim 1
1～C
12Alcoxyl halogenide or hydrohalogen.
4,, it is characterized in that described transistion metal compound is halogenide, oxyhalogenation thing, the C of titanium according to the described catalyzer of claim 3
1～C
12Alcoxyl halogenide or hydrohalogen.
5,, it is characterized in that described transistion metal compound is TiCl according to the described catalyzer of claim 4
4
6, the described catalyzer of claim 1 wherein also comprises the internal electron donor compound, and the mol ratio of internal electron donor compound and magnesium is 1: 4～14, and described internal electron donor is the ester of general formula (I) or the ether of general formula (II),
General formula (I) and (II) in, R
1～R
4Be C
1～C
18Alkyl, C
3～C
18Cycloalkyl, C
6～C
18Aryl, aralkyl or alkaryl.
7,, it is characterized in that the ester of formula (I) is selected from phthalic acid di-n-butyl ester, o-benzene butyl phthalate ester or phthalic acid di-n-octyl ester according to the described catalyzer of claim 6.
8,, it is characterized in that R in the general formula (II) according to the described catalyzer of claim 6
1, R
2Be C
1～C
6Alkyl, R
3, R
4Be methyl.
9, according to the described catalyzer of claim 8, the compound that it is characterized in that general formula (II) is 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-methyl-2-isobutyl--1,3-Propanal dimethyl acetal or 2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal.
10, the described Preparation of catalysts method of a kind of claim 1 comprises:
(1) in the presence of unreactive hydrocarbons solvent, is dissolved in magnesium halide in the polar organic solvent or makes it and Ti (OR)
4Form MgX
2NTi (OR)
4Title complex, Ti (OR) wherein
4In R be C
2～C
8Alkyl, C
3～C
8Cycloalkyl or C
6～C
8Aryl, n is 1～3,
(2) be that the clay of 1～20 times of magnesium halide is suspended in and reacted in the above-mentioned solution 0.5～6.0 hour with weight,
(3) add transistion metal compound, the mol ratio of transition metal and magnesium is 3～30,60～135 ℃ of reactions down, collects solid matter.
11, in accordance with the method for claim 10, it is characterized in that adding alkylaluminium cpd in the mixture of (2) step reaction, its mol ratio with magnesium halide is 2～20, and then carries out for (3) step and react.
12, in accordance with the method for claim 11, it is characterized in that alkylaluminium cpd is selected from triisobutyl aluminium, triethyl aluminum or aluminium diethyl monochloride.
13,, it is characterized in that described transistion metal compound is halogenide, oxyhalogenation thing, the C of one of Ti, Zr, Hf, V, Nb, Ta, Ni and Sc according to claim 10 or 11 described methods
1～C
12Alcoxyl halogenide or hydrohalogen.
14, in accordance with the method for claim 13, it is characterized in that described transistion metal compound is halogenide, oxyhalogenation thing, the C of titanium
1～C
12Alcoxyl halogenide or hydrohalogen.
15, in accordance with the method for claim 14, the halogenide that it is characterized in that described titanium is TiCl
4
16,, it is characterized in that described unreactive hydrocarbons solvent is C according to claim 10 or 11 described methods
6～C
10Alkane or C
6～C
8Aromatic hydrocarbons.
17,, it is characterized in that organic solvent is C in described (1) step according to claim 10 or 11 described methods
2～C
8Fatty Alcohol(C12-C14 and C12-C18), Ti (OR)
4Middle R is C
2～C
8Alkyl.
18,, it is characterized in that at the ester of (3) step back adding formulas (I) or the ether of formula (II) its amount is 0.1～0.5 times of the magnesium halide molar weight according to claim 10 or 11 described methods.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991003608A CN1152063C (en) | 1999-01-25 | 1999-01-25 | Solid catalyst for polymerization of olefin and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991003608A CN1152063C (en) | 1999-01-25 | 1999-01-25 | Solid catalyst for polymerization of olefin and its preparing process |
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| Publication Number | Publication Date |
|---|---|
| CN1262282A CN1262282A (en) | 2000-08-09 |
| CN1152063C true CN1152063C (en) | 2004-06-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB991003608A Expired - Fee Related CN1152063C (en) | 1999-01-25 | 1999-01-25 | Solid catalyst for polymerization of olefin and its preparing process |
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| CN105732854A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of catalyst for preparing polyethylene/kaolin composite material |
| CN112225631B (en) * | 2020-09-10 | 2023-03-31 | 江苏飞亚化学工业有限责任公司 | Novel catalytic process for alkylation of arylamine aromatic hydrocarbon |
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