CN1990509A - Loading type bimetal polyethylene catalyst and its preparation method - Google Patents
Loading type bimetal polyethylene catalyst and its preparation method Download PDFInfo
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- CN1990509A CN1990509A CN 200510135559 CN200510135559A CN1990509A CN 1990509 A CN1990509 A CN 1990509A CN 200510135559 CN200510135559 CN 200510135559 CN 200510135559 A CN200510135559 A CN 200510135559A CN 1990509 A CN1990509 A CN 1990509A
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Abstract
The invention discloses a supported-type bimetallic polyethylene catalyst, comprising following components that are loaded on hexahydrated magnesium chloride- silicon dioxide: (1) Z- N active component with its expression being Ti(OR)nX4-n, 0<n<=2, X is halegon, R is alkyl of C5- C10; (2) non-metallocene active component with its expression being LmZrX4- m, X is halegon, m equals to 1 or 2, L is group that removes hydrogen from formula (I) or (II); (3) organic aluminum compound. The proportion by weight of titanium in said catalyst is 3.0- 7.0, zirconium is 0.1- 3.0, magnesium is 1.0- 6.0, and aluminum is 1.0- 12.0 %. The method comprises: preparing Z-N active component loaded on the silicon dioxide first, then carrying out reaction between said active component and non-metallocene in aromatics. Said bimetallic catalyst is combined with assistant catalyst and used for ethylene polymerization. The produced ethylene possesses wide molecular weight distribution.
Description
Technical field
The present invention is a kind of load type bimetallic polyethylene catalyst and preparation method thereof, specifically, is bimetal polyethylene catalyst of a kind of load Ziegler-Natta type active ingredient and non-luxuriant active ingredient and preparation method thereof.
Background technology
Wide distribution polyethylene is one of important development field of polyethylene technology in recent years.Different with common polythene material, wide distribution polyethylene not only can keep mechanical property, hardness and the environmental stress cracking resistance of High molecular weight polyethylene, and can improve poly processing characteristics.The molecular weight distribution broad of this base polymer does not occur significantly bimodal.Preparation method wide or bimodal polyethylene resins has three kinds of methods at present: adopt bimetal or many metal active constituents catalyst system in melt blending method, step reaction method and the single reaction vessel.Consider that from the angle of polymerization technique and polymer performance adopting bimetal or many metal active constituents catalyst system in the single reaction vessel is comparatively desirable and feasible method.
CN1009647B discloses a kind of poly preparation method of middle molecular weight distribution, and this method adopts Ti, V bimetal site catalyst system, contains multiple properties-correcting agent in the system, and the poly melt-flow that makes is 40～70 than (MFR).
CN1138589A discloses a kind of composite catalyst system that is used for olefinic polymerization, wherein the composite catalyst system comprises magnesium halide, metallocene compound, non-cyclopentadinyl compound, organo phosphorous compounds or organic epoxy compounds, described non-cyclopentadinyl compound is the halogenide of the transition metal of 3,4,6 subgroups in the periodic table of elements, is mainly titanium tetrachloride.Its preparation method be with magnesium halide with after the organism dissolving, add metallocene compound, cooling is separated out the solid magnesium chloride again, metallocene compound promptly is carried on the magnesium chloride, and then titanium tetrachloride is carried on carrier makes composite catalyst.Its organo phosphorous compounds that is used to dissolve magnesium chloride is a phosphoric acid fat, and organic epoxy compounds is an epoxy chloropropane, thereby the inactive ingredients that contains in the catalyzer of its preparation is more.
A kind of solid catalyst that is used for olefinic polymerization is disclosed among the EP447071A1, this catalyzer is that 10～100 microns spheroidal particle is formed by median size, comprise the halogenide and the selectable organo-aluminium compound of the not hydrogenous organic electron donor compound of magnesium dichloride, 0.1～10mol%, zirconium cyclopentadinyl compound, at least a titanium or the vanadium of 90～99.9mol%, be preferably aikyiaiurnirsoxan beta.This catalyzer is that the halogenide with zirconium cyclopentadinyl compound, titanium or vanadium is carried on the magnesium dichloride carrier and makes catalyzer, when it is used for vinyl polymerization, can obtain the polymkeric substance of better particle form.But the M of the polyethylene product that this catalyzer makes
W/ M
nStill narrower, only be 5.1.
After the metallocene catalyst, the non-cyclopentadinyl compound that contains coordination heteroatom ligands such as aerobic, nitrogen in the another kind of conjugated system more and more causes people's attention and concern in the application aspect polyolefine, the especially polyethylene catalysts.The kind of non-cyclopentadinyl compound is more, thereby has opened up source more widely for polyolefin catalyst, makes its synthesis material more diversified.
Though it is wide slightly than metallocene synthetic polyethylene that non cyclopentadienyl catalyst synthetic molecular weight of polyethylene distributes, but still narrower, processing is still difficult.Therefore, how to widen the important topic that non-luxuriant poly molecular weight distribution still is non cyclopentadienyl catalyst research.
Summary of the invention
The purpose of this invention is to provide a kind of load type bimetallic polyethylene catalyst and preparation method thereof, this catalyzer contains Ziegler-Natta type and non-luxuriant two kinds of active ingredients, is used for ethylene polymerization and can obtains polyethylene than wide molecular weight distribution.
Load type bimetallic polyethylene catalyst provided by the invention comprises the following component that is carried on magnesium chloride-silica supports:
(1) expression formula is Ti (OR)
nX
4-nZ-N type active ingredient, 0＜n in the formula≤2, X is a halogen, R is C
5～C
10Alkyl;
(2) expression formula is L
mZrX
4-mNon-luxuriant active ingredient, X is a halogen in the formula, m is 1 or 2, L is that formula (I) or part (II) remove the group that forms behind the hydrogen proton, described formula (I) and (II) in, R
1For being selected from hydrogen or C
1～C
6The substituting group of alkyl, its number are 1～4, R
2Be selected from hydrogen or C
1～C
3Alkyl, R
3For being selected from hydrogen or C
1～C
6The substituting group of alkyl, its number are 1～5,
(3) organo-aluminium compound;
In the described catalyzer, titanium content is 3.0～7.0 quality %, and zirconium content is 0.1～3.0 quality %, and Mg content is 1～6 quality %, and aluminium content is 1～12 quality %.
Catalyzer of the present invention adopts in-situ synthesis to prepare Ziegler-Natta (Z-N) the type active ingredient that is carried on the silica supports, and the magnesium chloride of Sheng Chenging also is deposited on the silicon-dioxide simultaneously.In above-mentioned loading type Z-N active ingredient, introduce non-luxuriant active ingredient again and promptly make catalyzer.Described two kinds of active ingredients and carrier interact, produce organically combination, make catalyzer of the present invention be used for ethylene polymerization, not only have advantages of high catalytic activity, and the polyethylene product that makes has wider molecular weight distribution, improved the processing characteristics of polyethylene product.
Embodiment
The present invention forms magnesium chloride in the load Z-N type active ingredient on silica supports, and then non-luxuriant active ingredient is incorporated in the carrier of above-mentioned load Z-N type active ingredient and makes catalyzer.
Described formula (I) and (II) in, R
1For pyrrole ring or with phenyl ring that pyrrole ring links to each other on substituting group, its number can be one or more, preferred R
1Be single substituent part, R
1Preferred hydrogen or C
1～C
3Alkyl.Described R
2Preferred hydrogen or methyl, R
3For with phenyl ring that nitrogen-atoms links to each other on substituting group, its number can be one or more, R
3Preferred hydrogen or C
1～C
3Alkyl, replace number preferred 1～3.
Described organo-aluminium compound preferred alkyl aluminium or alkylaluminoxane.The preferred triethyl aluminum of described aluminum alkyls, triisobutyl aluminium, triisopropylaluminiuand or their mixture, described alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta.
Described expression formula is Ti (OR)
nX
4-nZ-N type active ingredient in, the preferred C of R
7～C
9The isomery alkyl.Titanium content is 6.0～8.0 quality % in the Z-N active ingredient of load, and Mg content is 2.0～5.0 quality %.
Preferred 4.0～6.0 quality % of titanium content in the catalyzer of the present invention, preferred 0.3～2.0 quality % of zirconium content, preferred 1.0～3.0 quality % of Mg content, preferred 3.0～8.0 quality % of aluminium content.
Preparation of catalysts method of the present invention is included in the aromatic solvent, and adding the expression formula that is carried on magnesium chloride-silica supports is Ti (OR)
nX
4-nZ-N type active ingredient and the organo-aluminium compound thorough mixing after, add described non-luxuriant active ingredient again and fully react, filter, drying formula Ti (OR) then
nX
4-nIn, 0＜n≤2, X is a halogen, preferred chlorine, R is C
5～C
10Alkyl, preferred C
7～C
9The isomery alkyl.
Aforesaid method earlier mixes the Z-N type active ingredient of load and organic aluminide making its activation, and then adds non-luxuriant active ingredient and fully react, with non-luxuriant active constituent loading on carrier.Above-mentioned load process is carried out in aromatic solvent, the preferred C of described aromatic hydrocarbons
7～C
10Alkane aromatic hydrocarbons, more preferably toluene.Described organo-aluminium compound preferred alkyl aluminium or alkylaluminoxane, preferred aluminum alkyls is triethyl aluminum, triisobutyl aluminium, triisopropylaluminiuand or their mixture, preferred alkylaluminoxane is a methylaluminoxane.
Preferred 30～50 ℃ of temperature of reaction after the non-luxuriant active ingredient of described adding, the suitable reaction times is 0.1～4 hour.Added aromatic hydrocarbons is 10～20 times of solid masses during reaction, and the mol ratio of zirconium is 1～60: 1 in the middle Ti of the load Z-N type active ingredient of adding and the non-luxuriant active ingredient, preferred 4.0～20: 1.
The preparation method of the Z-N type active ingredient of described load comprises the steps:
(1) among " MgR ' dialkyl magnesium reaction form the silicon-dioxide of load dialkyl magnesium, the R " MgR ' that in the presence of the stable hydrocarbon medium, makes silicon-dioxide and formula R, " and R ' is selected from C respectively to R
2～C
12Alkyl, the consumption of described dialkyl magnesium is every gram silicon-dioxide 0.5～2.5 mmole;
(2) silicon-dioxide of above-mentioned load dialkyl magnesium and the alkylol cpd of ROH are fully reacted, described ROH is C
5～C
10Fatty Alcohol(C12-C14 and C12-C18), described alcohol and R " MgR ' mol ratio be 0.90～1.3: 1;
(3) make the product and the TiX of step (2)
4Fully reaction, used TiX
4With R " MgR ' mol ratio be 1.2～3.0: 1, reaction after-filtration, drying, described formula TiX
4In, X is a halogen.
Aforesaid method (1) step, described stable hydrocarbon was selected from C
6～C
10Alkane, preferred hexane, heptane or octane.Dialkyl magnesium R " MgR ' in alkyl R " and the preferred C of R ' difference
2～C
6Alkyl, more preferably dibutylmagnesium.(2) the preferred C of alcohol roh described in the step
7～C
9The isomery Fatty Alcohol(C12-C14 and C12-C18), as iso-heptanol, isooctyl alcohol or isodecyl alcohol.(3) used TiX of step
4Preferred TiCl
4Each goes on foot temperature of reaction is 30～100 ℃, preferred 40～65 ℃.
Non-luxuriant active ingredient adopts the preparation of following method in the described catalyzer: in the presence of tetrahydrofuran (THF), make the ligand compound of formula (I) or formula (II) and sodium hydride mol ratio such as press and fully react, temperature of reaction is 15～40 ℃, adds ZrX then
4, make ZrX
4With the mol ratio of formula (I) or formula (II) part be 1: 1～2,30～60 ℃ of fully reactions, filter then, with get final product after solids wash, the drying non-luxuriant active ingredient.Described formula ZrX
4In, X is a halogen, preferred chlorine.
The preparation method of ligand compound described in the aforesaid method is: in the presence of Fatty Alcohol(C12-C14 and C12-C18), make pyrrole aldehyde derivative or benzopyrrole formaldehyde derivatives and anils, mol ratio fully reaction under reflux temperature such as press in the presence of organic acid catalyst.Reactant is cooled to separates out a large amount of crystal after-filtration, with gained solid thorough washing get final product the ligand compound of formula (I) or formula (II).Described pure preferred alcohol, the preferred acetate of organic acid.
Catalyzer of the present invention be applicable to ethene homopolymerization or with the copolyreaction of other alpha-olefin, be Primary Catalysts with catalyzer of the present invention during reaction, with aluminum alkyls or alkylaluminoxane is promotor, at 10～100 ℃, preferred 30～80 ℃, carry out ethylene polymerization under the condition of 0.1～1.0MPa.
In the described promotor, the preferred triethyl aluminum of aluminum alkyls, triisobutyl aluminium, triisopropylaluminiuand or their mixture.Alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta.The mol ratio of transition metal in Al during polyreaction in the promotor and the Primary Catalysts (Ti+Zr) is 20～1500: 1, preferred 20～500: 1.
Below by example in detail the present invention, but the present invention is not limited to this.
The measuring method of alkoxy group content is in the Z-N active ingredient of load described in the example: the Z-N active ingredient of getting 0.1 gram load, place 20 milliliters of acetone solvents, adding 1.0 ml concns is the HCl aqueous solution of 10 quality %, makes alkoxyl group wherein be converted into alcohol.After jolting strongly, get upper strata acetone clear liquid in 50 milliliters of volumetric flasks, with acetone diluted to the scale with liquid-phase chromatographic analysis pure content wherein, can obtain the content of alkoxyl group in the Z-N active ingredient of load.
Example 1
Prepare load type bimetal catalyst of the present invention.
(1) the Z-N type active ingredient a of preparation load
Get 16 gram silica gel, add 150 milliliters of normal heptanes, be heated to 55 ℃, add 23 milliliters of (23 mmole) dibutylmagnesiums, solution becomes canescence, and reaction is 1 hour under this temperature, adds 3.4 milliliters of (21.85 mmole) isooctyl alcohol, continue stirring reaction 1 hour, and added 4.4 milliliters of (40 mmole) TiCl
4, solution becomes light coffee color, reacts 3 hours, filters under nitrogen protection, and solid is with hexane wash three times, and 25 ℃ of drying under reduced pressure 3 hours obtain being carried on and consist of Ti (iC on magnesium chloride-silica supports
8H
17O)
0.66Cl
3.48Z-N type active ingredient a, wherein titanium content is 6.62 quality %, Mg content is 3.34 quality %, cl content is 17.01 quality %.
(2) preparation two (pyrrole aldehyde anil) zirconium dichloride
2 milliliters of (19.11 mmole) pyrrole aldehydes and 1.7 milliliters of (19.11 mmole) aniline are added in the there-necked flask of band return lines, add 10 milliliters of ethanol, and drip several Glacial acetic acid, 60 ℃ of back flow reaction 3 hours, color is from the light yellow dark-brown that becomes.Be cooled to-5 ℃ and produce a large amount of crystal, filter, with solids hexane wash 3 times, obtain 2.86 gram pyrrole aldehyde anils, yield is 78 quality %.
In the there-necked flask of the band return line of nitrogen protection, add 2 gram (10.0 mmole) pyrrole aldehyde anils and 0.24 gram (10.0 mmole) sodium hydride, 25 ℃ of reactions are 1 hour in 30 milliliters of tetrahydrofuran (THF) media.Add 1.21 gram (5.07 mmole) ZrCl
4, be warming up to 50 ℃ of reactions 3 hours.Filter under the nitrogen protection, solid hexane wash 3 times, drying is 3 hours under 25 ℃ of decompressions, gets 2.36 gram two (pyrrole aldehyde anil) zirconium dichlorides.Results of elemental analyses is: C:52.31 quality % (52.79 quality %), N:3.68 quality % (3.62 quality %) is a calculated value in the H:5.53 quality % (5.60 quality %), bracket, down together.
(3) preparation load type bimetal catalyst
In 250 milliliters of there-necked flasks that nitrogen replacement is crossed, add 30 milliliters of toluene; the Z-N type active ingredient a of 2 gram loads and the toluene solution of the methylaluminoxane (MAO) that 8.0 ml aluminium concentration are 1.55M stir; two (pyrrole aldehyde anil) zirconium dichloride that adds 0.2 gram again; 25 ℃ were reacted 15 minutes; 45 ℃ were reacted 3 hours, filtered solid hexane wash 3 times under nitrogen protection; drying is 5 hours under 25 ℃ of decompressions, gets the light yellow catalyst A of 2.15 grams.Plasma emission spectrum (ICP) method records that titanium content is 5.15 quality % in the catalyst A, and zirconium content is 1.19 quality %, and Mg content is 1.26 quality %.Aluminium content is 7.32 quality %.
Example 2
Method by example 1 prepares load type bimetal catalyst B, different is that the add-on of MAO solution was 4.0 milliliters during (3) went on foot, get the light yellow catalyst B of 2.1 grams behind the drying under reduced pressure, wherein titanium content is 5.1 quality %, zirconium content is 1.24 quality %, Mg content is 1.65 quality %, and aluminium content is 5.15 quality %.
Example 3
Method by example 1 prepares load type bimetal catalyst C, be that the hexane solution replacement MAO solution of the triethyl aluminum of 0.8M reacts with 3.0 ml aluminium content in different is (3) step, get 2.32 gram yellow catalyst C behind the drying under reduced pressure, wherein titanium content is 5.79 quality %, zirconium content is 1.59 quality %, Mg content is 1.68 quality %, and aluminium content is 4.12 quality %.
Example 4
Method by example 1 prepares load type bimetal catalyst D, be that the hexane solution replacement MAO solution of the triethyl aluminum of 0.8M reacts with 1.5 ml aluminium content in different is (3) step, get 2.12 gram yellow catalyst D behind the drying under reduced pressure, wherein titanium content is 5.86 quality %, zirconium content is 1.64 quality %, Mg content is 1.58 quality %, and aluminium content is 3.02 quality %.
Example 5
Method by example 1 prepares load type bimetal catalyst E, different is that two (pyrrole aldehyde anil) zirconium dichloride that adds in (3) step is 0.1 gram, get the light yellow catalyzer E of 2.13 grams behind the drying under reduced pressure, wherein titanium content is 5.28 quality %, zirconium content is 0.76 quality %, Mg content is 1.72 quality %, and aluminium content is 8.29 quality %.
Example 6
Method by example 1 prepares load type bimetal catalyst F, different is that two (pyrrole aldehyde anil) zirconium dichloride that adds in (3) step is 0.1 gram, the add-on of MAO solution is 4.0 milliliters, get the light yellow catalyzer F of 2.05 grams behind the drying under reduced pressure, wherein titanium content is 5.13 quality %, zirconium content is 1.08 quality %, and Mg content is 1.58 quality %, and aluminium content is 5.35 quality %.
Example 7
Method by example 1 prepares load type bimetal catalyst G, different is that two (pyrrole aldehyde anil) zirconium dichloride that adds in (3) step is 0.1 gram, and replace MAO solution to react with the hexane solution of the triethyl aluminum of 3.0 ml aluminium content 0.8M, get 2.32 gram yellow catalyst G behind the drying under reduced pressure, wherein titanium content is 5.58 quality %, zirconium content is 0.68 quality %, and Mg content is 1.72 quality %, and aluminium content is 4.23 quality %.
Example 8
Method by example 1 prepares load type bimetal catalyst H, different is that two (pyrrole aldehyde anil) zirconium dichloride that adds in (3) step is 0.1 gram, and replace MAO solution to react with the hexane solution of the triethyl aluminum of 1.5 ml aluminium content 0.8M, get 2.12 gram yellow catalyst H behind the drying under reduced pressure, wherein titanium content is 5.86 quality %, zirconium content is 1.04 quality %, and Mg content is 1.58 quality %, and aluminium content is 3.02 quality %.
Example 9
Method by example 1 prepares load type bimetal catalyst I, different is that two (pyrrole aldehyde anil) zirconium dichloride that adds in (3) step is 0.05 gram, get the light yellow catalyst I of 2.03 grams behind the drying under reduced pressure, wherein titanium content is 5.66 quality %, zirconium content is 0.31 quality %, Mg content is 1.82 quality %, and aluminium content is 7.49 quality %.
Example 10
Method by example 1 prepares load type bimetal catalyst J, different is that two (pyrrole aldehyde anil) zirconium dichloride that adds in (3) step is 0.4 gram, get the light yellow catalyzer J of 2.43 grams behind the drying under reduced pressure, wherein titanium content is 4.76 quality %, zirconium content is 2.18 quality %, Mg content is 1.82 quality %, and aluminium content is 7.59 quality %.
Example 11
Method by example 1 prepares load type bimetal catalyst K, different is that two (pyrrole aldehyde anil) zirconium dichloride that adds in (3) step is 0.05 gram, and replace MAO solution to react with the hexane solution of 3.0 ml aluminium content 0.8M triethyl aluminums, get the light yellow catalyzer K of 2.03 grams behind the drying under reduced pressure, wherein titanium content is 5.78 quality %, zirconium content is 0.38 quality %, and Mg content is 1.82 quality %, and aluminium content is 7.29 quality %.
Example 12
Method by example 1 prepares load type bimetal catalyst L, different is that two (pyrrole aldehyde anil) zirconium dichloride that adds in (3) step is 0.4 gram, and replace MAO solution to react with the hexane solution of 3.0 ml aluminium content 0.8M triethyl aluminums, get the light yellow catalyzer L of 2.03 grams behind the drying under reduced pressure, wherein titanium content is 5.23 quality %, zirconium content is 2.36 quality %, and Mg content is 1.82 quality %, and aluminium content is 7.09 quality %.
Example 13
(1) preparation non-luxuriant active ingredient two (pyrrole aldehyde contracts 2, the 4-xylidine) zirconium dichloride
With 2 of the pyrrole aldehyde of 2 milliliters (19.11 mmoles) and 1.9 milliliters (19.11 mmoles), the 4-xylidine joins in the there-necked flask of band return line, adds 10 milliliters of ethanol, and drips several Glacial acetic acid, 60 ℃ of back flow reaction 3 hours, color is from the light yellow dark-brown that becomes.Be cooled to-5 ℃ and produce a large amount of crystal, filter, with solids hexane wash 3 times, obtain 2.76 gram pyrrole aldehydes and contract 2,4-xylidine, yield are 76 quality %.
In the there-necked flask of the band return line of nitrogen protection, add 2.0 gram (8.88 mmole) pyrrole aldehydes and contract 2,4-xylidine and 0.213 gram (8.88 mmole) sodium hydride, 25 ℃ of reactions are 1 hour in 30 milliliters of tetrahydrofuran (THF) media.Add 1.04 gram (4.44 mmole) ZrCl
4, be warming up to 50 ℃ of reactions 3 hours.Filter under the nitrogen protection, solid hexane wash 3 times, drying is 3 hours under 25 ℃ of decompressions, gets 2.70 gram two (pyrrole aldehyde contracts 2, the 4-xylidine) zirconium dichlorides.Results of elemental analyses is: C:55.96 quality % (56.10 quality %), N:4.78 quality % (4.70 quality %), H:4.96 quality % (5.03 quality %).
(2) preparation load type bimetal catalyst
Method by 1 (3) step of example prepares load type bimetal catalyst M, different is add 0.2 gram (0.328 mmole) two (pyrrole aldehyde contracts 2, the 4-xylidine) zirconium dichloride reacts, get the light yellow catalyzer M of 2.21 grams behind the drying under reduced pressure, wherein titanium content is 5.25 quality %, zirconium content is 1.28 quality %, and Mg content is 2.64 quality %, and aluminium content is 8.27 quality %.
Example 14
(1) preparation non-luxuriant active ingredient two (pyrrole aldehyde contracts 2, the 6-diisopropyl aniline) zirconium dichloride
With 2 of the pyrrole aldehyde of 2 milliliters (19.11 mmoles) and 1.9 milliliters (19.11 mmoles), the 6-diisopropyl aniline joins in the there-necked flask of band return line, adds 10 milliliters of ethanol, and drips several Glacial acetic acid, 60 ℃ of back flow reaction 3 hours, color is from the light yellow dark-brown that becomes.Be cooled to-5 ℃ and produce a large amount of crystal, filter, with solids hexane wash 3 times, obtain 2.76 gram pyrrole aldehydes and contract 2,6-diisopropyl aniline, yield are 76 quality %.
In the there-necked flask of the band return line of nitrogen protection, add 2.25 gram (8.88 mmole) pyrrole aldehydes and contract 2,6-diisopropyl aniline and 0.213 gram (8.88 mmole) sodium hydride, 25 ℃ of reactions are 1 hour in 30 milliliters of tetrahydrofuran (THF) media.Add 1.04 gram (4.44 mmole) ZrCl
4, be warming up to 50 ℃ of reactions 3 hours.Filter under the nitrogen protection, solid hexane wash 3 times, drying is 3 hours under 25 ℃ of decompressions, gets 2.70 gram two (pyrrole aldehyde contracts 2, the 6-diisopropyl aniline) zirconium dichlorides.Results of elemental analyses is: C:60.95 quality % (61.05 quality %), N:4.06 quality % (4.19 quality %), H:6.41 quality % (6.33 quality %).
(2) preparation load type bimetal catalyst
Method by 1 (3) step of example prepares load type bimetal catalyst N, different is add 0.2 gram (0.15 mmole) two (pyrrole aldehyde contracts 2, the 6-diisopropyl aniline) zirconium dichloride reacts, get the light yellow catalyst n of 2.35 grams behind the drying under reduced pressure, wherein titanium content is 5.36 quality %, zirconium content is 1.09 quality %, and Mg content is 2.64 quality %, and aluminium content is 7.95 quality %.
Example 15
(1) the Z-N type active ingredient b of preparation load
Prepare active ingredient b by 1 (1) step of example and method, different is that the dibutylmagnesium consumption is 28 milliliters (28 mmoles), and the isooctyl alcohol consumption is 5.2 milliliters (33.6 mmoles), obtains being carried on consisting of Ti (iC on magnesium chloride-silica supports
8H
17O)
0.78Cl
3.12Z-N type active ingredient b, wherein titanium content is 6.71 quality %.Mg content is 3.86 quality %, and cl content is 17.35 quality %.
(2) preparation load type bimetal catalyst
Method by 1 (3) step of example prepares load type bimetal catalyst, different is to replace Z-N type active ingredient a with Z-N type active ingredient b, get the light yellow catalyzer O of 2.52 grams, wherein titanium content is 4.65 quality %, zirconium content is 1.29 quality %, Mg content is 1.12 quality %, and aluminium content is 7.02 quality %.
Example 16
Method by 1 (3) step of example prepares load type bimetal catalyst P, the different Z-N type active ingredient b that are to use replace Z-N type active ingredient a, get 2.62 gram yellow catalyst P, wherein titanium content is 4.72 quality %, zirconium content is 1.64 quality %, Mg content is 1.48 quality %, and aluminium content is 3.85 quality %.
Example 17～32
Following example carries out the high-pressure ethylene homopolymerization with catalyzer of the present invention.
In 1 liter of stainless steel autoclave, feed ethene, keep-uping pressure is 0.8MPa, adds promotor triethyl aluminum (TEA), adds by 0.1 gram catalyzer and 300 milliliters of solution that hexane is made into again, making Al/ (Ti+Zr) mol ratio is 150.80 ℃, hydrogen dividing potential drop are polyreaction 1 hour under the condition of 0.2MPa, use the HCl termination reaction, obtain polyethylene product.The character of the polyethylene product of each example catalyst system therefor, promotor, catalyst activity and generation sees Table 1.High load melt index (I in the table 1
21.6) and underload melt index (I
2.16) measure according to ASTM-D-1238, the molecular weight of polymkeric substance and molecular weight distribution adopt gel permeation chromatography.
Table 1
| Instance number | The catalyzer numbering | Catalytic activity | I 21.6/I 2.16 | Mw ×10 -4 | Mw/Mn | |
| ×10 -5， gPE/mol(Ti+ Zr)·hr | Gram PE/ gram catalyzer | |||||
| 17 | A | 8.65 | 1028 | 51.01 | 27.56 | 9.76 |
| 18 | B | 8.05 | 878 | 56.67 | 29.61 | 10.25 |
| 19 | C | 9.56 | 1205 | 41.95 | 25.46 | 8.22 |
| 20 | D | 9.12 | 1145 | 44.86 | 26.15 | 8.46 |
| 21 | E | 6.87 | 773 | 59.56 | 30.15 | 12.56 |
| 22 | F | 6.57 | 726 | 59.86 | 30.58 | 12.67 |
| 23 | G | 8.29 | 1023 | 40.83 | 29.31 | 7.98 |
| 24 | H | 7.51 | 932 | 52.16 | 30.79 | 9.88 |
| 25 | I | 14.56 | 1845 | 39.29 | 21.35 | 7.61 |
| 26 | J | 4.3 | 467 | 93.93 | 31.06 | 19.78 |
| 27 | K | 4.89 | 636 | 89.89 | 30.56 | 18.23 |
| 28 | L | 12.18 | 1402 | 40.26 | 23.09 | 7.89 |
| 29 | M | 8.15 | 943 | 55.35 | 29.35 | 10.03 |
| 30 | N | 9.22 | 1096 | 43.21 | 24.78 | 8.12 |
| 31 | O | 7.45 | 820 | 53.01 | 29.56 | 10.32 |
| 32 | P | 8.31 | 886 | 40.21 | 23.46 | 7.86 |
Claims (15)
1, a kind of load type bimetallic polyethylene catalyst comprises the following component that is carried on magnesium chloride-silica supports:
(1) expression formula is Ti (OR)
nX
4-nZ-N type active ingredient, 0＜n in the formula≤2, X is a halogen, R is C
5～C
10Alkyl;
(2) expression formula is L
mZrX
4-mNon-luxuriant active ingredient, X is a halogen in the formula, m is 1 or 2, L is that formula (I) or part (II) remove the group that forms behind the hydrogen proton, described formula (I) and (II) in, R
1For being selected from hydrogen or C
1～C
6The substituting group of alkyl, its number are 1～4, R
2Be selected from hydrogen or C
1～C
3Alkyl, R
3For being selected from hydrogen or C
1～C
6The substituting group of alkyl, its number are 1～5,
(3) organo-aluminium compound;
In the described catalyzer, titanium content is 3.0～7.0 quality %, and zirconium content is 0.1～3.0 quality %, and Mg content is 1.0～6.0 quality %, and aluminium content is 1.0～12.0 quality %.
2, according to the described catalyzer of claim 1, it is characterized in that described formula (I) and (II) in, R
1Be single substituting group, R
1Be selected from hydrogen or C
1～C
3Alkyl, R
2Be selected from hydrogen or methyl, R
3Be selected from hydrogen or C
1～C
3Alkyl, its number is 1～3.
3,, it is characterized in that described organo-aluminium compound is selected from aluminum alkyls or alkylaluminoxane according to the described catalyzer of claim 1.
4, according to the described catalyzer of claim 3, it is characterized in that described aluminum alkyls is selected from triethyl aluminum, triisobutyl aluminium, triisopropylaluminiuand or their mixture, described alkylaluminoxane is a methylaluminoxane.
5,, it is characterized in that described formula Ti (OR) according to the described catalyzer of claim 1
nX
4-nIn, R is selected from C
7～C
9The isomery alkyl.
6, the described Preparation of catalysts method of a kind of claim 1 is included in the aromatic solvent, and adding the expression formula that is carried on magnesium chloride-silica supports is Ti (OR)
nX
4-nZ-N type active ingredient and the organo-aluminium compound thorough mixing after, add non-luxuriant active ingredient again and fully react, filter, drying formula Ti (OR) then
nX
4-nIn, 0＜n≤2, X is a halogen, R is C
5～C
10Alkyl.
7, in accordance with the method for claim 6, it is characterized in that described aromatic hydrocarbons is C
7～C
10Alkane aromatic hydrocarbons, described organo-aluminium compound is selected from aluminum alkyls or alkylaluminoxane.
8, in accordance with the method for claim 7, it is characterized in that described aluminum alkyls is selected from triethyl aluminum, triisobutyl aluminium, triisopropylaluminiuand or their mixture, described alkylaluminoxane is a methylaluminoxane.
9, in accordance with the method for claim 6, it is characterized in that described temperature of reaction is 30～50 ℃.
10, in accordance with the method for claim 6, the preparation method who it is characterized in that described Z-N type active ingredient comprises the steps:
(1) among " MgR ' dialkyl magnesium reaction form the silicon-dioxide of load dialkyl magnesium, the R " MgR ' that in the presence of the stable hydrocarbon medium, makes silicon-dioxide and formula R, " and R ' is selected from C respectively to R
2～C
12Alkyl, the consumption of described dialkyl magnesium is every gram silicon-dioxide 0.5～2.5 mmole;
(2) silicon-dioxide of above-mentioned load dialkyl magnesium and the alkylol cpd of ROH are fully reacted, described ROH is C
5～C
10Fatty Alcohol(C12-C14 and C12-C18), described alcohol and R " MgR ' mol ratio be 0.90～1.3: 1;
(3) make the product and the TiX of step (2)
4Fully reaction, used TiX
4With R " MgR ' mol ratio be 1.2～3.0: 1, reaction after-filtration, drying, described formula TiX
4In, X is a halogen.
11, in accordance with the method for claim 10, it is characterized in that described stable hydrocarbon of (1) step is selected from C
6～C
10Alkane, R " MgR ' in R " and R ' are selected from C respectively
2～C
6Alkyl, (2) step described in alkylol cpd ROH be selected from C
7～C
9The isomery Fatty Alcohol(C12-C14 and C12-C18).
12, in accordance with the method for claim 11, it is characterized in that described stable hydrocarbon of (1) step is hexane or heptane, R " MgR ' be dibutylmagnesium, ROH is selected from isooctyl alcohol described in (2) step, used TiX of (3) step
4Be selected from TiCl
4
13, in accordance with the method for claim 10, it is characterized in that respectively going on foot temperature of reaction is 30～100 ℃.
14, a kind of ethene polymerization method comprises that with the described catalyzer of claim 1 be Primary Catalysts, is promotor with aluminum alkyls or alkylaluminoxane, makes vinyl polymerization at 10～100 ℃, the condition of 0.1～1.0MPa.
15, in accordance with the method for claim 14, it is characterized in that described aluminum alkyls is selected from triethyl aluminum, triisobutyl aluminium, triisopropylaluminiuand or their mixture, described alkylaluminoxane is selected from methylaluminoxane, and the mol ratio of transition metal is 20～500: 1 in Al during polyreaction in the promotor and the Primary Catalysts.
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