CN1827660A - Supported bimetal polyvinyl catalyst and preparation method thereof - Google Patents
Supported bimetal polyvinyl catalyst and preparation method thereof Download PDFInfo
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Abstract
A loadingtype bimetal polyvinyl catalyst and its process for preparing comprises the following components loaded in the magnesium chloride-silicon dioxide carrier: (1) Z-N type active components with expression of Ti(OR)nX4-n, in which n is more than zero but no less than four, X stands for halide, R stands for C4-C10 of alkyl; (2) non-metallocene active components with expression of LmMX4-m, in which X stands for halide, M selects from zirconium or titanium, m is one or two, L stands for ligand group formed by deprotonated formula (I) or formula(II) compound, in the said formula (I), R1, R2, R3 or R4 individually selects from hydrogen or alkyl of C1-C6, in the said formula(II), R5 or R6 individually selects from alkyl of C1-C4 or alkylaryl of C6-C9; (3) organo-aluminium compound. In the said catalyst, the mole ratio between titanium of Z-N type active components and transient metal of non-metallocene active components is 1-20:1, the magnesium content is 1-5 mass %, and the aluminium content is 1-12 mass %. The catalyst is of higher activity used in vinyl polymerization reaction, and the obtained polyethylene is of wider 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 Nonmetallocene 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 curve of this base polymer (gel permeation chromatography figure) distributes in the scope of broad, and tangible bimodal curve do not occur.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, Nonmetallocene compound, organo phosphorous compounds or organic epoxy compounds, described Nonmetallocene 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 d Nonmetallocene compound that contains coordination heteroatom ligands such as aerobic, nitrogen in the another kind of conjugated system causes more and more that in the application aspect polyolefine, the especially polyethylene catalysts people pay attention to and pay close attention to.The kind of Nonmetallocene compound is more, thereby has opened up source more widely for polyolefin catalyst, makes its synthesis material more diversified.
CN1297951A will be that the Nonmetallocene compound of part is used for the styrene polymerization reaction with the beta-diketon.The semi-metallocene that CN1400227A then adopts Grignard reagent will contain beta-diketon is carried on the silica-gel carrier, and the synthesizing chlorinated magnesium of while original position, and this catalyzer is used for vinyl polymerization and can use methylaluminoxane to be promotor.
Though it is wide slightly than metallocene synthetic polyethylene that non-metallocene catalyst synthetic molecular weight of polyethylene distributes, but still narrower, processing is still difficult.Therefore, how to widen the important topic that the poly molecular weight distribution of Nonmetallocene still is non-metallocene 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 is used for ethylene polymerization can obtain 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
4～C
10Alkyl;
(2) expression formula is L
mMX
4-mThe Nonmetallocene active ingredient, X is a halogen in the formula, M selected among zirconium or titanium, m is 1 or 2, L is that the compound of formula (I) or formula (II) removes the ligand groups that forms behind the proton, in the described formula (I), R
1, R
2, R
3Or R
4Be selected from hydrogen or C respectively
1～C
6Alkyl, in the formula (II), R
5, R
6Be selected from C respectively
1～C
4Alkyl or C
6～C
9Alkaryl;
(3) organo-aluminium compound;
In the described catalyzer, the mol ratio of the transition metal in the middle Ti of Z-N type active ingredient and the non-luxuriant active ingredient is 1～20: 1, and Mg content is 1～5 quality %, and aluminium content is 1～12 quality %.
Catalyzer of the present invention adopt special method for making with Ziegler-Natta (Z-N) type active ingredient and selected Nonmetallocene active constituent loading on silica supports, form magnesium chloride-silicon-dioxide complex carrier simultaneously.The active ingredient and the carrier that are carried on the carrier interact, and produce organically combination, thereby are distributed on the carrier more equably.Catalyzer of the present invention is used for ethylene polymerization, not only has advantages of high catalytic activity, and the polyethylene product that makes has wider molecular weight distribution, has improved the processing characteristics of polyethylene product.
Embodiment
The present invention is in load Z-N type active ingredient, on silica supports, form magnesium chloride, and then the Nonmetallocene active ingredient is incorporated in the carrier of above-mentioned load Z-N type active ingredient and makes catalyzer, thereby make loaded catalyst have high reaction activity and high.
Part in the used non-luxuriant active ingredient of the present invention is that the compound shown in formula (I) or the formula (II) removes the group that forms behind the proton.Its Chinese style (I) is the compound that forms after salicylaldehyde derivatives and the anils condensation, and formula (II) is a beta-diketone compound.In the described formula (I), R
1～R
3Be the substituting group on the aniline ring, can be identical or different, preferred hydrogen or C
1～C
3Alkyl, R
4Be the substituting group on the salicylic aldehyde phenyl ring, preferred hydrogen or C
1～C
3Alkyl.In the formula (II), R
5, R
6Can be identical or different, preferred C
1～C
4Alkyl or phenyl.
Ti described in the catalyzer of the present invention (OR)
nX
4-nBe Z-N type catalyzer, the preferred C of R wherein
7～C
9Alkyl.
Organo-aluminium compound preferred alkyl aluminium or alkylaluminoxane in the described catalyzer, the preferred triethyl aluminum of aluminum alkyls wherein, triisobutyl aluminium, triisopropylaluminiuand or their mixture, alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta.
Preferred 1.5～4 quality % of Mg content in the catalyzer of the present invention, preferred 1.5～10 quality % of aluminium content, the mol ratio preferred 2.5～15: 1 of Z-N type active ingredient and Nonmetallocene active ingredient.
Preparation of catalysts method provided by the 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 the Nonmetallocene active ingredient again and fully react, filter then, drying.
Described method is mixed the Z-N type active ingredient of load and organic aluminide earlier 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, and described aromatic hydrocarbons is selected from C
7～C
10Alkane aromatic hydrocarbons, preferred toluene.Described organo-aluminium compound is selected from aluminum alkyls or alkylaluminoxane, the wherein preferred triethyl aluminum of aluminum alkyls, triisobutyl aluminium, triisopropylaluminiuand or their mixture, alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta.
Described temperature of reaction is 30～50 ℃, and added aromatic hydrocarbons is 10～20 times of carrier quality during reaction, and the middle Ti of the Z-N type active ingredient of adding and the mol ratio of the transition metal in the non-luxuriant active ingredient are 1～20: 1, preferred 2.5～15: 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
4～C
10Fatty Alcohol(C12-C14 and C12-C18), described alcohol and R " MgR ' mol ratio be 0.90～1.05: 1;
(3) make the product and the TiX of step (2)
4Fully reaction, used TiX
4With R " MgR ' mol ratio be 1.5～3.0: 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
9Fatty Alcohol(C12-C14 and C12-C18), comprise the various isomer of described alcohol, more preferably n-Octanol or isooctyl alcohol.(3) used TiX of step
4Preferred TiCl
4Each goes on foot temperature of reaction is 30～100 ℃, preferred 40～65 ℃.
The Nonmetallocene active ingredient adopts following method preparation in the described catalyzer:
With formula (I) is that the preparation method of the Nonmetallocene active ingredient of ligand compound is: in the presence of tetrahydrofuran (THF), make the ligand compound of formula (I) and sodium hydride mol ratio such as press and fully react, temperature of reaction is 15～40 ℃, adds MX then
4, make MX
4With the mol ratio of formula (I) part be 1: 2,30～60 ℃ of fully reactions, filter then, with get final product after solids wash, the drying the following Nonmetallocene active ingredient of structure expression.Described formula MX
4In, M is selected from titanium or zirconium, and X is a halogen.
In the aforesaid method, the preparation method of formula (I) ligand compound is: in the presence of Fatty Alcohol(C12-C14 and C12-C18), make salicylaldehyde 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).Described pure preferred alcohol.
With formula (II) is that the preparation method of the Nonmetallocene active ingredient of part is: methylene dichloride exists down, makes MX
4Under reflux temperature, fully react by 1: 2 mol ratio with the described ligand compound of formula (II), remove methylene dichloride, solid drying is promptly got the following Nonmetallocene active ingredient of structural formula.Described reflux temperature is 20～70 ℃.
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, be promotor with aluminum alkyls or alkylaluminoxane, make ethene at 10～100 ℃, preferred 30～80 ℃; 0.1 carry out polyreaction under the condition of～1.0MPa.
In the described promotor, the preferred triethyl aluminum of aluminum alkyls, triisobutyl aluminium, three own butyl aluminium or their mixtures, preferred triethyl aluminum.Alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta.The mol ratio of transition metal is 20～1500: 1 in Al during polyreaction in the promotor and the Primary Catalysts, preferred 20～500: 1.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Prepare load type bimetal catalyst of the present invention.
(1) preparation Z-N type active ingredient
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)
0.72Cl
3.28Z-N type active ingredient a, wherein titanium content is 4.98 quality %.
(2) preparation two (salicylidene aniline) zirconium dichloride
2 milliliters of (19.11 mmole) salicylic 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 salicylidene aniline, yield is 78 quality %.Results of elemental analyses following (in the bracket is calculated value, is mass percent):
C：78.56(79.16)，N：7.13(7.10)，H：5.62(5.62)。
In the there-necked flask of the band return line of nitrogen protection, add 2 gram (10.0 mmole) salicylidene aniline 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 (salicylidene aniline) zirconium dichlorides.
(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 8.6 ml aluminium concentration are 1.55M stir; two (salicylidene aniline) zirconium dichloride that adds 0.2 gram (0.36 mmole) 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 2.1083 grams.Plasma emission spectrum (ICP) method records that titanium content is 4.01 quality % in the catalyst A, and zirconium content is 0.99 quality %, and Mg content is 1.39 quality %, and aluminium content is 7.97 quality %.
Example 2
Method by example 1 prepares load type bimetal catalyst B, different is that (3) step add-on of MAO solution is 4.3 milliliters, get the light yellow catalyst B of 2.1035 grams behind the drying under reduced pressure, wherein titanium content is 4.51 quality %, zirconium content is 0.81 quality %, Mg content is 1.55 quality %, and aluminium content is 5.40 quality %.
Example 3
Method by example 1 prepares load type bimetal catalyst C, different is that the hexane solution that (3) step two kinds of active ingredients is mixed the triethyl aluminum of back adding 1.6 ml aluminium content 0.8M replaces MAO solution to continue reaction, get 2.1058 gram yellow catalyst C behind the drying under reduced pressure, wherein titanium content is 4.67 quality %, zirconium content is 0.95 quality %, Mg content is 1.64 quality %, and aluminium content is 3.13 quality %.
Example 4
(1) two (diphenylpropane-1,3-dione(DPPO)) zirconium dichlorides (dbm) of preparation active ingredient
2ZrCl
2
In there-necked flask, add 2.33 gram (10.0 mmole) ZrCl
4, 4.48 gram (20.0 mmole) diphenylpropane-1,3-dione(DPPO)s (dbm), 60 milliliters of methylene dichloride, 50 ℃ of back flow reaction 2 hours, methylene dichloride is removed in underpressure distillation, the solid drying under reduced pressure is got (dbm) of 4.82 grams again
2ZrCl
2
(2) preparation load type bimetal catalyst
Method by 1 (3) step of example prepares load type bimetal catalyst D, and different is that the non-luxuriant active ingredient that adds is (dbm)
2ZrCl
2, the MAO solution of adding is 4.3 milliliters, gets 2.138 gram yellow catalyst D behind the drying under reduced pressure, and wherein titanium content is 4.60 quality %, and zirconium content is 1.37 quality %, and Mg content is 1.54 quality %, aluminium content is 4.79 quality %.
Example 5
(1) two (two formyl methane) zirconium dichlorides of preparation active ingredient
In there-necked flask, add 2.33 gram (10.0 mmole) ZrCl
4, 1.99 gram (20.0 mmole) two formyl methane and 60 milliliters of methylene dichloride, 50 ℃ of back flow reaction 2 hours, methylene dichloride is removed in underpressure distillation, the solid drying under reduced pressure is got two (two formyl methane) zirconium dichlorides of 4.21 grams again.
(2) preparation load type bimetal catalyst
Method by 1 (3) step of example prepares load type bimetal catalyst E, different is that the non-luxuriant active ingredient that adds is two (two formyl methane) zirconium dichlorides, the MAO solution that adds is 4.3 milliliters, get the light yellow catalyzer E of 2.148 grams behind the drying under reduced pressure, wherein titanium content is 4.36 quality %, zirconium content is 1.67 quality %, and Mg content is 1.34 quality %, and aluminium content is 4.39 quality %.
Example 6
(1) preparation Z-N type active ingredient
Prepare the Z-N type active ingredient of load by (1) one step process of example 1, different is that the dibutylmagnesium that adds is 11.5 milliliters (11.5 mmoles), and isooctyl alcohol is 1.7 milliliters (10.93 mmoles), TiCl
4Be 2.2 milliliters (20 mmoles), behind the drying under reduced pressure, obtain being carried on and consist of Ti (iC on magnesium chloride-silica supports
8H
17O)
1.05Cl
2.95Z-N type active ingredient b, wherein titanium content is 1.84 quality %.
(2) 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 b of 2 gram loads and the toluene solution of the methylaluminoxane (MAO) that 8.6 ml aluminium concentration are 1.55M stir; two (salicylidene aniline) zirconium dichloride that adds 0.2 gram again; 25 ℃ were reacted 15 minutes; 45 ℃ were reacted 3 hours; under nitrogen protection, filter; solid hexane wash 3 times; drying is 5 hours under 25 ℃ of decompressions; get the light yellow catalyzer F of 2.1088 grams, wherein titanium content is 1.34 quality %, and zirconium content is 1.45 quality %; Mg content is 1.04 quality %, and aluminium content is 9.73 quality %.
Example 7
Method by example 6 prepares load type bimetal catalyst G, different is that two (salicylidene aniline) zirconium dichloride that adds in (2) step is 0.1 gram, get the light yellow catalyzer G of 2.1038 grams behind the drying under reduced pressure, wherein titanium content is 1.40 quality %, zirconium content is 0.53 quality %, Mg content is 1.12 quality %, and aluminium content is 8.39 quality %.
Example 8
(1) preparation Z-N type active ingredient
Method by 1 (1) step of example prepares the Z-N type active ingredient of load, and different is that the dibutylmagnesium that adds is 34.5 milliliters (34.5 mmoles), and isooctyl alcohol is 5.1 milliliters (32.78 mmoles), TiCl
4Be 6.6 milliliters (60 mmoles), behind the drying under reduced pressure, obtain being carried on and consist of Ti (iC on magnesium chloride-silica supports
8H
17O)
0.74Cl
3.26Z-N type active ingredient c, wherein titanium content is 6.62 quality %.
(2) 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 c of 2 gram loads and the toluene solution of the methylaluminoxane (MAO) that 8.6 ml aluminium concentration are 1.55M stir; two (salicylidene aniline) zirconium dichloride that adds 0.2 gram (0.36 mmole) again; 25 ℃ were reacted 15 minutes; 45 ℃ were reacted 3 hours; under nitrogen protection, filter; solid hexane wash 3 times; drying is 5 hours under 25 ℃ of decompressions; get the light yellow catalyzer H of 2.1388 grams, wherein titanium content is 4.44 quality %, and zirconium content is 1.61 quality %; Mg content is 2.83 quality %, and aluminium content is 8.99 quality %.
Example 9
Method by example 8 prepares load type bimetal catalyst, different is that adding 4.3 ml aluminium concentration are the toluene solution of the methylaluminoxane (MAO) of 1.55M in (2) step, get the light yellow catalyst I of 2.1048 grams behind the drying under reduced pressure, wherein titanium content is 4.84 quality %, zirconium content is 1.76 quality %, Mg content is 2.84 quality %, and aluminium content is 8.98 quality %.
Example 10
Method by example 8 prepares load type bimetal catalyst, different is two (salicylidene aniline) zirconium dichloride that adds 0.1 gram in (2) step, get the light yellow catalyzer J of 2.1058 grams behind the drying under reduced pressure, wherein titanium content is 5.56 quality %, zirconium content is 1.21 quality %, Mg content is 3.33 quality %, and aluminium content is 8.78 quality %.
Example 11
Method by example 8 prepares load type bimetal catalyst, adds the MAO solution of 0.1 gram two (salicylidene aniline) zirconium dichlorides and 4.3 milliliters in different is (2) step.Get the light yellow catalyzer K of 2.1058 grams behind the drying under reduced pressure, wherein titanium content is 5.03 quality %, and zirconium content is 1.00 quality %, and Mg content is 3.03 quality %, and aluminium content is 8.01 quality %.
Example 12
Method by example 8 prepares load type bimetal catalyst, in different is (2) step with the hexane solution replacement MAO solution of the triethyl aluminum of 3.3 ml aluminium content 0.8M.Get the light yellow catalyzer L of 2.1158 grams behind the drying under reduced pressure, wherein titanium content is 4.63 quality %, and zirconium content is 1.06 quality %, and Mg content is 3.29 quality %, and aluminium content is 4.01 quality %.
Example 13
(1) preparation non-luxuriant active ingredient two (salicylidene 2,4-xylidine) zirconium dichloride
With 2 of the salicylic 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 salicylidenes 2,4-xylidine, yield are 76 quality %, results of elemental analyses following (in the bracket is calculated value, is mass percent):
C：79.33(79.86％)；N：6.24(6.22)；H：6.73(6.71)
In the there-necked flask of the band return line of nitrogen protection, add 2.0 gram (8.88 mmole) salicylidenes 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 (salicylidene 2,4-xylidine) zirconium dichlorides.
(2) preparation load type bimetal catalyst
Method by 8 (2) steps of example prepares load type bimetal catalyst, different is the two (salicylidenes 2 that add 0.2 gram (0.328 mmole), the 4-xylidine) zirconium dichloride reacts, get the light yellow catalyzer M of 2.1458 grams behind the drying under reduced pressure, wherein titanium content is 4.81 quality %, zirconium content is 1.56 quality %, and Mg content is 2.84 quality %, and aluminium content is 8.67 quality %.
Example 14～22
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 MAO or triethyl aluminum (TEA), adds the hexane solution of catalyzer 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.Each example catalyst system therefor, promotor and catalyst activity, poly high load melt index (HLMI) and molecular weight and molecular weight distribution see Table 1.Wherein high load melt index (HLMI) is measured according to ASTM-D-1238, and the molecular weight of polymkeric substance and molecular weight distribution are to use gel permeation chromatography.
Example 23～29
Following example carries out the reaction of normal pressure ethylene homo with catalyzer of the present invention.
250 milliliters of round-bottomed flasks are vacuumized back nitrogen purging three times, feed ethene behind the emptying nitrogen, making ethylene pressure is 0.1MPa, adds hexane and promotor, and 40 ℃ add polymerization catalysts reaction 0.5 hour, use the HCl termination reaction, obtain polyethylene product.Each example catalyst system therefor, promotor, Al/ (Ti+Zr) mole when catalytic activity see Table 2.
Table 1
| Instance number | The catalyzer numbering | Promotor | Catalytic activity * 10 -5， gPE/mol(Ti +Zr)·hr | Catalytic activity, gram PE/ gram catalyzer | HLMI， g/10min | Mw | Mn | Mw/ Mn |
| 14 | A | TEA | 27.5 | 2600 | 0.49 | 415342 | 53523 | 7.76 |
| 15 | B | TEA | 10.88 | 1120 | 0.2087 | 500321 | 63979 | 7.82 |
| 16 | C | TEA | 9.26 | 920 | 0.38 | 435628 | 51737 | 8.42 |
| 17 | D | TEA | 15.80 | 1520 | 2.3075 | 325503 | 35573 | 9.15 |
| 18 | D | MAO | 13.82 | 1732 | 1.7428 | 315876 | 48151 | 6.56 |
| 19 | E | TEA | 9.82 | 726 | 0.7428 | 383776 | 60437 | 6.35 |
| 20 | F | TEA | 5.94 | 260 | 0.4163 | 421367 | 50402 | 8.36 |
| 21 | G | TEA | 2.32 | 222 | 0.5232 | 398721 | 49407 | 8.07 |
| 22 | M | TEA | 9.03 | 588 | 0.6889 | 412345 | 62381 | 6.61 |
Table 2
| Instance number | The catalyzer numbering | Promotor | Al/ (Ti+Zr) mol ratio | Catalytic activity * 10 -5， gPE/mol(Ti+Zr)·hr |
| 23 | H | TEA | 150 | 0.83 |
| 24 | I | TEA | 150 | 0.76 |
| 25 | J | MAO | 500 | 2.15 |
| 26 | J | TEA | 150 | 1.01 |
| 27 | K | TEA | 150 | 0.84 |
| 28 | L | TEA | 150 | 0.73 |
| 29 | M | TEA | 150 | 0.80 |
Claims (16)
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
4～C
10Alkyl;
(2) expression formula is L
mMX
4-mThe Nonmetallocene active ingredient, X is a halogen in the formula, M selected among zirconium or titanium, m is 1 or 2, L is that the compound of formula (I) or formula (II) removes the ligand groups that forms behind the proton, in the described formula (I), R
1, R
2, R
3Or R
4Be selected from hydrogen or C respectively
1～C
6Alkyl, in the formula (II), R
5, R
6Be selected from C respectively
1～C
4Alkyl or C
6～C
9Alkaryl;
(3) organo-aluminium compound;
In the described catalyzer, the mol ratio of the transition metal in the middle Ti of Z-N type active ingredient and the non-luxuriant active ingredient is 1～20: 1, and Mg content is 1～5 quality %, and aluminium content is 1～12 quality %.
2,, it is characterized in that in the described formula (I) R according to the described catalyzer of claim 1
1～R
4Be selected from hydrogen or C respectively
1～C
3Alkyl, in the formula (II), R
5, R
6Be selected from C respectively
1～C
4Alkyl or phenyl.
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
9Alkyl.
6, according to the described catalyzer of claim 1, it is characterized in that Mg content 1～5 quality % in the described catalyzer, aluminium content is 1～12 quality %.
7, 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 the Nonmetallocene active ingredient again and fully react, filter then, drying.
8, in accordance with the method for claim 7, 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.
9, in accordance with the method for claim 8, it is characterized in that described aluminum alkyls is selected from triethyl aluminum, triisobutyl aluminium, triisopropylaluminiuand or their mixture, described alkylaluminoxane is a methylaluminoxane.
10, in accordance with the method for claim 7, it is characterized in that described temperature of reaction is 30～50 ℃.
11, in accordance with the method for claim 7, 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
4～C
10Fatty Alcohol(C12-C14 and C12-C18), described alcohol and R " MgR ' mol ratio be 0.90～1.05: 1;
(3) make the product and the TiX of step (2)
4Fully reaction, used TiX
4With R " MgR ' mol ratio be 1.5～3.0: 1, reaction after-filtration, drying, described formula TiX
4In, X is a halogen.
12, in accordance with the method for claim 11, 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
9Fatty Alcohol(C12-C14 and C12-C18).
13, 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 octanol or isooctyl alcohol described in (2) step, used TiX of (3) step
4Be selected from TiCl
4
14, in accordance with the method for claim 11, it is characterized in that respectively going on foot temperature of reaction is 30～100 ℃.
15, 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.
16, in accordance with the method for claim 15, it is characterized in that described aluminum alkyls is selected from triethyl aluminum, triisobutyl aluminium, three own butyl aluminium or their mixtures, 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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|---|---|---|---|
| CNB2005100089872A CN100363391C (en) | 2005-02-28 | 2005-02-28 | Supported bimetal polyvinyl catalyst and preparation method thereof |
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| CN100363391C CN100363391C (en) | 2008-01-23 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255204B (en) * | 2007-02-28 | 2010-05-19 | 中国石油化工股份有限公司 | Method for preparing supported non-metallocene olefin polymerization catalyst |
| CN102887969A (en) * | 2012-10-19 | 2013-01-23 | 河北工业大学 | Non-metallocene bimetal catalysis system for synthesizing branched polyethylene and application thereof |
| CN105085726A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and catalyst for olefin polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0472741B1 (en) * | 1990-03-16 | 1995-06-21 | Tonen Corporation | Olefin polymerization catalyst |
| CN1207313C (en) * | 1999-06-23 | 2005-06-22 | 中国石油兰州化学工业公司 | Compounded catalyst for olefinic polymerization |
| US6964937B2 (en) * | 2000-11-30 | 2005-11-15 | Univation Technologies, Llc | Bimetallic catalyst for producing polyethylene resins with bimodal molecular weight distribution, its preparation and use |
| CN1142195C (en) * | 2001-07-31 | 2004-03-17 | 中国石油化工股份有限公司 | Polythene catalyst loaded by semi-metallocene |
-
2005
- 2005-02-28 CN CNB2005100089872A patent/CN100363391C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255204B (en) * | 2007-02-28 | 2010-05-19 | 中国石油化工股份有限公司 | Method for preparing supported non-metallocene olefin polymerization catalyst |
| CN102887969A (en) * | 2012-10-19 | 2013-01-23 | 河北工业大学 | Non-metallocene bimetal catalysis system for synthesizing branched polyethylene and application thereof |
| CN102887969B (en) * | 2012-10-19 | 2014-02-26 | 河北工业大学 | Non-metallocene bimetal catalysis system for synthesizing branched polyethylene and application thereof |
| CN105085726A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and catalyst for olefin polymerization |
| CN105085726B (en) * | 2014-04-24 | 2017-11-07 | 中国石油化工股份有限公司 | A kind of catalytic component and catalyst for olefinic polymerization |
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| Publication number | Publication date |
|---|---|
| CN100363391C (en) | 2008-01-23 |
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