CN101255204A - Method for preparing supported non-metallocene olefin polymerization catalyst - Google Patents
Method for preparing supported non-metallocene olefin polymerization catalyst Download PDFInfo
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- CN101255204A CN101255204A CNA2007100641000A CN200710064100A CN101255204A CN 101255204 A CN101255204 A CN 101255204A CN A2007100641000 A CNA2007100641000 A CN A2007100641000A CN 200710064100 A CN200710064100 A CN 200710064100A CN 101255204 A CN101255204 A CN 101255204A
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Abstract
The invention provides a preparation method of load type non-metallocene polyolefin catalyst, comprising dispersing the carrier represented by general formula: (MgCl<SUB>2</SUB>)(R<SUP>1</SUP>MgCl)<SUB>p</SUB>Mg<SUB>q</SUB>[Ti(OR<SUP>2</SUP>)<SUB>4</SUB>]<SUB>x</SUB>[Si(OR<SUP>3</SUP>)<SUB>4</SUB>]<SUB>y</SUB> in inert organic solvent, wherein p is 0.4-0.8, q is 0.02-0.15, x is 0.03-0.09, y is 0.1-0.3; adding fatty alcohol represented by general formula: R'OH to fully perform catalyzed reaction to form slurry; adding schiff base ligand represented by general formula(I) to fully perform catalyzed reaction; adding MX<SUB>4</SUB> at -10-30 degree; and adding halogenated hydrocarbon; heating to 60-130 degree to fully react, wherein the M is selected from titanium or zirconium, X is halogen; filtering the reacted slurry; cleaning and drying. The catalyst obtained by the method has higher polymerization activity and comonomer insertion ratio.
Description
Technical field
The present invention is a kind of preparation method of carry type non-metallocene calalyst for polymerization of olefine, specifically, is a kind of preparation method who contains the load type non-metallocene of Schiff base ligand.
Background technology
After metallocene catalyst, non-metallocene catalyst becomes the another focus of polyolefin field research.Metallocene and non-metallocene catalyst are wanted loadization usually in application, to satisfy more polymerization technique process, as the needs of vapour phase polymerization, slurry polymerization.Simultaneously, loadization can improve the catalytic efficiency of active ingredient, can increase the stability in active centre, improves the form of polymkeric substance, improves the apparent density of polymkeric substance.In addition, the loadization of metallocene and non-metallocene catalyst can also reduce the consumption of promotor significantly, reduces the production cost of olefin polymer.
Usually the load method of metallocene or non-metallocene olefin polymerization catalyst is: first composite reactive component, i.e. and metallocene or Nonmetallocene title complex, and then title complex loaded on form supported catalyst on the carrier.Disclosing a kind of as USP5869417 is active ingredient with the metallocene, and molecular sieve is the preparation method of the loaded catalyst of carrier, and the used carrier of this patent is for having
The macroporous structure molecular sieve in aperture, as faujusite, SAPO-37 etc., the catalyzer that load metallocene makes on above-mentioned molecular sieve carrier can be used for ethene, propylene or cinnamic polymerization.
CN1461756A discloses a kind of non-metallocene catalyst and loaded catalyst thereof; the part of this catalyzer is the acyl-naphthaline phenolic compound; the an alkali metal salt of catalyzer employing acyl group naphthols and transition metal halide react at a lower temperature and make; its loaded catalyst is that described Nonmetallocene active ingredient solids is dispersed in the solvent, makes with the carrier reaction again.
CN1418227A discloses a kind of preceding body catalyst that comprises bidentate ligand that contains, and preceding body catalyst forms supported catalyst with the carrier reaction earlier with after the aluminum alkyls effect again.
CN02129042.3 disclose a kind of to the west of Buddhist alkali be the supported olefin polymerization catalyst and the preparation of part.This method is dissolved in butter and forms adduct solution in the tetrahydrofuran (THF), and in the presence of halogenated alkane, the abundant contact reacts of Nonmetallocene title complex with containing pyrrole aldehyde anil part makes load type non-metallocene catalyst then.
CN200510059771.9 discloses a kind of preparation method of load type non-metallocene catalyst, the nascent state magnesium chloride that adopts the reaction of magnesium powder and chloroparaffin to generate is a carrier, method by the original position load is reacted pyrrole aldehyde anil part earlier with carrier, add transition metal halide MX again
4Generate the polymerization activity component with ligand compound reaction, make synthetic directly on carrier, the carrying out of catalyzer and obtain loaded catalyst.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of load type non-metallocene polyolefin catalyst, the olefin polymerization catalysis of this method preparation, have high polymerization activity and comonomer insertion rate, and can add mode by different electron donors, obtain having the olefin polymerization catalysis of different polymerization kinetics curves.
The preparation method of load type non-metallocene polyolefin catalyst provided by the invention comprises:
(1) be (MgCl with general expression
2) (R
1MgCl)
pMg
q[Ti (OR
2)
4]
x[Si (OR
3)
4]
yCarrier be dispersed in the inert organic solvents, in the described expression formula, R
1And R
2Be selected from C respectively
2～C
4Alkyl, R
3Be selected from C
1～C
3Alkyl, the p value is 0.4～0.8, the q value is 0.02～0.15, the x value is 0.03～0.09, the y value is 0.1～0.3, the abundant contact reacts of Fatty Alcohol(C12-C14 and C12-C18) that adds general formula and be R ' OH forms slurries, R ' is selected from C among described R ' OH
1～C
8Alkyl,
(2) Schiff base ligand shown in the adding formula (I) in the slurries that in (1) step, make, abundant contact reacts,
In the formula (I), R is single the replacement or multi-substituent on the pyrrole ring, is selected from hydrogen, C
1～C
12Alkyl or C
6～C
14Aryl; If the substituting group on the pyrrole ring is two when above, adjacent substituting group can be connected with each other and pyrrole ring forms condensed ring, R
2Be selected from hydrogen or C
1～C
6Alkyl, the substituent R on the phenyl ring
1Number be 1 to 5, R
1Be selected from hydrogen or C
1～C
12Alkyl, C
6～C
9Alkaryl, nitro or halogen,
(3) under-10～30 ℃, in the slurries that make of above-mentioned (2) step, add MX
4Compound adds halohydrocarbon again, is warming up to 60～130 ℃ of fully reactions, described MX
4In, M is selected from titanium or zirconium, and X is a halogen, the dope filtration, washing, the drying that will obtain after will reacting then.
It is that the magnesium halide in active of feedstock production is a carrier that the present invention adopts with the magnesium powder, handle by alcohol, add the synthetic Nonmetallocene of Schiff base ligand and transition metal halide original position on carrier and make loaded catalyst, and, obtain three kinds of catalyzer with dissimilar ethylene polymerization dynamics curves by adjusting the adding mode of electron donor compound-siloxanes.In addition, the catalyst activity of the present invention preparation and hydrogen response height, copolymerized ability are strong, and the bulk density height of gained polyethylene product, form are good.
Description of drawings
Fig. 1 is the XRD figure of used carrier of the present invention.
The ethylene polymerization dynamics curve of the catalyzer that Fig. 2 prepares by different way for the present invention.
Fig. 3 depresses the kinetic curve of catalyzed ethylene polymerization at the different hydrogen branch for catalyzer C of the present invention.
Embodiment
The present invention adopts the active magnesium chloride support that contains titanic acid ester and siloxanes, through pure activation treatment, method by the original position load is reacted Schiff base ligand earlier with carrier again, add transition metal halide and part again and be reflected at and generate non-metallocene catalyst on the carrier, make catalytic activity increase.In addition,, also can change the polymerization kinetics curve of catalyzer, make it be slow ascendant trend, thereby prolong life of catalyst by in activation of carrier alcohol and catalyzer generative process, suitably regulating the adding of electron donor-siloxanes.
In the inventive method, (1) step is the pure activation treatment of carrier, contained MgCl in described Fatty Alcohol(C12-C14 and C12-C18) and the carrier
2Mol ratio be 0.1～2.0: 1, preferred 0.4～1.2: 1.Described Fatty Alcohol(C12-C14 and C12-C18) preferred alcohol, 1-propyl alcohol, 1-butanols, 2-methyl amyl alcohol or isooctyl alcohol.(1) the preferred C of described inert organic solvents of step
6～C
10Alkane or naphthenic hydrocarbon, as normal hexane, hexanaphthene, normal heptane, octane, positive nonane, n-decane, benzene, toluene or dimethylbenzene.The mass ratio of inert organic solvents and carrier is 5～30, preferred 10～20.
Described method (2) step is the Schiff base ligand shown in the formula (I) and the reaction of carrier, in the described Schiff base ligand, and the preferred C of R
1～C
4Alkyl, R
1Preferred hydrogen, C
1～C
4Alkyl, phenyl, nitro or fluorine, R
2Preferred hydrogen or methyl.
(2) contained MgCl in Schiff base ligand that adds in the step and the carrier
2Mol ratio be 0.03～1.0: 1, preferred 0.05～0.8: 1.The adding mode of described part can be direct adding, also can be to drip, drip and appropriate to the occasion part is dissolved in the varsol, described varsol is normal hexane, hexanaphthene, normal heptane, octane, positive nonane, n-decane, benzene, toluene or dimethylbenzene, preferred normal hexane, normal heptane, n-decane or toluene.
The suitable temperature of reaction of pure activation treatment of described (1) step and (2) step load part is 20～80 ℃, and preferred 40～60 ℃, the reaction times is 0.5～5 hour, preferred 1～3 hour.
The inventive method (3) step is the process of the synthetic non-metallocene catalyst of original position on carrier, earlier the temperature of reaction system is reduced to-10～30 ℃, preferred 0～10 ℃, slowly adds MX
4, be warming up to 60～130 ℃ after adding halohydrocarbon again, preferred 90～110 ℃ of fully reactions.Described MX
4Preferred TiCl
4Or ZrCl
4
(3) in the step, the preferred hydrochloric ether of described halohydrocarbon, the preferred C of the alkyl in the halohydrocarbon
1～C
8Alkyl or cycloalkyl, as chlorocyclohexane, chlorocyclopentane, chloro-butane, the mol ratio of the Schiff base ligand shown in halohydrocarbon and the formula (I) is 5～40: 1, preferred 5～20: 1.Schiff base ligand and MX shown in the formula (I)
4The mol ratio of compound is 0.3～15: 1, preferred 0.4～10: 1.Reaction finishes, and reaction product is filtered, washs, is drying to obtain and contains L
nMX
4-nThe loaded catalyst of Nonmetallocene title complex, described formula L
nMX
4-nIn, L is that part shown in the formula (I) removes the group that forms behind the hydrogen proton on the N atom, and M is titanium or zirconium, and X is a halogen.
The inventive method also can add electron donor in the different step of Preparation of Catalyst, to improve the polyreaction performance of catalyzer, reduce the activity of such catalysts decay, prolongs catalyst life.
A kind of mode that adds the electron donor compound is in the adding Fatty Alcohol(C12-C14 and C12-C18), to add by R in (1) step
4 nSi (OR
5)
4-nAnd Si (OR
5)
4The mixture of siloxanes of forming, described R
4 nSi (OR
5)
4-nWith contained MgCl in the carrier
2Mol ratio be 0.1～1.0: 1, preferred 0.3～0.8: 1.Described R
4 nSi (OR
5)
4-nWith Si (OR
6)
4Mol ratio be 1～3: 1.
The another kind of mode that adds the electron donor compound is to add MX with (3) step in the adding Fatty Alcohol(C12-C14 and C12-C18) in (1) step
4Compound adds by R respectively after heating up
4 nSi (OR
5)
4-nAnd Si (OR
5)
4The mixture of siloxanes of forming is proceeded reaction then, the preparation loaded catalyst, and the reaction times is 0.5～5 hour, preferred 1～3 hour.The R that described (1) step adds
4 nSi (OR
5)
4-nWith contained MgCl in the carrier
2Mol ratio be 0.1～1.0: 1, preferred 0.3～0.8: 1, the R of adding
4 nSi (OR
5)
4-nWith Si (OR
5)
4Mol ratio be 1～3: 1.(3) step goes on foot the R that adds with (1)
4 nSi (OR
5)
4-nMol ratio be 0.1～0.5: 1, preferred 0.15～0.4: 1, the Si (OR that (3) step and (1) step add
5)
4Mol ratio be 0.1～0.5: 1, preferred 0.15～0.4: 1.
Described R
4 nSi (OR
5)
4-nCompound and Si (OR
5)
4In the compound, R
4Be selected from C
1～C
6Alkyl, C
4～C
6Cycloalkyl or C
6～C
8Aryl, R
5Be selected from C
1～C
4Alkyl, n is 1～3 integer.
Preferred R
4 nSi (OR
5)
4-nCompound is a dimethyldimethoxysil,ne, dipropyl dimethoxy silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, dibutyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, cyclohexyl sec.-propyl dimethoxy silane, cyclopentyl isobutyl-dimethoxy silane, cyclopentyl sec.-propyl dimethoxy silane, cyclopentyl butyl dimethoxy silane, cyclopentyl propyl group dimethoxy silane, dicyclopentyl dimethoxyl silane, dimethoxydiphenylsilane, phenyltrimethoxysila,e, methyltrimethoxy silane, butyl trimethoxy silane, the isobutyl-Trimethoxy silane, dimethyldiethoxysilane, the dipropyl diethoxy silane, the di-isopropyl diethoxy silane, the diisobutyl diethoxy silane, the dibutyl diethoxy silane, the cyclohexyl methyl diethoxy silane, cyclohexyl sec.-propyl diethoxy silane, cyclopentyl isobutyl-diethoxy silane, cyclopentyl sec.-propyl diethoxy silane, cyclopentyl butyl diethoxy silane, cyclopentyl propyl group diethoxy silane, two cyclopentyl diethoxy silanes, the phenylbenzene diethoxy silane, phenyl triethoxysilane, Union carbide A-162, the butyl triethoxyl silane, the isobutyl-triethoxyl silane.
Preferred Si (OR
5)
4Compound is tetramethoxy-silicane, tetraethoxysilane or tetrapropoxysilane.
The preparation method of carrier of the present invention comprises: add the magnesium powder in varsol, the back that stirs adds the electron donor compound, and adding is 2.0～8.0: 1 with magnesium powder mol ratio then, and preferred 1.5～6.0: 1 C
2～C
4A chloroparaffin fully react, filter, collect solids washing and dry, described electron donor compound is that general formula is Si (OR
3)
4Siloxanes and Ti (OR
2)
4Mixture.For making a chloroparaffin and the accelerated reaction of magnesium powder, should in reactant, add a small amount of iodine as catalyzer.
The preferred chloro-propane of a described chloroparaffin, n-propylcarbinyl chloride, chloro-iso-butane, tert-butyl chloride or chloro iso-pentane.The temperature of reaction of a described magnesium powder and a chloroparaffin is 20～100 ℃, preferred 40 ℃～85 ℃, and preferred 0.5～8 hour of reaction times.
Described Si (OR
3)
4With the mol ratio of magnesium powder be 0.05～0.5, Ti (OR
2)
4With the mol ratio of magnesium powder be 0.01～0.05.
Described varsol is selected from C
5～C
8Alkane, naphthenic hydrocarbon or C
6～C
8Aromatic hydrocarbons, preferred normal hexane, hexanaphthene, normal heptane, octane, positive nonane, n-decane, benzene, toluene or dimethylbenzene, preferred normal hexane, normal heptane, n-decane or toluene.
The synthetic method of the described Schiff base ligand of the inventive method is: anils and the mol ratio of the carbonyl pyrrolidine derivative with formula (II) structure by 1: 1 are joined in the appropriate amount of organic, stirring and dissolving, add a small amount of organic acid as catalyzer, being heated to reflux temperature fully reacts, crystallisation by cooling then, filter, with the solids washing for several times, drying under reduced pressure gets final product.
In the formula (II), the number of the substituent R on the pyrrole ring is 1 to 3, and adjacent substituting group can be connected with each other and pyrrole ring forms condensed ring, and R is selected from hydrogen, C
1～C
12Alkyl or C
6～C
14Aryl, R
2Be selected from hydrogen or C
1～C
6Alkyl.
In the reaction of above-mentioned preparation part, organic solvent is selected from C
1～C
10Fatty Alcohol(C12-C14 and C12-C18), C
5～C
10Alkane or C
6～C
12Aromatic hydrocarbons, preferred alcohol, propyl alcohol, butanols, benzene, toluene or dimethylbenzene.Organic acid is selected from C
1～C
10Aliphatic carboxylic acid, preferable formic acid or acetate.
The catalyzer of the inventive method preparation is applicable to the copolyreaction of olefinic polymerization or ethene and alpha-olefin.Being Primary Catalysts with catalyzer provided by the invention during polymerization, is promotor with alkylaluminoxane or aluminum alkyls, makes olefinic polymerization or copolymerization under 10～100 ℃, the condition of 0.1～1.0MPa.
Described alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta, the preferred triethyl aluminum of aluminum alkyls, triisobutyl aluminium or triisopropylaluminiuand.The mol ratio of M is 20～500: 1 in Al during polyreaction in the promotor and the Primary Catalysts.
Describe the present invention in detail below by embodiment, but the present invention is not limited to this.
Embodiment 1
Preparation pyrrole aldehyde anil.
Getting the 0.2mol pyrrole aldehyde joins in the there-necked flask of being with return line, add the 25ml propyl carbinol, be warming up to 70 ℃, add 0.2mol aniline, splash into several Glacial acetic acid, reacted 2 hours, and be cooled to-10 ℃, promptly have a large amount of crystal to produce, filter, solids hexane wash 3 times obtain 30g pyrrole aldehyde anil, yield 88 quality %.Results of elemental analyses following (in the bracket is calculated value, is quality %),
C：77.32(77.62)；N：16.42(16.46)；H：5.96(5.92)
Get the 0.2mol pyrrole aldehyde and join in the there-necked flask of being with return line, add the 20ml propyl carbinol, be warming up to 70 ℃, add 2,4-xylidine 0.2mol splashes into several Glacial acetic acid reactions 2 hours, being cooled to-10 ℃ promptly has a large amount of crystal to produce, and filters solids hexane wash 3 times, obtain 29.7 gram pyrrole aldehydes and contract 2,4-xylidine, yield are 75 quality %, and results of elemental analyses is following, and (in the bracket is calculated value, be mass percent)
C：78.70(78.75)；N：14.05(14.13)；H：7.10(7.12)
Embodiment 3
Prepare carrier of the present invention.
Get 0.2mol magnesium powder and place the 500ml there-necked flask of crossing through nitrogen replacement, add 150ml hexane, 6mmol tetrabutyl titanate, 36mmol tetraethoxy and 0.02g iodine, be heated to 75 ℃ of stir-activatings 2 hours, and dripped 1mol exsiccant n-propylcarbinyl chloride, can be observed tangible reaction, continue reaction 3 hours, filter,, obtain carrier a gained solid hexane wash after drying, its XRD spectra is seen Fig. 1, consists of: (MgCl
2) (BuMgCl)
0.58Mg
0.08[Ti (OC
4H
9)
4)]
0.07[Si (OC
2H
5)
4]
0.23
Method by embodiment 3 prepares carrier, and the add-on of different is tetrabutyl titanate is 3mmol, and the add-on of tetraethoxy is 18mmol, obtains active carrier b after the drying, and its composition formula is as follows:
(MgCl
2)(BuMgCl)
0.58Mg
0.04[Ti(OC
4H
9)
4]
0.04[Si(OC
2H
5)
4]
0.12
Embodiment 5
Method by embodiment 1 prepares carrier, and the add-on of different is tetrabutyl titanate is 3mmol, obtains active carrier c after the drying, and its composition formula is as follows:
(MgCl
2)(BuMgCl)
0.58Mg
0.06[Ti(OC
4H
9)
4]
0.04[Si(OC
2H
5)
4]
0.24
Embodiment 6
Prepare load type non-metallocene catalyst with the load of the inventive method original position.
250ml with the good there-necked flask of nitrogen replacement in, the carrier a (containing magnesium chloride 11.86mmol) that adds 2.8g embodiment 3 preparations, 30ml n-decane and 11.8mmol isooctyl alcohol, being warming up to 50 ℃ stirred 1 hour, dropping is dissolved with the mixing solutions by 20ml normal hexane and the preparation of 10ml toluene of 5.9mmol pyrrole aldehyde anil, color changes gradually, add the back that finishes and under this temperature, continue reaction 1 hour, be cooled to 0 ℃, slow while stirring Dropwise 5 0mmol titanium tetrachloride, after dropwising, be warming up to 110 ℃, add the 50mmol chlorocyclohexane, continue reaction 3 hours.Filter, the gained solid washs with normal hexane, drains, and obtains the 3.3g brown solid, is the catalyzer G of load (pyrrole aldehyde anil) titanous chloride.It is 3.93 quality % that the plasma emission spectroscopy method is measured its Ti content, and Mg content is 13.25 quality %, down together.
Embodiment 7
250ml with the good there-necked flask of nitrogen replacement in, the carrier a (containing magnesium chloride 11.86mmol) that adds 2.8g embodiment 3 preparations, the 30ml n-decane, the 5mmol diisopropyl dimethoxy silane, 4mmol tetraethoxysilane and 11.8mmol isooctyl alcohol, being warming up to 50 ℃ stirred 1 hour, dropping is dissolved with the mixing solutions by 20ml normal hexane and the preparation of 10ml toluene of 5.9mmol pyrrole aldehyde anil, color changes gradually, add the back that finishes and under this temperature, continue reaction 1 hour, be cooled to 0 ℃, slow while stirring Dropwise 5 0mmol titanium tetrachloride, after dropwising, be warming up to 110 ℃, add the 50mmol chlorocyclohexane, continue reaction 3 hours.Filter, the gained solid washs with normal hexane, drains, and obtains the 3.25g brown solid, is load type non-metallocene catalyst F, and its Ti content is 3.82 quality %, and Mg content is 14.16 quality %.
Embodiment 8
250ml with the good there-necked flask of nitrogen replacement in, the carrier a (containing magnesium chloride 11.86mmol) that adds 2.8g embodiment 3 preparations, the 30ml n-decane, the 5mmol diisopropyl dimethoxy silane, 4mmol tetraethoxysilane and 11.8mmol isooctyl alcohol, being warming up to 50 ℃ stirred 1 hour, dropping is dissolved with the mixing solutions by 20ml normal hexane and the preparation of 10ml toluene of 5.9mmol pyrrole aldehyde anil, color changes gradually, add the back that finishes and under this temperature, continue reaction 1 hour, be cooled to 0 ℃, slow while stirring Dropwise 5 0mmol titanium tetrachloride, after dropwising, be warming up to 110 ℃, add the 1.25mmol diisopropyl dimethoxy silane, 1mmol tetraethoxysilane and 50mmol chlorocyclohexane continue reaction 3 hours.Filter, the gained solid washs with normal hexane, drains, and obtains the 3.43g brown solid, is load type non-metallocene catalyst A, and its Ti content is 2.56 quality %, and Mg content is 15.23 quality %.
Embodiment 9
Method by embodiment 8 prepares catalyzer, and different is that the propyl carbinol that adds 11.8mmol replaces isooctyl alcohol, and the Ti content of the catalyst B that obtains is 3.18 quality %, and Mg content is 14.27 quality %.
Method by embodiment 8 prepares catalyzer, and different is that the dehydrated alcohol that adds 11.8mmol replaces isooctyl alcohol, and the Ti content of the catalyzer C that obtains is 4.17 quality %, and Mg content is 12.93 quality %.
Embodiment 11
Method by embodiment 8 prepares catalyzer, and that different is the carrier b that used carrier makes for embodiment 4, and the Ti content of the catalyzer D that obtains is 2.61 quality %, and Mg content is 15.11 quality %.
Method by embodiment 8 prepares catalyzer, and that different is the carrier c that used carrier makes for embodiment 4, and the Ti content of the catalyzer E that obtains is 2.67 quality %, and Mg content is 15.02 quality %.
Embodiment 13
Method by embodiment 8 prepares catalyzer, and different is that the Schiff base ligand that adds contracts 2 for the 5.9mmol pyrrole aldehyde, and 4-xylidine, the Ti content of the catalyzer H that obtains are 2.36 quality %, and Mg content is 15.78 quality %.
Comparative Examples 1
Method by CN200510059771.9 embodiment 1 prepares catalyzer.
(1) preparation nascent state magnesium chloride
Get 12.4mmol magnesium powder and place the there-necked flask through the 250ml of nitrogen replacement, add 25ml heptane and 0.02g iodine, 75 ℃ of stir-activatings 2 hours drip the 62mmol n-propylcarbinyl chloride, react 3 hours, obtain the suspension of nascent state magnesium chloride.
(2) the original position load prepares catalyzer
Nascent state magnesium chloride suspension is reduced to 25 ℃, dropping is dissolved with the 20ml normal hexane of 3.8mmol pyrrole aldehyde anil and the mixing solutions of 10ml toluene, it is red that the system color gradually becomes, react cooling after 1 hour, slowly drip the 18.2mmol titanium tetrachloride under 0 ℃ while stirring, be warming up to 50 ℃ and continue reaction 3 hours, filter, solid washs three times with normal hexane, drain solvent, obtain being loaded with on the 1.31g magnesium chloride brown solid catalyzer M of (pyrrole aldehyde anil) titanous chloride, its Ti content is that 4.55 quality %, Mg content are 13.05 quality %.
Below investigate the normal pressure ethylene homo performance of catalyzer of the present invention.
The 250ml there-necked flask with twice of nitrogen replacement, ethene displacement three times, is fed ethylene gas, and keep-uping pressure is 0.1MPa, and adding 100ml hexane and 5.0ml concentration is the toluene solution of the methylaluminoxane (MAO) of 10 quality %, and making the Al/Ti mol ratio is 500.40 ℃ add catalyzer, react 30 minutes, stop to feed ethene, add ethanol and hydrochloric acid termination reaction.Filter the back solid and wash, weigh after the products therefrom drying with clear water.Each embodiment catalyst system therefor and catalyst activity see Table 1.
Embodiment 23～31
Following examples are investigated the high-pressure ethylene homopolymerization performance of catalyzer of the present invention.
In 2 liters of stainless steel autoclaves that nitrogen replacement is crossed, adjusting the hydrogen dividing potential drop is prescribed value, feed ethene again, the maintenance total pressure is 0.8MPa, adding 1000ml hexane, 2.0ml concentration are the hexane solution and the catalyzer of the triethyl aluminum of 1.0M, making the Al/Ti mol ratio is 200,80 ℃ of polyreactions 1 hour, obtains polyethylene product.The hydrogen dividing potential drop of each embodiment catalyst system therefor, control and the bulk density of catalyst activity and ethene see Table 2, and wherein embodiment 23,29 and 30 polymerization kinetics curve are seen Fig. 2, and the polymerization kinetics curve of embodiment 25～28 is seen Fig. 3.
As shown in Figure 2, the inventive method is when the preparation catalyzer, and the catalyzer that obtains by the adding mode of adjusting electron donor has different polymer kinetics curves.Fig. 3 shows that the catalyzer that the inventive method makes has better hydrogen regulation sensitivity.
Embodiment 32～35
Following examples are investigated the copolymerization performance of catalyzer.
In 2 liters of stainless steel autoclaves that nitrogen replacement is crossed, adjusting the hydrogen dividing potential drop is 0.2MPa, feed ethene again, the maintenance total pressure is 0.8MPa, adding 1000ml hexane, 2.0ml concentration are hexane solution, catalyzer C and the comonomer of the triethyl aluminum of 1.0M, making the Al/Ti mol ratio is 200,80 ℃ of polyreactions 1 hour, obtains the ethylene copolymer product.Used comonomer of each embodiment and dosage, polymerisate character see Table 3, and the described comonomer insertion of table 3 rate is the molar fraction of comonomer in the ternary sequence in the multipolymer nuclear magnetic spectrogram.
Table 1
| Embodiment number | The catalyzer numbering | Bearer number | Catalyzer carries titanium amount, quality % | Catalyst activity, 10 5gPE/(molTi·h) |
| 14 | G | a | 3.93 | 3.23 |
| 15 | F | a | 3.82 | 3.82 |
| 16 | A | a | 2.56 | 4.08 |
| 17 | B | a | 3.18 | 3.51 |
| 18 | C | a | 4.17 | 3.43 |
| 19 | D | b | 3.22 | 3.17 |
| 20 | E | c | 3.58 | 2.45 |
| 21 | H | a | 2.36 | 3.48 |
| 22 | M | Nascent state MgCl 2 | 4.55 | 1.34 |
Table 2
| Embodiment number | The catalyzer numbering | The hydrogen dividing potential drop, MPa | Catalyst activity, 10 6gPE/molTi.h | The PE bulk density, g/cm 3 |
| 23 | A | 0.2 | 4.61 | 0.287 |
| 24 | B | 0.2 | 4.53 | 0.320 |
| 25 | |
0 | 12.74 | 0.328 |
| 26 | C | 0.1 | 5.56 | 0.329 |
| 27 | C | 0.2 | 3.66 | 0.330 |
| 28 | C | 0.3 | 1.81 | 0.320 |
| 29 | F | 0.2 | 4.48 | 0.283 |
| 30 | G | 0.2 | 3.87 | 0.279 |
| 31 | M | 0.2 | 2.71 | 0.220 |
Table 3
| Embodiment number | Comonomer and dosage | Catalytic activity, 10 6gPE/molTi.h | Comonomer insertion rate, mol% | Fusing point, ℃ | Degree of crystallinity, % | The PE bulk density, g/cm 3 |
| 32 | 16 gram 1-butylene | 5.21 | 1.531 | 127.68 | 54.23 | 0.298 |
| 33 | 16 gram 1-hexenes | 4.83 | 0.315 | 131.75 | 65.34 | 0.303 |
| 34 | 32 gram 1-hexenes | 4.61 | 0.321 | 130.03 | 59.51 | 0.296 |
| 35 | 40 gram 1-hexenes | 5.12 | 0.556 | 129.96 | 60.37 | 0.288 |
Claims (18)
1. the preparation method of a load type non-metallocene polyolefin catalyst comprises:
(1) be (MgCl with general expression
2) (R
1MgCl)
pMg
q[Ti (OR
2)
4]
x[Si (OR
3)
4]
yCarrier be dispersed in the inert organic solvents, in the described expression formula, R
1And R
2Be selected from C respectively
2～C
4Alkyl, R
3Be selected from C
1～C
3Alkyl, the p value is 0.4～0.8, the q value is 0.02～0.15, the x value is 0.03～0.09, the y value is 0.1～0.3, the abundant contact reacts of Fatty Alcohol(C12-C14 and C12-C18) that adds general formula and be R ' OH forms slurries, R ' is selected from C among described R ' OH
1～C
8Alkyl,
(2) Schiff base ligand shown in the adding formula (I) in the slurries that in (1) step, make, abundant contact reacts,
In the formula (I), R is single the replacement or multi-substituent on the pyrrole ring, is selected from hydrogen, C
1～C
12Alkyl or C
6～C
14Aryl; If the substituting group on the pyrrole ring is two when above, adjacent substituting group can be connected with each other and pyrrole ring forms condensed ring, R
2Be selected from hydrogen or C
1～C
6Alkyl, the substituent R on the phenyl ring
1Number be 1 to 5, R
1Be selected from hydrogen or C
1～C
12Alkyl, C
6～C
9Alkaryl, nitro or halogen,
(3) under-10～30 ℃, in the slurries that make of above-mentioned (2) step, add MX
4Compound adds halohydrocarbon again, is warming up to 60～130 ℃ of fully reactions, described MX
4In, M is selected from titanium or zirconium, and X is a halogen, the dope filtration, washing, the drying that will obtain after will reacting then.
2. in accordance with the method for claim 1, it is characterized in that the temperature of reaction that (1) step and (2) go on foot is 20～80 ℃.
3. in accordance with the method for claim 1, it is characterized in that described halohydrocarbon of (3) step is selected from a hydrochloric ether, the alkyl in the halohydrocarbon is selected from C
1～C
8Alkyl or cycloalkyl.
4. in accordance with the method for claim 1, it is characterized in that described inert organic solvents of (1) step is selected from C
6～C
10Alkane or naphthenic hydrocarbon.
5. in accordance with the method for claim 1, it is characterized in that contained MgCl in described Fatty Alcohol(C12-C14 and C12-C18) of (1) step and the carrier
2Mol ratio be 0.1～2.0: 1.
6. in accordance with the method for claim 1, it is characterized in that contained MgCl in Schiff base ligand that (2) step adds and the carrier
2Mol ratio be 0.03～1.0: 1.
7. Schiff base ligand and the MX shown in the formula (I) that it is characterized in that adding in accordance with the method for claim 1,
4The mol ratio of compound is 0.4～10: 1.
8. in accordance with the method for claim 1, it is characterized in that R is selected from C in the Schiff base ligand shown in the formula (I)
1～C
4Alkyl, R
1Be selected from hydrogen, C
1～C
4Alkyl, phenyl, nitro or fluorine, R
2Be selected from hydrogen or methyl.
9. when it is characterized in that adding Fatty Alcohol(C12-C14 and C12-C18) in (1) step, also add in accordance with the method for claim 1, by R
4 nSi (OR
5)
4-nAnd Si (OR
5)
4The mixture of siloxanes of forming, wherein R
4Be selected from C
1～C
6Alkyl, C
4～C
6Cycloalkyl or C
6～C
8Aryl, R
5Be selected from C
1～C
4Alkyl, n is 1～3 integer.
10. in accordance with the method for claim 9, it is characterized in that described R
4 nSi (OR
5)
4-nWith contained MgCl in the carrier
2Mol ratio be 0.1～1.0: 1, described R
4 nSi (OR
5)
4-nWith Si (OR
5)
4Mol ratio be 1～3: 1.
11. add MX with (3) step when it is characterized in that in accordance with the method for claim 1, adding Fatty Alcohol(C12-C14 and C12-C18) in (1) step
4Compound adds by R respectively after heating up
4 nSi (OR
5)
4-nAnd Si (OR
5)
4The mixture of siloxanes of forming, wherein R
4Be selected from C
1～C
6Alkyl, C
4～C
6Cycloalkyl or C
6～C
8Aryl, R
5Be selected from C
1～C
4Alkyl, n is 1～3 integer.
12. it is characterized in that in accordance with the method for claim 11, the R that (1) step adds
4 nSi (OR
5)
4-nWith contained MgCl in the carrier
2Mol ratio be 0.1～1.0: 1, the R of adding
4 nSi (OR
5)
4-nWith Si (OR
5)
4Mol ratio be 1～3: 1.
13. it is characterized in that in accordance with the method for claim 11, the R that (3) step and (1) step add
4 nSi (OR
5)
4-nMol ratio be 0.1～0.5: 1, the Si (OR that (3) step and (1) step add
5)
4Mol ratio be 0.1～0.5: 1.
14. in accordance with the method for claim 1, it is characterized in that the preparation method of described carrier of (1) step comprises: add the magnesium powder in varsol, the back that stirs adds the electron donor compound, and adding then with magnesium powder mol ratio is 2.0～8.0: 1 C
2～C
4A chloroparaffin fully react, filter, collect solids washing and dry, described electron donor compound is that general formula is Si (OR
3)
4Siloxanes and Ti (OR
2)
4Mixture.
15. in accordance with the method for claim 14, it is characterized in that a described chloroparaffin is chloro-propane, n-propylcarbinyl chloride, chloro-iso-butane, tert-butyl chloride or chloro iso-pentane.
16. it is characterized in that in accordance with the method for claim 14, the temperature of reaction of a described magnesium powder and a chloroparaffin is 20～100 ℃.
17. in accordance with the method for claim 14, it is characterized in that described Si (OR
3)
4With the mol ratio of magnesium powder be 0.05～0.5, Ti (OR
2)
4With the mol ratio of magnesium powder be 0.01～0.05.
18. in accordance with the method for claim 3, it is characterized in that described varsol is selected from C
5～C
8Alkane or C
6～C
8Aromatic hydrocarbons.
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| CN116769087A (en) * | 2023-07-13 | 2023-09-19 | 湖北昱泓高新材料科技有限公司 | Preparation method of catalyst for preparing ultra-high molecular weight polyethylene |
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| CN1176118C (en) * | 2002-08-29 | 2004-11-17 | 中国石油化工股份有限公司 | Loading type olefine polymerization catalyst using xifu alkali as ligand its preparation method |
| CN1332949C (en) * | 2003-07-31 | 2007-08-22 | 中国石油化工股份有限公司 | Olefine oligomerization catalyst, and its preparation method and use |
| CN100363391C (en) * | 2005-02-28 | 2008-01-23 | 中国石油化工股份有限公司 | Supported bimetal polyvinyl catalyst and preparation method thereof |
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| CN111499777B (en) * | 2020-04-29 | 2023-02-17 | 江苏扬农化工集团有限公司 | Ultrahigh molecular weight polyethylene catalyst, and preparation method and application thereof |
| CN116769087A (en) * | 2023-07-13 | 2023-09-19 | 湖北昱泓高新材料科技有限公司 | Preparation method of catalyst for preparing ultra-high molecular weight polyethylene |
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