CN105440179A - Olefin polymerization catalyst carrier and preparation method and application thereof - Google Patents
Olefin polymerization catalyst carrier and preparation method and application thereof Download PDFInfo
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- CN105440179A CN105440179A CN201410403189.9A CN201410403189A CN105440179A CN 105440179 A CN105440179 A CN 105440179A CN 201410403189 A CN201410403189 A CN 201410403189A CN 105440179 A CN105440179 A CN 105440179A
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Abstract
The present invention discloses an olefin polymerization catalyst carrier and a preparation method and application thereof. The olefin polymerization catalyst carrier is a product obtained by reaction of a compound represented by a formula (1) and an oxirane compound represented by a formula (2), wherein R is a C1-C12 straight-chain or branched-chain alkyl group; X and Y are same or different, andare each independently halogen; R'1 and R'2 are same or different, and are each independently hydrogen, a C1-C5 straight or branched alkyl group or a halogenated alkyl; p is 1-5, and q is 0.001-0.6. When a catalyst prepared by the carrier is used for olefin (particularly propylene) polymerization, bulk density of a polymerization product can be reduced, hydrogen regulation sensitivity of the catalyst is improved, and the polymerization product is substantially free of heterogeneous materials. The formula (1) is shown as MgXY.(ROH)p.(H2O)q, and the formula (2) is as shown in the specification.
Description
Technical field
The present invention relates to a kind of carrier for olefin polymerization catalyst, the preparation method of this kind of carrier for olefin polymerization catalyst and above-mentioned carrier for olefin polymerization catalyst and prepare the application in olefin polymerization catalysis.
Background technology
As everyone knows, when the Ziegler-Natta catalyst of magnesium chloride alcohol adduct load is polymerized for alkene (particularly propylene), its performance is obviously better than the catalyzer of other carrier institute load.Therefore, mostly prepare by halogenated titanium being carried on magnesium chloride alcohol adduct for the catalyzer of olefinic polymerization at present.In order to obtain ball type carrier, extrude by spraying dry, spray cooling, high pressure, the method preparation such as high-speed stirring, mulser method and high-gravity rotating bed method, spherical alcohol adduct can be formed by quenching after high-speed stirring emulsified magnesium chloride alcohol adduct system under high temperature as WO99/44009 and US4399054 etc. discloses.
But, when the catalyzer prepared by above-mentioned published magnesium chloride alcohol adduct is used for olefinic polymerization, is easy to the Fragmentation Phenomena that polymer particle occurs in the course of the polymerization process, thus causes fine polymer powder more.In order to overcome this shortcoming, people attempt again electron donor compound to be incorporated in advance in the carrier preparation of magnesium chloride alcohol adduct, such as: known for industry internal electron donor phthalate compound is incorporated in the synthesis of magnesium chloride alcohol adduct carrier by CN1169840C and CN1286863C, thus obtain " magnesium dichloride-alcohol-phthalic ester " ball type carrier, then by this carrier and titanium tetrachloride reaction to form catalyzer.But described mixture ball type carrier is easily clamminess in preparation process, be difficult to form the suitable spheroidal particle of size.
CN102040683A discloses a kind of method reacting to prepare carrier by magnesium halide alcohol adduct and oxirane compound, and specifically discloses after magnesium halide alcohol adduct melting dispersion, adds oxirane compound; Or in the reactor directly joining containing oxirane compound after magnesium halide alcohol adduct melting is disperseed.But, adopt the method Kaolinite Preparation of Catalyst carrier to there is preparation process instability, easily carrier adhesion occurs, and the shortcoming that carrier molding effect is bad.
In US4861847, epoxy compounds and tributyl phosphate compounds is used to dissolve magnesium chloride, re-use titanium tetrachloride after forming uniform solution separate out carrier and carry out titanium load, reaction product is very complicated, the by product generated is difficult to process, in the process using titanium tetrachloride to separate out, also can use some precipitation additives, this makes byproduct of reaction more complicated, and carrier pattern is difficult to control.In addition, in above-mentioned dissolution system, add alcohol, accelerate the adding of alcohol tributyl phosphate and epoxy to its solvency action, but itself can be had an effect with titanium tetrachloride and can have an impact to follow-up catalyzer pattern and performance.These technology are all use titanium tetrachloride to separate out carrier with Kaolinite Preparation of Catalyst, and as previously described, reaction is complicated, and waste liquid cannot reclaim for this process, and after particularly introducing alcohol in dissolution system, its carrier pattern is difficult to control more.
Summary of the invention
First object of the present invention is the above-mentioned defect in order to overcome existing carrier for olefin polymerization catalyst, and provides a kind of new carrier for olefin polymerization catalyst.
Second object of the present invention is to provide the preparation method of described carrier for olefin polymerization catalyst.
3rd object of the present invention is to provide above-mentioned carrier for olefin polymerization catalyst and is preparing the application in olefin polymerization catalysis.
The invention provides a kind of carrier for olefin polymerization catalyst, wherein, the product that described carrier for olefin polymerization catalyst is obtained by reacting for the oxirane compound shown in the compound shown in formula (1) and formula (2),
MgXY (ROH)
p(H
2o)
qformula (1),
formula (2),
Wherein, R is C
1-C
12the alkyl of straight or branched; X and Y is identical or different, is halogen independently of one another; R '
1and R '
2identical or different, be hydrogen, C independently of one another
1-C
5the alkyl of straight or branched or haloalkyl; P is 1-5, q is 0.001-0.6.
In addition, the invention provides a kind of preparation method of above-mentioned carrier for olefin polymerization catalyst, wherein, the method comprises: under the existence of the 3rd inert media, by the oxirane compound contact reacts shown in the compound shown in formula (1) and formula (2).
In addition, present invention also offers above-mentioned carrier for olefin polymerization catalyst and prepare the application in olefin polymerization catalysis.
The present inventor is surprised to find that, magnesium halide alcohol adduct and oxirane compound are reacted, can make that the particle form of the new olefine polymerization catalyst carrier obtained is good, smooth surface, substantially there will not be irregular particle, and when being polymerized for alkene (particularly propylene) with catalyzer prepared by the carrier of gained, the bulk density of polymerisate can also be reduced, improve the hydrogen response of catalyzer, and substantially without the appearance of opposite sex material.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by preparation example 1;
Fig. 2 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by preparation example 2.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of carrier for olefin polymerization catalyst, wherein, the product that described carrier for olefin polymerization catalyst is obtained by reacting for the oxirane compound shown in the compound shown in formula (1) and formula (2),
MgXY (ROH)
p(H
2o)
qformula (1),
formula (2),
Wherein, R is C
1-C
12the alkyl of straight or branched; X and Y is identical or different, is halogen independently of one another; R '
1and R '
2identical or different, be hydrogen, C independently of one another
1-C
5the alkyl of straight or branched or haloalkyl; P is 1-5, q is 0.001-0.6.
Main improvement of the present invention is magnesium halide alcohol adduct and oxirane compound to react the catalyzer that the carrier of gained can be made to prepare and is used for alkene (particularly propylene) when being polymerized, the bulk density of polymerisate can also be reduced, improve the hydrogen response of catalyzer, and substantially without the appearance of opposite sex material.
According to the present invention, in the magnesium halide alcohol adduct shown in formula (1), preferably, R is preferably C
1-C
8straight or branched alkyl, be more preferably C
2-C
5straight or branched alkyl, as ethyl, propyl group, butyl or amyl group.Particularly, general formula be the compound of ROH specific examples can for but be not limited to: one or more in alcohol of ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol and 2-ethyl-1-, be preferably in ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol and primary isoamyl alcohol one or more.
According to the present invention, preferably, X and Y is bromine or chlorine independently of one another, most preferably is chlorine.
According to the present invention, preferably, p is 1.5-3, q is 0.001-0.005, and most preferably, p is 2.6, q is 0.001-0.005.
In the oxirane compound shown in formula (2), preferably, R '
1and R '
2identical or different, be preferably hydrogen or C independently of one another
1-C
3straight or branched alkyl or haloalkyl.Described C
1-C
3the alkyl of straight or branched or haloalkyl can for but be not limited to: methyl, ethyl, propyl group, chloromethyl, chloroethyl, chloropropyl, brooethyl, bromotrifluoromethane, bromopropyl, methyl fluoride, dichloromethyl, two brooethyls, difluoromethyl, trichloromethyl, trifluoromethyl, trisbromomethyl, chlorine methyl fluoride.Further preferably, the specific examples of described oxirane compound can be but be not limited to: at least one in oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide.
According to the present invention, the consumption of the oxirane compound shown in the compound shown in formula (1) and formula (2) can adjust according to the composition of the carrier for olefin polymerization catalyst of expecting, the weight ratio of the oxirane compound consumption shown in the compound shown in formula (1) and formula (2) can be 1:0.02-0.5, is preferably 1:0.09-0.23.
According to the present invention, the compound shown in described formula (1) can be prepared according to the method preparing magnesium halide alcohol adduct of this area routine, such as, according to the method that embodiment in CN1718595A 1 is recorded.
In a preferred embodiment, the compound shown in described formula (1) can be prepared by the following method:
(1) be the magnesium halide shown in MgXY by general formula, general formula to mix with the first inert media for the alcohol compound shown in ROH and heat, and obtains liquid form mixt;
(2) by liquid form mixt emulsification that step (1) obtains, and it is shaping and carry out solid-liquid separation gained emulsification product to be passed into chilling in the second inert media being cooled to-40 DEG C to 10 DEG C, obtain the solid product of the compound shown in formula (1)
Wherein, X and Y is identical or different, is halogen independently of one another; R is C
1-C
12the alkyl of straight or branched.
In the magnesium halide shown in formula M gXY, preferably, X and Y is bromine or chlorine independently of one another.More preferably, described magnesium halide is selected from magnesium dichloride and/or dibrominated magnesium, most preferably is magnesium dichloride.
At general formula in the alcohol compound shown in ROH, R is preferably C
1-C
8straight or branched alkyl, be more preferably C
2-C
5straight or branched alkyl, as ethyl, propyl group, butyl or amyl group.Particularly, general formula be the compound of ROH specific examples can for but be not limited to: one or more in alcohol of ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol and 2-ethyl-1-, be preferably in ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol and primary isoamyl alcohol one or more.
According to the present invention, general formula can the composition of compound according to the formula (1) of expection be selected for the magnesium halide shown in MgXY and the general formula consumption that is the alcohol compound shown in ROH.Preferably, in every mole of magnesium elements in described magnesium halide, the consumption that general formula is the alcohol compound shown in ROH is 1-6mol; More preferably, in every mole of magnesium elements in described magnesium halide, the consumption that general formula is the alcohol compound shown in ROH is 2-3mol.
According to invention, the minor amount of water in above-mentioned each reactant also can participate in the reaction forming carrier for olefin polymerization catalyst.
According to the present invention, in step (1), for be the magnesium halide shown in MgXY by general formula, general formula is not particularly limited for the blend heated condition of the alcohol compound shown in ROH and the first inert media, as long as the condition of described heating can make general formula for the magnesium halide melting shown in MgXY and with general formula for the alcohol compound shown in ROH reacts.Usually, the condition of described heating comprises: temperature can be 100-130 DEG C, and the time can be 0.5-5 hour; Preferably, described temperature is 120-125 DEG C, and the time is 2-3 hour.
According to the present invention, in step (1), the consumption that the consumption of described first inert media can be the magnesium halide shown in MgXY according to general formula is selected.Usually, in every mole of magnesium elements in described magnesium halide, the consumption of described first inert media can be 0.5-10L, is preferably 0.5-3L.Chemically interactive liquid medium can be there is not with reactant and reaction product in described second inert media for conventional various in this area.Such as: described first inert media can be silicone oil and/or inert liq varsol.Particularly, described first inert media can be one or more in kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.First inert media of the present invention is particularly preferably white oil.
According to the present invention, the liquid form mixt emulsification that well known to a person skilled in the art that step (1) obtains by various method can be adopted.Such as, described liquid form mixt can be carried out low velocity shear or high speed shear, thus by its emulsification.The stir speed (S.S.) of described low velocity shear is generally 400-800 rev/min.The method of described high speed shear is conventionally known to one of skill in the art, high-speed mixing method (that is, being stirred with the speed of 2000-5000 rev/min by the solution containing liquid halogenated magnesium adducts) disclosed in CN1151183C.In addition, by disclosed for described liquid form mixt emulsification: CN1267508C, the solution containing liquid halogenated magnesium adducts can also be carried out rotating dispersion (speed of rotation can be 100-3000 rev/min) in hypergravity bed with reference to method disclosed in following patent; CN1463990A is disclosed to be exported the solution containing liquid halogenated magnesium adducts with the speed of 1500-8000 rev/min in mulser; US6020279 disclosed by spray method by the emulsifying soln containing liquid halogenated magnesium adducts.
According to the present invention, gained emulsification product is passed into chilling in the second inert media being cooled to-40 DEG C to 10 DEG C shaping and carry out solid-liquid separation, preferably, gained emulsification product is passed into chilling in the second inert media being cooled to-35 DEG C to-20 DEG C shaping and carry out solid-liquid separation.
According to the present invention, described second inert media is the unreactive hydrocarbons compounds that boiling point is lower.In every mole of magnesium elements in described magnesium halide, the consumption of described second inert media can be 0.5-15L, is preferably 1-12L; Described second inert media can be one or more in hexane, heptane and toluene, and preferably, described second inert media is hexane and/or heptane.
According to the present invention, described solid-liquid separation can be the existing various method that can realize solid phase and liquid phase separation, such as suction filtration, press filtration or centrifugation, and under preferable case, the method for described solid-liquid separation is filter press technique.
According to the present invention, preferably, the preparation method of the compound shown in formula (1) also comprises and to be carried out by the solid product that step (2) obtains washing and dry.Described washing can adopt the method for well known to a person skilled in the art to be washed by the solid product obtained, inert hydrocarbon solvent (such as: pentane, hexane, heptane, sherwood oil and gasoline) such as can be adopted to wash the solid granulates obtained, preferably washing 3-5 time.To the condition of described drying, there is no particular limitation in the present invention, and the temperature of such as described drying can be 30-50 DEG C, and the time of described drying can be 0.5-10 hour.According to the present invention, described drying can be carried out under normal pressure or reduced pressure.
A preferred embodiment of the invention, the average particulate diameter of described carrier for olefin polymerization catalyst is 10-100 micron, and size distribution is less than 1.2; Preferably, the average particulate diameter of described carrier for olefin polymerization catalyst is 40-60 micron, and size distribution is 0.6-1.1.In this preferred implementation, the catalyzer prepared by this carrier for olefin polymerization catalyst can have higher hydrogen response and obtain having the olefin polymer of lower bulk density.In the present invention, the average particulate diameter of described carrier for olefin polymerization catalyst and size distribution can adopt MasterSizer2000 laser particle analyzer (being manufactured by MalvernInstrumentsLtd) to record.
A second aspect of the present invention provides a kind of method of above-mentioned carrier for olefin polymerization catalyst, the method comprises: under the existence of the 3rd inert media, by the oxirane compound contact reacts shown in the compound shown in formula (1) and formula (2)
MgXY (ROH)
p(H
2o)
qformula (1),
formula (2),
Wherein, R is C
1-C
12the alkyl of straight or branched; X and Y is identical or different, is halogen independently of one another; R '
1and R '
2identical or different, be hydrogen, C independently of one another
1-C
5the alkyl of straight or branched or haloalkyl; P is 1-5, q is 0.001-0.6.
According to the present invention, about R, X, Y, p, q and R '
1and R '
2selection with describe consistent above, do not repeat them here.
According to the present invention, the consumption of the oxirane compound shown in the compound shown in formula (1) and formula (2) can adjust according to the composition of the carrier for olefin polymerization catalyst of expecting, the weight ratio of the oxirane compound consumption shown in the compound shown in formula (1) and formula (2) can be 1:0.02-0.5, is preferably 1:0.09-0.23.
According to the present invention, the compound shown in described formula (1) can be prepared according to the preparation method of the magnesium halide alcohol adduct of this area routine, and under preferable case, the compound shown in described formula (1) can be prepared by the following method:
(1) be the magnesium halide shown in MgXY by general formula, general formula to mix with the first inert media for the alcohol compound shown in ROH and heat, and obtains liquid form mixt;
(2) by liquid form mixt emulsification that step (1) obtains, and it is shaping and carry out solid-liquid separation gained emulsification product to be passed into chilling in the second inert media being cooled to-40 DEG C to 10 DEG C, obtain the solid product of the compound shown in formula (1)
Wherein, X and Y is identical or different, is halogen independently of one another; R is C
1-C
12the alkyl of straight or branched.
According to the present invention, about the compounds process for production thereof shown in described formula (1) with describe above identical, the selection of the raw material namely used and condition with describe consistent above, do not repeat them here.
According to the present invention, the kind of the oxirane compound shown in described formula (2) with describe identical above, do not repeat them here.
According to the present invention, described 3rd inert media can be the unreactive hydrocarbons compounds that boiling point is lower, and with the oxirane compound described in 1g formula (2) for benchmark, the consumption of described 3rd inert media is 3-20mL, is preferably 3-15mL; Described 3rd inert media can be one or more in hexane, heptane, decane and white oil, and preferably, described 3rd inert media is one or more in hexane, heptane and decane.
According to the present invention, the catalytic condition of oxirane compound shown in compound shown in formula (1) and formula (2) can adjust according to the composition of the carrier for olefin polymerization catalyst of expecting, described catalytic condition comprises: temperature is 0-100 DEG C, and the time is 0.5-10h; Preferably, described catalytic condition comprises: temperature is 10-80 DEG C, and the time is 1-6h.
According to the present invention, under preferable case, the product that the preparation method of this carrier for olefin polymerization catalyst also comprises the oxirane compound contact reacts shown in the compound shown in formula (1) and formula (2) obtains carries out press filtration, washing and drying.
The method that described press filtration can adopt those skilled in the art to understand is carried out, and repeats no more herein.
Described washing can adopt the method for well known to a person skilled in the art to be washed by the solid product obtained, and carries out press filtration to remove cleaning solvent after each washing.Inert hydrocarbon solvent (such as: pentane, hexane, heptane, sherwood oil and gasoline) such as can be adopted to wash the solid product obtained, preferably washing 3-5 time.
To the condition of described drying, there is no particular limitation in the present invention, and the temperature of such as described drying can be 25-50 DEG C, and the time of described drying can be 0.5-10 hour.According to the present invention, described drying can be carried out under normal pressure or reduced pressure.
According to the present invention, the water contained in described carrier for olefin polymerization catalyst come from synthesis material and reaction medium with minor amount of water.
According to a third aspect of the present invention, described carrier for olefin polymerization catalyst is reacted with halogenated titanium and electron donor compound further, the catalyzer being suitable for being polymerized as alkene (particularly propylene) can be obtained.Thus, the present invention further provides above-mentioned carrier for olefin polymerization catalyst and prepare the application in olefin polymerization catalysis.
Below will be described the present invention by embodiment.
1, the average particulate diameter of carrier for olefin polymerization catalyst and size distribution adopt MastersSizer2000 particle size analyzer (being manufactured by MalvernInstrumentsLtd) to measure;
2, the apparent form of carrier for olefin polymerization catalyst is observed by the opticmicroscope that to be purchased from the model of Nikon company be EclipseE200;
3, the method that the bulk density of polyolefine powder adopts GB/T1636-2008 to specify measures.
4, melt index is measured according to ASTMD1238-99 method for measuring.
Preparation example 1
This preparation example is for illustration of carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
(1) magnesium chloride alcohol adduct solid prepares according to method disclosed in embodiment in CN1718595A 1, specific as follows:
In the reactor of the 150L of band whipping appts, it is in the white oil of 30 centipoises (20 DEG C) that 10kg (105mol) magnesium chloride and 12.6kg ethanol (273mol) are added 60L viscosity, reacts 2 hours at 125 DEG C.Then being transferred to by the mixed solution of the molten adduct obtained and white oil is preheated in the methyl-silicone oil medium of 125 DEG C, and the viscosity of methyl-silicone oil is 300 centipoises (20 DEG C), and the consumption of methyl-silicone oil is 120L; Stir 10-30 minute with the rotating speed of 200 revs/min, obtain mixed solution.Described mixed solution is introduced high-gravity rotating bed dispersion, and under agitation, by dispersion after mixed solution introduce be cooled in the hexane medium of-35 DEG C in advance, the consumption of hexane is 1200L, be separated into the cooled solidification of magnesium chloride/alcohol adducts melt of small droplets, become spherical solid particles.After chilling gained suspension filter out particulate solid, at room temperature wash this particulate matter with hexane, hexane consumption is 100L/ time, washs 5 times altogether, vacuumizes 1h drying and obtain magnesium chloride alcohol adduct solid A1 at 30 DEG C, through infrared spectroscopy and
1h-NMR method measures, and the molecular formula of this magnesium chloride alcohol adduct solid A1 is MgCl
2(C
2h
5oH)
2.6(H
2o)
0.001.
(2) in the reactor of 1.5L, add 600mL hexane, 60g (0.279mol) magnesium chloride alcohol adduct solid A1,1.8mL (0.023mol) epoxy chloropropane, at 40 DEG C, react press filtration after 5 hours.Gained press filtration product hexane is washed 5 times.Finally by product vacuum-drying 1 hour at 25 DEG C, obtain carrier for olefin polymerization catalyst Z1.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z1 is 53 microns, and size distribution ((D90-D10)/D50) is 1.1.Adopt the particle morphology of observation by light microscope as shown in Figure 1.As can be seen from the figure, the particle form of carrier for olefin polymerization catalyst Z1 is more regular, smooth surface, and be all spherical substantially, particle size distribution is more concentrated.
Preparation example 2
This preparation example is for illustration of carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
Magnesium chloride alcohol adduct solid A2 is prepared according to the step (1) in preparation example 1.
In the reactor of 0.6L, add 200mL hexane, 60g (0.279mol) magnesium chloride alcohol adduct solid A2, epoxy chloropropane 3.9mL (0.05mol), at 10 DEG C, react press filtration after 6 hours.Gained press filtration product hexane is washed 5 times.Finally by product vacuum-drying 2 hours at 50 DEG C, obtain carrier for olefin polymerization catalyst Z2.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z2 is 52 microns, and size distribution ((D90-D10)/D50) is 0.8.Adopt the particle morphology of observation by light microscope as shown in Figure 2.As can be seen from the figure, the particle form of carrier for olefin polymerization catalyst Z2 is more regular, smooth surface, and be all spherical substantially, particle size distribution is more concentrated.
Preparation example 3
This preparation example is for illustration of carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
Magnesium chloride alcohol adduct solid A3 is prepared according to the step (1) in preparation example 1.
In the reactor of 0.6L, add 200mL hexane, 60g (0.279mol) magnesium chloride alcohol adduct carrier A 3, propylene oxide 3.4mL (0.043mol), at 80 DEG C, react press filtration after 1 hour.Gained press filtration product hexane is washed 5 times.Finally by product vacuum-drying 2 hours at 30 DEG C, obtain carrier for olefin polymerization catalyst Z3.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z3 is 52 microns, and size distribution ((D90-D10)/D50) is 1.0.Adopt observation by light microscope particle morphology, the particle form of Z3 is more regular, smooth surface, and be all spherical substantially, particle size distribution is more concentrated.
Preparation example 4
This preparation example is for illustration of carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
Magnesium chloride alcohol adduct solid A4 is prepared according to the step (1) in preparation example 1.
In the reactor of 0.6L, add 200mL hexane, 60g (0.279mol) magnesium chloride alcohol adduct carrier A 4, add oxyethane 5mL (0.064mol), at 20 DEG C, react press filtration after 5 hours.Gained press filtration product hexane is washed 5 times.Finally by product vacuum-drying 1 hour at 25 DEG C, obtain carrier for olefin polymerization catalyst Z4.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z4 is 53 microns, and size distribution ((D90-D10)/D50) is 1.0.Adopt observation by light microscope particle morphology, the particle form of Z4 is more regular, smooth surface, and be all spherical substantially, particle size distribution is more concentrated.
Contrast preparation example 1
Magnesium chloride alcohol adduct solid is prepared, as reference carrier DZ1 according to the step (1) in embodiment 1.
Embodiment 1
This embodiment is for illustration of the application of carrier for olefin polymerization catalyst provided by the invention in olefin polymerization catalysis.
(1) preparation of olefin polymerization catalyst components
In the glass reaction bottle of 300mL, add the titanium tetrachloride of 100mL, be cooled to-20 DEG C, the described carrier for olefin polymerization catalyst Z1 obtained of 40 grams is added wherein, and stir 30min by preparation example 1 at-20 DEG C.Afterwards, start slowly to be warming up to 110 DEG C, in temperature-rise period, add the diisobutyl phthalate of 1.5mL, elimination liquid maintain 30min at 110 DEG C after.Then, add titanium tetrachloride and wash 2 times, finally wash 3 times with hexane, after drying, obtain olefin polymerization catalyst components C1.
(2) propylene polymerization
In the stainless steel autoclave of a 5L, adopt stream of nitrogen gas to purge, in stream of nitrogen gas, then introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of 1mmol, the hydrogen of olefin polymerization catalyst components C1,1.5L (standard volume) obtained by step (1) of the Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg and the liquid propene of 2.5L.Be warming up to 70 DEG C, and react 1 hour at such a temperature, cooling, bleed off pressure, discharging drying obtains polypropylene powder.Weigh to gained polypropylene powder and analyze, result is as shown in table 1.In addition, this polypropylene powder particle form is good, substantially there is not abnormity material.
Embodiment 2
This embodiment is for illustration of the application of carrier for olefin polymerization catalyst provided by the invention in olefin polymerization catalysis.
Carry out preparation and the propylene polymerization of olefin polymerization catalyst components according to the method for embodiment 1, difference is, in propylene polymerization processes, added hydrogen is 6.5L (standard volume).Weigh to gained polypropylene powder and analyze, result is as shown in table 1.In addition, this polypropylene powder particle form is good, substantially there is not abnormity material.
Embodiment 3
This embodiment is for illustration of the application of carrier for olefin polymerization catalyst provided by the invention in olefin polymerization catalysis.
Preparation and the propylene polymerization of olefin polymerization catalyst components is carried out according to the method for embodiment 1, difference is, in the preparation process of olefin polymerization catalyst components, substitute described carrier for olefin polymerization catalyst Z1 with the described carrier for olefin polymerization catalyst Z2 that the preparation example 2 of identical weight obtains and obtain polypropylene powder.Weigh to gained polypropylene powder and analyze, result is as shown in table 1.In addition, this polypropylene powder particle form is good, substantially there is not abnormity material.
Embodiment 4
This embodiment is for illustration of the application of carrier for olefin polymerization catalyst provided by the invention in olefin polymerization catalysis.
Carry out preparation and the propylene polymerization of olefin polymerization catalyst components according to the method for embodiment 3, difference is, in propylene polymerization processes, added hydrogen is 6.5L (standard volume).Weigh to gained polypropylene powder and analyze, result is as shown in table 1.In addition, this polypropylene powder particle form is good, substantially there is not abnormity material.
Embodiment 5
This embodiment is for illustration of the application of carrier for olefin polymerization catalyst provided by the invention in olefin polymerization catalysis.
Preparation and the propylene polymerization of olefin polymerization catalyst components is carried out according to the method for embodiment 1, difference is, in the preparation process of olefin polymerization catalyst components, substitute described carrier for olefin polymerization catalyst Z1 with the described carrier for olefin polymerization catalyst Z3 that the preparation example 3 of identical weight obtains and obtain polypropylene powder.Weigh to gained polypropylene powder and analyze, result is as shown in table 1.In addition, this polypropylene powder particle form is good, substantially there is not abnormity material.
Embodiment 6
This embodiment is for illustration of the application of carrier for olefin polymerization catalyst provided by the invention in olefin polymerization catalysis.
Carry out preparation and the propylene polymerization of olefin polymerization catalyst components according to the method for embodiment 5, difference is, in propylene polymerization processes, added hydrogen is 6.5L (standard volume).Weigh to gained polypropylene powder and analyze, result is as shown in table 1.In addition, this polypropylene powder particle form is good, substantially there is not abnormity material.
Embodiment 7
This embodiment is for illustration of the application of carrier for olefin polymerization catalyst provided by the invention in olefin polymerization catalysis.
Preparation and the propylene polymerization of olefin polymerization catalyst components is carried out according to the method for embodiment 1, difference is, in the preparation process of olefin polymerization catalyst components, substitute described carrier for olefin polymerization catalyst Z1 with the described carrier for olefin polymerization catalyst Z4 that the preparation example 4 of identical weight obtains and obtain polypropylene powder.Weigh to gained polypropylene powder and analyze, result is as shown in table 1.In addition, this polypropylene powder particle form is good, substantially there is not abnormity material.
Embodiment 8
This embodiment is for illustration of the application of carrier for olefin polymerization catalyst provided by the invention in olefin polymerization catalysis.
Carry out preparation and the propylene polymerization of olefin polymerization catalyst components according to the method for embodiment 7, difference is, in propylene polymerization processes, added hydrogen is 6.5L (standard volume).Weigh to gained polypropylene powder and analyze, result is as shown in table 1.In addition, this polypropylene powder particle form is good, substantially there is not abnormity material.
Comparative example 1
Preparation and the propylene polymerization of olefin polymerization catalyst components is carried out according to the method for embodiment 1, difference is, substitute described carrier for olefin polymerization catalyst Z1 with the carrier for olefin polymerization catalyst DZ1 that the contrast preparation example 1 of identical weight obtains, obtain polypropylene powder.Weigh to gained polypropylene powder and analyze, result is as shown in table 1.
Comparative example 2
Carry out preparation and the propylene polymerization of olefin polymerization catalyst components according to the method for comparative example 1, difference is, added hydrogen is 6.5L (standard volume).Weigh to gained polypropylene powder and analyze, result is as shown in table 1.
Table 1
From the results shown in Table 1, the particle form of the carrier for olefin polymerization catalyst adopting method of the present invention to prepare is good, smooth surface, substantially there will not be irregular particle, and when being polymerized for alkene (particularly propylene) with catalyst component prepared by the carrier of gained, the bulk density of polymerisate can also be reduced, improve the hydrogen response of catalyzer, substantially without the appearance of opposite sex material.In addition, as can be seen from the contrast of embodiment 1 and embodiment 2 and comparative example 1 and comparative example 2, the hydrogen regulation performance of the catalyzer prepared by new olefine polymerization catalyst carrier is relatively good, has prospects for commercial application.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (14)
1. a carrier for olefin polymerization catalyst, is characterized in that, the product that described carrier for olefin polymerization catalyst is obtained by reacting for the oxirane compound shown in the compound shown in formula (1) and formula (2),
MgXY (ROH)
p(H
2o)
qformula (1),
formula (2),
Wherein, R is C
1-C
12the alkyl of straight or branched; X and Y is identical or different, is halogen independently of one another; R '
1and R '
2identical or different, be hydrogen, C independently of one another
1-C
5the alkyl of straight or branched or haloalkyl; P is 1-5, q is 0.001-0.6.
2. carrier according to claim 1, wherein, R is C
1-C
8the alkyl of straight or branched; R '
1and R '
2be hydrogen, C independently of one another
1-C
3the alkyl of straight or branched or haloalkyl; X and Y is bromine or chlorine independently of one another; P is 1.5-3, q is 0.001-0.005.
3. carrier according to claim 1, wherein, the mol ratio of the oxirane compound consumption shown in the compound shown in formula (1) and formula (2) is 1:0.02-0.5, is preferably 1:0.09-0.23.
4. the carrier according to claim 1 or 3, wherein, the oxirane compound shown in described formula (2) is selected from one or more in oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide.
5. the carrier according to claim 1 or 3, wherein, the compound shown in described formula (1) is prepared by the following method:
(1) be the magnesium halide shown in MgXY by general formula, general formula to mix with the first inert media for the alcohol compound shown in ROH and heat, and obtains liquid form mixt;
(2) by liquid form mixt emulsification that step (1) obtains, and it is shaping and carry out solid-liquid separation gained emulsification product to be passed into chilling in the second inert media being cooled to-40 DEG C to 10 DEG C, obtain the solid product of the compound shown in formula (1)
Wherein, X and Y is identical or different, is halogen independently of one another; R is C
1-C
12the alkyl of straight or branched.
6. carrier according to claim 5, wherein, in every mole of magnesium elements in described magnesium halide, the consumption that general formula is the alcohol compound shown in ROH is 1-6mol; Preferably, in every mole of magnesium elements in described magnesium halide, the consumption that general formula is the alcohol compound shown in ROH is 2-3mol.
7. carrier according to claim 5, wherein, in step (1), the temperature of described heating is 100-130 DEG C, and the time is 0.5-5 hour; Preferably, the temperature of described heating is 120-125 DEG C, and the time is 2-3 hour.
8. carrier according to claim 5, wherein, in step (1), in every mole of magnesium elements in described magnesium halide, the consumption of described first inert media is 0.5-10L; Described first inert media is silicone oil and/or inert liq varsol; Preferably, described first inert media is one or more in kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
9. carrier according to claim 5, wherein, in step (2), in every mole of magnesium elements in described magnesium halide, the consumption of described second inert media is 0.5-15L; Described second inert media is one or more in hexane, heptane and toluene, and preferably, described second inert media is hexane and/or heptane.
10. according to the carrier in claim 1-9 described in any one, wherein, the average particulate diameter of described carrier for olefin polymerization catalyst is 10-100 micron, and size distribution is less than 1.2; Preferably, the average particulate diameter of described carrier for olefin polymerization catalyst is 40-60 micron, and size distribution is 0.6-1.1.
The method of the carrier for olefin polymerization catalyst in 11. preparation claim 1-10 described in any one, the method comprises: under the existence of the 3rd inert media, by the oxirane compound contact reacts shown in the compound shown in formula (1) and formula (2).
12. methods according to claim 11, wherein, with the compound shown in 1g formula (1) for benchmark, the consumption of described 3rd inert media is 3-20mL; Described 3rd inert media is one or more in hexane, heptane, decane and white oil, and preferably, described 3rd inert media is one or more in hexane, heptane and decane.
13. methods according to claim 11, wherein, described catalytic condition comprises: temperature is 0-100 DEG C, and the time is 0.5-10h; Preferably, described catalytic condition comprises: temperature is 10-80 DEG C, and the time is 1-6h.
The carrier for olefin polymerization catalyst that method in carrier for olefin polymerization catalyst in 14. claim 1-10 described in any one and 11-13 described in any one prepares is preparing the application in olefin polymerization catalysis.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745406A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Process for preparing polyethylene catalyst with low content of fine powder |
| WO2021218913A1 (en) * | 2020-04-28 | 2021-11-04 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization or copolymerization and preparation method therefor, and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1718595A (en) * | 2004-07-05 | 2006-01-11 | 中国石油化工股份有限公司 | Globular catalyst component used for olefine polymerization and its catalyst |
| CN102040681A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Carrier for preparing olefin polymerization catalyst and preparation method thereof |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1718595A (en) * | 2004-07-05 | 2006-01-11 | 中国石油化工股份有限公司 | Globular catalyst component used for olefine polymerization and its catalyst |
| CN102040681A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Carrier for preparing olefin polymerization catalyst and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745406A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Process for preparing polyethylene catalyst with low content of fine powder |
| WO2021218913A1 (en) * | 2020-04-28 | 2021-11-04 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization or copolymerization and preparation method therefor, and application |
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