CN103788240A - 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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- CN103788240A CN103788240A CN201210421112.5A CN201210421112A CN103788240A CN 103788240 A CN103788240 A CN 103788240A CN 201210421112 A CN201210421112 A CN 201210421112A CN 103788240 A CN103788240 A CN 103788240A
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Abstract
The invention provides an olefin polymerization catalyst carrier, a preparation method thereof, and an application of the olefin polymerization catalyst carrier in the preparation of olefin polymerization catalysts. The olefin polymerization catalyst carrier contains magnesium halide with the general formula of MgXY, a compound with the general formula of R1OH, a compound with the general formula of R4OH and an oxirane compound, wherein X is halogen, Y is halogen, a C1-C14 alkyl group, a C1-C14 alkyloxy group, a C6-C14 aryl group or a C6-C14 aryloxy group, R1 is a C1-C8 alkyl group or a C3-C8 cycloalkyl group, R2 and R3 respectively independently represent H, and C1-C5 alkyl or halogenated alkyl groups, R4 is a C16-C24 alkyl or aralkyl group. The carrier has the advantages of good particle form, smooth and special-shaped particles-free surface, and increase of the bulk density of a polymerized product.
Description
Technical field
The present invention relates to the preparation method of a kind of carrier for olefin polymerization catalyst, a kind of carrier for olefin polymerization catalyst and the carrier being prepared by the method and above-mentioned carrier for olefin polymerization catalyst in the application of preparing in olefin polymerization catalysis.
Background technology
As everyone knows, when the Ziegler-Natta catalyst of magnesium chloride alcohol adduct load is used for alkene (particularly propylene) polymerization, its performance is obviously better than the catalyzer of other carrier institute load.Therefore, the current catalyzer for olefinic polymerization is mostly by being carried on halogenated titanium on magnesium chloride alcohol adduct and preparing.In order to obtain ball type carrier, can be dry by spraying, the method preparation such as spray cooling, high pressure extrude, high-speed stirring, mulser method and high-gravity rotating bed method, can form spherical alcohol adduct by quenching after high-speed stirring emulsification magnesium chloride alcohol adduct system under high temperature as WO99/44009 and US4399054 etc. disclose.
But, when the catalyzer of being prepared by above-mentioned published magnesium chloride alcohol adduct during for olefinic polymerization, is easy to occur the Fragmentation Phenomena of polymer particle, thereby causes fine polymer powder more in polymerization process.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, for example: CN1169840C and CN1286863C are incorporated into known industry internal electron donor phthalate compound in synthesizing of magnesium chloride alcohol adduct carrier, thereby obtain " magnesium dichloride-alcohol-phthalic ester " ball type carrier, then by this carrier and titanium tetrachloride reaction to form catalyzer.But the spherical carrier of described mixture is easily clamminess in preparation process, be difficult to form the spheroidal particle that size is suitable.
In addition, above-mentioned magnesium chloride alcohol adduct is all to adopt cryogenic quenching to solidify the alcohol adduct melt of high temperature to make, not only, complicated process of preparation large to the consumption of the energy, must combine preparation by multiple reactors, and the size distribution of prepared alcohol adduct is wider.In order to address this problem, CN102040683A discloses and has a kind ofly reacted to prepare the method for carrier by magnesium halide alcohol adduct with oxyethane compounds, and after specifically disclosing magnesium halide alcohol adduct melting being disperseed, adds oxyethane compounds; Or after being disperseed, magnesium halide alcohol adduct melting directly joins in the reactor containing oxyethane compounds.But, adopt the method Kaolinite Preparation of Catalyst carrier to exist preparation process unstable, easily there is carrier adhesion, and the bad shortcoming of carrier molding effect.
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 a kind of new carrier for olefin polymerization catalyst is provided.
Second object of the present invention is to provide the preparation method of described carrier for olefin polymerization catalyst.
The 3rd object of the present invention is to provide the carrier for olefin polymerization catalyst that aforesaid method prepares.
The 4th object of the present invention is to provide described carrier for olefin polymerization catalyst in the application of preparing in olefin polymerization catalysis.
The invention provides a kind of carrier for olefin polymerization catalyst, wherein, it is R that this carrier for olefin polymerization catalyst contains magnesium halide, the general formula that general formula is MgXY
1the compound of OH, general formula are R
4the compound of OH, oxyethane compounds; In formula M gXY, X is halogen, and Y is halogen, C
1-C
14alkyl, C
1-C
14alkoxyl group, C
6-C
14aryl or C
6-C
14aryloxy; At general formula R
1in OH, R
1for C
1-C
8alkyl or C
3-C
8cycloalkyl; At general formula R
4in OH, R
4for C
16-C
24alkyl or aralkyl; The structure of described oxyethane compounds is as shown in the formula (I):
Wherein, R
2and R
3independent is separately hydrogen, C
1-C
5alkyl or haloalkyl.
The present invention also provides a kind of preparation method of carrier for olefin polymerization catalyst, and the method comprises the following steps:
(1) magnesium halide that is MgXY by general formula, general formula are R
1the compound of OH, general formula are R
4the compound of OH mixes with inert liquid medium and heats, and obtains liquid form mixt;
(2) liquid form mixt emulsification step (1) being obtained, and by emulsification product and oxyethane compounds contact reacts;
In formula M gXY, X is halogen, and Y is halogen, C
1-C
14alkyl, C
1-C
14alkoxyl group, C
6-C
14aryl or C
6-C
14aryloxy; At general formula R
1in OH, R
1for C
1-C
8alkyl or C
3-C
8cycloalkyl; At general formula R
4in OH, R
4for C
16-C
24alkyl or aralkyl; The structure of described oxyethane compounds is as shown in the formula (I):
Wherein, R
2and R
3independent is separately hydrogen, C
1-C
5alkyl or haloalkyl.
The present invention also provides the carrier for olefin polymerization catalyst being prepared by aforesaid method.
In addition, the present invention also provides above-mentioned carrier for olefin polymerization catalyst in the application of preparing in olefin polymerization catalysis.
The present inventor is surprised to find that, in the preparation process of described carrier for olefin polymerization catalyst, adding general formula is R
4the compound of OH, not only can reduce the interparticle collision probability of not moulding, reduce the adhesion between carrier grain, thereby significantly improve stability and dispersiveness prepared by described carrier, make the particle form of the carrier obtaining good, smooth surface, substantially there will not be irregular particle, and the catalyzer of preparing with the carrier of gained is during for alkene (particularly propylene) polymerization, can also improve the bulk density of polymerisate.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is to be 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;
Fig. 3 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by preparation example 3;
Fig. 4 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by preparation example 4;
Fig. 5 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by contrast preparation example 1.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
According to a first aspect of the invention, to contain magnesium halide, the general formula that general formula is MgXY be R for carrier for olefin polymerization catalyst provided by the invention
1the compound of OH, general formula are R
4the compound of OH, oxyethane compounds; In formula M gXY, X is halogen, and Y is halogen, C
1-C
14alkyl, C
1-C
14alkoxyl group, C
6-C
14aryl or C
6-C
14aryloxy; At general formula R
1in OH, R
1for C
1-C
8alkyl or C
3-C
8cycloalkyl; At general formula R
4in OH, R
4for C
16-C
24alkyl or aralkyl; The structure of described oxyethane compounds is as shown in the formula (I):
Wherein, R
2and R
3independent is separately hydrogen, C
1-C
5alkyl or haloalkyl.
According to the present invention, the content of the above-mentioned each component in described carrier for olefin polymerization catalyst can be selected in the larger context and change, and for example, the magnesium halide take 1mol general formula as MgXY is benchmark, and general formula is R
1the content of the compound of OH can be 4-30mol, and general formula is R
4the content of the compound of OH can be 0.001-1.5mol, and the content of structure oxyethane compounds as shown in the formula (I) can be 1-10mol; Preferably, the magnesium halide take 1mol general formula as MgXY is benchmark, and general formula is R
1the content of the compound of OH is 6-20mol, and general formula is R
4the content of the compound of OH is 0.01-1mol, and the content of structure oxyethane compounds is as shown in the formula (I) 2-6mol.
In the present invention, in formula M gXY, X is preferably chlorine or bromine, and Y is preferably chlorine, bromine, C
1-C
5alkyl, C
1-C
5alkoxyl group, C
6-C
10aryl or C
6-C
10aryloxy.Described C
1-C
5alkyl can be for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl or neo-pentyl, described C
1-C
5alkoxyl group can be for example methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or isobutoxy, described C
6-C
10aryl can be for example phenyl, o-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene, an ethylbenzene, to ethylbenzene or naphthyl, described C
6-C
10aryloxy can be for example phenoxy group or naphthyloxy.General formula is that the magnesium halide of MgXY can be a kind of magnesium halide, or the mixture of multiple magnesium halide.General formula is that the specific examples of the magnesium halide of MgXY can be but be not limited to: one or more in magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium.From the angle of being easy to get property of raw material, be preferably magnesium chloride.
According to the present invention, at general formula R
1in OH, R
1be preferably C
1-C
8alkyl.Described C
1-C
8alkyl can be for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, hexyl, isohexyl, heptyl, different heptyl, octyl group or iso-octyl.General formula is R
1the specific examples of the compound of OH can be but be not limited to: one or more in ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol and 2-Ethylhexyl Alcohol.
According to the present invention, at general formula R
4in OH, R
4be preferably C
16-C
20alkyl or aralkyl.General formula is R
4the specific examples of the compound of OH can be but be not limited to: hexadecanol and stearyl alcohol.
According to the present invention, in structure oxyethane compounds as shown in the formula (I), R
2and R
3preferably independent is separately hydrogen, C
1-C
3alkyl or haloalkyl.The specific examples of described oxyethane compounds can be but be not limited to: one or more in oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide.
A preferred embodiment of the invention, the average particulate diameter of described carrier for olefin polymerization catalyst can be 10-100 micron, be preferably 30-70 micron, and size distribution is less than 1.2, is preferably 0.7-0.9.In this preferred implementation, the catalyzer of being prepared by this carrier for olefin polymerization catalyst can obtain having the more olefin polymer of high-bulk-density.In the present invention, the average particulate diameter of described carrier for olefin polymerization catalyst and size distribution can adopt Master Sizer 2000 laser particle analyzers (being manufactured by Malvern Instruments Ltd) to record.
According to the present invention, the water containing in described carrier for olefin polymerization catalyst come from synthesis material and reaction medium with minor amount of water.
According to a second aspect of the invention, the preparation method of carrier for olefin polymerization catalyst provided by the invention comprises the following steps:
(1) magnesium halide that is MgXY by general formula, general formula are R
1the compound of OH, general formula are R
4the compound of OH mixes with inert liquid medium and heats, and obtains liquid form mixt;
(2) liquid form mixt emulsification step (1) being obtained, and by emulsification product and oxyethane compounds contact reacts;
In formula M gXY, X is halogen, and Y is halogen, C
1-C
14alkyl, C
1-C
14alkoxyl group, C
6-C
14aryl or C
6-C
14aryloxy; At general formula R
1in OH, R
1for C
1-C
8alkyl or C
3-C
8cycloalkyl; At general formula R
4in OH, R
4for C
16-C
24alkyl or aralkyl; The structure of described oxyethane compounds is as shown in the formula (I):
Wherein, R
2and R
3independent is separately hydrogen, C
1-C
5alkyl or haloalkyl.
According to the present invention, magnesium halide, general formula that general formula is MgXY are R
1the compound of OH, general formula are R
4the compound of OH, the consumption of structure oxyethane compounds as shown in the formula (I) can carry out appropriate selection according to the composition of the carrier for olefin polymerization catalyst of expection, and preferably, the magnesium halide take 1mol general formula as MgXY is benchmark, and general formula is R
1the consumption of the compound of OH is 4-30mol, and general formula is R
4the consumption of the compound of OH is 0.001-1.5mol, and the consumption of structure oxyethane compounds is as shown in the formula (I) 1-10mol; More preferably, the magnesium halide take 1mol general formula as MgXY is benchmark, and general formula is R
1the consumption of the compound of OH is 6-20mol, and general formula is R
4the consumption of the compound of OH is 0.01-1mol, and the consumption of structure oxyethane compounds is as shown in the formula (I) 2-6mol.
In the method according to the invention, the minor amount of water in above-mentioned each reactant also can participate in forming the reaction of carrier for olefin polymerization catalyst.
According to the present invention, in step (1), be R for the magnesium halide that is MgXY by general formula, general formula
1the compound of OH, general formula are R
4the blend heated condition of the compound of OH and inert liquid medium is not particularly limited, if the condition of described heating make general formula be the magnesium halide melting of MgXY and with general formula be R
1the compound of OH and general formula are R
4the compound of OH reacts.Usually, the condition of described heating comprises: temperature can be 80-120 ℃, and the time can be 0.5-5 hour; Preferably, described temperature can be 80-100 ℃, and the time can be 0.5-3 hour.
According to the present invention, the consumption of the magnesium halide that the consumption of described inert liquid medium can be MgXY according to general formula is selected.Usually, the magnesium halide take 1mol general formula as MgXY is benchmark, and the consumption of described inert liquid medium can be 0.8-10L, be preferably 2-8L.Can not there is not chemically interactive liquid medium with reactant and reaction product for conventional various in this area in described inert liquid medium.For example: described inert liquid medium can be silicone oil and/or inert liq varsol.Particularly, described inert liquid medium 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.Inert liquid medium of the present invention is particularly preferably white oil.
According to the present invention, can adopt the liquid form mixt emulsification that well known to a person skilled in the art that the whole bag of tricks obtains step (1).For example, described liquid form mixt can be carried out to high speed shear, thereby by its emulsification.The method of described high speed shear is conventionally known to one of skill in the art, high-speed mixing method as disclosed in CN1151183C (, the solution that contains liquid adduct of magnesium halides being stirred with the speed of 2000-5000 rev/min).In addition, can also the solution that contain liquid adduct of magnesium halides be rotated in hypergravity bed to dispersions (speed of rotation can be 100-3000 rev/min) by disclosed described liquid form mixt emulsification: CN1267508C with reference to following patent disclosed method; CN1463990A is disclosed exports the solution that contains liquid adduct of magnesium halides speed with 1500-8000 rev/min in mulser; US6020279 is disclosed will contain the emulsifying soln of liquid adduct of magnesium halides by spray method.
According to the present invention, in step (2), can be the existing various conditions that can form carrier for olefin polymerization catalyst by emulsification product and the catalytic condition of oxyethane compounds, for example, described catalytic condition comprises that temperature can be 80-120 ℃, and the time can be 20-60 minute; Preferably, described catalytic condition comprises that temperature is 80-100 ℃, and the time is 20-50 minute.
According to the present invention, the method can also comprise in the product that contact reacts is obtained carries out solid-liquid separation, and solid product is washed and is dried.Described solid-liquid separation can be the existing various method that can realize solid phase and liquid phase separation, for example suction filtration, press filtration or centrifugation, and under preferable case, the method for described solid-liquid separation is filter press technique.The present invention is not particularly limited the condition of press filtration, is as the criterion with separating of liquid phase to realize as far as possible fully solid phase.Described washing can adopt the method for well known to a person skilled in the art that the solid product obtaining is washed, for example, can adopt inert hydrocarbon solvent (for example: pentane, hexane, heptane, sherwood oil and gasoline) to wash the solid product obtaining.The present invention is not particularly limited for described dry condition, and for example: described dry temperature can be 20-70 ℃, the described dry time can be 0.5-10 hour.According to the present invention, described dry can carrying out under normal pressure or reduced pressure.
According to a third aspect of the present invention, the present invention also provides the carrier for olefin polymerization catalyst of being prepared by aforesaid method.
According to a fourth aspect of the present invention, described carrier for olefin polymerization catalyst is further reacted with halogenated titanium and electron donor compound, can obtain being suitable for the catalyzer as alkene (particularly propylene) polymerization.Thus, the present invention further provides above-mentioned carrier for olefin polymerization catalyst in the application of preparing in olefin polymerization catalysis.
Below will describe the present invention by embodiment.
1, the average particulate diameter of carrier for olefin polymerization catalyst and size distribution adopt Masters Sizer2000 particle size analyzer (being manufactured by Malvern Instruments Ltd) to measure;
2, the apparent pattern of carrier for olefin polymerization catalyst is observed by the opticmicroscope that to be purchased from the model of Nikon company be Eclipse E200;
3, the bulk density of polyolefine powder adopts the method for GB/T 1636-2008 regulation to measure.
Preparation example 1
This preparation example is used for illustrating carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reactor of 1.6L, add 200mL white oil, 8.0g(0.08mol) magnesium chloride, 5g(0.02mol) stearyl alcohol, 100mL(1.7mol) ethanol, be under agitation warming up to 90 ℃.After isothermal reaction 1 hour, mixture high-speed stirring (1600rpm) is disperseed 30 minutes, to carry out emulsification.And add 25mL(0.3mol in above-mentioned emulsification product) epoxy chloropropane, press filtration after reaction half hour, by hexane washing 5 times for press filtration product, vacuum-drying, obtains carrier for olefin polymerization catalyst Z1.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z1 is 35 microns, and size distribution ((D90-D10)/D50) is 0.8.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, and smooth surface is all spherical substantially, and particle size distribution is more concentrated, and there is no that irregular particle exists.
Preparation example 2
This preparation example is used for illustrating carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reactor of 1.6L, add 200mL white oil, 8.0g(0.08mol) magnesium chloride, 10.8g(0.04mol) stearyl alcohol, 28mL(0.48mol) ethanol, be under agitation warming up to 100 ℃.After isothermal reaction 0.5 hour, mixture high-speed stirring (1600rpm) is disperseed 30 minutes, to carry out emulsification.And add 12.5mL(0.16mol in above-mentioned emulsification product) epoxy chloropropane, press filtration after reaction half hour, by hexane washing 5 times for press filtration product, vacuum-drying, obtains carrier for olefin polymerization catalyst Z2.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z2 is 36 microns, and size distribution ((D90-D10)/D50) is 0.75.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, and smooth surface is all spherical substantially, and particle size distribution is more concentrated, and there is no that irregular particle exists.
Preparation example 3
This preparation example is used for illustrating carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reactor of 1.6L, add 200mL white oil, 8.0g(0.08mol) magnesium chloride, 21.1g(0.08mol) stearyl alcohol, 56mL(0.96mol) ethanol, be under agitation warming up to 80 ℃.After isothermal reaction 3 hours, mixture high-speed stirring (1600rpm) is disperseed 30 minutes, to carry out emulsification.And add 37.6mL(0.48mol in above-mentioned emulsification product) epoxy chloropropane, press filtration after reaction half hour, by hexane washing 5 times for press filtration product, vacuum-drying, obtains carrier for olefin polymerization catalyst Z3.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z3 is 38 microns, and size distribution ((D90-D10)/D50) is 0.8.Adopt the particle morphology of observation by light microscope as shown in Figure 3.As can be seen from the figure, the particle form of carrier for olefin polymerization catalyst Z3 is more regular, and smooth surface is all spherical substantially, and particle size distribution is more concentrated, and there is no that irregular particle exists.
Preparation example 4
This preparation example is used for illustrating carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
Method according to preparation example 1 is prepared carrier for olefin polymerization catalyst, different, and described stearyl alcohol substitutes with the hexadecanol of identical mole number, obtains carrier for olefin polymerization catalyst Z4.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z4 is 45 microns, and size distribution ((D90-D10)/D50) is 0.85.Adopt the particle morphology of observation by light microscope as shown in Figure 4.As can be seen from the figure, the particle form of carrier for olefin polymerization catalyst Z4 is more regular, and smooth surface is all spherical substantially, and particle size distribution is more concentrated, and there is no that irregular particle exists.
Preparation example 5
This preparation example is used for illustrating carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reactor of 1.6L, add 600mL methyl-silicone oil, 8.0g(0.08mol) magnesium bromide, 29.1g(0.12mol) hexadecanol, 13mL(0.32mol) methyl alcohol, be under agitation warming up to 110 ℃.After isothermal reaction 0.3 hour, mixture high-speed stirring (1600rpm) is disperseed 30 minutes, to carry out emulsification.And add 4mL(0.08mol in above-mentioned emulsification product) oxyethane, press filtration after reaction half hour, by hexane washing 5 times for press filtration product, vacuum-drying, obtains carrier for olefin polymerization catalyst Z5.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst Z5 is 46 microns, and size distribution ((D90-D10)/D50) is 0.9.Adopt the pattern of observation by light microscope particle to find, the particle form of carrier for olefin polymerization catalyst Z4 is more regular, and surface is comparatively smooth, is all spherical substantially, and particle size distribution is more concentrated, and there is no that irregular particle exists.
Contrast preparation example 1
This contrast preparation example is used for illustrating reference carrier for olefin polymerization catalyst and preparation method thereof.
Method according to preparation example 5 is prepared carrier for olefin polymerization catalyst, different, and described stearyl alcohol substitutes with the ethanol of identical mole number, obtains carrier for olefin polymerization catalyst DZ1.
The average particulate diameter (D50) of described carrier for olefin polymerization catalyst DZ1 is 47 microns, and size distribution ((D90-D10)/D50) is 1.3.Adopt the particle morphology of observation by light microscope as shown in Figure 5.As can be seen from the figure, in carrier for olefin polymerization catalyst DZ1, have a large amount of irregular particles, and surface is comparatively coarse.
Embodiment 1
This embodiment is for illustrating the preparation of alkene provided by the invention.
(1) preparation of olefin polymerization catalysis
In the glass reaction bottle of 300mL, add the titanium tetrachloride of 100mL, be cooled to-20 ℃, the described carrier for olefin polymerization catalyst Z1 being obtained by preparation example 1 of 40 grams is added wherein, and stir 30min at-20 ℃.Afterwards, start be slowly warming up to 110 ℃, in temperature-rise period, add the diisobutyl phthalate of 1.5mL, at 110 ℃, maintain 30min after elimination liquid.Then, add titanium tetrachloride washing 2 times, finally wash 3 times with hexane, after being dried, obtain olefin polymerization catalysis C1.
(3) propylene polymerization
In the stainless steel autoclave of a 5L, adopt stream of nitrogen gas purge, then in stream of nitrogen gas, introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of 1mmol, Cyclohexylmethyldimethoxysilane, the anhydrous hexane of 10mL and the olefin polymerization catalysis C1 being obtained by step (1), the 1.5L(standard volume of 10mg of 0.05mmol) hydrogen and the liquid propene of 2.5L.Be warming up to 70 ℃, and at this temperature, react 1 hour, cooling, bleeds off pressure, the dry polypropylene powder that obtains of discharging.The bulk density of this polypropylene powder is 0.44g/cm
3, in addition, this polypropylene powder particle form is good, does not substantially have abnormity material.
Embodiment 2
This embodiment is for illustrating the preparation of alkene provided by the invention.
Carry out propylene polymerization according to the method for embodiment 1, different, the described carrier for olefin polymerization catalyst Z2 that described carrier for olefin polymerization catalyst Z1 obtains by preparation example 2 substitutes, and obtains polypropylene powder.The bulk density of this polypropylene powder is 0.44g/cm
3, in addition, this polypropylene powder particle form is good, without abnormity material.
Embodiment 3
This embodiment is for illustrating the preparation of alkene provided by the invention.
Carry out propylene polymerization according to the method for embodiment 1, different, the described carrier for olefin polymerization catalyst Z3 that described carrier for olefin polymerization catalyst Z1 obtains by preparation example 3 substitutes, and obtains polypropylene powder.The bulk density of this polypropylene powder is 0.44g/cm
3, in addition, this polypropylene powder particle form is good, without abnormity material.
Embodiment 4
This embodiment is for illustrating the preparation of alkene provided by the invention.
Carry out propylene polymerization according to the method for embodiment 1, different, the described carrier for olefin polymerization catalyst Z4 that described carrier for olefin polymerization catalyst Z1 obtains by preparation example 4 substitutes, and obtains polypropylene powder.The bulk density of this polypropylene powder is 0.43g/cm
3, in addition, this polypropylene powder particle form is good, without abnormity material.
Embodiment 5
This embodiment is for illustrating the preparation of alkene provided by the invention.
Carry out propylene polymerization according to the method for embodiment 1, different, the described carrier for olefin polymerization catalyst Z5 that described carrier for olefin polymerization catalyst Z1 obtains by preparation example 5 substitutes, and obtains polypropylene powder.The bulk density of this polypropylene powder is 0.43g/cm
3, in addition, this polypropylene powder particle form is good, without abnormity material.
Comparative example 1
This comparative example is for illustrating the preparation of reference alkene.
Carry out propylene polymerization according to the method for embodiment 1, different, described carrier for olefin polymerization catalyst Z1 substitutes with the described carrier for olefin polymerization catalyst DZ1 that contrast preparation example 1 obtains, and obtains polypropylene powder.The bulk density of this polypropylene powder is 0.40g/cm
3, in addition, in this polypropylene powder particle, there is more abnormity material.
As can be seen from the above results, adopt the particle form of the carrier for olefin polymerization catalyst that method of the present invention prepares good, smooth surface, substantially there will not be irregular particle, and the catalyzer of preparing with the carrier of gained is during for alkene (particularly propylene) polymerization, can also improve the bulk density of polymerisate, substantially without the appearance of opposite sex material, have 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 characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various 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, it is R that this carrier for olefin polymerization catalyst contains magnesium halide, the general formula that general formula is MgXY
1the compound of OH, general formula are R
4the compound of OH, oxyethane compounds; In formula M gXY, X is halogen, and Y is halogen, C
1-C
14alkyl, C
1-C
14alkoxyl group, C
6-C
14aryl or C
6-C
14aryloxy; At general formula R
1in OH, R
1for C
1-C
8alkyl or C
3-C
8cycloalkyl; At general formula R
4in OH, R
4for C
16-C
24alkyl or aralkyl; The structure of described oxyethane compounds is as shown in the formula (I):
Wherein, R
2and R
3independent is separately hydrogen, C
1-C
5alkyl or haloalkyl.
2. carrier for olefin polymerization catalyst according to claim 1, wherein, the magnesium halide take 1mol general formula as MgXY is benchmark, general formula is R
1the content of the compound of OH is 4-30mol, and general formula is R
4the content of the compound of OH is 0.001-1.5mol, and the content of structure oxyethane compounds is as shown in the formula (I) 1-10mol; Preferably, the magnesium halide take 1mol general formula as MgXY is benchmark, and general formula is R
1the content of the compound of OH is 6-20mol, and general formula is R
4the content of the compound of OH is 0.01-1mol, and the content of structure oxyethane compounds is as shown in the formula (I) 2-6mol.
3. carrier for olefin polymerization catalyst according to claim 1 and 2, wherein, in formula M gXY, X is chlorine or bromine, Y is chlorine, bromine, C
1-C
5alkyl, C
1-C
5alkoxyl group, C
6-C
10aryl or C
6-C
10aryloxy; Preferably, the magnesium halide that general formula is MgXY is selected from one or more in magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium.
4. carrier for olefin polymerization catalyst according to claim 1 and 2, wherein, at general formula R
1in OH, R
1for C
1-C
8alkyl; Preferably, general formula is R
1the compound of OH is selected from one or more in ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol and 2-Ethylhexyl Alcohol.
5. carrier for olefin polymerization catalyst according to claim 1 and 2, wherein, at general formula R
4in OH, R
4for C
16-C
20alkyl or aralkyl; Preferably, general formula is R
4the compound of OH is hexadecanol and/or stearyl alcohol.
6. carrier for olefin polymerization catalyst according to claim 1 and 2, wherein, in structure oxyethane compounds as shown in the formula (I), R
2and R
3independent is separately hydrogen, C
1-C
3alkyl or haloalkyl; Preferably, described oxyethane compounds is selected from one or more in oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide.
7. carrier for olefin polymerization catalyst according to claim 1 and 2, wherein, the average particulate diameter of described carrier for olefin polymerization catalyst is 10-100 micron, size distribution is less than 1.2; Preferably, the average particulate diameter of described carrier for olefin polymerization catalyst is 30-70 micron, and size distribution is 0.7-0.9.
8. a preparation method for carrier for olefin polymerization catalyst, the method comprises the following steps:
(1) magnesium halide that is MgXY by general formula, general formula are R
1the compound of OH, general formula are R
4the compound of OH mixes with inert liquid medium and heats, and obtains liquid form mixt;
(2) liquid form mixt emulsification step (1) being obtained, and by emulsification product and oxyethane compounds contact reacts;
In formula M gXY, X is halogen, and Y is halogen, C
1-C
14alkyl, C
1-C
14alkoxyl group, C
6-C
14aryl or C
6-C
14aryloxy; At general formula R
1in OH, R
1for C
1-C
8alkyl or C
3-C
8cycloalkyl; At general formula R
4in OH, R
4for C
16-C
24alkyl or aralkyl; The structure of described oxyethane compounds is as shown in the formula (I):
Wherein, R
2and R
3independent is separately hydrogen, C
1-C
5alkyl or haloalkyl.
9. method according to claim 8, wherein, the magnesium halide take 1mol general formula as MgXY is benchmark, general formula is R
1the consumption of the compound of OH is 4-30mol, and general formula is R
4the consumption of the compound of OH is 0.001-1.5mol, and the consumption of structure oxyethane compounds is as shown in the formula (I) 1-10mol; Preferably, the magnesium halide take 1mol general formula as MgXY is benchmark, and general formula is R
1the consumption of the compound of OH is 6-20mol, and general formula is R
4the consumption of the compound of OH is 0.01-1mol, and the consumption of structure oxyethane compounds is as shown in the formula (I) 2-6mol.
10. method according to claim 8 or claim 9, wherein, in step (1), the temperature of described heating is 80-120 ℃, the time is 0.5-5 hour; Preferably, the temperature of described heating is 80-100 ℃, and the time is 0.5-3 hour.
11. methods according to claim 8 or claim 9, wherein, in step (2), described catalytic condition comprises that temperature is 80-120 ℃, the time is 20-60 minute; Preferably, described catalytic condition comprises that temperature is 80-100 ℃, and the time is 20-50 minute.
12. methods according to claim 8 or claim 9, wherein, the magnesium halide take 1mol general formula as MgXY is benchmark, the consumption of described inert liquid medium is 0.8-10L; Described inert liquid medium is silicone oil and/or inert liq varsol; Preferably, described inert liquid medium 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.
13. carrier for olefin polymerization catalyst that prepared by the method described in any one in claim 8-12.
Carrier for olefin polymerization catalyst in 14. claim 1-7 and 13 described in any one is in the application of preparing in olefin polymerization catalysis.
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| CN105440175A (en) * | 2014-08-15 | 2016-03-30 | 中国石油化工股份有限公司 | Catalyst component used for olefin polymerization and preparation method thereof and catalyst used for olefin polymerization and application |
| CN106543300A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of catalyst support used for olefinic polymerization and its preparation method and application |
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