CN103788248B - For the catalyst component of olefinic polymerization and application thereof with for the catalyzer of olefinic polymerization and application thereof and olefine polymerizing process - Google Patents
For the catalyst component of olefinic polymerization and application thereof with for the catalyzer of olefinic polymerization and application thereof and olefine polymerizing process Download PDFInfo
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Abstract
The invention provides a kind of catalyst component for olefinic polymerization and application thereof, this catalyst component contains the product be obtained by reacting by carrier for olefin polymerization catalyst and titanium compound, and described carrier for olefin polymerization catalyst contains magnesium halide that general formula is MgXY, general formula is R
1the compound of OH, general formula are R
4the compound of OH, oxirane compound.The present invention also provides a kind of catalyzer for olefinic polymerization and application thereof, and olefine polymerizing process.Catalyzer for olefinic polymerization according to the present invention is when being used as the catalyzer of olefinic polyreaction, and the bulk density being polymerized the polymkeric substance obtained improves greatly.
Description
Technical field
The present invention relates to a kind of catalyst component for olefinic polymerization, the described catalyst component for olefinic polymerization is for the application in the catalyzer of olefinic polymerization, for a catalyzer for olefinic polymerization, the application of this catalyzer being used for olefinic polymerization in olefinic polyreaction and olefine polymerizing process.
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.
In addition, above-mentioned magnesium chloride alcohol adduct is all adopt the alcohol adduct melt of cryogenic quenching solidification high temperature to obtain, and not only, complicated process of preparation, palpus multiple reactor comparatively large to the consumption of the energy combine preparation, and the size distribution of obtained alcohol adduct is wider.In order to solve this problem, 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.
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 catalyst component for olefinic polymerization containing new carrier for olefin polymerization catalyst.
Second object of the present invention is to provide the described catalyst component for olefinic polymerization for the application in the catalyzer of olefinic polymerization.
3rd object of the present invention is to provide a kind of catalyzer for olefinic polymerization.
4th object of the present invention is to provide the application of the catalyzer for olefinic polymerization of the present invention in olefinic polyreaction.
5th object of the present invention is to provide a kind of olefine polymerizing process.
For realizing aforementioned object, first aspect, the invention provides a kind of catalyst component for olefinic polymerization, this catalyst component contains the product be obtained by reacting by carrier for olefin polymerization catalyst, titanium compound, wherein, described carrier for olefin polymerization catalyst contains magnesium halide that general formula is MgXY, general formula is R
1the compound of OH, general formula are R
4the compound of OH, oxirane compound; 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 oxirane compound is as shown in the formula (I):
Wherein, R
2and R
3be hydrogen, C independently of one another
1-C
5alkyl or haloalkyl.
Present invention also offers a kind of catalyst component for olefinic polymerization, wherein, described catalyst component contains the product be obtained by reacting by carrier for olefin polymerization catalyst and titanium compound and internal electron donor compound, wherein, described carrier for olefin polymerization catalyst contains magnesium halide that general formula is MgXY, general formula is R
1the compound of OH, general formula are R
4the compound of OH, oxirane compound; 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 oxirane compound is as shown in the formula (I):
Wherein, R
2and R
3be hydrogen, C independently of one another
1-C
5alkyl or haloalkyl.
Second aspect, the invention provides a kind of catalyst component for olefinic polymerization of the present invention for the application in the catalyzer of olefinic polymerization.
The third aspect, the invention provides a kind of catalyzer for olefinic polymerization, and this catalyzer contains:
(1) catalyst component for olefinic polymerization of the present invention;
(2) alkylaluminium cpd; And
(3) optional external donor compound.
Fourth aspect, the invention provides the application of the catalyzer for olefinic polymerization of the present invention in olefinic polyreaction.
5th aspect, the invention provides a kind of olefine polymerizing process, the method comprises: under olefin polymerization conditions, is contacted by one or more alkene with the catalyst component for olefinic polymerization of the present invention, alkylaluminium cpd and optional external donor compound.
The present inventor is surprised to find that, in the preparation process of described carrier for olefin polymerization catalyst, add general formula is R
4the compound of OH, the adhesion between the collision probability between non-shaped particle, minimizing carrier grain can not only be reduced, thus significantly improve stability and dispersiveness prepared by described carrier, make that the particle form of the 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 improved.
Catalyzer for olefinic polymerization according to the present invention employs the catalyst component for olefinic polymerization containing carrier for olefin polymerization catalyst of the present invention according to the present invention.Therefore the catalyzer for olefinic polymerization according to the present invention is when being used as the catalyzer of olefinic polyreaction, and the bulk density being polymerized the polymkeric substance obtained improves greatly.
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;
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 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.
According to a first aspect of the invention, the invention provides a kind of catalyst component for olefinic polymerization, this catalyst component contains the product be obtained by reacting by carrier for olefin polymerization catalyst, titanium compound, wherein, described carrier for olefin polymerization catalyst contains magnesium halide that general formula is MgXY, general formula is R
1the compound of OH, general formula are R
4the compound of OH, oxirane compound; 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 oxirane compound is as shown in the formula (I):
Wherein, R
2and R
3be hydrogen, C independently of one another
1-C
5alkyl or haloalkyl.
According to the present invention, preferred described catalyst component of the present invention contains the product be obtained by reacting by carrier for olefin polymerization catalyst and titanium compound and internal electron donor compound.Namely present invention also offers a kind of catalyst component for olefinic polymerization, wherein, described catalyst component contains the product be obtained by reacting by carrier for olefin polymerization catalyst and titanium compound and internal electron donor compound, wherein, described carrier for olefin polymerization catalyst contains magnesium halide that general formula is MgXY, general formula is R
1the compound of OH, general formula are R
4the compound of OH, oxirane compound; 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 oxirane compound is as shown in the formula (I):
Wherein, R
2and R
3be hydrogen, C independently of one another
1-C
5alkyl or haloalkyl.
In the present invention, described internal electron donor compound can be the conventional various internal electron donor compound used in the process for the preparation of the catalyzer of olefinic polymerization, can be such as one or more in carboxylicesters, alcohol ester, ether, ketone, nitrile, amine and silane, be preferably one or more in unitary or polyhydric aliphatic race carboxylicesters, unitary or polynary aromatic carboxylic acid esters, binary alcohol esters and binary ether.In the present invention, the selection of the concrete kind of described unitary or polyhydric aliphatic race carboxylicesters, unitary or polynary aromatic carboxylic acid esters, binary alcohol esters and binary ether all can refer to prior art and selects, and the present invention is no longer described in detail at this.
In the present invention, described in the catalyst component of olefinic polymerization, the weight ratio of titanium elements, magnesium elements and internal electron donor compound can be 1:5-15:2-15, is preferably 1:6-13:3-12.
In the present invention, there is no particular limitation for the condition of the reaction of described carrier for olefin polymerization catalyst, titanium compound and internal electron donor compound, under preferable case, the condition of this reaction can comprise: temperature of reaction is 80-130 DEG C, and the reaction times is 0.5-10 hour.
According to the present invention, the content of the above-mentioned each component in described carrier for olefin polymerization catalyst can carry out selecting and changing in the larger context, and such as, the magnesium halide being MgXY with 1mol general formula 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 oxirane compound as shown in the formula (I) can be 1-10mol; Preferably, the magnesium halide being MgXY with 1mol general formula 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 oxirane compound is as shown in the formula (I) 2-6mol.
In the present invention, in described carrier for olefin polymerization catalyst, 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 such as 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
5alkoxy as being methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or isobutoxy, described C
6-C
10aryl can be such as phenyl, o-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene, an ethylbenzene, to ethylbenzene or naphthyl, described C
6-C
10aryloxy can be such as phenoxy group or naphthyloxy.General formula is the magnesium halide of MgXY can be a kind of magnesium halide, or the mixture of multiple magnesium halide.General formula be the magnesium halide of MgXY specific examples can for 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 that raw material is ready availability, be preferably magnesium chloride.
According to the present invention, in described carrier for olefin polymerization catalyst, at general formula R
1in OH, R
1be preferably C
1-C
8alkyl.Described C
1-C
8alkyl can be such as 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 for 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, in described carrier for olefin polymerization catalyst, 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 described carrier for olefin polymerization catalyst, in structure oxirane compound as shown in the formula (I), R
2and R
3be preferably hydrogen, C independently of one another
1-C
3alkyl or haloalkyl.The specific examples of described oxirane compound can for 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, is preferably 30-70 micron; Size distribution is less than 1.2, is preferably 0.7-0.9.In this preferred implementation, the catalyzer prepared by this carrier for olefin polymerization catalyst can obtain the olefin polymer with more high-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.
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.
In the present invention, described titanium compound can be the conventional various titanium compounds used in the process for the preparation of the catalyzer of olefinic polymerization.Usually, described titanium compound is general formula Ti (OR
a)
4-mx
mcompound, wherein, R
afor C
1-C
14aliphatic group, X is F, Cl or Br, and m is the integer of 1-4; Described titanium compound be preferably in titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, three butoxy titanium chlorides, dibutoxy titanium dichloride, butoxy titanous chloride, triethoxy titanium chloride, diethoxy titanium dichloride and oxyethyl group titanous chloride one or more.
In the present invention, as long as ensure can realize object of the present invention containing carrier for olefin polymerization catalyst of the present invention, particularly to the preparation method of described carrier for olefin polymerization catalyst without particular requirement, for the present invention, particularly preferably carrier for olefin polymerization catalyst of the present invention prepares in accordance with the following steps:
(1) be the magnesium halide of MgXY by general formula, general formula is 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) by the liquid form mixt emulsification that step (1) obtains, and by emulsification product and oxirane compound 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 oxirane compound is as shown in the formula (I):
Wherein, R
2and R
3be hydrogen, C independently of one another
1-C
5alkyl or haloalkyl.
According to the present invention, general formula is the magnesium halide of MgXY, general formula is R
1the compound of OH, general formula are R
4the compound of OH, the consumption of structure oxirane compound 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 being MgXY with 1mol general formula 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 oxirane compound is as shown in the formula (I) 1-10mol; More preferably, the magnesium halide being MgXY with 1mol general formula 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 oxirane compound is as shown in the formula (I) 2-6mol.
According to the present 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), be R for being magnesium halide, the general formula of MgXY by general formula
1the compound of OH, general formula are R
4the compound of OH and the blend heated condition of inert liquid medium are not particularly limited, as long as the condition of described heating makes general formula be the magnesium halide melting of MgXY and is R with general formula
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 DEG C, and the time can be 0.5-5 hour; Preferably, described temperature can be 80-100 DEG C, and the time can be 0.5-3 hour.
According to the present invention, the consumption that the consumption of described inert liquid medium can be the magnesium halide of MgXY according to general formula is selected.Usually, the magnesium halide being MgXY with 1mol general formula is benchmark, and the consumption of described inert liquid medium is 0.8-10L, is preferably 2-8L.Chemically interactive liquid medium can be there is not with reactant and reaction product in described inert liquid medium for conventional various in this area.Such as: 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, 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 high speed shear, thus by its emulsification.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, in step (2), can be the existing various condition that can form carrier for olefin polymerization catalyst by emulsification product and the catalytic condition of oxirane compound, such as, it can be 80-120 DEG C that described catalytic condition comprises temperature, and the time can be 20-60 minute; Preferably, it is 80-100 DEG C that described catalytic condition comprises temperature, and the time is 20-50 minute.
According to the present invention, the method can also comprise in product contact reacts obtained carries out solid-liquid separation, is washed by solid product and carries out drying.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.The condition of the present invention to press filtration is not particularly limited, and is as the criterion with being separated of liquid phase to realize solid phase as far as possible fully.Described washing can adopt the method for well known to a person skilled in the art to be washed by the solid product obtained, such as, inert hydrocarbon solvent (such as: pentane, hexane, heptane, sherwood oil and gasoline) can be adopted to wash the solid product obtained.The present invention is not particularly limited for the condition of described drying, and such as: the temperature of described drying can be 20-70 DEG C, 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 a second aspect of the invention, the invention provides the catalyst component for olefinic polymerization of the present invention for the application in the catalyzer of olefinic polymerization.
According to a third aspect of the invention we, the invention provides a kind of catalyzer for olefinic polymerization, this catalyzer contains:
(1) catalyst component for olefinic polymerization of the present invention;
(2) alkylaluminium cpd; And
(3) optional external donor compound.
The composition of the described catalyst component for olefinic polymerization is described in detail in the preceding article, does not repeat them here.
Catalyzer for olefinic polymerization according to the present invention employs the catalyst component for olefinic polymerization according to the present invention, therefore the catalyzer for olefinic polymerization according to the present invention is when being used as the catalyzer of olefinic polyreaction, and the bulk density being polymerized the polymkeric substance obtained improves greatly.Therefore, the catalyzer for olefinic polymerization according to the present invention is all not particularly limited for the kind of alkylaluminium cpd and external donor compound and consumption.
Usually, described in the catalyzer of olefinic polymerization, for 1-2000:1,20-500:1 can be preferably in the alkylaluminium cpd of aluminium with in the mol ratio of the catalyst component for olefinic polymerization of titanium; The mol ratio of described external donor compound and alkylaluminium cpd can be 0.005-0.5:1, is preferably 0.01-0.4:1.
According to the catalyzer for olefinic polymerization of the present invention, the various alkylaluminium cpds that described alkylaluminium cpd can be commonly used for this area.Such as, described alkylaluminium cpd can be one or more in triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminium, a chlorine di-n-hexyl aluminium, dichloro one aluminium triethyl, dichloro one aluminium isobutyl, dichloro one n-butylaluminum and dichloro one n-hexyl aluminium.
According to the catalyzer for olefinic polymerization of the present invention, the various external donor compounds that described external donor compound can be commonly used for this area, such as, described external electron donor can be one or more in carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organo phosphorous compounds and silicon compound; Preferably, described external electron donor is for having general formula R
8 ar
9 bsi (OR
10)
csilicon compound, wherein, a and b is the integer of 0,1 or 2 separately, and c is the integer of 1-3, and a+b+c's and be 4, R
8, R
9, R
10be C independently of one another
1-C
18substituted or unsubstituted alkyl; More preferably, a and b is 1, c is separately 2, R
8, R
9be C independently of one another
3-C
10substituted or unsubstituted alkyl, R
10for C
1-C
10substituted or unsubstituted alkyl.Particularly, the example of described silicoorganic compound can be but be not limited to: Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-t-butyldimethoxysilane and (1,1, the fluoro-2-propyl group of 1-tri-)-2-ethyl piperidine base dimethoxysilane and (1, the fluoro-2-propyl group of 1,1-tri-)-methyl dimethoxysilane.
According to a forth aspect of the invention, the invention provides the application of the catalyzer for olefinic polymerization of the present invention in olefinic polyreaction.
According to a fifth aspect of the invention, the invention provides a kind of olefine polymerizing process, the method comprises: under olefin polymerization conditions, is contacted by one or more alkene with the catalyst component for olefinic polymerization of the present invention, alkylaluminium cpd and optional external donor compound.
Olefine polymerizing process according to the present invention, by using the catalyzer for olefinic polymerization according to the present invention, can prepare the polymkeric substance that particle form is good, bulk density is high.Described olefine polymerizing process of the present invention is not particularly limited for olefin polymerization conditions and the alkene used.
Described alkene can be such as one or more in ethene, propylene, 1-butylene, 2-butylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-butene, 1-amylene, 2-amylene, 1-hexene and vinylbenzene, is preferably one or more in ethene, propylene, 1-butylene, 2-butylene and vinylbenzene.
According to olefine polymerizing process of the present invention, described olefinic polymerization can be carried out according to the ordinary method of this area.Such as, described olefinic polymerization can be mass polymerization, vapour phase polymerization or slurry polymerization.According to olefine polymerizing process of the present invention, described olefin polymerization conditions can be the normal condition of this area, and such as, polymerization temperature can be 0-150 DEG C, is preferably 60-90 DEG C; Polymerization pressure can be normal pressure or pressurization.
The invention will be further described by the following examples.But should be understood that, these embodiments, only for instruction and explanation of the present invention, are not limited to the present invention.
Below will be described the present invention by embodiment.
In embodiment and comparative example:
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.
Preparation example 1
This preparation example is for illustration of carrier for olefin polymerization catalyst 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 DEG C.Mixture high-speed stirring (1600rpm), after 1 hour, is disperseed 30 minutes by isothermal reaction, to carry out emulsification.And 25mL(0.3mol is added in above-mentioned emulsification product) epoxy chloropropane, press filtration after reaction half hour, by press filtration product hexanes wash 5 times, 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, smooth surface, and be all spherical substantially, particle size distribution is more concentrated, and there is no that irregular particle exists.
Preparation example 2
This preparation example is for illustration of carrier for olefin polymerization catalyst 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 DEG C.Mixture high-speed stirring (1600rpm), after 0.5 hour, is disperseed 30 minutes by isothermal reaction, to carry out emulsification.And 12.5mL(0.16mol is added in above-mentioned emulsification product) epoxy chloropropane, press filtration after reaction half hour, by press filtration product hexanes wash 5 times, 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, smooth surface, and be all spherical substantially, particle size distribution is more concentrated, and there is no that irregular particle exists.
Preparation example 3
This preparation example is for illustration of carrier for olefin polymerization catalyst 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 DEG C.Mixture high-speed stirring (1600rpm), after 3 hours, is disperseed 30 minutes by isothermal reaction, to carry out emulsification.And 37.6mL(0.48mol is added in above-mentioned emulsification product) epoxy chloropropane, press filtration after reaction half hour, by press filtration product hexanes wash 5 times, 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, smooth surface, and be all spherical substantially, particle size distribution is more concentrated, and there is no that irregular particle exists.
Preparation example 4
This preparation example is for illustration of carrier for olefin polymerization catalyst and preparation method thereof.
Carrier for olefin polymerization catalyst is prepared according to the method for preparation example 1, unlike, the described stearyl alcohol hexadecanol of identical mole number substitutes, and 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, smooth surface, and be all spherical substantially, particle size distribution is more concentrated, and there is no that irregular particle exists.
Preparation example 5
This preparation example is for illustration of carrier for olefin polymerization catalyst 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 DEG C.Mixture high-speed stirring (1600rpm), after 0.3 hour, is disperseed 30 minutes by isothermal reaction, to carry out emulsification.And 4mL(0.08mol is added in above-mentioned emulsification product) oxyethane, press filtration after reaction half hour, by press filtration product hexanes wash 5 times, 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, and be all spherical substantially, particle size distribution is more concentrated, and there is no that irregular particle exists.
Contrast preparation example 1
This contrast preparation example is for illustration of reference carrier for olefin polymerization catalyst and preparation method thereof.
Carrier for olefin polymerization catalyst is prepared according to the method for preparation example 5, unlike, the described stearyl alcohol ethanol of identical mole number substitutes, and 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, there is a large amount of irregular particles in carrier for olefin polymerization catalyst DZ1, and surface is comparatively coarse.
Embodiment 1
This embodiment is for illustration of 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 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 catalysis 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, olefin polymerization catalysis C1,1.5L(standard volume obtained by step (1) of the Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg) hydrogen 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.The bulk density of this polypropylene powder is 0.44g/cm
3, in addition, this polypropylene powder particle form is good, substantially there is not abnormity material.
Embodiment 2
This embodiment is for illustration of the preparation of alkene provided by the invention.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, the described carrier for olefin polymerization catalyst Z2 that described carrier for olefin polymerization catalyst Z1 preparation example 2 obtains 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 illustration of the preparation of alkene provided by the invention.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, the described carrier for olefin polymerization catalyst Z3 that described carrier for olefin polymerization catalyst Z1 preparation example 3 obtains 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 illustration of the preparation of alkene provided by the invention.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, the described carrier for olefin polymerization catalyst Z4 that described carrier for olefin polymerization catalyst Z1 preparation example 4 obtains 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 illustration of the preparation of alkene provided by the invention.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, the described carrier for olefin polymerization catalyst Z5 that described carrier for olefin polymerization catalyst Z1 preparation example 5 obtains 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 prepared for illustration of the reference of alkene.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, the described carrier for olefin polymerization catalyst DZ1 that described carrier for olefin polymerization catalyst Z1 contrast preparation example 1 obtains substitutes, 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, 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 catalyzer prepared by the carrier of gained, the bulk density of polymerisate can also be improved, 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 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 (31)
1. for a catalyst component for olefinic polymerization, this catalyst component contains the product be obtained by reacting by carrier for olefin polymerization catalyst, titanium compound, it is characterized in that, described carrier for olefin polymerization catalyst contains magnesium halide that general formula is MgXY, general formula is R
1the compound of OH, general formula are R
4the compound of OH, oxirane compound; 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 oxirane compound is such as formula shown in (I):
Wherein, R
2and R
3be hydrogen, C independently of one another
1-C
5alkyl or haloalkyl;
The magnesium halide being MgXY with 1mol general formula is benchmark, and 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 described oxirane compound is 1-10mol.
2. the catalyst component for olefinic polymerization, wherein, described catalyst component contains the product be obtained by reacting by carrier for olefin polymerization catalyst and titanium compound and internal electron donor compound, it is characterized in that, described carrier for olefin polymerization catalyst contains magnesium halide that general formula is MgXY, general formula is R
1the compound of OH, general formula are R
4the compound of OH, oxirane compound; 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 oxirane compound is such as formula shown in (I):
Wherein, R
2and R
3be hydrogen, C independently of one another
1-C
5alkyl or haloalkyl;
The magnesium halide being MgXY with 1mol general formula is benchmark, and 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 described oxirane compound is 1-10mol.
3. catalyst component according to claim 2, wherein, described internal electron donor compound is one or more in carboxylicesters, alcohol ester, ether, ketone, nitrile, amine and silane.
4. catalyst component according to claim 3, wherein, described internal electron donor compound is one or more in unitary or polyhydric aliphatic race carboxylicesters, unitary or polynary aromatic carboxylic acid esters, binary alcohol esters and binary ether.
5. catalyst component according to claim 2, wherein, described in the catalyst component of olefinic polymerization, the weight ratio of titanium elements, magnesium elements and internal electron donor compound is 1:5-15:2-15.
6. catalyst component according to claim 5, wherein, described in the catalyst component of olefinic polymerization, the weight ratio of titanium elements, magnesium elements and internal electron donor compound is 1:6-13:3-12.
7. according to the catalyst component in claim 1-6 described in any one, wherein, in described carrier for olefin polymerization catalyst, the magnesium halide being MgXY with 1mol general formula 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 structure is 2-6mol such as formula the content of the oxirane compound shown in (I).
8. according to the catalyst component in claim 1-6 described in any one, wherein, in described carrier for olefin polymerization catalyst, in formula M gXY, X is chlorine or bromine, and Y is chlorine, bromine, C
1-C
5alkyl, C
1-C
5alkoxyl group, C
6-C
10aryl or C
6-C
10aryloxy.
9. according to Claim 8 described in catalyst component, wherein, in described carrier for olefin polymerization catalyst, general formula be the magnesium halide of MgXY be selected from magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium one or more.
10. according to the catalyst component in claim 1-6 described in any one, wherein, in described carrier for olefin polymerization catalyst, at general formula R
1in OH, R
1for C
1-C
8alkyl.
11. according to the catalyst component described in claim 10, and wherein, in described carrier for olefin polymerization catalyst, general formula is R
1the compound of OH be selected from ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol and 2-Ethylhexyl Alcohol one or more.
12. according to the catalyst component in claim 1-6 described in any one, wherein, in described carrier for olefin polymerization catalyst, at general formula R
4in OH, R
4for C
16-C
20alkyl or aralkyl.
13. according to the catalyst component described in claim 12, and wherein, in described carrier for olefin polymerization catalyst, general formula is R
4the compound of OH is hexadecanol and/or stearyl alcohol.
14. according to the catalyst component in claim 1-6 described in any one, wherein, in described carrier for olefin polymerization catalyst, in structure such as formula in the oxirane compound shown in (I), and R
2and R
3be hydrogen, C independently of one another
1-C
3alkyl or haloalkyl.
15. according to the catalyst component described in claim 14, wherein, in described carrier for olefin polymerization catalyst, described oxirane compound be selected from oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide one or more.
16. according to the catalyst component in claim 1-6 described in any one, and wherein, in described carrier for olefin polymerization catalyst, the average particulate diameter of described carrier for olefin polymerization catalyst is 10-100 micron, and size distribution is less than 1.2.
17. according to the catalyst component described in claim 16, and wherein, in described carrier for olefin polymerization catalyst, the average particulate diameter of described carrier for olefin polymerization catalyst is 30-70 micron, and size distribution is 0.7-0.9.
18. according to the catalyst component in claim 1-6 described in any one, and wherein, described titanium compound is general formula Ti (OR
a)
4-mx
mcompound, wherein, R
afor C
1-C
14aliphatic group, X is F, Cl or Br, and m is the integer of 1-4.
19. according to the catalyst component described in claim 18, wherein, described titanium compound is one or more in titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, three butoxy titanium chlorides, dibutoxy titanium dichloride, butoxy titanous chloride, triethoxy titanium chloride, diethoxy titanium dichloride and oxyethyl group titanous chloride.
20. according to the catalyst component in claim 1-6 described in any one, and wherein, the preparation method of described carrier for olefin polymerization catalyst comprises the following steps:
(1) be the magnesium halide of MgXY by general formula, general formula is 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) by the liquid form mixt emulsification that step (1) obtains, and by emulsification product and oxirane compound 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 oxirane compound is such as formula shown in (I):
Wherein, R
2and R
3be hydrogen, C independently of one another
1-C
5alkyl or haloalkyl;
The magnesium halide being MgXY with 1mol general formula 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 described oxirane compound is 1-10mol.
21. catalyst components according to claim 12, wherein, the magnesium halide being MgXY with 1mol general formula 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 structure is 2-6mol such as formula the consumption of the oxirane compound shown in (I).
22. catalyst components according to claim 20, wherein, in step (1), the temperature of described heating is 80-120 DEG C, and the time is 0.5-5 hour.
23. catalyst components according to claim 22, wherein, in step (1), the temperature of described heating is 80-100 DEG C, and the time is 0.5-3 hour.
24. catalyst components according to claim 20, wherein, in step (2), it is 80-120 DEG C that described catalytic condition comprises temperature, and the time is 20-60 minute.
25. catalyst components according to claim 24, wherein, in step (2), it is 80-100 DEG C that described catalytic condition comprises temperature, and the time is 20-50 minute.
26. catalyst components according to claim 20, wherein, the magnesium halide being MgXY with 1mol general formula is benchmark, and the consumption of described inert liquid medium is 0.8-10L; Described inert liquid medium is silicone oil and/or inert liq varsol.
27. catalyst components according to claim 26, wherein, 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.
The catalyst component for olefinic polymerization described in 28. claim 1-27 any one is for the application in the catalyzer of olefinic polymerization.
29. 1 kinds of catalyzer for olefinic polymerization, this catalyzer contains:
(1) catalyst component for olefinic polymerization in claim 1-27 described in any one;
(2) alkylaluminium cpd; And
(3) optional external donor compound.
30. application of the catalyzer for olefinic polymerization according to claim 29 in olefinic polyreaction.
31. 1 kinds of olefine polymerizing process, the method comprises: under olefin polymerization conditions, is contacted by one or more alkene with the catalyst component being used for olefinic polymerization described in any one in claim 1-27, alkylaluminium cpd and optional external donor compound.
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| CN106543307B (en) * | 2015-09-23 | 2018-11-30 | 中国石油化工股份有限公司 | The preparation method and catalyst for olefines polymerizing of catalyst for olefines polymerizing and its application |
| CN106543299B (en) * | 2015-09-23 | 2018-11-30 | 中国石油化工股份有限公司 | Catalyst for olefines polymerizing and its preparation method and application and the method for olefinic polymerization |
| CN106543300B (en) * | 2015-09-23 | 2018-11-30 | 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 |
| CN107915789B (en) * | 2016-10-09 | 2021-02-05 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier and preparation method thereof, olefin polymerization catalyst component and olefin polymerization catalyst and application thereof |
| CN111072804B (en) * | 2018-10-19 | 2022-07-12 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component and application thereof, olefin polymerization catalyst and olefin polymerization method |
| CN114149523B (en) * | 2020-09-05 | 2022-11-18 | 中国石油化工股份有限公司 | Catalyst spherical carrier for olefin polymerization, preparation method and application thereof, and catalyst and application thereof |
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| CN1887918A (en) * | 2005-06-30 | 2007-01-03 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization or copolymerization at high temperature |
| CN101942050A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization in slurry process and preparation method thereof |
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| CN1887918A (en) * | 2005-06-30 | 2007-01-03 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization or copolymerization at high temperature |
| CN101942050A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization in slurry process and preparation method thereof |
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