CN103788255B - A kind of polypropylene product and preparation method thereof - Google Patents
A kind of polypropylene product and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polypropylene product and preparation method thereof, wherein, the weight average molecular weight of described polypropylene product is 1.5 3.4 × 105Molecular weight distributing index is 3 15, the isotactic index of described polypropylene product is 96.5 99.5%, and the described melt flow rate (MFR) of polypropylene product meets following formula: 0.258ln (x)+98.97 0.28≤y≤0.258ln (x)+98.97+0.28 with the numerical value of isotactic index, wherein, y is the isotactic index of polypropylene product, and x is the melt flow rate (MFR) measured according to ASTM D1238 99 of polypropylene product, and unit is g/10 minute.The polypropylene product that the present invention provides, compared with the polypropylene product of the melt strength identical with prior art, isotacticity is high.
Description
Technical field
The present invention relates to a kind of polypropylene product and preparation method thereof.
Background technology
Polypropylene has many merits, such as, and, bending modulus lighter than water and fusing point is the highest, processing characteristics is good, tool
Propylene feedstocks needed for having fabulous chemical stability, electrical insulating property, manufacture polypropylene is cheap and easily-available etc..Although polypropylene material
Have these advantages, but in some field, due to the characteristic of itself so that it is possessing higher melt mass flow index
Time, isotacticity is relatively low；And isotacticity higher time, melt index is relatively low.In prior art, when the isotacticity of acrylic polymers is
During 96-99%, often it is only 0.5-35 gram/10 minutes according to the melt flow rate (MFR) that ASTM D1238-99 measures；And according to
When the melt flow rate (MFR) that ASTM D1238-99 measures is 40-50 gram/10 minutes, the isotacticity of acrylic polymers is only 91-
When 95%.Above-mentioned situation causes polypropylene under specific melt index, has the field that higher isotacticity requires and can not get
Application.It is therefore desirable to change polyacrylic performance, to adapt to the use demand in these fields.Due to polyacrylic properties
Mutually pining down, the raising of performance indications is often possible to cause the decline of another performance indications, therefore, changes polypropylene
Performance remarkable.
In thin-walled injection moulding field, it is desirable to acrylic resin has higher melt mass flow index (MFI).Produce at present
High melt flow rate polypropylene time mostly use chemical degradation to improve the melt flow rate (MFR) of product, but adopt in this way
The polypropylene articles prepared easily turns to be yellow, embrittlement, has abnormal flavour, and cost increases.And feed stock due to different batches
Can not be guaranteed, cause the product obtained unstable.
The melt flow rate (MFR) of polymerizate can be improved by adding substantial amounts of hydrogen in polymer reactor, but simultaneously
Also reducing polymer isotactic index, being likely to result in polymer tacky causing cannot normally produce.And due to substantial amounts of hydrogen
Use, add the resistance to pressure request of reactor, also make production process hydrogen yield increase.
US6686433B1 discloses a kind of catalyst with higher hydrogen tune sensitivity, although the method is by just using
Silester (TEOS) can improve the melt mass flow index of polymer, but after adding tetraethyl orthosilicate (TEOS),
Causing catalyst activity to be substantially reduced, and the polymer molecular weight obtained declines, the isotactic index of polymer also ratio is relatively low.
For acrylic polymers, it is generally the case that isotactic index can significantly reduce along with melt flow rate (MFR) rising,
Therefore, how to prepare and have the polypropylene product of high high isotactic index and melt flow rate (MFR) concurrently and be still one and need asking of solution badly
Topic.
Summary of the invention
It is an object of the invention to provide a kind of polypropylene product and preparation method thereof, the polypropylene that the present invention provides produces
Product, the polypropylene of melt mass flow index same as the prior art is compared, and has high isotactic index.
The present invention provides a kind of polypropylene product, wherein, the weight average molecular weight of described polypropylene product be 1.5-3.4 ×
105, molecular weight distributing index is 3-15, and the isotactic index of described polypropylene product is 96.5-99.5%, and, described polypropylene
The melt flow rate (MFR) of product and the numerical value of isotactic index meet following formula:
-0.258ln(x)+98.97-0.28≤y≤-0.258ln(x)+98.97+0.28
Wherein, y is the isotactic index of polypropylene product, and x is the melting according to ASTMD1238-99 mensuration of polypropylene product
Body flow rate, unit is g/10 minute.
Present invention also offers the preparation method of a kind of polypropylene product, the method is included under olefin polymerization conditions,
In the presence of catalyst, propylene or propylene are polymerized with the mixture of ethylene and/or alpha-olefin, obtain polypropylene product,
Described catalyst contains solid constituent, alkyl aluminum compound and external donor compound, described solid constituent contain magnesium, titanium,
Halogen and internal electron donor compound, described internal electron donor compound contains 1,3-diether compound, wherein, described solid
Component uses following methods to prepare:
(1) magnesium-containing carrier is reacted with the first titanium compound, and react it at described magnesium-containing carrier and the first titanium compound
Before, during and after one or more time periods in add internal electron donor；
(2) product that step (1) obtains is carried out solid-liquid separation, and solid product that solid-liquid separation is obtained and the second titanium
Compound contacts, the condition of described contact include temperature be-10 DEG C to 120 DEG C, the time is more than 4 hours.
Present invention also offers the polypropylene product of a kind of prepared in accordance with the method for the present invention.
Refer to it was found by the inventors of the present invention that existing olefin polymerization catalyst is usually with the isotactic of sacrificial polymer
Number improves its melt flow rate (MFR), but, the reduction of polymer isotactic index is extremely disadvantageous to application downstream.
In prior art, when preparing the solid constituent in the catalyst of propylene polymerization, the way generally used is: prepare magnesium-containing carrier；
Prepared magnesium-containing carrier is reacted with the first titanium compound, prepares magnesium-containing carrier；Prepared magnesium-containing carrier and the first titanizing are closed
Thing reacts, and in the one or more time periods before and after, during described magnesium-containing carrier and the first titanium compound react
Add the internal electron donor containing 1,3-diether compound；Magnesium-containing carrier and the first titanium compound are reacted the product obtained enter
After row solid-liquid separation, solid product solid-liquid separation obtained and the contact of the second titanium compound, it is little that the time of contact is usually 2-3
Time, obtain solid constituent.The present inventor finds through long-term research, and described internal electron donor compound is 1,3-bis-
During ether compound, when the solid product aforementioned prior art solid-liquid separation obtained and the second titanium compound extend time of contact
For more than 4 hours, so can unexpectedly make the catalyst solid constituent prepared not only have higher hydrogen response, also have
There are preferable stereotaxis ability and higher polymerization activity.The solid constituent prepared in this way, with alkyl aluminum compound
When being used for propylene polymerization with external donor compound together as catalyst, prepared acrylic polymers energy, with prior art
The acrylic polymers of same melt mass flow index compare, isotactic index is high.
The preparation method of the polypropylene product according to the present invention, owing to the catalyst solid constituent used not only has higher
Hydrogen response, also there is preferable stereotaxis ability and higher polymerization activity, by one-step polymerization reaction can make
The polypropylene product that isotacticity is high compared by the standby polypropylene obtaining melt strength same as the prior art.Wherein, according to this
The melt flows speed of polypropylene product (catalyst with 1,3-diether compound as internal electron donor) prepared by bright method
When rate is 10.8-11.6 gram/10 minutes, isotactic index is up between 97.9-99.5%；The melt flows speed of polypropylene product
When rate is 92.4-93 gram/10 minutes, isotactic index is between 97-98%.And the polypropylene product that prior art provides is (with 1,3-
Diether compound is the catalyst of internal electron donor) in, use polypropylene prepared by the technological parameter identical with the present invention
When the melt flow rate (MFR) of product is 10.8-11.6 gram/10 minutes, between isotactic index is only capable of as 97-98.5%；Polypropylene produces
When the melt flow rate (MFR) of product is 92.4-93 gram/10 minutes, isotactic index is only between 91-96%.
Detailed description of the invention
According to the polypropylene product of the present invention, wherein, the weight average molecular weight of described polypropylene product is 1.5-3.4 × 105,
Molecular weight distributing index is 3-15, and the isotactic index of described polypropylene product is 96.5-99.5%, and described polypropylene product
The numerical value of melt flow rate (MFR) and isotactic index meets following formula:
-0.258ln(x)+98.97-0.28≤y≤-0.258ln(x)+98.97+0.28
Wherein, y is the isotactic index of polypropylene product, and x is the melting according to ASTMD1238-99 mensuration of polypropylene product
Body flow rate, unit is g/10 minute.Preferably, the weight average molecular weight of described polypropylene product is 1.55-3.3 × 105, point
Son amount profile exponent is 3.5-6, and the isotactic index of described polypropylene product is 97-99%.
According to the acrylic polymers of the present invention, wherein, on the basis of the weight of acrylic polymers, 1,3-diether compound
Content can be 0.5-5ppm, preferably 2.5-4.5ppm.
The preparation method of the polypropylene product according to the present invention, the method is included under olefin polymerization conditions, at catalyst
In the presence of, propylene or propylene are polymerized with the mixture of ethylene and/or alpha-olefin, obtain polypropylene product, described in urge
Agent contains solid constituent, alkyl aluminum compound and external donor compound, described solid constituent contain magnesium, titanium, halogen and
Internal electron donor compound, described internal electron donor compound contains 1, and 3-diether compound, wherein, described solid constituent is adopted
Prepare using the following method:
(1) magnesium-containing carrier is reacted with the first titanium compound, and react it at described magnesium-containing carrier and the first titanium compound
Before, during and after one or more time periods in add internal electron donor；
(2) product that step (1) obtains is carried out solid-liquid separation, and solid product that solid-liquid separation is obtained and the second titanium
Compound contacts, the condition of described contact include temperature be-10 DEG C to 120 DEG C, the time is more than 4 hours.
Well known to those skilled in the art, in step (2), when the time of described contact was abutment more than 4 hours
Between lower limit be 4 hours, in the present invention, as long as the time of contact in step (2) is more than just can realizing goal of the invention in 4 hours.
Prolongation over time, the ageing effect of catalytic component is more preferable.Those skilled in the art should could be aware that, the time
The upper limit can determine according to time cost and the selection of the ageing factors such as effect.
According to the present invention, although as long as described solid product and the second titanium compound being surpassed at-10 DEG C to 120 DEG C
It's 4 hours the pasting contact can improve the hydrogen response of described catalyst solid component of olefin polymerization, stereotaxis ability and gather
Close activity, so that the acrylic polymers prepared can have high isotactic index and melt flow rate (MFR) concurrently, but so that arrive
The condition that described solid product and the second titanium compound contact more preferably, under preferable case, is included temperature by propylene polymerization physical performance
For 0-120 DEG C, the time be 8-24 hour；Preferably, the temperature of contact be 25-120 DEG C, the time be 8-24 hour.
According to the present invention, in step (2), the consumption of described solid product and the second titanium compound can be in wider scope
Inside selecting, such as, the weight ratio of described solid product and the second titanium compound is 0.1-80:100, preferably 5-15:
100。
Preparation in accordance with the present invention, although the present invention is to 1, the kind of 3-diether compound the most particularly limits
System, described 1,3-diether compound can be existing various gives within preparing in catalyst solid component of olefin polymerization
The 1 of electron, 3-diether compound compound, such as, described 1,3-diether compound can be for structure as shown in formula I
Compound:
Formula I,
Wherein, R1And R2Can be identical or different, and it is each independently C1-C20Alkyl, C3-C20Cycloalkyl, C6-
C20Aryl or C7-C20Aralkyl；R3-R8Can be identical or different, and can be each hydrogen, halogen, C1-C20Alkane
Base, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Aralkyl or R3-R8In two or more bonding formed rings
Structure；Preferably, R1And R2Identical or different, and it is each independently C1-C10Alkyl；R3、R4、R7And R8It is hydrogen；R5And R6
Identical or different, and respectively C1-C18Alkyl, C3-C18Cycloalkyl, C6-C18Aryl, C7-C18Aralkyl or R5
And R6It is mutually bonded the ring structure of formation.
The instantiation of described 1,3-diether compound includes but not limited to: 2-(2-ethylhexyl)-1,3-dimethoxy
Base propane, 2-isopropyl-1,3-dimethoxy propane, 2-butyl-1,3-dimethoxy propane, 2-sec-butyl-1,3-dimethoxy
Base propane, 2-cyclohexyl-1,3-dimethoxy propane, 2-phenyl-1,3-dimethoxy propane, 2-(2-phenylethyl)-1,3-
Dimethoxy propane, 2-(2-cyclohexyl-ethyl)-1,3-dimethoxy propane, 2-(p-chlorphenyl)-1,3-dimethoxy third
Alkane, 2-(diphenyl methyl)-1,3-dimethoxy propane, 2,2-dicyclohexyl-1,3-dimethoxy propane, 2,2-bicyclo-penta
Base-1,3-dimethoxy propane, 2,2-diethyl-1,3-dimethoxy propane, 2,2-dipropyl-1,3-dimethoxy propane,
2,2-diisopropyl-1,3-dimethoxy propane, 2,2-dibutyl-1,3-dimethoxy propane, 2-methyl-2-propyl-1,3-
Dimethoxy propane, 2-methyl-2-benzyl-1,3-dimethoxy propane, 2-methyl-2-ethyl-1,3-dimethoxy propane, 2-
Methyl-2-isopropyl-1,3-dimethoxy propane, 2-methyl-2-phenyl-1,3-dimethoxy propane, 2-methyl-2-hexamethylene
Base-1,3-dimethoxy propane, 2,2-double (2-cyclohexyl-ethyl)-1,3-dimethoxy propane, 2-methyl-2-isobutyl group-1,
3-dimethoxy propane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxy propane, 2,2-diisobutyl-1,3-dimethoxy
Double (the cyclohexyl of base propane, 2,2-diphenyl-1,3-dimethoxy propane, 2,2-dibenzyl-1,3-dimethoxy propane, 2,2-
Methyl)-1,3-dimethoxy propane, 2-isobutyl group-2-isopropyl-1,3-dimethoxy propane, 2-(1-methyl butyl)-2-be different
Propyl group-1,3-dimethoxy propane, 2-isopropyl-2-isopentyl-1,3-dimethoxy propane, 2-phenyl-2-isopropyl-1,3-
Dimethoxy propane, 2-phenyl-2-sec-butyl-1,3-dimethoxy propane, 2-benzyl-2-isopropyl-1,3-dimethoxy third
Alkane, 2-cyclopenta-2-isopropyl-1,3-dimethoxy propane, 2-cyclopenta-2-sec-butyl-1,3-dimethoxy propane, 2-
Cyclohexyl-2-isopropyl-1,3-dimethoxy propane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxy propane, 2-isopropyl
Base-2-sec-butyl-1,3-dimethoxy propane, 2-cyclohexyl-2-cyclohexyl methyl-1,3-dimethoxy propane and 9,9-bis-
One or more in methoxy fluorenes.
In the present invention, described magnesium-containing carrier can be the various solids containing magnesium elements that olefin polymerization catalysis field is conventional
Material, usually contains magnesium halide and alcohol compound；Under a kind of embodiment, described magnesium-containing carrier contains the halogen that formula is MgXY
Change magnesium, formula is the compound of ROH, formula is the compound of R'OH, two oxyl hydrocarbon compounds；Wherein, the X in formula M gXY
For halogen, Y is halogen, C1-C14Alkyl, C1-C14Alkoxyl, C6-C14Aryl or C6-C14Aryloxy group；General formula R OH
In, R is C1-C8Alkyl or C3-C8Cycloalkyl；General formula R ' in OH, R' is C16-C24Alkyl or aralkyl；Described two hydrocarbon oxygen
The structure of base hydrocarbon compound is as shown in formula II, and the structure of described oxirane compound is as shown in formula III:
Formula II,Formula III；
Wherein, R '1、R’2、R’3And R '4Each stand alone as hydrogen, C1-C10Alkyl or haloalkyl, C3-C10Cycloalkyl or
Halogenated cycloalkyl, C6-C10Aryl or halogenated aryl, C7-C10Alkaryl or haloalkylaryl, C7-C10Aralkyl or halogen
For aralkyl；R’5And R '6Each stand alone as hydrogen, C1-C5Alkyl or haloalkyl.
According to the present invention, described magnesium-containing carrier can use the method for well known to a person skilled in the art to be prepared, a kind of
In the case of embodiment, the preparation of described magnesium-containing carrier can include by formula be the magnesium halide of MgXY, formula be the change of ROH
Compound, formula are that the compound of R'OH, two oxyl hydrocarbon compounds are mixed and heated with inert liquid medium, obtain liquid mixing
Thing；The liquefied mixture emulsifying that will obtain, and by emulsification product and oxirane compound haptoreaction；In formula M gXY
In, X is halogen, and Y is halogen, C1-C14Alkyl, C1-C14Alkoxyl, C6-C14Aryl or C6-C14Aryloxy group；Logical
In formula ROH, R is C1-C8Alkyl or C3-C8Cycloalkyl；General formula R ' in OH, R' is C16-C24Alkyl or aralkyl；Institute
Stating the structure of two oxyl hydrocarbon compounds as shown in formula II, the structure of described oxirane compound is as shown in formula III:
Formula II,Formula III；
Wherein, R '1、R’2、R’3And R '4Each stand alone as hydrogen, C1-C10Alkyl or haloalkyl, C3-C10Cycloalkyl or
Halogenated cycloalkyl, C6-C10Aryl or halogenated aryl, C7-C10Alkaryl or haloalkylaryl, C7-C10Aralkyl or halogen
For aralkyl；R’5And R '6Each stand alone as hydrogen, C1-C5Alkyl or haloalkyl.
According to the present invention, formula be the magnesium halide of MgXY, formula be the compound of ROH, formula be the compound of R ' OH, knot
The structure two oxyl hydrocarbon compounds as shown in formula II, structure oxirane compound as shown in formula III consumption permissible
Composition according to intended magnesium-containing carrier properly selects, it is preferable that on the basis of the 1mol formula magnesium halide as MgXY,
Formula be the consumption of the compound of ROH be 4-30mol, formula be the consumption of the compound of R'OH be 0.001-1.5mol, structure
The consumption of two oxyl hydrocarbon compounds as shown in formula II is 0.001-1.5mol, structure oxirane as shown in formula III
The consumption of compounds is 1-10mol；It is highly preferred that on the basis of the 1mol formula magnesium halide as MgXY, formula is the change of ROH
The consumption of compound is 6-20mol, formula be the consumption of the compound of R'OH be 0.01-1mol, structure as shown in formula II two
The consumption of oxyl hydrocarbon compound is 0.01-1mol, and the consumption of structure oxirane compound as shown in formula III is 2-
6mol。
According to the present invention, in formula M gXY, X is preferably chlorine or bromine, and Y is preferably chlorine, bromine, C1-C5Alkyl, C1-C5's
Alkoxyl, C6-C10Aryl or C6-C10Aryloxy group.Described C1-C5Alkyl can be such as methyl, ethyl, propyl group, isopropyl
Base, butyl or isobutyl group, described C1-C5Alkoxy as can be methoxyl group, ethyoxyl, propoxyl group, isopropoxy, fourth oxygen
Base or isobutoxy, described C6-C10Aryl can be such as phenyl, o-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene
Base, an ethylbenzene, to ethylbenzene or naphthyl, described C6-C10Aryloxy group can be such as phenoxy group or naphthoxy.Formula is
The magnesium halide of MgXY can be a kind of magnesium halide, or the mixture of multiple magnesium halide.Formula is the tool of the magnesium halide of MgXY
Body example can be but be not limited to: magnesium dichloride, dibrominated magnesium, Benzene Chloride epoxide magnesium, chlorination isopropoxy magnesium and the positive fourth of chlorination
One or more in epoxide magnesium.From the angle that raw material is ready availability, preferably magnesium dichloride.
According to the present invention, in general formula R OH, R is preferably C1-C8Alkyl.Described C1-C8Alkyl can be such as first
Base, ethyl, propyl group, isopropyl, butyl, isobutyl group, amyl group, isopentyl, hexyl, isohesyl, heptyl, different heptyl, octyl group or different
Octyl group.Formula is that the instantiation of the compound of ROH can be but is not limited to: ethanol, propanol, isopropanol, n-butyl alcohol, isobutyl
One or more in alcohol, amylalcohol, isoamyl alcohol, hexanol, n-octyl alcohol and 2-Ethylhexyl Alcohol.
According to the present invention, general formula R ' in OH, R' is preferably C16-C20Alkyl or aralkyl.Formula is the chemical combination of R'OH
The instantiation of thing can be but be not limited to: one or more in oleyl alcohol, hexadecanol, octadecanol, preferably octadecanol.
According to the present invention, in the structure two oxyl hydrocarbon compounds as shown in formula II, R '1、R’2、R’3And R '4' preferably
Each stand alone as hydrogen, C1-C3Alkyl, C6-C8Aryl；Described C1-C3Alkyl can be such as methyl, ethyl, propyl group or
Isopropyl；Described C6-C8Aryl can be such as phenyl, o-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene, a second
Phenyl or to ethylbenzene；The instantiation of described two oxyl hydrocarbon compounds can be but be not limited to: 2,2-dimethoxy propane,
2,2-dimethoxy-butane, 2,2-dimethoxy pentane, 3,3-dimethoxy pentane, 2,2-di ethyl propyl ether and 2,2-hexichol
One or more in epoxide propane.
According to the present invention, in structure oxirane compound as shown in formula III, R '5And R '6Preferably each independent
For hydrogen, C1-C3Alkyl or haloalkyl.The instantiation of described oxirane compound can be but be not limited to: epoxy second
One or many in alkane, expoxy propane, epoxy butane, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide
Kind.
The present invention to by formula be the magnesium halide of MgXY, formula be the compound of ROH, formula be the compound of R'OH, two
Oxyl hydrocarbon compound is not particularly limited with the blend heated condition of inert liquid medium, if the bar of described heating
Part enable to magnesium halide that formula is MgXY melted and with formula be the compound of ROH, formula be R'OH compound and
Two oxyl hydrocarbon compounds react.Usually, the condition of described heating includes: temperature can be 80-120 DEG C, time
Between can be 0.5-5 hour；Preferably, described temperature is 80-100 DEG C, and the time is 0.5-3 hour.
According to the present invention, the consumption of described inert liquid medium can select according to the consumption of the magnesium halide that formula is MgXY
Select.Usually, on the basis of the 1mol formula magnesium halide as MgXY, the consumption of described inert liquid medium is 0.8-10L；Preferably
Ground, on the basis of the 1mol formula magnesium halide as MgXY, the consumption of described inert liquid medium is 2-8L.Described inert fluid is situated between
Matter can be commonly used in the art various with reactant and product, chemically interactive liquid medium not to occur.Such as:
Described inert liquid medium can be silicone oil and/or inert fluid varsol.Specifically, described inert liquid medium can be
Kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil and aminomethyl phenyl silicon
One or more in oil.Inert liquid medium of the present invention is particularly preferably white oil.
Well known to a person skilled in the art that various method is by described liquefied mixture emulsifying according to the present invention it is possible to use.
For example, it is possible to described liquefied mixture is carried out high speed shear, thus it is emulsified.The method of described high speed shear is this area
Well known to technical staff, as disclosed in CN1151183C high-speed mixing method (that is, by the solution containing liquid halogenated magnesium adduct with
The speed of 2000-5000 rev/min is stirred).Further, it is also possible to described liquid is mixed with reference to method disclosed in following patent
Disclosed being carried out in hypergravity bed by the solution containing liquid halogenated magnesium adduct of compound emulsifying: CN1267508C rotates dispersion
(speed of rotation can be 100-3000 rev/min)；Disclosed molten by containing liquid halogenated magnesium adduct of CN1463990A
Liquid exports with the speed of 1500-8000 rev/min in mulser；US6020279 is disclosed will be containing liquid by nebulization
The emulsifying soln of adduct of magnesium halides.
According to the present invention, can be existing various by catalytic to emulsification product and oxirane compound condition
Can form the condition of magnesium-containing carrier, such as, described catalytic condition includes that temperature can be 80-120 DEG C, and the time is permissible
For 20-60 minute；Preferably, described temperature is 80-100 DEG C, and the time is 20-50 minute.
The present invention provide solid constituent preparation method in, described magnesium-containing carrier, the first titanium compound and interior give electricity
The consumption of daughter can select in the larger context and change, under preferable case, magnesium-containing carrier in terms of magnesium elements, with
First titanium compound of titanium elements meter and the mol ratio of internal electron donor addition are 1:20-150:0.005-1, preferably 1:
30-120:0.01-0.6.
According to the present invention, the first titanium compound and the second titanium compound can be to prepare catalyst solid component of olefin polymerization
During conventional use of various titanium compounds.Under normal circumstances, the first titanium compound and the second titanium compound can be the most only
It is on the spot formula Ti (OR ")3-aZaAnd/or Ti (OR ")4-bZbTitanium compound, wherein, R is " for C1-C20Alkyl, Z is F, Cl,
Br or I, a are the integer of 1-3, and b is the integer of 1-4.Under preferable case, the first titanium compound and the second titanium compound are each independent
Ground is titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, three butoxy titanium chlorides, dibutoxy titanium chloride, butoxy tri-chlorination
One or more in titanium, triethoxy titanium chloride, diethoxy titanium chloride, ethyoxyl titanous chloride. and titanous chloride..
According to the present invention, in the preparation process of described solid constituent, described magnesium-containing carrier and the first titanium compound anti-
Should carry out according to mode same as the prior art, for example, it is possible to the first titanium compound is cooled to less than 0 DEG C (preferably
For-5 to-25 DEG C), and add the magnesium-containing carrier that step (1) prepares, and stirring mixing 10-60 minute at such a temperature, it
After be warming up to reaction temperature (the most about 80-130 DEG C), and maintain 0.5-10 hour under this reaction temperature.Described internal electron donor
Add in one or more time periods before and after, during described magnesium-containing carrier and the first titanium compound react, preferably
Add in time period before described magnesium-containing carrier reacts with the first titanium compound.Described magnesium-containing carrier and the first titanium compound
Time period before reaction refer to after described magnesium-containing carrier adds in reactor and be warming up to before reaction temperature time
Between section.
In the case of according to the invention it is preferred to, the preparation method of described solid constituent be additionally included in by described solid product with
Before second titanium compound is performed for more than the contact of 4 hours at-10 DEG C to 120 DEG C, by described solid product titanium compound
Washing, or described solid product is carried out with titanium compound the short period contact (typically smaller than 2 hours).Described titanium compound
Can be identical with the first titanium compound, will not be described in great detail at this.
According to the present invention, the product that step (2) obtains is carried out the method for solid-liquid separation can be existing various can
The method realizing solid phase and liquid phase separation, such as sucking filtration, filter pressing or centrifugation, under preferable case, the side of described solid-liquid separation
Method is filter press technique.The condition of filter pressing is not particularly limited by the present invention, with realize the most fully solid phase and liquid phase point
From being as the criterion.
Can be all the normal of this area according to the present invention, described alkyl aluminum compound and the kind of external electron donor and consumption
Rule select.Such as, the formula of described alkyl aluminum compound can be Al (R7)3, R7For C1-C8Alkyl or haloalkyl；Described
Alkyl aluminum compound can be such as triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, aluminium diethyl monochloride,
One chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminum, a chlorine di-n-hexyl aluminum, dichloro one aluminium ethide, dichloro one aluminium isobutyl, dichloro
One or more in one n-butylaluminum and dichloro one n-hexyl aluminum.Usually, in described olefin polymerization catalysis, in terms of aluminum
Alkyl aluminum compound and the mol ratio for catalyst solid component of olefin polymerization counted with titanium can be as 1-2000:1, preferably
For 20-500:1.
Described external electron donor can be various external electron donors commonly used in the art, and such as, described external electron donor can
Think one or more in carboxylic acid, anhydride, ester, ketone, ether, alcohol, organic phosphorus compound and organo-silicon compound；Preferably, institute
State external electron donor and be 1,3-diether compound and/or formula is (R8)a(R9)bSi(OR10)cSilicon compound.Wherein, R8、
R9And R10For C1-C18Alkyl, a and b each stands alone as the integer of 0-2, and c is the integer of 1-3, and a, b and c and be 4.Described
The instantiation of external electron donor can be but be not limited to: Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silicon
Alkane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl tertbutyl two
Methoxy silane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-t-butyldimethoxysilane, (1,1,1-tri-
Fluoro-2-propyl group) in-2-ethyl piperidine base dimethoxysilane and (1,1,1-tri-fluoro-2-propyl group)-methyl dimethoxysilane
One or more.Described external electron donor and the mol ratio typically 0.005-0.5:1 of alkyl aluminum compound, be preferably
0.01-0.4:1.
Present invention also offers a kind of polypropylene product, this polypropylene product is by prepared according to the methods of the invention.
Polypropylene product according to the present invention not only have higher melt strength (that is, relatively low melt flow rate (MFR)) and
Higher isotactic index and there is wider molecular weight distribution.
Describe in detail according to polypropylene product of the present invention and preparation method thereof below in conjunction with embodiment.
The method of testing used in following example is as follows:
1, polymer molecular weight and molecular weight distributing index (Mw/Mn): use gel permeation chromatography method, use commercially available from
The model of Polymer Laboratories is the chromatograph of gel permeation of PL-GPC220, with homo-trichloro-benzene as solvent, 150
Measure at DEG C.Wherein, standard specimen is polystyrene, and flow velocity is 1.0 ml/min, and chromatographic column is 3 Plgel 10 μm M posts and 1
Root ED-B 300 × 7.5nm post.
2, polymer isotactic index: use heptane extraction process to measure: by 2 grams of dry polymer samples, to be placed on Soxhlet and take out
Carry in device and extracting after 6 hours with boiling heptane, residue is dried to constant weight gained polymer weight with 2 ratio be
Rule index.
3, melt flow rate is measured according to ASTM D1238-99 method for measuring.
4, particle diameter distribution tests: the mean diameter of adduct of magnesium halides granule and particle size distribution MastersSizer
2000 particle size analyzers (being manufactured by Malvern Instruments Ltd) measure.
5, the mensuration of the content of 1,3-diether compound in polymer: by the 1,3-in liquid chromatogram measuring catalyst
The content ω of diether compound1, used catalyst quality is ω2, the quality of resulting polymers is ω3, by formula ω1×
ω2÷ω3It is calculated 1,3-diether compound content in polymer.
6, the average particulate diameter of magnesium-containing carrier and particle size distribution use Masters Sizer 2000 particle size analyzer (by
Malvern Instruments Ltd manufactures) it is measured；
7, the apparent form of magnesium-containing carrier is by the optical microphotograph that model is Eclipse E200 commercially available from Nikon company
Mirror is observed；
8, the polymerization activity computational methods of catalyst: the catalyst quality of polymerization is m1, obtained polymer quality
For m2, activity is by formula m2÷m1It is calculated.
Preparation example 1
This preparation example is for the catalyst solid constituent used in the preparation method of the polypropylene product preparing the present invention.
(1) preparation of magnesium-containing carrier
In the reactor of 1.6L, add 200ml white oil, 8.0g(0.08mol) magnesium chloride, 3g(0.01mol) octadecanol,
95ml(1.6mol) ethanol, 9.8ml(0.08mol) 2,2-dimethoxypropane, under agitation it is warming up to 90 DEG C.Isothermal reaction 1
After hour, mixture high-speed stirred (400rpm) is disperseed 30 minutes, to carry out emulsifying.And add in above-mentioned emulsification product
35ml(0.45mol) epoxychloropropane, filter pressing after reaction half an hour, filter pressing product hexane is washed 5 times, vacuum drying,
Obtain magnesium-containing carrier Z1.
The average particulate diameter (D50) of described magnesium-containing carrier Z1 is 57 microns, and particle size distribution ((D90-D10)/D50) is
0.8.The particle morphology using observation by light microscope is found out, the particle shape of magnesium-containing carrier Z1 is more regular, smooth surface, base
Being all spherical in basis, particle size distribution compares concentration, and there is no that irregular particle exists.
(2) preparation of catalyst solid component of olefin polymerization
In the glass reaction bottle of 2000ml, add the titanium tetrachloride of 500ml and be cooled to-20 DEG C, above-mentioned by 40 grams
(1) the magnesium-containing carrier Z1 prepared in is added thereto, and stirs 30min at-20 DEG C.Afterwards, start to be to slowly warm up to 110 DEG C,
And in temperature-rise period, add 2-isopropyl-2-isopentyl-1 of 5mmol, 3-dimethoxy propane, maintain at 110 DEG C
Filter off liquid after 30min, add titanium tetrachloride afterwards and wash 2 times, obtain solid product.100ml is added in solid product
Titanium tetrachloride, and react at 25 DEG C 16 hours, finally wash 4 times with hexane, obtain olefin polymerization catalysis solid after drying
Component C1.
Preparation example 2
This preparation example is for the catalyst solid constituent used in the preparation method of the polypropylene product preparing the present invention.
(1) preparation of magnesium-containing carrier
In the reactor of 1.6L, add 300ml white oil, 8.0g(0.08mol) magnesium chloride, 10.8g(0.04mol) 18
Alcohol, 28ml(0.48mol) ethanol, 1ml(0.008mol) 2,2-dimethoxypropane, be under agitation warming up to 100 DEG C.Constant temperature is anti-
After answering 0.5 hour, mixture high-speed stirred (800rpm) is disperseed 30 minutes, to carry out emulsifying.And in above-mentioned emulsification product
Add 12.5ml(0.16mol) epoxychloropropane, filter pressing after reacting 20 minutes, filter pressing product hexane to be washed 5 times, vacuum is done
Dry, obtain magnesium-containing carrier Z2.
The average particulate diameter (D50) of described magnesium-containing carrier Z2 is 48 microns, and particle size distribution ((D90-D10)/D50) is
0.6.Use observation by light microscope particle morphology it can be seen that the particle shape of magnesium-containing carrier Z2 is more regular, surface light
Sliding, it is essentially all spherical, particle size distribution compares concentration, and there is no that irregular particle exists.
(2) preparation of catalyst solid component of olefin polymerization
In the glass reaction bottle of 2000ml, add the titanium tetrachloride of 500ml, be cooled to-20 DEG C, above-mentioned by 40 grams
(1) the magnesium-containing carrier Z2 prepared in is added thereto, and stirs 30min at-20 DEG C.Afterwards, start to be to slowly warm up to 110 DEG C,
2-isopropyl-2-isopentyl-1,3-dimethoxy propane and the phthalic acid of 1.0ml of 6.5ml is added in temperature-rise period
Diisobutyl ester, filters off liquid after maintaining 30min at 110 DEG C.Then, add titanium tetrachloride and wash 3 times, obtain solid product.
In solid product, add 100ml titanium tetrachloride, and react 16 hours at 25 DEG C, finally wash 5 times with hexane, obtain after drying
Catalyst solid component of olefin polymerization C2.
Preparation example 3
This preparation example is for the catalyst solid constituent used in the preparation method of the polypropylene product preparing the present invention.
(1) preparation of magnesium-containing carrier
In the reactor of 1.6L, add 500ml white oil, 8.0g(0.08mol) magnesium chloride, 21.6g(0.08mol) 18
Alcohol, 58ml(1mol) ethanol, 3.5ml(0.04mol) 2,2-dimethoxypropane, be under agitation warming up to 80 DEG C.Isothermal reaction 3
After hour, mixture high-speed stirred (800rpm) is disperseed 30 minutes, to carry out emulsifying.And add in above-mentioned emulsification product
23.5ml(0.3mol) epoxychloropropane, filter pressing after reacting 50 minutes, filter pressing product hexane is washed 5 times, vacuum drying,
To magnesium-containing carrier Z3.
The average particulate diameter (D50) of described magnesium-containing carrier Z3 is 50 microns, and particle size distribution ((D90-D10)/D50) is
0.7.The pattern using observation by light microscope particle finds, the particle shape of magnesium-containing carrier Z3 is more regular, smooth surface, base
Being all spherical in basis, particle size distribution compares concentration, and there is no that irregular particle exists.
(2) preparation of catalyst solid component of olefin polymerization
In the glass reaction bottle of 2000ml, add the titanium tetrachloride of 500ml and be cooled to-20 DEG C, above-mentioned by 40 grams
(1) the magnesium-containing carrier Z3 prepared in is added thereto, and stirs 30min at-20 DEG C.Afterwards, start to be to slowly warm up to 110 DEG C,
And in temperature-rise period, adding the 2-(2-ethylhexyl)-1 of 7.5ml, 3-dimethoxy propane, after maintaining 30min at 110 DEG C
Filter off liquid, add titanium tetrachloride afterwards and wash 2 times, obtain solid product.100ml tetra-chlorination is added in solid product
Titanium, and react at 25 DEG C 16 hours, finally wash 4 times with hexane, obtain catalyst solid component of olefin polymerization C3 after drying.
Preparation example 4
This preparation example is for the catalyst solid constituent used in the preparation method of the polypropylene product preparing the present invention.
Method according to preparation example 1 prepares catalyst solid component of olefin polymerization, except that, described magnesium-containing carrier is pressed
Prepare according to method disclosed in embodiment in CN1718595A 1, specific as follows:
In the reactor of the 150L of band stirring, 10kg anhydrous magnesium chloride and 12.6kg ethanol are added 60L viscosity is 30
In the white oil of centipoise (20 DEG C), react 2 hours at 125 DEG C.Then the mixed liquor of the molten adduct obtained with white oil is turned
Move on to be pre-heated in the methyl-silicone oil medium of 125 DEG C；The viscosity of methyl-silicone oil is 300 centipoises (20 DEG C), the use of methyl-silicone oil
Amount is 120L；Stir 10-30 minute with the rotating speeds of 200 revs/min, obtain mixed liquor.Described mixed liquor is introduced hypergravity rotate
Bed disperses, and under agitation, the mixed liquor after dispersion introduced be cooled in advance in the hexane medium of-35 DEG C, oneself
The consumption of alkane is 1200L, is separated into the cooled solidification of magnesium chloride/alcohol adducts melt of droplet, becomes spherical solid particles.
Filtering out particulate solid the suspension of gained after chilling, at room temperature wash this particulate matter with hexane, hexane consumption is
100L/ time, washing 5 times altogether, at 30-50 DEG C, evacuation i.e. obtains magnesium-containing carrier Z4.Correspondingly, the olefinic polymerization prepared
Catalyst solid constituent is designated as C4.
The average particulate diameter (D50) of described magnesium-containing carrier Z4 is 52 microns, and particle size distribution ((D90-D10)/D50) is
1.1.The pattern using observation by light microscope particle finds, the particle shape of carrier for olefin polymerization catalyst Z4 is more regular,
Surface is relatively smooth, and with the presence of a small amount of irregular particle, particle size distribution compares concentration.
Preparation example 5
This preparation example is for the catalyst solid constituent used in the preparation method of the polypropylene product preparing the present invention.
It is the diisobutyl phthalate of 5mmol, 2-isopropyl-2-isopentyl-1 except using total amount, 3-dimethoxy
Base propane, 2,3-diisopropyl succinate, 2-cyano group-2,3-diisopropyl succinate, 4-ethyl-3,5-heptandiol hexichol
The mixture (mol ratio is 9:0.25:0.25:0.25:0.25) of formic acid esters substitutes 5mmol2-(2-ethylhexyl)-1,3-diformazan
Epoxide propane, remaining obtains catalyst solid component of olefin polymerization C5 with preparation example 1.
Preparation comparative example 1
Prepare magnesium-containing carrier according to the method for preparation example 1, prepare catalyst solid component of olefin polymerization, except that,
Do not include during preparing catalyst solid component of olefin polymerization in solid product add 100ml titanium tetrachloride, and
React at 25 DEG C 16 hours, finally wash the step of 4 times with hexane, obtain catalyst solid component of olefin polymerization DC1.
Preparation comparative example 2
Prepare magnesium-containing carrier according to the method for preparation example 1, prepare catalyst solid component of olefin polymerization, except that,
In solid product, add 100ml titanium tetrachloride, and the time reacted at 25 DEG C is to be changed into by 16 hours in preparation example 1
3.5 hours, finally wash the step of 4 times with hexane, obtain catalyst solid component of olefin polymerization DC2.
Preparation comparative example 3
Prepare magnesium-containing carrier according to the method for preparation example 4, prepare catalyst solid component of olefin polymerization, except that,
During preparing catalyst solid component of olefin polymerization, do not include adding 100ml titanium tetrachloride in described solid product,
And at 25 DEG C, react the step of 16 hours, obtain catalyst solid component of olefin polymerization DC3.
Preparation comparative example 4
Method according to preparation example 1 is prepared magnesium-containing carrier, is prepared catalyst solid component of olefin polymerization, except that,
By 2-isopropyl-2-isopentyl-1,3-dimethoxy propane changes to diisobutyl phthalate and obtains olefinic polymerization catalysis
Agent solid constituent DC4.
Embodiment 1
The present embodiment is used for polypropylene product according to the present invention and preparation method thereof is described.
In the autoclave of a 5L, use stream of nitrogen gas to purge, in stream of nitrogen gas, then introduce 5ml's
The hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of triethyl aluminum, the Cyclohexyl Methyl Dimethoxysilane of 1ml
(CHMMS) consolidating of hexane solution (concentration of CHMMS is 0.1mmol/ml), the anhydrous hexane of 10ml and 8mg preparation example 1 preparation
Body component.Close autoclave, add 1.5L(normal volume) hydrogen and the liquid propene of 2.3L, be warming up to 70 DEG C, and at this
At a temperature of react 1 hour.
Embodiment 2
The present embodiment is used for polypropylene product according to the present invention and preparation method thereof is described.
Method according to embodiment 1 carries out propylene polymerization, except that, hydrogen during propylene polymerization
Addition is 6.5L(normal volume).
Embodiment 3
The present embodiment is used for polypropylene product according to the present invention and preparation method thereof is described.
Propylene polymerization is carried out according to the method for embodiment 1, except that, prepare by the preparation example 2 of identical weight
Catalytic component C2 replace catalytic component C1.
Embodiment 4
The present embodiment is used for polypropylene product according to the present invention and preparation method thereof is described.
Method according to embodiment 3 carries out propylene polymerization, except that, hydrogen during propylene polymerization
Addition is 6.5L(normal volume).
Embodiment 5
The present embodiment is used for polypropylene product according to the present invention and preparation method thereof is described.
Propylene polymerization is carried out according to the method for embodiment 1, except that, prepare by the preparation example 3 of identical weight
Catalytic component C3 replace catalytic component C1.
Embodiment 6
The present embodiment is used for polypropylene product according to the present invention and preparation method thereof is described.
Method according to embodiment 5 carries out propylene polymerization, except that, hydrogen during propylene polymerization
Addition is 6.5L(normal volume).
Embodiment 7
The present embodiment is used for polypropylene product according to the present invention and preparation method thereof is described.
Method according to embodiment 1 carries out propylene polymerization, except that, prepare by the preparation example 4 of identical weight
Catalytic component C4 replace catalytic component C1.
Embodiment 8
The present embodiment is used for polypropylene product according to the present invention and preparation method thereof is described.
Method according to embodiment 7 carries out propylene polymerization, except that, hydrogen during propylene polymerization
Addition is 6.5L(normal volume).
Embodiment 9
The present embodiment is used for polypropylene product according to the present invention and preparation method thereof is described.
Method according to embodiment 1 carries out propylene polymerization, except that, prepare by the preparation example 5 of identical weight
Catalytic component C5 replace catalytic component C1.
Embodiment 10
Method according to embodiment 9 prepare magnesium-containing carrier, prepare catalyst solid component of olefin polymerization and carry out propylene gather
Close reaction, except that, during propylene polymerization, the addition of hydrogen is 6.5L(normal volume).
Embodiment 11
Except the propylene polymerization time is 2 hours, other is with embodiment 7.
Embodiment 12
Except the propylene polymerization time is 2 hours, other is with embodiment 8.
Comparative example 1
Use method same as in Example 1 to prepare polypropylene, except for the difference that, use the solid that preparation comparative example 1 prepares
Component, obtains polypropylene.
Comparative example 2
Method according to comparative example 1 carries out propylene polymerization, except that, add during propylene polymerization
6.5L(normal volume) hydrogen.
Comparative example 3
Use method same as in Example 1 to prepare polypropylene, except for the difference that, use the solid that preparation comparative example 2 prepares
Component, obtains polypropylene.
Comparative example 4
Method according to comparative example 2 carries out propylene polymerization, except that, add during propylene polymerization
6.5L(normal volume) hydrogen.
Comparative example 5
Use method same as in Example 1 to prepare polypropylene, except for the difference that, use the solid that preparation comparative example 3 prepares
Component, obtains polypropylene.
Comparative example 6
Method according to comparative example 3 carries out propylene polymerization, except that, add during propylene polymerization
6.5L(normal volume) hydrogen.
Comparative example 7
Use method same as in Example 1 to prepare polypropylene, except for the difference that, use the solid that preparation comparative example 3 prepares
Component, obtains polypropylene.
Comparative example 8
Method according to comparative example 7 carries out propylene polymerization, except that, add during propylene polymerization
6.5L(normal volume) hydrogen.
The isotactic index of the acrylic polymers that embodiment 1-12 and comparative example 1-8 obtain, melt flow rate (MFR), Weight-average molecular
The content of the 1,3-diether compound in amount, molecular weight distributing index and acrylic polymers is as shown in table 1:
Table 1
From the data of table 1 it can be seen that use the melt flows of polymer that the olefin polymerization catalysis of the present invention obtains
Speed is relatively big, shows that the hydrogen response of the olefin polymerization catalysis using the processing method of the present invention to obtain has obtained very great Cheng
Improvement on degree, has obvious superiority.Additionally, current olefin polymerization catalyst is usually with sacrificial polymer
Isotactic index (i.e. reducing its isotactic index, this is disadvantageous to the downstream application of polymer) improves its melt flow rate (MFR),
But the acrylic polymers from the results shown in Table 1, using the catalyst of the present invention to prepare can have high melt concurrently
Flow rate and isotactic index, i.e. the acrylic polymers that the present invention provides is compared with acrylic polymers of the prior art, melted
After index raises, isotacticity is the highest.
Claims (17)
1. a preparation method for polypropylene product, the method is included under olefin polymerization conditions, in the presence of a catalyst, by third
Alkene or propylene are polymerized with the mixture of ethylene and/or alpha-olefin, obtain polypropylene product, and described catalyst contains solid
Component, alkyl aluminum compound and external donor compound, described solid constituent contains magnesium, titanium, halogen and internal electron donor
Compound, described internal electron donor compound contains 1,3-diether compound, it is characterised in that below described solid constituent uses
Prepared by method:
(1) magnesium-containing carrier is reacted with the first titanium compound, and before described magnesium-containing carrier reacts with the first titanium compound, the phase
Between and one or more time periods afterwards in add internal electron donor；
(2) product that step (1) obtains is carried out solid-liquid separation, and the solid product and the second titanizing that solid-liquid separation are obtained are closed
Thing contacts, the condition of described contact include temperature be-10 DEG C to 120 DEG C, the time be 16-24 hour；
Wherein, the preparation of described magnesium-containing carrier include by formula be the magnesium halide of MgXY, formula be that the compound of ROH, formula are
The compound of R ' OH, two oxyl hydrocarbon compounds are mixed and heated with inert liquid medium, obtain liquefied mixture；By obtain
Liquefied mixture emulsifying, and by emulsification product and oxirane compound haptoreaction；In formula M gXY, X is halogen, Y
For halogen, C1-C14Alkyl, C1-C14Alkoxyl, C6-C14Aryl or C6-C14Aryloxy group；In general formula R OH, R is
C1-C8Alkyl or C3-C8Cycloalkyl；In general formula R ' OH, R ' is C16-C24Alkyl or aralkyl；Described two oxyl hydrocarbon
The structure of compound is as shown in formula II, and the structure of described oxirane compound is as shown in formula III:
Wherein, R '1、R’2、R’3And R '4Each stand alone as hydrogen, C1-C10Alkyl or haloalkyl, C3-C10Cycloalkyl or halo ring
Alkyl, C6-C10Aryl or halogenated aryl, C7-C10Alkaryl or haloalkylaryl, C7-C10Aralkyl or araalkyl
Base；R’5And R '6Each stand alone as hydrogen, C1-C5Alkyl or haloalkyl.
Preparation method the most according to claim 1, wherein, in step (2), described contact conditions includes that temperature is 0-120
℃。
Preparation method the most according to claim 1, wherein, in step (2), described contact conditions includes that temperature is 25-120
℃。
Preparation method the most according to claim 1, wherein, in step (2), described solid product and the second titanium compound
Weight ratio is 0.1-80:100.
Preparation method the most according to claim 4, wherein, in step (2), described solid product and the second titanium compound
Weight ratio is 5-15:100.
Preparation method the most according to claim 1, wherein, described 1,3-diether compound has the knot shown in formula I
Structure:
Wherein, R1And R2Can be identical or different, and it is each independently C1-C20Alkyl, C3-C20Cycloalkyl, C6-C20's
Aryl or C7-C20Aralkyl；R3-R8Can be identical or different, and can be each hydrogen, halogen, C1-C20Alkyl, C3-
C20Cycloalkyl, C6-C20Aryl, C7-C20Aralkyl or R3-R8In two or more bonding formed ring structures.
Preparation method the most according to claim 6, wherein, described 1,3-diether compound has the knot shown in formula I
Structure:
Wherein, R1And R2Identical or different, and it is each independently C1-C10Alkyl；R3、R4、R7And R8It is hydrogen；R5And R6Phase
Same or different, and respectively C1-C18Alkyl, C3-C18Cycloalkyl, C6-C18Aryl, C7-C18Aralkyl or R5With
R6It is mutually bonded the ring structure of formation.
Preparation method the most according to claim 7, wherein, described 1,3-diether compound be 2-(2-ethylhexyl)-
1,3-dimethoxy propane, 2-isopropyl-1,3-dimethoxy propane, 2-butyl-1,3-dimethoxy propane, 2-sec-butyl-
1,3-dimethoxy propane, 2-cyclohexyl-1,3-dimethoxy propane, 2-phenyl-1,3-dimethoxy propane, 2-(2-phenyl
Ethyl)-1,3-dimethoxy propane, 2-(2-cyclohexyl-ethyl)-1,3-dimethoxy propane, 2-(diphenyl methyl)-1,3-
Dimethoxy propane, 2,2-dicyclohexyl-1,3-dimethoxy propane, 2,2-bicyclopentyl-1,3-dimethoxy propane, 2,2-
Diethyl-1,3-dimethoxy propane, 2,2-dipropyl-1,3-dimethoxy propane, 2,2-diisopropyl-1,3-dimethoxy
Propane, 2,2-dibutyl-1,3-dimethoxy propane, 2-methyl-2-propyl-1,3-dimethoxy propane, 2-methyl-2-benzyl
Base-1,3-dimethoxy propane, 2-methyl-2-ethyl-1,3-dimethoxy propane, 2-methyl-2-isopropyl-1,3-dimethoxy
Base propane, 2-methyl-2-phenyl-1,3-dimethoxy propane, 2-methyl-2-cyclohexyl-1,3-dimethoxy propane, 2,2-are double
(2-cyclohexyl-ethyl)-1,3-dimethoxy propane, 2-methyl-2-isobutyl group-1,3-dimethoxy propane, 2-methyl-2-(2-
Ethylhexyl)-1,3-dimethoxy propane, 2,2-diisobutyl-1,3-dimethoxy propane, 2,2-diphenyl-1,3-diformazan
Double (the cyclohexyl methyl)-1,3-dimethoxy propane of epoxide propane, 2,2-dibenzyl-1,3-dimethoxy propane, 2,2-, 2-are different
Butyl-2-isopropyl-1,3-dimethoxy propane, 2-(1-methyl butyl)-2-isopropyl-1,3-dimethoxy propane, 2-are different
Propyl group-2-isopentyl-1,3-dimethoxy propane, 2-phenyl-2-isopropyl-1,3-dimethoxy propane, 2-phenyl-2-sec-
Butyl-1,3-dimethoxy propane, 2-benzyl-2-isopropyl-1,3-dimethoxy propane, 2-cyclopenta-2-isopropyl-1,3-
Dimethoxy propane, 2-cyclopenta-2-sec-butyl-1,3-dimethoxy propane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxy
Base propane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxy propane, 2-isopropyl-2-sec-butyl-1,3-dimethoxy third
One or more in alkane, 2-cyclohexyl-2-cyclohexyl methyl-1,3-dimethoxy propane and 9,9-dimethoxy-methyl fluorenes.
Preparation method the most according to claim 1, wherein, on the basis of the 1mol formula magnesium halide as MgXY, formula is
The consumption of the compound of ROH is 4-30mol, formula be the consumption of the compound of R ' OH be 0.001-1.5mol, structure such as formula
(II) consumption of two oxyl hydrocarbon compounds shown in is 0.001-1.5mol, structure such as formula III) shown in ethylene oxide
The consumption of compound is 1-10mol.
Preparation method the most according to claim 9, wherein, on the basis of the 1mol formula magnesium halide as MgXY, formula is
The consumption of the compound of ROH is 6-20mol, formula be the consumption of the compound of R ' OH be 0.01-1mol, structure such as formula II institute
The consumption of the two oxyl hydrocarbon compounds shown is 0.01-1mol, structure such as formula III) shown in the use of oxirane compound
Amount is 2-6mol.
11. according to the preparation method described in any one in claim 1 and 9-10, wherein, by described emulsification product and epoxy
The catalytic condition of ethane compound includes that temperature is 80-120 DEG C, and the time is 20-60 minute.
12. preparation methoies according to claim 11, wherein, contact described emulsification product with oxirane compound
The condition of reaction includes that temperature is 80-100 DEG C, and the time is 20-50 minute.
13. preparation methoies according to claim 1, wherein, the magnesium-containing carrier in terms of magnesium elements, in terms of titanium elements first
The mol ratio of titanium compound and internal electron donor addition is 1:20-150:0.005-1.
14. preparation methoies according to claim 13, wherein, the magnesium-containing carrier in terms of magnesium elements, in terms of titanium elements
The mol ratio of one titanium compound and internal electron donor addition is 1:30-120:0.01-0.6.
15. preparation methoies according to claim 1, wherein, described first titanium compound and the second titanium compound is identical or
Difference, is each independently formula Ti (OR ")3-aZaAnd/or Ti (OR ")4-bZbTitanium compound, wherein, R is " for C1-C20Alkane
Base, Z is F, Cl, Br or I, and a is the integer of 1-3, and b is the integer of 1-4；The formula of described alkyl aluminum compound is Al (R7)3, R7
For C1-C8Alkyl or haloalkyl；Described external electron donor is 1,3-diether compound and/or formula is (R8)a(R9)bSi
(OR10)cSilicon compound, wherein, R8、R9And R10For C1-C18Alkyl, a and b each stands alone as the integer of 0-2, and c is 1-3's
Integer, and a, b and c and be 4.
16. preparation methoies according to claim 15, wherein, described first titanium compound and the second titanium compound are the most only
It is on the spot titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, three butoxy titanium chlorides, dibutoxy titanium chloride, butoxy tri-chlorination
One or more in titanium, triethoxy titanium chloride, diethoxy titanium chloride, ethyoxyl titanous chloride. and titanous chloride.；Institute
State alkyl aluminum compound selected from triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, aluminium diethyl monochloride, a chlorine
Diisobutyl aluminum, a chlorine di-n-butyl aluminum, a chlorine di-n-hexyl aluminum, dichloro one aluminium ethide, dichloro one aluminium isobutyl, dichloro one
One or more in n-butylaluminum and dichloro one n-hexyl aluminum；Described external electron donor is selected from cyclohexyl methyl dimethoxy silicon
Alkane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, diphenyl diformazan
One or more in TMOS, methyl-t-butyldimethoxysilane and dicyclopentyl dimethoxyl silane.
17. polypropylene products prepared according to the method described in any one in claim 1-16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210423299.2A CN103788255B (en) | 2012-10-29 | 2012-10-29 | A kind of polypropylene product and preparation method thereof |
Applications Claiming Priority (1)
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| CN112625157B (en) * | 2020-12-17 | 2023-04-28 | 黄河三角洲京博化工研究院有限公司 | Catalyst for preparing ultra-pure polypropylene and preparation method for preparing ultra-pure polypropylene by batch bulk method |
| CN112920305B (en) * | 2021-01-28 | 2023-03-24 | 中国神华煤制油化工有限公司 | Polypropylene and preparation method thereof, polypropylene composition, modified polypropylene and preparation method thereof |
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| CN1173879A (en) * | 1995-10-11 | 1998-02-18 | 三井石油化学工业株式会社 | Solid titanium catalyst component and utilization thereof in olefin polymerization catalyst |
| CN1137155C (en) * | 1999-12-06 | 2004-02-04 | 中国石油化工集团公司 | Catalyst system for polymerization or copolymerization of olefine |
| CN1863830A (en) * | 2003-10-07 | 2006-11-15 | 陶氏环球技术公司 | Polypropylene composition for air quenched blown films |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1173879A (en) * | 1995-10-11 | 1998-02-18 | 三井石油化学工业株式会社 | Solid titanium catalyst component and utilization thereof in olefin polymerization catalyst |
| CN1137155C (en) * | 1999-12-06 | 2004-02-04 | 中国石油化工集团公司 | Catalyst system for polymerization or copolymerization of olefine |
| CN1863830A (en) * | 2003-10-07 | 2006-11-15 | 陶氏环球技术公司 | Polypropylene composition for air quenched blown films |
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