CN103788245B - A kind of catalyst solid component of olefin polymerization and olefin polymerization catalysis and application thereof - Google Patents
A kind of catalyst solid component of olefin polymerization and olefin polymerization catalysis and application thereof Download PDFInfo
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- CN103788245B CN103788245B CN201210421455.1A CN201210421455A CN103788245B CN 103788245 B CN103788245 B CN 103788245B CN 201210421455 A CN201210421455 A CN 201210421455A CN 103788245 B CN103788245 B CN 103788245B
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Abstract
The invention provides a kind of catalyst solid component of olefin polymerization, a kind of olefin polymerization catalysis and the application in olefinic polyreaction of this olefin polymerization catalysis.Described catalyst solid component of olefin polymerization contains titanium, magnesium and internal electron donor, and the DSC spectrogram of described catalyst solid component of olefin polymerization includes that a heat release both shoulders peak, the peak separation at described heat release both shoulders peak are 55 DEG C 65 DEG C.Described catalyst solid component of olefin polymerization not only has higher hydrogen response, also has preferable stereotaxis ability and higher polymerization activity.
Description
Technical field
The present invention relates to a kind of catalyst solid component of olefin polymerization, a kind of olefin polymerization catalysis and
The application in olefinic polyreaction of this olefin polymerization catalysis.
Background technology
Sponsor it is known that catalyst for polymerization of propylene generally includes Z-N (Ziegler-Natta)
Agent, alkyl aluminum compound, internal electron donor and external electron donor.Ziegler-Natta catalyst is used for
Performance Evaluating Indexes during olefinic polymerization is mainly hydrogen response, polymerization activity and stereotaxis ability.
The structure of Ziegler-Natta catalyst is complex, and the composition structure in its active center does not the most still have
There is a qualitative conclusions.The active center of catalyst changes, and the character of polymer certainly also can be therewith
Change, cannot characterize the change determining active sites due to the limitation of current technological means, but
The mensuration that characterizes of polymer property has been relatively easy to, and therefore, the character in active center can be passed through
The character of polymer characterizes, if the performance of the polymer obtained under same polymerizing condition changes
Become, then the active center of this catalyst must there occurs change, say, that catalyst has different
Structure.
The performance of acrylic resin is fundamentally to be determined by the performance of polypropylene catalyst.In thin-walled injection moulding
Field, it is desirable to acrylic resin has higher melt mass flow index (MFI).The addition energy of hydrogen
Improve the melt flow rate (MFR) of polymerizate, but also reduce the isotactic index of polymer simultaneously, cause
Product cannot meet use requirement.Use current industrial catalyst to prepare polypropylene, only add a large amount of
Hydrogen after just can obtain the polymer with higher melt mass flow index, cause production process hydrogen
Gas yield increases.Additionally, add substantial amounts of hydrogen to also improve the resistance to pressure request to reactor simultaneously.
At present, the main method using chemical degradation improves polyacrylic melt mass flow index, but
The polypropylene articles using the method to obtain easily turns to be yellow, embrittlement, has abnormal flavour, and relatively costly.Additionally,
The material performance of different batches can not be guaranteed, and causes product unstable.
Summary of the invention
The invention aims to overcome poor the lacking of existing olefin polymerization catalysis hydrogen response
Fall into, and provide and a kind of there is higher hydrogen adjust the catalyst solid component of olefin polymerization of sensitivity, a kind of alkene
Polymerized hydrocarbon catalyst and the application in olefinic polyreaction of this olefin polymerization catalysis.
The invention provides a kind of catalyst solid component of olefin polymerization, wherein, this olefin polymerization catalysis
Solid constituent contains titanium, magnesium and internal electron donor, and the DSC of described catalyst solid component of olefin polymerization
Spectrogram includes a heat release both shoulders peak, and the peak separation at described heat release both shoulders peak is 55 DEG C-65 DEG C.
Present invention also offers a kind of olefin polymerization catalysis, this catalyst contains described olefinic polymerization catalysis
Agent solid constituent, alkyl aluminum compound and optional external electron donor.
Additionally, present invention also offers the application in olefinic polyreaction of the described olefin polymerization catalysis.
It was found by the inventors of the present invention that existing olefin polymerization catalyst is usually with sacrificial polymer
Isotactic index improve its melt flow rate (MFR), but, the reduction of polymer isotactic index is under it
The application of trip is extremely disadvantageous.And the present inventor is by substantial amounts of experiment, composed by DSC
Figure includes a heat release both shoulders peak, and the alkene that peak separation is 55 DEG C-65 DEG C at described heat release both shoulders peak
The olefin polymerization catalysis that polymerization catalyst solid constituent obtains not only has higher hydrogen response, also
There is preferable stereotaxis ability and higher polymerization activity.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 is the optical microscope photograph of the magnesium-containing carrier Z1 of embodiment 1 preparation；
Fig. 2 is the optical microscope photograph of the magnesium-containing carrier Z2 of embodiment 3 preparation.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The catalyst solid component of olefin polymerization that the present invention provides contains titanium, magnesium and internal electron donor, and institute
The DSC spectrogram stating catalyst solid component of olefin polymerization includes a heat release both shoulders peak, and described heat release is double
The peak separation of acromion is 55 DEG C-65 DEG C.Wherein, the test condition of DSC includes that heating rate is 10 DEG C
/ min, sweep limits is 50 DEG C-250 DEG C.
In accordance with the present invention it is preferred that, the peak at described heat release both shoulders peak is respectively at 130 DEG C-220 DEG C
Between and between 190 DEG C-280 DEG C；It is highly preferred that total heat enthalpy corresponding to described heat release both shoulders peak is
150-350 joule/gram.
According to the present invention, above-mentioned catalyst solid component of olefin polymerization can be prepared by various methods,
Preferable case, the preparation method of described catalyst solid component of olefin polymerization comprises the following steps:
(1) magnesium-containing carrier is reacted with the first titanium compound, and in described magnesium-containing carrier and the first titanizing
Internal electron donor is added in one or more time periods before and after, during the reaction of compound；
(2) product that step (1) obtains is carried out solid-liquid separation, and solid solid-liquid separation obtained
Product and the contact of the second titanium compound, the condition of described contact includes that temperature is-10 DEG C to 120 DEG C, time
More than 4 hours.
According to the present invention, the consumption of described magnesium-containing carrier, the first titanium compound and internal electron donor can be
Select in bigger scope and change, under preferable case, magnesium-containing carrier in terms of magnesium elements, with titanium
First titanium compound of element meter and the mol ratio of internal electron donor addition are 1:20-150:0.005-1,
It is preferably 1:30-120:0.01-0.6.
In the present invention, described magnesium-containing carrier can be conventional various containing magnesium unit in olefin polymerization catalysis field
The solid matter of element, usually contains magnesium halide and alcohol compound；Under preferable case, described magnesium-containing carrier
Containing formula be the magnesium halide of MgXY, formula be the compound of ROH, formula be the chemical combination of R'OH
Thing, two oxyl hydrocarbon compounds, oxirane compound；Wherein, in formula M gXY, X
For halogen, Y is halogen, C1-C14Alkyl, C1-C14Alkoxyl, C6-C14Aryl or C6-C14
Aryloxy group；In general formula R OH, R is C1-C8Alkyl or C3-C8Cycloalkyl；At formula
In R'OH, R' is C16-C24Alkyl or aralkyl；The structure such as formula of described two oxyl hydrocarbon compounds
(I), shown in, the structure of described oxirane compound is as shown in formula II:
Formula (I),
Formula II；
Wherein, R1、R2、R3And R4Each stand alone as hydrogen, C1-C10Alkyl or haloalkyl, C3-C10
Cycloalkyl or halogenated cycloalkyl, C6-C10Aryl or halogenated aryl, C7-C10Alkaryl or alkyl halide
Aryl, C7-C10Aralkyl or haloaralkyl；R5And R6Each stand alone as hydrogen, C1-C5Alkyl
Or haloalkyl.
According to the present invention, described magnesium-containing carrier is commercially available, can also use those skilled in the art
Known method is prepared, it is preferable that the preparation of described magnesium-containing carrier includes that by formula be MgXY
Magnesium halide, formula be the compound of ROH, formula be the compound of R'OH, two oxyl hydrocarbonylations
Compound is mixed and heated with inert liquid medium, obtains liquefied mixture；The liquefied mixture breast that will obtain
Change, and by emulsification product and oxirane compound haptoreaction；In formula M gXY, X is
Halogen, Y is halogen, C1-C14Alkyl, C1-C14Alkoxyl, C6-C14Aryl or C6-C14
Aryloxy group；In general formula R OH, R is C1-C8Alkyl or C3-C8Cycloalkyl；At formula
In R'OH, R' is C16-C24Alkyl or aralkyl；The structure such as formula of described two oxyl hydrocarbon compounds
(I), shown in, the structure of described oxirane compound is as shown in formula II:
Formula (I),
Formula II；
Wherein, R1、R2、R3And R4Each stand alone as hydrogen, C1-C10Alkyl or haloalkyl, C3-C10
Cycloalkyl or halogenated cycloalkyl, C6-C10Aryl or halogenated aryl, C7-C10Alkaryl or alkyl halide
Aryl, C7-C10Aralkyl or haloaralkyl；R5And R6Each stand alone as hydrogen, C1-C5Alkyl
Or haloalkyl.
According to the present invention, formula be the magnesium halide of MgXY, formula be that the compound of ROH, formula are
The compound of R'OH, structure two oxyl hydrocarbon compounds as shown in the formula (I), structure such as formula II
The consumption of shown oxirane compound can be carried out suitably according to the composition of intended magnesium-containing carrier
Selection, it is preferable that on the basis of the 1mol formula magnesium halide as MgXY, formula is ROH's
The consumption of compound is 4-30mol, formula be the consumption of the compound of R'OH be 0.001-1.5mol, knot
The consumption of structure two oxyl hydrocarbon compounds as shown in the formula (I) is 0.001-1.5mol, structure such as formula II
The consumption of shown oxirane compound is 1-10mol；It is highly preferred that with 1mol formula as MgXY
Magnesium halide on the basis of, formula be the consumption of the compound of ROH be 6-20mol, formula is R'OH's
The consumption of compound is 0.01-1mol, the consumption of structure two oxyl hydrocarbon compounds as shown in the formula (I)
For 0.01-1mol, the consumption of structure oxirane compound as shown in formula II is 2-6mol.
According to the present invention, in formula M gXY, X is preferably chlorine or bromine, Y be preferably chlorine, bromine,
C1-C5Alkyl, C1-C5Alkoxyl, C6-C10Aryl or C6-C10Aryloxy group.Described C1-C5
Alkyl can be such as methyl, ethyl, propyl group, isopropyl, butyl or isobutyl group, described C1-C5
Alkoxy as can be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl
Base, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl or neopentyl, described C6-C10Aryl such as may be used
Think phenyl, o-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene, an ethylbenzene, to ethylbenzene
Base or naphthyl, described C6-C10Aryloxy group can be such as phenoxy group or naphthoxy.Formula is MgXY
Magnesium halide can be a kind of magnesium halide, or the mixture of multiple magnesium halide.Formula is MgXY
The instantiation of magnesium halide can be but be not limited to: magnesium chloride, magnesium bromide, Benzene Chloride epoxide magnesium, chlorine
Change one or more in isopropoxy magnesium and chlorination n-butoxy magnesium.The angle ready availability from raw material goes out
Send out, preferably magnesium chloride.
According to the present invention, in general formula R OH, R is preferably C1-C8Alkyl.Described C1-C8Alkane
Base can be such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, uncle
Butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, hexyl, isohesyl, heptyl, different heptyl,
Octyl group or iso-octyl.Formula is that the instantiation of the compound of ROH can be but is not limited to: ethanol,
Propanol, isopropanol, n-butyl alcohol, isobutanol, amylalcohol, isoamyl alcohol, hexanol, n-octyl alcohol and 2-ethyl
One or more in hexanol.
According to the present invention, general formula R ' in OH, R' is preferably C16-C20Alkyl or aralkyl.Formula
Instantiation for the compound of R'OH can be but be not limited to: hexadecanol and octadecanol.
According to the present invention, in structure two oxyl hydrocarbon compounds as shown in the formula (I), R1、R2、R3
And R4The most each stand alone as hydrogen, C1-C3Alkyl, C6-C8Aryl；Described C1-C3Alkyl example
As being methyl, ethyl, propyl group or isopropyl；Described C6-C8Aryl can be such as phenyl,
O-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene, an ethylbenzene or to ethylbenzene；Described two
The instantiation of oxyl hydrocarbon compound can be but be not limited to: 2,2-dimethoxy propane, 2,2-dimethoxy
Base butane, 2,2-dimethoxy pentane, 3,3-dimethoxy pentane, 2,2-di ethyl propyl ether and 2,2-bis-
One or more in phenoxypropane.
According to the present invention, in structure oxirane compound as shown in formula II, R5And R6
The most each stand alone as hydrogen, C1-C3Alkyl or haloalkyl.The tool of described oxirane compound
Body example can be but be not limited to: oxirane, expoxy propane, epoxy butane, epoxychloropropane, ring
One or more in oxygen chlorobutane, epoxy bromopropane and epoxy n-butyl bromide.
The present invention to 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 do not have with the blend heated condition of inert liquid medium
Have and limit especially, if the condition of described heating enable to magnesium halide that formula is MgXY melted,
And with formula be the compound of ROH, formula be compound and the two oxyl hydrocarbon compounds of R'OH
React.Usually, the condition of described heating includes that temperature can be 80-120 DEG C, be preferably
80-100 DEG C, the time can be 0.5-5 hour, be preferably 0.5-3 hour.
According to the present invention, the consumption of described inert liquid medium can be the halogenation of MgXY according to formula
The consumption of magnesium selects.Usually, on the basis of the 1mol formula magnesium halide as MgXY, described lazy
Property liquid medium consumption be 0.8-10L, be preferably 2-8L.Described inert liquid medium can be ability
Territory there is not chemically interactive liquid medium with reactant and product in conventional various.Such as:
Described inert liquid medium can be silicone oil and/or inert fluid varsol.Specifically, described inert liquid
Body medium can be kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, methyl
One or more in ethyl silicon oil, phenyl silicone oil and methyl phenyl silicone oil.Inert fluid of the present invention
Medium is particularly preferably white oil.
Well known to a person skilled in the art that described liquid is mixed by various method according to the present invention it is possible to use
Thing emulsifying.For example, it is possible to described liquefied mixture is carried out low velocity shear or high speed shear, thus by it
Emulsifying.The stir speed (S.S.) of described low velocity shear is usually 400-800 rev/min.The side of described high speed shear
Method is known to those skilled in the art, and as disclosed in CN1151183C, high-speed mixing method (that is, will contain
The solution having liquid halogenated magnesium adduct is stirred with the speed of 2000-5000 rev/min).Additionally,
Can also be open by described liquefied mixture emulsifying: CN1267508C with reference to method disclosed in following patent
The solution containing liquid halogenated magnesium adduct is carried out in hypergravity bed rotate dispersion (the speed of rotation
Can be 100-3000 rev/min)；CN1463990A is disclosed by containing liquid halogenated magnesium adduct
Solution exports with the speed of 1500-8000 rev/min in mulser；US6020279 is disclosed by spray
Mist method is by the emulsifying soln containing liquid halogenated magnesium adduct.
According to the present invention, can be existing by emulsification product and the catalytic condition of oxirane compound
The various conditions that can form magnesium-containing carrier having, such as, described catalytic condition includes that temperature can
Thinking 80-120 DEG C, be preferably 80-100 DEG C, the time can be 20-60 minute, preferably 20-50 divides
Clock.
According to the present invention, the first titanium compound and the second titanium compound can be to prepare olefin polymerization catalysis
Conventional use of various titanium compounds during solid constituent.Under normal circumstances, the first titanium compound and
Two titanium compounds can identical, can also be different, and formula Ti (OR ") can be each independently3-aZa
And/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, b is the integer of 1-4.Under preferable case, the first titanium compound and second
Titanium compound be each independently titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, three butoxy titanium chlorides,
Dibutoxy titanium chloride, butoxy titanous chloride., triethoxy titanium chloride, diethoxy titanium chloride,
One or more in ethyoxyl titanous chloride. and titanous chloride..
According to the present invention, described internal electron donor can be existing various for preparing olefinic polymerization catalysis
The internal electron donor of agent solid constituent, such as, can be in carboxylate, alcohol ester, ether, ketone, amine and silane
One or more, preferably phthalate compound, diol-lipid compound, 1,3-diether
One or more in compounds and succinate compounds, more preferably 1,3-diether compound.
The structure of described phthalate compound is as shown in formula III:
Formula III,
Wherein, R1' and R2' it is each independently C1-C10Alkyl, C3-C20Cycloalkyl, C6-C10Virtue
Base, C7-C10Alkaryl or aryl；R3'-R6' it is each independently hydrogen, C1-C10Alkyl, C1-C10
Cycloalkyl, C6-C10Aryl, C7-C10Alkaryl or aralkyl；Preferably, R1' and R2' the most only
It is on the spot C1-C8Alkyl, R3'-R6' it is each independently hydrogen, C1-C8Alkyl.Described O-phthalic
The instantiation of acid esters compound can be but be not limited to: diethyl phthalate, phthalic acid
Diisobutyl ester, n-butyl phthalate, diisooctyl phthalate, phthalic acid two are the most pungent
One or more in ester, triethyl trimellitate and tributyl trimellitate.
According to the present invention, the structure of described diol-lipid compound is as shown in formula IV:
Formula IV,
Wherein, R11' and R12' can be identical or different, and can be each halogen, C1-C20Alkyl,
C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Aralkyl or C2-C20Alkylene；Formula IV
In, the content representation of bracket [] has d carbon atom to be bonded successively, and each carbon atom also takes with 2
Dai Ji is bonded, i.e. total d carbon atom and R in bracket1、R2、R3…R2dDeng 2d substituent group,
R7'-R10' and R1-R2dIdentical or different, and respectively hydrogen, halogen, C1-C20Alkyl, C3-C20's
Cycloalkyl, C6-C20Aryl, C7-C20Aralkyl, C2-C20Alkylene, containing heteroatomic
C1-C20Alkyl, containing heteroatomic C3-C20Cycloalkyl, containing heteroatomic C6-C20Aryl,
Containing heteroatomic C7-C20Aralkyl, containing heteroatomic C2-C20Alkylene, or R7'-R10'
And R1-R2dIn two or more bondings form saturated or undersaturated ring structure, described hetero atom is permissible
For one or more in halogen, nitrogen, oxygen, sulfur, silicon and phosphorus, d is the integer of 0-10, as d=0,
Then in the binary alcohol esters compounds shown in formula IV, substituent group is R7'、R8' carbon atom directly with take
Dai Jiwei R9'、R10' carbon atom be bonded.
Under preferable case, shown in the structure such as formula (V) of described diol-lipid compound:
Formula (V),
Wherein, R19' and R20' with above-mentioned formula IV in R11' and R12' definition identical；R13′-R18' permissible
Identical or different, and each stand alone as hydrogen, halogen, C1-C20Alkyl, C3-C20Cycloalkyl, C6-C20
Aryl, C7-C20Aralkyl, C2-C20Alkylene, containing heteroatomic C1-C20Alkyl,
Containing heteroatomic C3-C20Cycloalkyl, containing heteroatomic C6-C20Aryl, containing heteroatomic
C7-C20Aralkyl, containing heteroatomic C2-C20Alkylene or R10′-R18In ' two or
Multiple bondings form saturated or undersaturated ring structure, described hetero atom can be halogen, nitrogen, oxygen, sulfur,
One or more in silicon and phosphorus.
In the present invention, described diol-lipid compound can be such as 1,3-PD dibenzoate,
2-methyl-1,3-propanediol dibenzoate, 2-ethyl-1,3-propylene glycol dibenzoate, 2,2-dimethyl
-1,3-propylene glycol dibenzoate, (R)-1-phenyl-1,3-propylene glycol dibenzoate, 1,3-diphenyl-1,3-
Propylene glycol dibenzoate, 1,3-diphenyl-1,3-propylene glycol two n Propanoic acid ester, 1,3-diphenyl-2-methyl
-1,3-propylene glycol dipropionate, 1,3-diphenyl-2-methyl-1,3-propanediol diacetate esters, 1,3-diphenyl
-2,2-dimethyl-1,3-propylene glycol dibenzoate, 1,3-diphenyl-2,2-dimethyl-1,3-propylene glycol dipropionic acid
Ester, 1,3-di-t-butyl-2-ethyl-1,3-propylene glycol dibenzoate, 1,3-diphenyl-1,3-propylene glycol diethyl
Acid esters, 1,3-diisopropyl-1,3-propanol two (4-butylbenzoic acid) ester, 1-phenyl-2-amino-1,3-propylene glycol
Dibenzoate, 1-phenyl-2-methyl isophthalic acid, 3-butanediol dibenzoate, 2,4-PD dibenzoate,
3-butyl-2,4-PD dibenzoate, 3,3-dimethyl-2,4-PD dibenzoate, 2,4-penta 2
Alcohol two (parachlorobenzoic-acid) ester, 2,4-PD two (m-chlorobenzoic acid) ester, 2,4-PD two are (to bromobenzene first
Acid) ester, 2,4-PD two (o-bromobenzoic acid) ester, 2,4-PD two (p-methylbenzoic acid) ester, 2,4-
Pentanediol two (p-tert-butyl benzoic acid) ester, 2,4-PD two (to butylbenzoic acid) ester, 2-methyl isophthalic acid, 3-
Pentanediol two (parachlorobenzoic-acid) ester, 2-methyl isophthalic acid, 3-pentanediol two (p-methylbenzoic acid) ester, 2-butyl
-1,3-pentanediol two (p-methylbenzoic acid) ester, 2-methyl isophthalic acid, 3-pentanediol two (p-tert-butyl benzoic acid) ester,
2-methyl isophthalic acid, 3-pentanediol pivalate, 2-methyl isophthalic acid, 3-pentanediol benzoic acid cinnamate, 2,2-dimethyl
-1,3-glycol dibenzoate, 2,2-dimethyl-1,3-pentanediol benzoic acid cinnamate, 2-ethyl-1,3-
Glycol dibenzoate, 2-butyl-1,3-glycol dibenzoate, 2-pi-allyl-1,3-pentanediol two
Benzoate, 2-methyl isophthalic acid, 3-glycol dibenzoate, 2-ethyl-1,3-glycol dibenzoate,
2-propyl group-1,3-glycol dibenzoate, 2-butyl-1,3-glycol dibenzoate, 1,3-pentanediol two
(parachlorobenzoic-acid) ester, 1,3-pentanediol two (m-chlorobenzoic acid) ester, 1,3-pentanediol two (parabromobenzoic acid)
Ester, 1,3-pentanediol two (o-bromobenzoic acid) ester, 1,3-pentanediol two (p-methylbenzoic acid) ester, 1,3-penta 2
Alcohol two (p-tert-butyl benzoic acid) ester, 1,3-pentanediol two (to butylbenzoic acid) ester, 1,3-pentanediol benzene first
Acid cinnamate, 1,3-pentanediol two cinnamate, 1,3-pentanediol dipropionate, 2,2,4-trimethyl-1,3-
Pentanediol diisopropyl formic acid esters, 1-trifluoromethyl-3-methyl-2,4-PD dibenzoate, 2,4-penta
Glycol two to fluoromethyl benzoate, 2,4-pentanediol two (2-furancarboxylic acid) ester, 2-methyl-6-heptene-2,
4-heptandiol dibenzoate, 3-methyl-6-heptene-2,4-heptandiol dibenzoate, 4-methyl-6-heptene
-2,4-heptandiol dibenzoate, 5-methyl-6-heptene-2,4-heptandiol dibenzoate, 6-methyl-6-heptan
Alkene-2,4-heptandiol dibenzoate, 3-ethyl-6-heptene-2,4-heptandiol dibenzoate, 4-ethyl-6-
Heptene-2,4-heptandiol dibenzoate, 5-ethyl-6-heptene-2,4-heptandiol dibenzoate, 6-ethyl
-6-heptene-2,4-heptandiol dibenzoate, 3-propyl group-6-heptene-2,4-heptandiol dibenzoate, 4-third
Base-6-heptene-2,4-heptandiol dibenzoate, 5-propyl group-6-heptene-2,4-heptandiol dibenzoate, 6-
Propyl group-6-heptene-2,4-heptandiol dibenzoate, 3-butyl-6-heptene-2,4-heptandiol dibenzoate,
4-butyl-6-heptene-2,4-heptandiol dibenzoate, 5-butyl-6-heptene-2,4-heptandiol dibenzoic acid
Ester, 6-butyl-6-heptene-2,4-heptandiol dibenzoate, 3,5-dimethyl-6-heptene-2,4-heptandiol two
Benzoate, 3,5-diethyl-6-heptene-2,4-heptandiol dibenzoate, 3,5-dipropyl-6-heptene-2,4-
Heptandiol dibenzoate, 3,5-dibutyl-6-heptene-2,4-heptandiol dibenzoate, 3,3-dimethyl-6-
Heptene-2,4-heptandiol dibenzoate, 3,3-diethyl-6-heptene-2,4-heptandiol dibenzoate, 3,3-
Dipropyl-6-heptene-2,4-heptandiol dibenzoate, 3,3-dibutyl-6-heptene-2,4-heptandiol hexichol first
Acid esters, 3-ethyl-3,5-heptandiol dibenzoate, 4-ethyl-3,5-heptandiol dibenzoate, 3-third
Base-3,5-heptandiol dibenzoate, 4-propyl group-3,5-heptandiol dibenzoate, 3-butyl-3,5-heptan two
Alcohol dibenzoate, 2,3-dimethyl-3,5-heptandiol dibenzoate, 2,4-dimethyl-3,5-heptandiol two
Benzoate, 2,5-dimethyl-3,5-heptandiol dibenzoate, 4,4-dimethyl-3,5-heptandiol hexichol first
Acid esters, 4,5-dimethyl-3,5-heptandiol dibenzoate, 4,6-dimethyl-3,5-heptandiol dibenzoate,
6,6-dimethyl-3,5-heptandiol dibenzoate, 2-methyl-3-ethyl-3,5-heptandiol dibenzoate,
2-methyl-4-ethyl-3,5-heptandiol dibenzoate, 2-methyl-5-ethyl-3,5-heptandiol dibenzoic acid
Ester, 3-methyl-4-ethyl-3,5-heptandiol dibenzoate, 3-methyl-5-ethyl-3,5-heptandiol hexichol first
Acid esters, 4-methyl-3-ethyl-3,5-heptandiol dibenzoate, 4-methyl-4-ethyl-3,5-heptandiol hexichol
Double (benzoyloxy methyl) fluorenes of formic acid esters, 9,9-, 9,9-double ((meta-methoxy benzoyloxy) methyl) fluorenes, 9,9-
Double ((to the chlorobenzene carboxyphenyl) methyl) fluorenes of double ((m-chloro benzoyloxy) methyl) fluorenes, 9,9-, double (the Cortex Cinnamomi carboxyl of 9,9-
Methyl) fluorenes, 9-(benzoyloxy methyl)-9-(the third carboxymethyl group) fluorenes, 9,9-double (the third carboxymethyl group) fluorenes, 9,9-
Double (propylene carboxymethyl group) fluorenes and 9, one or more in double (neopentyl carboxymethyl group) fluorenes of 9-, cited
Part binary alcohol esters is commercially available, and other are referred to the method described in CN1436796A and close
Become.
The structure of described 1,3-diether compound is as shown in formula VI:
Formula VI,
Wherein, R21' and R22' can be identical or different, and it is each independently C1-C20Alkyl, C3-C20
Cycloalkyl, C6-C20Aryl or C7-C20Aralkyl；R23′-R28' can be identical or different, and
Can be each hydrogen, halogen, C1-C20Alkyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20
Aralkyl or R23′-R28The ring structure that two or more bondings in ' are formed.In the preferred case,
R21' and R22' identical or different, and it is each independently C1-C10Alkyl；R23′、R24′、R27' and
R28' it is hydrogen；R25' and R26' identical or different, and respectively C1-C18Alkyl, C3-C18Cycloalkanes
Base, C6-C18Aryl, C7-C18Aralkyl or R25' and R26' it is mutually bonded the ring structure of formation.
In the present invention, described 1,3-diether compound can be such as 2-(2-ethylhexyl)-1,3-bis-
Methoxy propane, 2-isopropyl-1,3-dimethoxy propane, 2-butyl-1,3-dimethoxy propane, 2-are secondary
Butyl-1,3-dimethoxy 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 third
Alkane, 2-(p-chlorphenyl)-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
Base 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-
Cyclohexyl-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 propane, 2,2-diphenyl-1,3-dimethoxy propane, 2,2-dibenzyl-1,3-
Dimethoxy propane, 2,2-double (cyclohexyl methyl)-1,3-dimethoxy propane, 2-isobutyl group-2-isopropyl
-1,3-dimethoxy propane, 2-(1-methyl butyl)-2-isopropyl-1,3-dimethoxy propane, 2-isopropyl-2-
Isopentyl-1,3-dimethoxy propane, 2-phenyl-2-isopropyl-1,3-dimethoxy propane, 2-phenyl-2-are secondary
-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 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
With one or more in 9,9-dimethoxy-methyl fluorenes.
According to the present invention, the structure such as formula (VII) of described succinate compounds or formula (VIII) Suo Shi:
Formula (VII),
Formula (VIII),
Wherein, in formula (VII), R "1With R "2Each stand alone as C1-C20Alkyl, C1-C20Ring
Alkyl, C1-C20Aryl, C1-C20Aralkyl or alkaryl, optionally comprise hetero atom；R″3-R″6
Can each stand alone as hydrogen, C1-C20Alkyl, C1-C20Cycloalkyl, C1-C20Aryl, C1-C20
Aralkyl or alkaryl, optionally comprise hetero atom.In formula (VIII), R "7-R″8The most independent
For hydrogen, C1-C14Alkyl, C3-C10Cycloalkyl, C6-C10Aryl, C7-C10Alkaryl or aralkyl；
R″9With R "10Each stand alone as C1-C10Alkyl, C3-C10Cycloalkyl, C6-C20Aryl, C7-C20
Alkaryl or aralkyl.
In the present invention, described succinate compounds can be such as 2,3-diisopropyl succinic acid two
Ethyl ester, 2,3-diisopropyl di-iso-octyl succinate, 2,3-diisopropyl dibutyl succinate, 2,3-bis-
Isopropyl succinic acid dimethyl esters, 2,2-dimethyl succinate diisobutyl ester, 2-Ethyl-2-Methyl succinic acid
In diisobutyl ester, 2-Ethyl-2-Methyl diethyl succinate and 2-cyano group-2-diisopropyl succinate one
Plant or multiple.
According to the present invention, in the preparation process of described catalyst solid component of olefin polymerization, described containing magnesium
The reaction of carrier and the first titanium compound can be carried out according to mode same as the prior art, such as, and can
The first titanium compound is cooled to less than 0 DEG C (preferably-5 to-25 DEG C), and add described containing magnesium load
Body, and stirring mixing 10-60 minute at such a temperature, be warming up to reaction temperature (the most about 80-130 afterwards
DEG C), and maintain 0.5-10 hour under this reaction temperature.Described internal electron donor is at described magnesium-containing carrier
Add in one or more time periods before and after, during reacting with the first titanium compound, preferably exist
Described magnesium-containing carrier react with the first titanium compound before time period in add.Described magnesium-containing carrier and
Time period before one titanium compound reaction refer to after described magnesium-containing carrier adds in reactor and
It is warming up to the time period before reaction temperature.
According to the present invention, the method that the product that step (1) obtains carries out solid-liquid separation can be existing
The various methods being capable of solid phase and liquid phase separation, such as sucking filtration, filter pressing or centrifugation, preferably
In the case of, the method for described solid-liquid separation is filter press technique.The condition of filter pressing is limited by the present invention the most especially
Fixed, separate with liquid phase and be as the criterion realizing solid phase the most fully.
In the case of according to the invention it is preferred to, the preparation method of described catalyst solid component of olefin polymerization is also
It is included in and described solid product and the second titanium compound are performed for more than 4 hours at-10 DEG C to 120 DEG C
Before contact, described solid product titanium compound is washed, or by described solid product and titanium compound
Carry out the contact (typically smaller than 2 hours) of short period.Described titanium compound can close with the first titanizing
Thing is identical, will not be described in great detail at this.
According to the present invention, although as long as by described solid product and the second titanium compound at-10 DEG C to 120
It is performed for more than the contact of 4 hours at DEG C to improve the hydrogen of described catalyst solid component of olefin polymerization and adjust quick
Perception, stereotaxis ability and polymerization activity, but in order to the effect making process is the most notable, obtain comprehensive
The catalyst solid component of olefin polymerization that performance is the most excellent, under preferable case, by described solid product with
The condition of the second titanium compound contact include temperature be 0-120 DEG C, the time be 8-24 hour, it is preferable that
The temperature of described contact is 25-120 DEG C, the time is 8-24 hour.
According to the present invention, in step (2), the consumption of described solid product and the second titanium compound is permissible
Selecting in wider scope, such as, the weight ratio of described solid product and the second titanium compound is
0.1-80:100, preferably 5-15:100.
Present invention also offers a kind of olefin polymerization catalysis, this catalyst contains above-mentioned olefinic polymerization catalysis
Agent solid constituent, alkyl aluminum compound and optional external electron donor.Described olefin polymerization catalysis
Containing above-mentioned catalyst solid component of olefin polymerization, therefore, it not only has higher polymerization activity, and
And there is more excellent hydrogen response and higher stereotaxis ability.
Can be all this according to the present invention, described alkyl aluminum compound and the kind of external electron donor and consumption
The conventional selection in field.Such as, the formula of described alkyl aluminum compound can be Al (R7)3, R7For C1-C8
Alkyl or haloalkyl；Described alkyl aluminum compound can be such as triethyl aluminum, triisobutyl aluminium,
Three n-butylaluminum, tri-n-hexyl aluminum, aluminium diethyl monochloride, a 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 n-butylaluminum and
One or more in dichloro one n-hexyl aluminum.Usually, in described olefin polymerization catalysis, with aluminum
The alkyl aluminum compound of meter and the mol ratio for catalyst solid component of olefin polymerization in terms of titanium are permissible
For 1-2000:1, preferably 20-500:1.
Described external electron donor can be various external electron donors commonly used in the art, such as, described outer gives
Electron can be carboxylic acid, anhydride, ester, ketone, ether, alcohol, organic phosphorus compound and organo-silicon compound
In one or more；Preferably, described external electron donor is 1, and 3-diether compound and/or formula are
(R8)a(R9)bSi(OR10)cSilicon compound.Wherein, R8、R9And R10C1-C18Alkyl, a and b
Each standing alone as the integer of 0-2, c is the integer of 1-3, and a, b and c and be 4.Give outside described
The instantiation of electron can be but be not limited to: Cyclohexyl Methyl Dimethoxysilane, diisopropyl two
Methoxy silane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, diphenyl diformazan
TMOS, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine
Base-2-t-butyldimethoxysilane, (1,1,1-tri-fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silicon
One or more in alkane and (1,1,1-tri-fluoro-2-propyl group)-methyl dimethoxysilane.Described outer to electricity
Daughter and the mol ratio typically 0.005-0.5:1, preferably 0.01-0.4:1 of alkyl aluminum compound.
Additionally, present invention also offers the application in olefinic polyreaction of the described olefin polymerization catalysis.
The invention will be further described by the following examples.It is to be understood, however, that these are real
Execute example be merely to illustrate and explain the present invention, be not limited to the present invention.
In embodiment and comparative example:
1, average particulate diameter and the particle diameter distribution of magnesium-containing carrier uses Masters Sizer 2000 particle size analyzer
(being manufactured by Malvern Instruments Ltd) is measured；
2, the apparent form of magnesium-containing carrier is by being Eclipse E200 commercially available from the model of Nikon company
Optical microscope observe；
3, DSC: use the differential scanning calorimeter that model is PE DSC-7 purchased from PE company of the U.S.
Being measured, wherein, test condition includes that heating rate is 10 DEG C/min, and sweep limits is 50 DEG C-250
℃。
Embodiment 1
This embodiment is used for catalyst solid component of olefin polymerization and the preparation side thereof that the present invention provides is described
Method and olefin polymerization catalysis and application thereof.
(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-dimethoxy
Propane, is under agitation warming up to 90 DEG C.After isothermal reaction 1 hour, by (the stirring of mixture stirring at low speed
Speed is 400 revs/min) disperse 30 minutes, to carry out emulsifying.And add in above-mentioned emulsification product
35mL(0.45mol) epoxychloropropane, filter pressing after reaction half an hour, time of filter pressing is 9 minutes.
Being washed 5 times by filter pressing product hexane, washed rear filter pressing every time, filter pressing operation total time is 20 points
Clock.Finally product vacuum is dried, obtains magnesium-containing carrier Z1.
The average particulate diameter (D50) of described magnesium-containing carrier Z1 is 57 microns, and particle diameter is distributed
((D90-D10)/D50) is 0.8.Use the particle morphology of observation by light microscope as shown in Figure 1.
It can be seen that the particle shape of magnesium-containing carrier Z1 is more regular, smooth surface, it is substantially all
Being 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 300mL, add the titanium tetrachloride of 100mL and be cooled to-20 DEG C, will
The magnesium-containing carrier Z1 prepared in above-mentioned (1) of 8 grams 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 the phthalic acid two of 1.5mL
Isobutyl ester, filters off liquid after maintaining 30min at 110 DEG C, adds titanium tetrachloride afterwards and washs 2 times,
Obtain solid product.In solid product, add 100mL titanium tetrachloride, and it is little to react 16 at 25 DEG C
Time, finally wash 4 times with hexane, obtain catalyst solid component of olefin polymerization C1 after drying.
In the DSC spectrogram of described catalyst solid component of olefin polymerization C1, there are heat release both shoulders
Peak, the peak at this heat release both shoulders peak is respectively 204.1 DEG C and 264.5 DEG C, the total heat corresponding to two peaks
Enthalpy is 210.2 joule/gram.
(3) propylene polymerization:
In the autoclave of a 5L, stream of nitrogen gas is used to purge, then in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of middle introducing 2mL,
The Cyclohexyl Methyl Dimethoxysilane (CHMMS) of 5mmol and the olefin polymerization catalysis of 10mg
Solid constituent C1.Close autoclave, add 1.5L(normal volume) hydrogen and the liquid third of 2.5L
Alkene, is warming up to 70 DEG C, and reaction 1 hour at such a temperature.
Embodiment 2
This embodiment is used for catalyst solid component of olefin polymerization and the preparation side thereof that the present invention provides is described
Method and olefin polymerization catalysis and application thereof.
Method according to embodiment 1 is prepared magnesium-containing carrier, is prepared catalyst solid component of olefin polymerization and enter
Row propylene polymerization, except that, during propylene polymerization, the addition of hydrogen is 6.5L.
Embodiment 3
This embodiment is used for catalyst solid component of olefin polymerization and the preparation side thereof that the present invention provides is described
Method and olefin polymerization catalysis and application thereof.
(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) octadecanol, 28mL(0.48mol) ethanol, 1mL(0.008mol) 2,2-dimethoxy
Propane, is under agitation warming up to 100 DEG C.After isothermal reaction 0.5 hour, mixture stirring at low speed (is stirred
Mixing speed is 800 revs/min) disperse 30 minutes, to carry out emulsifying.And add in above-mentioned emulsification product
Enter 12.5mL(0.16mol) epoxychloropropane, filter pressing after reacting 20 minutes, time of filter pressing is 10 points
Clock.Being washed 5 times by filter pressing product hexane, washed rear filter pressing every time, filter pressing operation total time is 25
Minute.Finally product vacuum is dried, obtains magnesium-containing carrier Z2.
The average particulate diameter (D50) of described magnesium-containing carrier Z2 is 48 microns, and particle diameter is distributed
((D90-D10)/D50) is 0.6.Use the particle morphology of observation by light microscope as shown in Figure 2.
It can be seen that the particle shape of magnesium-containing carrier Z2 is more regular, smooth surface, it is substantially all
Being 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,
The magnesium-containing carrier Z2 prepared in above-mentioned (1) of 40 grams is added thereto, and at-20 DEG C, stirs 30min.
Afterwards, start to be to slowly warm up to 110 DEG C, temperature-rise period adds the 2 of 6.5mL, 4-pentanediol hexichol
2-isopropyl-2-isopentyl-1 of formic acid esters and 1mL, 3-dimethoxy propane, maintain at 110 DEG C
Liquid is filtered off after 30min.Then, add titanium tetrachloride and wash 3 times, obtain solid product.Toward solid
Product adds 100mL titanium tetrachloride, and reacts 8 hours at 120 DEG C, finally wash 5 times with hexane,
Obtain catalyst solid component of olefin polymerization C2 after drying.
In the DSC spectrogram of described catalyst solid component of olefin polymerization C2, there are heat release both shoulders
Peak, the peak at this heat release both shoulders peak is respectively 200.2 DEG C and 261.9 DEG C, the total heat corresponding to two peaks
Enthalpy is 253.1 joule/gram.
(3) propylene polymerization:
Propylene polymerization is carried out according to the method for embodiment 1, except that, with urging of identical weight
Agent component C2 replaces catalytic component C1.
Embodiment 4
This embodiment is used for catalyst solid component of olefin polymerization and the preparation side thereof that the present invention provides is described
Method and olefin polymerization catalysis and application thereof.
Method according to embodiment 3 is prepared magnesium-containing carrier, is prepared catalyst solid component of olefin polymerization and enter
Row propylene polymerization, except that, during propylene polymerization, the addition of hydrogen is 6.5L.
Embodiment 5
This embodiment is used for catalyst solid component of olefin polymerization and the preparation side thereof that the present invention provides is described
Method and olefin polymerization catalysis and application thereof.
(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) octadecanol, 58mL(1mol) ethanol, 3.5mL(0.04mol) 2,2-dimethoxy third
Alkane, is under agitation warming up to 80 DEG C.After isothermal reaction 3 hours, by mixture stirring at low speed (stirring speed
Rate is 800 revs/min) disperse 30 minutes, to carry out emulsifying.And add in above-mentioned emulsification product
23.5mL(0.3mol) epoxychloropropane, filter pressing after reacting 50 minutes, time of filter pressing is 8 minutes.
Being washed 5 times by filter pressing product hexane, washed rear filter pressing every time, filter pressing operation total time is 22 points
Clock.Finally product vacuum is dried, obtains magnesium-containing carrier Z3.
The average particulate diameter (D50) of described magnesium-containing carrier Z3 is 50 microns, and particle diameter is distributed
((D90-D10)/D50) is 0.7.The pattern using observation by light microscope particle finds, carries containing magnesium
The particle shape of body Z3 is more regular, smooth surface, is essentially all spherical, particle size distribution
Relatively concentrate, 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,
The magnesium-containing carrier Z3 prepared in above-mentioned (1) of 40 grams is added thereto, and at-20 DEG C, stirs 30min.
Afterwards, start to be to slowly warm up to 110 DEG C, and in temperature-rise period, add the phthalic acid two of 7.5mL
N-butyl, filters off liquid after maintaining 30min at 110 DEG C, adds titanium tetrachloride afterwards and washs 2 times,
Obtain solid product.In solid product, add 100mL titanium tetrachloride, and it is little to react 10 at 80 DEG C
Time, finally wash 4 times with hexane, obtain catalyst solid component of olefin polymerization C3 after drying.
In the DSC spectrogram of described catalyst solid component of olefin polymerization C3, there are heat release both shoulders
Peak, the peak at this heat release both shoulders peak is respectively 203.7 DEG C and 265.9 DEG C, the total heat corresponding to two peaks
Enthalpy is 241.5 joule/gram.
(3) propylene polymerization:
Propylene polymerization is carried out according to the method for embodiment 1, except that, with urging of identical weight
Agent component C3 replaces catalytic component C1.
Embodiment 6
This embodiment is used for catalyst solid component of olefin polymerization and the preparation side thereof that the present invention provides is described
Method and olefin polymerization catalysis and application thereof.
Method according to embodiment 5 is prepared magnesium-containing carrier, is prepared catalyst solid component of olefin polymerization and enter
Row propylene polymerization, except that, during propylene polymerization, the addition of hydrogen is 6.5L.
Embodiment 7
This embodiment is used for catalyst solid component of olefin polymerization and the preparation side thereof that the present invention provides is described
Method and olefin polymerization catalysis and application thereof.
Method according to embodiment 1 prepares catalyst solid component of olefin polymerization and to carry out propylene polymerization anti-
Should, except that, described magnesium-containing carrier is according to method system disclosed in embodiment in CN1718595A 1
For obtaining, 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 in the white oil of 30 centipoises (20 DEG C), reacts 2 hours at 125 DEG C.Then will obtain
The mixed liquor of molten adduct and white oil transfer to be pre-heated in the methyl-silicone oil medium of 125 DEG C；First
Base silicon oil viscosity is 300 centipoises (20 DEG C), and the consumption of methyl-silicone oil is 120L；With 200 revs/min
Rotating speed stirs 10-30 minute, obtains mixed liquor.Described mixed liquor is introduced high-gravity rotating bed carry out point
Dissipate, and under agitation, the mixed liquor after dispersion introduced be cooled to the hexane medium of-35 DEG C in advance
In, the consumption of hexane is 1200L, is separated into the cooled solidification of magnesium chloride/alcohol adducts melt of droplet,
Become spherical solid particles.After chilling, the suspension of gained filters out particulate solid, exist with hexane
This particulate matter of washes at room temperature, hexane consumption is 100L/ time, altogether washing 5 times, takes out true at 30-50 DEG C
Sky i.e. obtains magnesium-containing carrier Z4.
The average particulate diameter (D50) of described magnesium-containing carrier Z4 is 52 microns, and particle diameter is distributed
((D90-D10)/D50) is 1.1.The pattern using observation by light microscope particle finds, alkene gathers
The particle shape closing catalyst carrier Z4 is more regular, and surface is relatively smooth, has a small amount of irregular particle to deposit
, particle size distribution compares concentration.
Correspondingly, the catalyst solid component of olefin polymerization prepared is designated as C4.Gather at described alkene
Close in the DSC spectrogram of catalyst solid constituent C4, there is a heat release both shoulders peak, this heat release both shoulders peak
Peak be respectively 207.2 DEG C and 268.7 DEG C, the total heat enthalpy corresponding to two peaks is 200.8 joules/
Gram.
Embodiment 8
This embodiment is used for catalyst solid component of olefin polymerization and the preparation side thereof that the present invention provides is described
Method and olefin polymerization catalysis and application thereof.
Method according to embodiment 7 is prepared magnesium-containing carrier, is prepared catalyst solid component of olefin polymerization and enter
Row propylene polymerization, except that, during propylene polymerization, the addition of hydrogen is 6.5L.
Embodiment 9
This embodiment is used for catalyst solid component of olefin polymerization and the preparation side thereof that the present invention provides is described
Method and olefin polymerization catalysis and application thereof.
Method according to embodiment 7 is prepared magnesium-containing carrier, is prepared catalyst solid component of olefin polymerization and enter
Row propylene polymerization, except that, the time of propylene polymerization is 2 hours.
Embodiment 10
This embodiment is used for catalyst solid component of olefin polymerization and the preparation side thereof that the present invention provides is described
Method and olefin polymerization catalysis and application thereof.
Method according to embodiment 8 is prepared magnesium-containing carrier, is prepared catalyst solid component of olefin polymerization and enter
Row propylene polymerization, except that, the time of propylene polymerization is 2 hours.
Embodiment 11
This embodiment is used for catalyst solid component of olefin polymerization and the preparation side thereof that the present invention provides is described
Method and olefin polymerization catalysis and application thereof.
Method according to implementing 7 is prepared magnesium-containing carrier, is prepared catalyst solid component of olefin polymerization and carry out
Propylene polymerization, except that, described Cyclohexyl Methyl Dimethoxysilane (CHMMS)
Addition is 2.5mL(12.5mmol), the addition of hydrogen is 6L.
Comparative example 1
This comparative example is used for reference catalyst solid component of olefin polymerization and preparation method thereof and alkene are described
Polymerization catalyst and application thereof.
Prepare magnesium-containing carrier according to the method for embodiment 7, prepare catalyst solid component of olefin polymerization and enter
Row propylene polymerization, except that, during preparing catalyst solid component of olefin polymerization not
Including adding 100mL titanium tetrachloride in described solid product, and at 25 DEG C, react the step of 16 hours
Suddenly, catalyst solid component of olefin polymerization DC1 is obtained after drying.
In the DSC spectrogram of described catalyst solid component of olefin polymerization DC1, there is a heat release double
Acromion, the peak at this heat release both shoulders peak is respectively 175.2 DEG C and 218.6 DEG C, total corresponding to two peaks
Heat enthalpy value is 923.2 joule/gram.
Comparative example 2
This comparative example is used for reference catalyst solid component of olefin polymerization and preparation method thereof and alkene are described
Polymerization catalyst and application thereof.
Method according to comparative example 1 is prepared magnesium-containing carrier, is prepared catalyst solid component of olefin polymerization and enter
Row propylene polymerization, except that, during propylene polymerization, the addition of hydrogen is 6.5L.
Test case
(1) melt index of polymer is detected according to the method for ASTM D1238-99:
(2) using heptane extraction process detection polymer isotacticity, the method includes: dry by 2 grams
Polymer samples is placed in extractor, after extracting 6 hours with boiling heptane, is dried residue to constant weight,
The polymer weight (g) of gained and the ratio of 2 are isotacticity；
Result according to said method detection is as shown in table 1 below.
Table 1
As can be seen from the above results, the DSC spectrogram of the catalyst solid component of olefin polymerization of the present invention
In, the peak separation at heat release both shoulders peak is 55-65 DEG C, and the olefin polymerization catalysis solid of comparative example 1
The peak separation at the heat release both shoulders peak of component is 43.4 DEG C.From embodiment 1-11 and the contrast of comparative example 1-2
It can be seen that in the polymerization process of propylene, when added hydrogen is 1.5L, use this
The melt flow rate (MFR) of the polymer that the olefin polymerization catalysis of bright offer obtains is not less than 10, and use right
The melt flows of the polymer that the catalyst (current industrial wide variety of catalyst) that ratio obtains obtains
Speed is 7.2；When added hydrogen is 6.5L, the olefin polymerization catalysis using the present invention to provide obtains
To the melt flow rate (MFR) of polymer be not less than 45, and that the catalyst using comparative example to obtain obtains is poly-
The melt flow rate (MFR) of compound is 36.As can be seen here, the alkene using the processing method of the present invention to obtain gathers
The hydrogen response closing catalyst has obtained improvement largely, has obvious superiority.Additionally,
Current olefin polymerization catalyst is usually and (i.e. reduces its isotactic with the isotactic index of sacrificial polymer
Index, this is disadvantageous to the downstream application of polymer) improve its melt flow rate (MFR), but from table
The result of 1 is it can be seen that use the isotactic index also phase of the polymer that the catalyst of the present invention prepares
Work as height.Structure at academia all Ziegler-Nata catalyst forms and mechanism of polymerization also fails at present
It is elucidated with, but can indirectly be reflected the feature of catalyst by the feature of polymer, use the present invention
The preparation-obtained polymer of catalyst provided has polymer preparation-obtained with other catalyst
The performance differed, illustrates that the active center of catalyst there occurs that change, this change cause polymer
Can be more excellent.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (18)
1. a catalyst solid component of olefin polymerization, it is characterised in that this olefin polymerization catalysis is solid
Body component contains titanium, magnesium and internal electron donor, and the DSC of described catalyst solid component of olefin polymerization
Spectrogram includes a heat release both shoulders peak, and the peak separation at described heat release both shoulders peak is 55 DEG C-65 DEG C；
Described catalyst solid component of olefin polymerization is prepared by the preparation method comprised the following steps:
(1) magnesium-containing carrier is reacted with the first titanium compound, and in described magnesium-containing carrier and the first titanizing
Internal electron donor is added in one or more time periods before and after, during the reaction of compound；
(2) product that step (1) obtains is carried out solid-liquid separation, and solid solid-liquid separation obtained
Product and the contact of the second titanium compound, the condition of described contact includes that temperature is-10 DEG C to 120 DEG C, time
More than 4 hours；
The preparation method of described magnesium-containing carrier include by formula be the magnesium halide of MgXY, formula be ROH
Compound, formula be the compound of R'OH, the structure compound as shown in formula (I) and inert fluid
Medium is mixed and heated, and obtains liquefied mixture；The liquefied mixture emulsifying that will obtain, and emulsifying is produced
Thing and oxirane compound haptoreaction；In formula M gXY, X is halogen, Y be halogen,
C1-C14Alkyl, C1-C14Alkoxyl, C6-C14Aryl or C6-C14Aryloxy group；At formula
In ROH, R is C1-C8Alkyl or C3-C8Cycloalkyl；General formula R ' in OH, R' is C16-C24
Alkyl or aralkyl；The structure of described oxirane compound is as shown in formula II:
Wherein, R1、R2、R3And R4Each stand alone as hydrogen, C1-C10Alkyl or haloalkyl, C3-C10
Cycloalkyl or halogenated cycloalkyl, C6-C10Aryl or halogenated aryl, C7-C10Alkaryl or alkyl halide
Aryl, C7-C10Aralkyl or haloaralkyl；R5And R6Each stand alone as hydrogen, C1-C5Alkyl
Or haloalkyl；
On the basis of the 1mol formula magnesium halide as MgXY, formula is the consumption of the compound of ROH
For 4-30mol, formula be the consumption of the compound of R'OH be 0.001-1.5mol, structure such as formula (I)
The consumption of shown compound is 0.001-1.5mol, structure ethylene oxide as shown in formula II
The consumption of compound is 1-10mol；
Wherein, in step (1), the magnesium-containing carrier in terms of magnesium elements, the first titanizing in terms of titanium elements
Compound is 1:20-150:0.005-1 with the mol ratio of the addition of internal electron donor；In step (2),
The weight ratio of described solid product and the second titanium compound is 0.1-80:100.
Catalyst solid component of olefin polymerization the most according to claim 1, wherein, described heat release
The peak at both shoulders peak is respectively between 130 DEG C-220 DEG C and between 190 DEG C-280 DEG C；Described heat release
The total heat enthalpy that both shoulders peak is corresponding is 150-350 joule/gram.
Catalyst solid component of olefin polymerization the most according to claim 1, wherein, step (2)
In, the condition of described contact include temperature be 0-120 DEG C, the time be 8-24 hour.
Catalyst solid component of olefin polymerization the most according to claim 3, wherein, step (2)
In, the condition of described contact include temperature be 25-120 DEG C, the time be 8-24 hour.
Catalyst solid component of olefin polymerization the most according to claim 1, wherein, step (2)
In, the weight ratio of described solid product and the second titanium compound is 5-15:100.
Catalyst solid component of olefin polymerization the most according to claim 1, wherein, step (1)
In, the magnesium-containing carrier in terms of magnesium elements, the first titanium compound in terms of titanium elements add with internal electron donor
The mol ratio entering amount is 1:30-120:0.01-0.6.
Catalyst solid component of olefin polymerization the most according to claim 1, wherein, with 1mol
On the basis of formula is the magnesium halide of MgXY, formula be the consumption of the compound of ROH be 6-20mol,
Formula be the consumption of the compound of R'OH be 0.01-1mol, structure compound as shown in formula (I)
Consumption is 0.01-1mol, and the consumption of structure oxirane compound as shown in formula II is 2-6mol.
Catalyst solid component of olefin polymerization the most according to claim 1, wherein, by described breast
Changing product and the catalytic condition of oxirane compound and include that temperature is 80-120 DEG C, the time is
20-60 minute.
Catalyst solid component of olefin polymerization the most according to claim 8, wherein, by described breast
Changing product and the catalytic condition of oxirane compound and include that temperature is 80-100 DEG C, the time is
20-50 minute.
Catalyst solid component of olefin polymerization the most according to claim 1, wherein, described first
Titanium compound and the second titanium compound are identical or different, and are each independently formula Ti (OR ")3-aZaWith/
Or Ti (OR ")4-bZbTitanium compound, wherein, R is " for C1-C20Alkyl, Z be F, Cl, Br or
I, a are the integer of 1-3, and b is the integer of 1-4.
11. catalyst solid component of olefin polymerization according to claim 10, wherein, described
One titanium compound and the second titanium compound each stand alone as titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, three
Butoxy titanium chloride, dibutoxy titanium chloride, butoxy titanous chloride., triethoxy titanium chloride, two
One or more in ethyoxyl titanium chloride, ethyoxyl titanous chloride. and titanous chloride..
12. catalyst solid component of olefin polymerization according to claim 1, wherein, described in give
Electron selected from phthalate compound, diol-lipid compound, 1,3-diether compound and
One or more in succinate compounds.
13. 1 kinds of olefin polymerization catalysis, this catalyst contains any one institute in claim 1-12
Catalyst solid component of olefin polymerization, alkyl aluminum compound and the optional external electron donor stated.
14. olefin polymerization catalysis according to claim 13, wherein, described alkyl aluminum chemical combination
The formula of thing is Al (R7)3, R7For C1-C8Alkyl or haloalkyl.
15. olefin polymerization catalysis according to claim 14, wherein, described alkyl aluminum chemical combination
One or more in triethyl aluminum, triisobutyl aluminium, three n-butylaluminum and tri-n-hexyl aluminum of thing.
16. olefin polymerization catalysis according to claim 15, wherein, described external electron donor
It is (R for 1,3-diether compound and/or formula8)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.
17. olefin polymerization catalysis according to claim 16, wherein, described external electron donor
Selected from Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy
Silane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl tertbutyl dimethoxy
One or more in silane and dicyclopentyl dimethoxyl silane.
In 18. claim 13-17, the olefin polymerization catalysis described in any one is at olefinic polyreaction
In application.
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