CN105504114B - A kind of polypropylene and preparation method thereof - Google Patents
A kind of polypropylene and preparation method thereof Download PDFInfo
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- CN105504114B CN105504114B CN201410549339.7A CN201410549339A CN105504114B CN 105504114 B CN105504114 B CN 105504114B CN 201410549339 A CN201410549339 A CN 201410549339A CN 105504114 B CN105504114 B CN 105504114B
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Abstract
The invention provides a kind of polypropylene, the content for the unit group mmmm of meso five that the polypropylene is determined by nuclear magnetic resonance spectroscopy is 70 80 moles of %, and the unit group mm of meso three content is 75 85 moles of %.Present invention also offers the polyacrylic preparation method, it is included in the presence of carried metallocene catalyst and the second alkylaluminoxane, propylene is polymerize, wherein, the carried metallocene catalyst includes metallocene compound, alkyl aluminum and the first alkylaluminoxane of carrier and load on the carrier, and the metallocene compound is rac R1 2‑Si(2‑R2‑4‑Ar‑Ind)2MX2, R1And R2Respectively C1‑C5Alkyl in one kind, Ar is aryl, and Ind is indenyl, and M is one kind in titanium, zirconium and hafnium, and X is one kind in halogen.The polyacrylic haze value of the present invention is low, has the good transparency.
Description
Technical field
The present invention relates to a kind of polypropylene and preparation method thereof.
Background technology
Polypropylene have good mechanical property, nontoxic, relative density is low, heat-resisting, chemical-resistant resistance, be easily worked shaping etc. it is excellent
Good characteristic, and it is cheap, it has also become the product that growth rate is most fast in five big general synthetic resins, new product development is the most active
Kind.Transparent polypropylene is one of polypropylene new product developed in recent years.
Existing transparent polypropylene is usually the copolymer of propylene and a small amount of alpha-olefin.
CN1290885C discloses a kind of method for preparing propylene copolymer compositions, the propylene copolymer compositions bag
Contain：
A) 50-80 weight % propylene copolymer, the propylene copolymer contain 1 to 20 weight % non-propylene alkene, and
B) 20-50 weight % at least one propylene copolymer, the propylene copolymer contain non-the third of 10 to 30 weight %
Alkene alkene,
Wherein, the propylene copolymer A and propylene copolymer B is the phase of separation and dissolves in the ratio of n-hexane
For≤2.6 weight %,
Wherein, this method be it is a kind of based on the catalyst system of specific metallocene compound in the presence of, by extremely
What few two polymerization procedures were carried out.
The content of the invention
It is an object of the invention to provide a kind of polypropylene, and the polyacrylic haze value is low, has the good transparency.
According to the first aspect of the invention, the invention provides a kind of polypropylene, the polypropylene is by NMR spectrum
The unit group mmmm of meso five of method measure content is 70-80 moles of %, and the unit group mm of meso three content is rubbed for 75-85
You are %, and the polyacrylic haze value is less than 6%, and the haze value is measured using method specified in GB/T2410-2008.
According to the second aspect of the invention, the invention provides one kind to prepare polyacrylic method, and this method is included in
In the presence of carried metallocene catalyst and the second alkylaluminoxane, propylene is polymerize, wherein, the support type cyclopentadienyl
Metallic catalyst includes metallocene compound, alkyl aluminum and the first alkylaluminoxane of carrier and load on the carrier,
The metallocene compound is rac-R1 2-Si(2-R2-4-Ar-Ind)2MX2, R1And R2Respectively C1-C5Alkyl in one kind,
Ar is aryl, and Ind is indenyl, and M is one kind in titanium, zirconium and hafnium, and X is one kind in halogen.
According to the third aspect of the present invention, the invention provides polypropylene prepared by a kind of method by the present invention.
The polyacrylic haze value of the present invention is less than 6%, generally 3-5%, has the good transparency.
The method of the present invention is by selecting suitable metallocene compound and the metallocene compound being supported on through alkyl
On aluminium and the carrier of alkylaluminoxane processing, when propylene is carried out into homopolymerization, obtained polypropylene shows low haze value
(can be less than 6%, generally 3-5%), thus there is the good transparency.
Embodiment
According to the first aspect of the invention, the invention provides a kind of polypropylene, the polypropylene is by NMR spectrum
The unit group mmmm of meso five of method measure content is 70-80 moles of %, and the unit group mm of meso three content is rubbed for 75-85
You are %.Polypropylene in the present invention is the homopolymer of propylene.
The unit group of meso five and the unit group of meso three are used for the stereoregularity for representing polypropylene molecular chain, its
It is specifically defined and is referred to method of testing《Catalysts for Olefin Polymerization and polyolefin》(Xiao Shijing, the raw work of remaining tax, Beijing work
Industry university press, 2002) 266-267 pages of record.
It is less than 6% according to the polyacrylic haze value of the present invention, generally 3-5%.The haze value uses GB/
Method measures specified in T2410-2008.
The polyacrylic molecular weight and molecualr weight distribution index of the present invention can be according to the polyacrylic concrete application occasion
Appropriate selection is carried out, disclosure satisfy that requirement is defined.Usually, the polyacrylic number-average molecular weight can be
5000-30000, preferably 7000-25000.Polyacrylic molecular weight distributing index (the Mw/Mn) typically can be with 1.5-3.Institute
State number-average molecular weight and molecular weight distributing index is measured using gel permeation chromatography (that is, GPC).
According to the polypropylene of the present invention, its fusing point is typically within the scope of 120-140 DEG C.The fusing point is swept using differential
Retouch calorimetry (that is, DSC) measure.
According to the second aspect of the invention, the invention provides one kind to prepare polyacrylic method, and this method is included in
In the presence of carried metallocene catalyst and the second alkylaluminoxane, propylene is polymerize.
The carried metallocene catalyst includes metallocene compound, the alkyl of carrier and load on the carrier
Aluminium and the first alkylaluminoxane.
The metallocene compound is rac-R1 2-Si(2-R2-4-Ar-Ind)2MX2, R1And R2It is identical or different, it is respectively
C1-C5Alkyl in one kind；Ar is aryl, such as phenyl or naphthyl；Ind is indenyl；M is one kind in titanium, zirconium and hafnium, excellent
Elect zirconium as；X is one kind in halogen, such as fluorine, chlorine or bromine, preferably chlorine.
The C1-C5Alkyl include C1-C5Straight chained alkyl and C3-C5Branched alkyl, its instantiation can include
But it is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and
Neopentyl.
One kind that the instantiation of the metallocene compound can include but is not limited in following metallocene compound or
It is two or more：
rac-(CH3)2-Si(2-CH3-4-Ph-Ind)2ZrCl2；
rac-(CH3CH2)2-Si(2-CH3-4-Ph-Ind)2ZrCl2；
rac-[CH(CH3)2]2-Si(2-CH3-4-Ph-Ind)2ZrCl2；
rac-(CH3CH2CH2)2-Si(2-CH3-4-Ph-Ind)2ZrCl2；
rac-(CH3CH2CH2CH2)2-Si(2-CH3-4-Ph-Ind)2ZrCl2；
rac-(CH3)2-Si(2-CH3CH2-4-Ph-Ind)2ZrCl2；
rac-(CH3)2-Si(2-CH3CH2CH2-4-Ph-Ind)2ZrCl2；
rac-(CH3)2-Si(2-CH(CH3)2-4-Ph-Ind)2ZrCl2；
rac-(CH3)2-Si(2-CH3CH(CH3)CH2-4-Ph-Ind)2ZrCl2；
rac-(CH3)2-Si(2-CH3CH2CH2CH2-4-Ph-Ind)2ZrCl2；
rac-(CH3)2-Si(2-(CH3)3CCH2-4-Ph-Ind)2ZrCl2；
rac-(CH3)2-Si(2-CH3-4-Naph-Ind)2ZrCl2；
rac-(CH3CH2)2-Si(2-CH3-4-Naph-Ind)2ZrCl2；
rac-[CH(CH3)2]2-Si(2-CH3-4-Naph-Ind)2ZrCl2；
rac-(CH3CH2CH2)2-Si(2-CH3-4-Naph-Ind)2ZrCl2；
rac-(CH3CH2CH2CH2)2-Si(2-CH3-4-Naph-Ind)2ZrCl2；
rac-(CH3)2-Si(2-CH3CH2-4-Naph-Ind)2ZrCl2；
rac-(CH3)2-Si(2-CH3CH2CH2-4-Naph-Ind)2ZrCl2；
rac-(CH3)2-Si(2-CH(CH3)2-4-Naph-Ind)2ZrCl2；
rac-(CH3)2-Si(2-CH3CH(CH3)CH2-4-Naph-Ind)2ZrCl2；
rac-(CH3)2-Si(2-CH3CH2CH2CH2-4-Naph-Ind)2ZrCl2；
rac-(CH3)2-Si(2-(CH3)3CCH2-4-Naph-Ind)2ZrCl2；
Wherein, Ph is phenyl, and Naph is naphthyl.
Preferably, the metallocene compound is rac- (CH3)2-Si(2-CH3-4-Ph-Ind)2ZrCl2And/or rac-
(CH3)2-Si(2-CH3-4-Naph-Ind)2ZrCl2。
Load capacity of the metallocene compound on carrier polymerize and obtained with expected molecular weight that can trigger
Polypropylene is defined.Usually, the load capacity of the metallocene compound on the carrier can cause with support type cyclopentadienyl
On the basis of the total amount of metallic catalyst, metal M content is 0.1-2 weight %, preferably 0.2-1 weight %.
The alkyl aluminum can be conventional various alkyl-substituted organo-aluminum compounds, be specifically as follows shown in Formulas I
It is more than one or both of compound,
In Formulas I, R1、R2And R3It is identical or different, respectively C1-C5Alkyl in one kind.The C1-C5Alkyl include
C1-C5Straight chained alkyl and C3-C5Branched alkyl, its instantiation can include but is not limited to：Methyl, ethyl, n-propyl,
Isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and neopentyl.
The alkyl aluminum is specifically as follows but is not limited to trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand,
It is more than one or both of three n-butylaluminums, three sec-butyl aluminium, tri-tert aluminium, triisobutyl aluminium and three amyl group aluminium.It is preferred that
Ground, the alkyl aluminum compound are triethyl aluminum.
The carried metallocene catalyst is preferably prepared by the following method：By the carrier successively with alkyl aluminum and the
One alkylaluminoxane contacts, and obtains modified carrier；And in the supported on carriers metallocene compound of the modification.
The method that the carrier successively contacts with alkyl aluminum and the first alkylaluminoxane is included：
(1) at a temperature of 30 DEG C -100 DEG C, preferably 85 DEG C -100 DEG C, by the carrier and alkyl aluminum in the first solvent
The first contact is carried out, and collects the solid matter in the mixture obtained by the first contact；
(2) at a temperature of 30 DEG C -100 DEG C, preferably 40 DEG C -80 DEG C, more preferably 50 DEG C -60 DEG C, will be connect by described first
Tactile obtained solid matter carries out second in the second solvent with the first alkylaluminoxane and contacted, and collects and obtained by the second contact
Mixture in solid matter, obtain modified carrier.
The dosage of the alkyl aluminum and first alkylaluminoxane is with the carried metallocene catalyst that finally gives
The amount of aluminium disclosure satisfy that requirement is defined.Preferably, the alkyl aluminum and first alkylaluminoxane and the carrier
Carried metallocene catalyst of the weight than causing final preparation in aluminium total amount and metallocene compound in metal M
Mol ratio is 50-500：1, preferably 60-200：1.Usually, the alkyl aluminum, first alkylaluminoxane and the load
The weight ratio of body can be 0.2-3：0.2-3：1, preferably 1-2.5：1-2：1.
The time of first contact and the described second contact can be each 2-15 hours, preferably 4-10 hours.
Metallocene compound described in supported on carriers of the conventional various methods in the modification can be used.Such as can be with
It is at a temperature of -50 DEG C to 80 DEG C, preferably -20 DEG C to 50 DEG C, the carrier of the modification is molten the 3rd with metallocene compound
The 3rd contact is carried out in agent, and collects the solid matter in the mixture obtained by the 3rd contact.
The time of 3rd contact can be conventional selection, typically can be 2-10 hours, preferably 4-6 hours.
In the present invention, for purposes of clarity, the solvent used in the first contact, the second contact and the 3rd contact is distinguished
Referred to as the first solvent, the second solvent and the 3rd solvent.First solvent, second solvent and the 3rd solvent each may be used
Think more than one or both of hydrocarbon system solvent, preferably more than one or both of aromatic hydrocarbons series solvent.The aromatic hydrocarbons system
Solvent is specifically as follows but is not limited to benzene, more than one or both of toluene, ethylbenzene and dimethylbenzene, preferably toluene.
Can use mixture that mixture, the second contact that conventional various methods obtain from the first contact obtain and
Solid matter is isolated in the mixture that 3rd contact obtains.Specifically, the mixture that the first contact can be obtained, second connect
The mixture that tactile obtained mixture and the 3rd contact obtain is stood, and is then separated supernatant, is collected the pulpous state of bottom
Thing.Obtained slurry is collected before contact next time, it is preferred to use conventional method is washed.The washing uses
Detergent solvent identical reagent for using when being preferably with obtaining the slurry.
First contact, second contact and the 3rd contact are carried out preferably in inert atmosphere.It is described non-
Reactive atmosphere refers to the atmosphere that chemically interactive gas is formed does not occur with reactant and reaction product, such as nitrogen
The atmosphere that atmosphere and/or group 0 element (such as argon gas) are formed.
The carrier can be one kind in conventional selection, such as silica, alundum (Al2O3), magnesium chloride and molecular sieve
Or two or more mixtures, preferably silica (such as silica gel).
The method according to the invention, the polyacrylic molecule of the dosage of the carried metallocene catalyst finally to prepare
Amount disclosure satisfy that specifically used requirement is defined, and can be selected according to specific polymerizing condition.Usually, the support type cyclopentadienyl
The polyacrylic number-average molecular weight that the dosage of metallic catalyst finally to prepare is 5000-30000, preferably 7000-
25000.Come the dosage of selecting catalyst it is those skilled in the art under the teaching of prior art according to expected molecular weight
Experiment by limited number of time is confirmable, is no longer described in detail herein.
In the present invention, for purposes of clarity, the alkylaluminoxane in carried metallocene catalyst is referred to as the first alkane
Base aikyiaiurnirsoxan beta, during by being polymerize, it is referred to as the second alkyl aluminum with the alkylaluminoxane that carried metallocene catalyst is used cooperatively
Oxygen alkane.
First alkylaluminoxane and second alkylaluminoxane are identical or different, can be each known various
Alkylaluminoxane.Usually, the alkyl in first alkylaluminoxane and second alkylaluminoxane can be each C1-
C5Alkyl.The C1-C5Alkyl include C1-C5Straight chained alkyl and C3-C5Branched alkyl, its instantiation can include
But it is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and
Neopentyl.
First alkylaluminoxane and second alkylaluminoxane are each specifically as follows but are not limited to methyl alumina
Alkane, ethylaluminoxane and isobutyl aluminium alkoxide are one or more kinds of, preferably MAO.
The dosage of second alkylaluminoxane can be conventional amount used.Usually, in second alkylaluminoxane
Aluminium and the metal M on the carried metallocene catalyst mol ratio can be 5 × 103-5×106：1, preferably 1 × 105-
1×106：1.
The method according to the invention, the condition that propylene is polymerize are not particularly limited, and can be conventional selection.Typically
Ground, the polymerization can be carried out at a temperature of 30 DEG C -100 DEG C, preferably carried out at a temperature of 60 DEG C -80 DEG C.The polymerization
It can carry out under 0.1-5MPa pressure, preferably be carried out under 0.2-1MPa pressure.The pressure is gauge pressure.
The method according to the invention, the polymerization can be carried out in the gas phase, can also be carried out in the liquid phase, preferably in liquid
Carried out in phase.When being polymerize in the liquid phase, the solvent used can be conventional selection, such as can be various hydrocarbon system solvents,
Preferably alkane series solvent, such as butane and its isomers, pentane and its isomers, hexane and its isomers and heptane and its isomery
Body.The dosage of the solvent can be conventional selection, be not particularly limited.
The method according to the invention, be aggregated in inert atmosphere and carry out, the inert atmosphere refer to by not with reaction
The atmosphere that chemically interactive gas is formed occurs for thing and reaction product, such as nitrogen atmosphere and/or group 0 element are (such as
Argon gas) formed atmosphere.
The method according to the invention, after completion of polymerization, can using method commonly used in the art come terminating reaction, such as
Add the alcohol containing acid and carry out terminating reaction.
According to the third aspect of the present invention, the invention provides polypropylene prepared by a kind of method by the present invention.
The polyacrylic haze value prepared by the method for the present invention is low, can be less than 6%, generally 3-5%.
The unit group mmmm's of meso five that the polypropylene prepared by the method for the present invention is determined by nuclear magnetic resonance spectroscopy
Content is 70-80 moles of %, and the unit group mm of meso three content is 75-85 moles of %.
It is low according to the polypropylene haze value of the present invention, there is the good transparency, can be to be used as transparent material.
Describe the present invention in detail with reference to embodiments.
In following examples and comparative example, using plasma emission spectrum method measure carried metallocene catalyst
Composition.
In following examples and comparative example, NMR spectrum is tested in the model commercially available from Bruker companies of Switzerland
Carried out on BRUKER 400 nuclear magnetic resonance chemical analyser.
In following examples and comparative example, gel permeation chromatography is tested in the model PL-GPC commercially available from PL companies of Britain
Carried out on 220 gel permeation chromatograph, wherein, mobile phase is trichloro-benzenes, and test temperature is 150 DEG C.
In following examples and comparative example, in the differential scanning of the model Diamond DSC commercially available from PE companies of the U.S.
The fusing point of polymer is determined on calorimeter.
In following examples and comparative example, the haze value of polymer is determined using method specified in GB/T2410-2008.
Embodiment 1-5 is used to illustrate polypropylene of the present invention and preparation method thereof.
Embodiment 1
(1) preparation of catalyst
1g silica gel and 10mmol triethyl aluminums are added in toluene, is reacted 5 hours at 100 DEG C, is removed supernatant liquor and obtain
To after slurry, slurry is washed 5 times with toluene.Then, the weight % of 12g 10 methylaluminoxane toluene solution is added, with
Above-mentioned slurry reacts 4 hours at 60 DEG C, after removing supernatant liquor, will obtain slurry and is washed 5 times with toluene.Add
40mgrac-(CH3)2Si(2-CH3-4-Ph-Ind)2ZrCl2, reacted 4 hours at 50 DEG C with the slurry, remove supernatant liquor
Afterwards, slurry will be obtained to be washed 5 times with toluene, finally dried 1 hour in 50 DEG C of vacuum drying oven, obtain loaded metallocene
Catalyst.
After testing, in the carried metallocene catalyst, the content of metal zirconium is 0.5 weight %, and the mol ratio of aluminium/zirconium is
101：1.
(2) propylene homo
Autoclave is purged with nitrogen, then nitrogen is replaced with propylene, repeats three times.Then, provided according to table 1
Amount sequentially add solvent, MAO (that is, MAO, be 10 weight % MAO toluene solution, similarly hereinafter) and step (1) make
Standby carried metallocene catalyst, stir 10 minutes.Then propylene is passed through with 0.1MPa pressure, in the condition that table 1 provides
Under polymerize.After reaction terminates, acidic ethanol (containing 10 volume % hydrochloric acid) is added into reactor with terminating reaction, is gone forward side by side
Row filtering, obtains pulverulent solids, and with 100mL ethanol and 200mL water washings three times after, by obtained pulverulent solids in temperature
Spend in the vacuum drying oven for 50 DEG C and dry to constant weight, so as to obtain the polypropylene of the present invention.
Obtained polypropylene is tested, as a result listed in table 2.
Comparative example 1
(1) preparation of catalyst
By 1g silica gel and the weight % of 18.9g 10 methylaluminoxane toluene solution, react 4 hours, remove at 60 DEG C
Slurry is obtained after layer clear liquid and is washed 5 times with toluene.Add 40mgrac- (CH3)2Si(2-CH3-4-Ph-Ind)2ZrCl2,
Reacted 4 hours at 50 DEG C, slurry is obtained after removing supernatant liquor, after washing 5 times with toluene, done in 50 DEG C of vacuum drying oven
Dry 1 hour, obtain carried metallocene catalyst.
After testing, in the carried metallocene catalyst, the content of metal zirconium is 0.5 weight %, and the mol ratio of aluminium/zirconium is
100：1.
(2) homopolymerization of propylene
The homopolymerization of propylene is carried out using method same as Example 1, unlike, catalyst is the step of comparative example 1 (1)
The carried metallocene catalyst of preparation.
Obtained polypropylene is tested, as a result listed in table 2.
Comparative example 2
(1) carried metallocene catalyst is prepared using method same as Example 1, unlike, use equivalent
rac-Et(Ind)2ZrCl2Instead of rac- (CH3)2Si(2-CH3-4-Ph-Ind)2ZrCl2.After testing, the loaded metallocene is urged
In agent, the content of metal zirconium is 0.5 weight %, and the mol ratio of aluminium/zirconium is 100：1.
(2) polypropylene is prepared using method same as Example 1, unlike, catalyst is the step of comparative example 2 (1)
The carried metallocene catalyst of preparation.
Obtained polypropylene is tested, as a result listed in table 2.
Embodiment 2
(1) carried metallocene catalyst is prepared using with the step of embodiment 1 (1) identical method.
(2) use and propylene is subjected to homopolymerization with the step of embodiment 1 (2) identical method, unlike, listed in table 1
Under the conditions of polymerize, so as to obtain the present invention polypropylene.
Obtained polypropylene is tested, as a result listed in table 2.
Embodiment 3
(1) carried metallocene catalyst is prepared using with the step of embodiment 1 (1) identical method.
(2) use and propylene is subjected to homopolymerization with the step of embodiment 1 (2) identical method, unlike, listed in table 1
Under the conditions of polymerize, so as to obtain the present invention polypropylene.
Obtained polypropylene is tested, as a result listed in table 2.
Embodiment 4
(1) preparation of catalyst
1g silica gel and 10mmol triethyl aluminums are added in toluene, reacted 5 hours at 100 DEG C, after removing supernatant liquor
After obtaining slurry, washed 5 times with toluene.Then, the weight % of 12g 10 methylaluminoxane toluene solution is added, at 50 DEG C
Reaction 4 hours, obtains slurry after removing supernatant liquor and is washed 5 times with toluene.Add 80mg rac- (CH3)2-Si(2-
CH3-4-Naph-Ind)2ZrCl2, reacted 4 hours under the conditions of 50 DEG C, obtain slurry after removing supernatant liquor, washed with toluene
After washing 5 times, dried 1 hour in 50 DEG C of vacuum drying oven, obtain carried metallocene catalyst.
After testing, in the carried metallocene catalyst, the content of metal zirconium is 0.7 weight %, and the mol ratio of aluminium/zirconium is
80：1.
(2) propylene homo
Autoclave is purged with nitrogen, then nitrogen is replaced with propylene, repeats three times.Then, provided according to table 1
Amount sequentially add solvent, carried metallocene catalyst prepared by MAO and step (1), stir 10 minutes.Then
Propylene is passed through with 0.1MPa pressure, polymerize under conditions of table 1 provides.After reaction terminates, acid is added into reactor
Change ethanol (contain 10 volume % hydrochloric acid) terminating reaction, and being filtered, obtain pulverulent solids, and with 100mL ethanol with
200mL water washings three times after, obtained pulverulent solids are dried to constant weight in temperature is 50 DEG C of vacuum drying oven, so as to
To the polypropylene of the present invention.
Obtained polypropylene is tested, as a result listed in table 2.
Embodiment 5
(1) preparation of catalyst
1g silica gel and 20mmol triethyl aluminums are added in toluene, reacted 8 hours at 100 DEG C, after removing supernatant liquor
After obtaining slurry, washed 5 times with toluene.Then, the weight % of 20g 10 methylaluminoxane toluene solution is added, at 50 DEG C
Reaction 6 hours, obtains slurry after removing supernatant liquor and is washed 5 times with toluene.Add 30mg rac- (CH3)2-Si(2-
CH3-4-Ph-Ind)2ZrCl2, reacted 4 hours under the conditions of -20 DEG C, obtain slurry after removing supernatant liquor, washed with toluene
After 5 times, dried 1 hour in 50 DEG C of vacuum drying oven, obtain carried metallocene catalyst.
After testing, in the carried metallocene catalyst, the content of metal zirconium is 0.4 weight %, and the mol ratio of aluminium/zirconium is
200：1.
(2) propylene homo
Autoclave is purged with nitrogen, then nitrogen is replaced with propylene, repeats three times.Then, provided according to table 1
Amount sequentially add solvent, carried metallocene catalyst prepared by MAO and step (1), stir 10 minutes.Then
Propylene is passed through with 0.1MPa pressure, polymerize under conditions of table 1 provides.After reaction terminates, acid is added into reactor
Change ethanol (contain 10 volume % hydrochloric acid) terminating reaction, and being filtered, obtain pulverulent solids, and with 100mL ethanol with
200mL water washings three times after, obtained pulverulent solids are dried to constant weight in temperature is 50 DEG C of vacuum drying oven, so as to
To the polypropylene of the present invention.
Obtained polypropylene is tested, as a result listed in table 2.
Table 1
Table 2
Table 2 as a result, it was confirmed that had according to the polypropylene of the present invention compared with low haze valus, thus with compared with high transparency.
Claims (12)
1. one kind prepares polyacrylic method, this method is included in carried metallocene catalyst and the second alkylaluminoxane
In the presence of, propylene is polymerize, wherein, the carried metallocene catalyst includes carrier and load on the carrier
Metallocene compound, alkyl aluminum and the first alkylaluminoxane, the metallocene compound is rac-R1 2-Si(2-R2-4-Ar-
Ind)2MX2, R1And R2Respectively C1-C5Alkyl in one kind, Ar is aryl, and Ind is indenyl, and M is one in titanium, zirconium and hafnium
Kind, X is one kind in halogen；
The preparation method of the carried metallocene catalyst includes：By carrier priority and alkyl aluminum and the first alkyl alumina
Alkane contacts, and obtains modified carrier；And in the supported on carriers metallocene compound of the modification.
2. according to the method for claim 1, wherein, the carrier is successively contacted with alkyl aluminum and the first alkylaluminoxane
Method include：
(1) at a temperature of 30-100 DEG C, the carrier is carried out first in the first solvent with alkyl aluminum and contacted, and collect by
Solid matter in the mixture that first contact obtains；
(2) at a temperature of 30-100 DEG C, by by the described first obtained solid matter of contact and the first alkylaluminoxane the
The second contact is carried out in two solvents, and collects the solid matter in the mixture obtained by the second contact, obtains modified carrier；
First solvent and second solvent are respectively more than one or both of aromatic hydrocarbons series solvent.
3. method according to claim 1 or 2, wherein, the alkyl aluminum, first alkylaluminoxane and the carrier
Weight ratio be 0.2-3：0.2-3：1.
4. the method according to claim 11, wherein, in the method bag of the supported on carriers metallocene compound of the modification
Include：At a temperature of -50 DEG C to 80 DEG C, the carrier of the modification is carried out the 3rd in the 3rd solvent with metallocene compound and connect
Touch, and collect the solid matter in the mixture obtained by the 3rd contact, the 3rd solvent is one kind in aromatic hydrocarbons series solvent
It is or two or more.
5. the method according to claim 2 or 4, wherein, the aromatic hydrocarbons series solvent is C6-C12Substituted or unsubstituted virtue
It is more than one or both of hydrocarbon.
6. according to the method described in any one in claim 1,2 and 4, wherein, the metallocene compound, alkyl aluminum and
The load capacity of one alkylaluminoxane on the carrier causes on the basis of the total amount of the carried metallocene catalyst, described
The content of metal M in metallocene compound is 0.1-2 weight %, the aluminium in the alkyl aluminum and first alkylaluminoxane
Total amount and the metallocene compound in metal M mol ratio be 50-500：1.
7. according to the method described in any one in claim 1,2 and 4, wherein, the alkyl aluminum is the compound shown in Formulas I
One or both of more than,
In Formulas I, R1、R2And R3It is identical or different, respectively C1-C5Alkyl in one kind.
8. according to the method for claim 7, wherein, the alkyl aluminum is triethyl aluminum.
9. the method according to claim 11, wherein, aluminium and the loaded metallocene in second alkylaluminoxane
The mol ratio of metal M on catalyst is 5 × 103-5×106：1.
10. according to the method described in any one in claim 1,2,4 and 9, wherein, first alkylaluminoxane and described
Second alkylaluminoxane is MAO.
11. according to the method described in any one in claim 1,2,4 and 9, wherein, the metallocene compound is rac-
(CH3)2-Si(2-CH3-4-Ph-Ind)2ZrCl2And/or rac- (CH3)2-Si(2-CH3-4-Naph-Ind)2ZrCl2, Ph is benzene
Base, Naph are naphthyl.
12. according to the method described in any one in claim 1,2,4 and 9, wherein, the carrier is silica.
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| CN1384848A (en) * | 1999-10-26 | 2002-12-11 | 出光石油化学株式会社 | Polypropylene film and multilayered laminate |
| EP1291365A2 (en) * | 1997-01-30 | 2003-03-12 | Fina Technology, Inc. | Selective activity of metallocene-type catalyst for isotactic poly-alpha-olefin production |
| CN1726235A (en) * | 2002-12-16 | 2006-01-25 | 巴塞尔聚烯烃股份有限公司 | Preparation of supported catalyst systems containing reduced amounts of aluminoxanes |
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| JP2002206006A (en) * | 2000-11-13 | 2002-07-26 | Basell Technology Co Bv | Method for producing olefin polymer |
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| EP1291365A2 (en) * | 1997-01-30 | 2003-03-12 | Fina Technology, Inc. | Selective activity of metallocene-type catalyst for isotactic poly-alpha-olefin production |
| CN1384848A (en) * | 1999-10-26 | 2002-12-11 | 出光石油化学株式会社 | Polypropylene film and multilayered laminate |
| CN1726235A (en) * | 2002-12-16 | 2006-01-25 | 巴塞尔聚烯烃股份有限公司 | Preparation of supported catalyst systems containing reduced amounts of aluminoxanes |
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