CN102796210B - Catalyst component and catalyst system for olefin polymerization, application of catalyst component and catalyst system, and olefin polymerization method - Google Patents
Catalyst component and catalyst system for olefin polymerization, application of catalyst component and catalyst system, and olefin polymerization method Download PDFInfo
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Abstract
The invention provides a catalyst component for olefin polymerization and application of the catalyst component. The catalyst component contains a product obtained by reacting a magnesium halide adduct, a titanium compound and at least one optional internal electron donor compound, wherein the magnesium halide adduct is shown as MgX<1>Y-mEtOH-n(LB1)-k(LB2)-p(LB3). The invention also provides a catalyst system for olefin polymerization and application of the catalyst system. The catalyst system contains the catalyst component and one or more organic aluminum compounds. The invention also provides an olefin polymerization method. The method comprises the following step of: contacting one or more olefins and the catalyst system under the condition of olefin polymerization. The catalyst system has high hydrogen regulation sensitivity and stereospecificity in olefin polymerization, and good balance between the hydrogen regulation sensitivity and the stereospecificity of the catalyst system is achieved.
Description
Technical field
The present invention relates to a kind of catalyst component for olefinic polymerization and catalyst system and application and olefine polymerizing process.
Background technology
That prior art is known by titanium compound and the compound loaded Ziegler-Natta catalyst of preparing in magnesium halide in active of electron donor.Wherein, described magnesium halide in active often adopts the adducts of magnesium halide and alcohol, set it as after carrier reacts with halogenated titanium and electron donor compound and obtain spherical catalyst, described spherical catalyst is when for alkene (particularly propylene) polymerization, have higher polymerization activity and stereotaxis ability, resulting polymers also has good particle form and higher apparent density.
Published magnesium halide alcohol adducts is the alcohol adduct of magnesium chloride mostly, conventionally contains magnesium chloride and alcohol binary composition.Wherein, the adducts of some published magnesium chloride and alcohol also contains a small amount of water.For example: the adducts of the disclosed magnesium chloride of US4421674, US4469648, WO8707620, WO9311166, US5100849, US6020279, US4399054, EP0395383, US6127304 and US6323152 and alcohol.This type of adducts can be dry by spraying, spray cooling, high pressure are extruded or the method preparation such as high-speed stirring.
But, when the catalyzer of being prepared by the adducts of above-mentioned published magnesium chloride and alcohol during for olefinic polymerization, is easy to occur the phenomenon of polymer particle fragmentation, thereby causes fine polymer powder more in polymerization process.In order to overcome this shortcoming, people attempt again electron donor compound to be incorporated in advance in the preparation process of adducts of magnesium chloride and alcohol, for example: CN1169840C and CN1286863C are incorporated into the phthalate compound (for example: diisobutyl phthalate or n-butyl phthalate) that is typically used as internal electron donor in field of olefin polymerisation in the building-up process of adducts of magnesium chloride and alcohol, thereby obtain " magnesium dichloride-alcohol-phthalic ester " ball type carrier, then by this carrier and titanium tetrachloride reaction to form catalyzer.But, described " magnesium dichloride-alcohol-phthalic ester " ball type carrier is easily clamminess in preparation process, be difficult to form the spheroidal particle that size is suitable, and the catalyzer of being prepared by this carrier is during for propylene polymerization, polymerization activity is low and hydrogen response is poor.
In the disclosed technology of CN100491410C, C, C-bis--oxyl hydrocarbon compounds are introduced in adduct of magnesium halides.The catalyzer of being prepared as carrier by this polycomponent adduct of magnesium halides is during for propylene polymerization, and its hydrogen response obtains certain raising, and in polymkeric substance, fine powder content has minimizing to a certain degree.But, in the preparation process of this adducts carrier, easily form abnormity material (for example: spheroid particle and/or bar shaped particle etc.), and, when the catalyzer of being prepared by this adducts carrier carries out propylene polymerization under high hydrogen concentration, its stereotaxis ability, the degree of isotacticity particularly with the polymkeric substance of high fusion index needs further to improve.
CN101486722A by reaction in－situ or the mode directly adding in the preparation process of adduct of magnesium halides, introduce o-alkoxyl benzoate compounds, make the catalyzer making take described adduct of magnesium halides as carrier there is good hydrogen response and higher stereotaxis ability, and its polymerization activity is higher, the fine powder of resulting polymers is also less.But, the cooling efficiency must carefully control the shaping of adduct of magnesium halides chilling in the preparation process of carrier time, otherwise easily cause the inter-adhesive of carrier particle; And the balance between hydrogen response and the stereotaxis ability of the catalyzer of being prepared by this adducts carrier needs further to improve.
Summary of the invention
The object of the present invention is to provide a kind of novel catalyst component for olefinic polymerization and catalyst system and application thereof.According to there is not adhesion between the particle of the adduct of magnesium halides of the catalyst component for olefinic polymerization of the present invention, also there is no abnormity material, thereby olefin polymerization catalyst components particle form of the present invention is good; And, the present inventor is also surprised to find that, when catalyst according to the invention component and catalyst body thereof tie up to for alkene (particularly propylene) polymerization, demonstrate excellent hydrogen response and high stereotaxis ability, between its hydrogen tune ability and stereotaxis ability, reach good balance, its polymerization activity is higher in addition, and the form of resulting polymers is very perfect.
The invention provides a kind of catalyst component for olefinic polymerization, the reaction product that this catalyst component comprises adduct of magnesium halides, titanium compound and optional at least one internal electron donor compound, wherein, described adduct of magnesium halides is suc as formula shown in I,
MgX
1Y-mEtOH-n(LB
1)-k(LB
2)-p(LB
3) (I)
In formula I, X
1for chlorine or bromine, Y is chlorine, bromine, C
1-C
14straight or branched alkyl, C
6-C
14replacement or unsubstituted aryl, C
1-C
14straight or branched alkoxyl group and C
6-C
14replacement or unsubstituted aryloxy in one; LB
1, LB
2and LB
3respectively do for oneself carboxylic acid, aldehyde, ether, ester, ketone, silane, amine, nitrile, phenol and be different from the one in the alcohol of ethanol,
In formula I, m is 1-5, is preferably 2-3.5; N is 0.005-2, is preferably 0.01-0.8; K is 0.0005-0.3, is preferably 0.001-0.1; P is 0.0005-0.3, is preferably 0.001-0.1.
The present invention also provides catalyst according to the invention component in the application of preparing in olefin polymerization catalyst system.
The present invention also provides a kind of catalyst system for olefinic polymerization, and this catalyst system comprises catalyst according to the invention component and one or more organo-aluminium compounds; In the described organo-aluminium compound of aluminium with take the mol ratio of the described catalyst component of titanium as 1-2000: 1, be preferably 20-700: 1.
The present invention also provides the application of a kind of catalyst according to the invention system in olefinic polyreaction.
The present invention further provides a kind of olefine polymerizing process, the method is included under olefinic polymerization condition, and one or more alkene are contacted with catalyst system provided by the invention.
Good according to the particle form of the spherical adduct of magnesium halides of the catalyst component for olefinic polymerization of the present invention, without abnormity material (as spheroid material, bar material etc.), and between particle also without adhesion phenomenon.Thereby, use catalyst according to the invention component and catalyst system thereof, when for alkene (particularly propylene) polymerization, resulting polymers particle shape is good.The present inventor is also surprised to find that, catalyst component of the present invention and catalyst body thereof tie up to not only has higher polymerization activity in olefinic polymerization, also demonstrate excellent hydrogen response and high stereotaxis ability, between its hydrogen tune ability and stereotaxis ability, reached good balance.
Accompanying drawing explanation
Fig. 1 is the particle morphology optical microscope photograph of the spherical adduct of magnesium halides prepared of embodiment 1;
Fig. 2 is the particle morphology optical microscope photograph of the spherical catalyst component prepared of embodiment 1;
Fig. 3 is the particle morphology optical microscope photograph of the spherical adduct of magnesium halides prepared of embodiment 2;
Fig. 4 is the particle morphology optical microscope photograph of the spherical catalyst component prepared of embodiment 2;
Fig. 5 is the particle morphology optical microscope photograph of the spherical adduct of magnesium halides prepared of comparative example 2;
Fig. 6 is the particle morphology optical microscope photograph of the spherical catalyst component prepared of comparative example 2.
Embodiment
The invention provides a kind of catalyst component for olefinic polymerization, the reaction product that this catalyst component comprises adduct of magnesium halides, titanium compound and optional at least one internal electron donor compound, wherein, described adduct of magnesium halides is suc as formula shown in I,
MgX
1Y-mEtOH-n(LB
1)-k(LB
2)-p(LB
3) (I)
In formula I, X
1for chlorine or bromine, Y is chlorine, bromine, C
1-C
14straight or branched alkyl, C
6-C
14replacement or unsubstituted aryl, C
1-C
14straight or branched alkoxyl group and C
6-C
14replacement or unsubstituted aryloxy in one; LB
1, LB
2and LB
3being selected from separately Lewis base, for example, can be the one in carboxylic acid, aldehyde, ether, ester, ketone, silane, amine, nitrile, phenol and the alcohol that is different from ethanol.
According to the present invention, in formula I, Et represents ethyl, and EtOH represents ethanol.
In the present invention, term " carboxylic acid " comprises aliphatic carboxylic acid and aromatic carboxylic acid, is preferably aromatic carboxylic acid.In the present invention, term " ester " comprises aliphatic carboxylic acid esters, and aromatic carboxylic acid esters, is preferably aromatic carboxylic acid esters.In the present invention, term " amine " comprises primary amine, secondary amine and tertiary amine.In the present invention, term " silane " refers to SiH
4in one or more hydrogen atoms by containing or containing heteroatomic alkyl, containing or containing heteroatomic alkoxyl group, containing or containing heteroatomic aryl or containing or the organosilane that do not replace containing heteroatomic aryloxy, described silane is preferably alkylalkoxy silane or organoalkoxysilane.
In the present invention, term " replacement " refers to that the hydrogen atom on carbon or Siliciumatom is substituted base and replaces.
According to the present invention, in formula I, Y is preferably chlorine, bromine, C
1-C
5straight or branched alkyl, C
6-C
10replacement or unsubstituted aryl, C
1-C
5straight or branched alkoxyl group and C
6-C
10replacement or unsubstituted aryloxy in one.In the present invention, in formula I, MgX
1y can be a kind of halogenated magnesium compound, can be also the mixture of multiple halogenated magnesium compound.More preferably, in formula I, MgX
1y is one or more in magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium.From the angle of being easy to get property of raw material, in formula I, MgX
1y is magnesium dichloride more preferably.
According to the present invention, in formula I, LB
1be preferably the compound shown in formula II:
R
7X
2 (II)
In formula II, X
2for-NH
2,-NHR
7' and-one in OH, R
7' be C
1-C
20alkyl, R
7for C
1-C
20alkyl or the C being replaced by heteroatom group
1-C
20alkyl, and at X
2during for-OH, R
7it is not ethyl.
Preferably, in formula II, X
2for-OH; R
7for methyl, C
3-C
10alkyl, or quilt-NH
2,-NHR
7' and-C of one or more replacements in OH
1-C
10alkyl; R
7' be C
1-C
5straight or branched alkyl.
More preferably, in formula II, X
2for-OH, R
7for methyl, C
3-C
10straight or branched alkyl, C
6-C
10replacement or unsubstituted aryl or quilt-NH
2and/or-OH replace C
1-C
10straight or branched alkyl.
In the present invention, LB
1specific examples can for but be not limited to: methyl alcohol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, ethylene glycol, 1,3-PD and phenol.
In the present invention, term " alkyl " refers to that hydrocarbon molecule loses the group forming after a hydrogen atom, for example: described " alkyl " can be C
1-C
20alkyl, C
2-C
20thiazolinyl, C
2-C
20alkynyl and C
6-C
20aryl; Be preferably C
1-C
10alkyl, C
2-C
10thiazolinyl, C
2-C
10alkynyl and C
6-C
10aryl.
According to the present invention, in formula I, LB
2be preferably the alkoxybenzoic acid ester based compound shown in the alkoxybenzoic acid based compound shown in formula III or formula III,
In formula III, R
1for hydrogen, C
1-C
20straight or branched alkyl, C
3-C
20replacement or unsubstituted cycloalkyl, C
6-C
20replacement or unsubstituted aryl and C
7-C
20replacement or unsubstituted aralkyl in one;
R
2, R
3, R
4and R
5hydrogen, halogen, nitro, C respectively do for oneself
1-C
20straight or branched alkyl, C
3-C
20replacement or unsubstituted cycloalkyl, C
6-C
20replacement or unsubstituted aryl and C
7-C
20replacement or unsubstituted aralkyl in one; Or, R
2, R
3, R
4and R
5in two or more mutual bondings, to form ring;
R
6for C
1-C
20straight or branched alkyl, C
3-C
20replacement or unsubstituted cycloalkyl, C
6-C
20replacement or unsubstituted aryl and C
7-C
20replacement or unsubstituted aralkyl in one.
Preferably, in formula III, R
1for hydrogen, C
1-C
6straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
R
2, R
3, R
4and R
5hydrogen, C respectively do for oneself
1-C
8straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
R
6for C
1-C
6straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one.
More preferably, in formula III, R
1and R
6the one of respectively doing for oneself in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and styroyl;
R
2, R
3, R
4and R
5the one of respectively doing for oneself in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and aminomethyl phenyl.
According to the present invention, at LB
2during for alkoxybenzoic acid ester based compound shown in the alkoxybenzoic acid based compound shown in formula III or formula III, LB
2the more preferably one in 4-alkoxybenzoic acid based compound, 4-alkoxybenzoic acid ester based compound, 2-alkoxybenzoic acid based compound and 2-alkoxybenzoic acid ester based compound; The more preferably one in 2-alkoxybenzoic acid based compound and 2-alkoxybenzoic acid ester based compound.
In the present invention, LB
2specific examples can for but be not limited to: O-Anisic Acid methyl esters, O-Anisic Acid ethyl ester, O-Anisic Acid n-propyl, 2-methoxy benzoic acid isopropyl ester, the positive butyl ester of O-Anisic Acid, O-Anisic Acid isobutyl ester, O-Anisic Acid n-pentyl ester, the just own ester of O-Anisic Acid, O-Anisic Acid benzyl ester, O-Anisic Acid phenethyl ester, 2-methoxyl group-3-methyl-toluate, 2-methoxyl group-methyl 4 methylbenzoate, 2-methoxyl group-5-methyl-toluate, 2-methoxyl group-3-ethyl benzoate methyl esters, 2-methoxyl group-4-ethyl benzoate methyl esters, 2-methoxyl group-5-ethyl benzoate methyl esters, 2-methoxyl group-3-tolyl acid ethyl ester, 2-methoxyl group-4-tolyl acid ethyl ester, 2-methoxyl group-5-tolyl acid ethyl ester, 2-methoxyl group-3-ethylamino benzonitrile acetoacetic ester, 2-methoxyl group-4-ethylamino benzonitrile acetoacetic ester, 2-methoxyl group-5-ethylamino benzonitrile acetoacetic ester, 2-methoxyl group-3-tolyl acid n-propyl, 2-methoxyl group-4-tolyl acid n-propyl, 2-methoxyl group-5-tolyl acid n-propyl, 2-methoxyl group-3-ethyl benzoate n-propyl, 2-methoxyl group-4-ethyl benzoate n-propyl, 2-methoxyl group-5-ethyl benzoate n-propyl, 2-methoxyl group-3-tolyl acid isopropyl ester, 2-methoxyl group-4-tolyl acid isopropyl ester, 2-methoxyl group-5-tolyl acid isopropyl ester, 2-methoxyl group-3-ethylamino benzonitrile isopropyl propionate, 2-methoxyl group-4-ethylamino benzonitrile isopropyl propionate, 2-methoxyl group-5-ethylamino benzonitrile isopropyl propionate, 2-methoxyl group-3-tolyl acid isobutyl ester, 2-methoxyl group-4-tolyl acid isobutyl ester, 2-methoxyl group-5-tolyl acid isobutyl ester, 2-methoxyl group-3-ethyl benzoate isobutyl ester, 2-methoxyl group-4-ethyl benzoate isobutyl ester, 2-methoxyl group-5-ethyl benzoate isobutyl ester, 2-methoxyl group-3-propylbenzoic acid ethyl ester, 2-methoxyl group-4-propylbenzoic acid ethyl ester, 2-methoxyl group-5-propylbenzoic acid ethyl ester, 2-methoxyl group-4-isopropyl acid ethyl ester, 2-methoxyl group-4-isobutyl-benzene ethyl formate, 2-methoxyl group-4-p t butylbenzoic acid ethyl ester, 2-methoxyl group-4-amylbenzene ethyl formate, 2-methoxyl group-4-isoamylbenzene ethyl formate, 2-methoxyl group-4-cyclopentyl ethyl benzoate, 2-ethoxy-benzoic acid methyl ester, 2-ethoxy benzonitrile acetoacetic ester, 2-ethoxybenzoic acid n-propyl, 2-ethoxy isopropyl benzoate, the positive butyl ester of 2-ethoxybenzoic acid, 2-ethoxybenzoic acid isobutyl ester, 2-ethoxybenzoic acid n-pentyl ester, the just own ester of 2-ethoxybenzoic acid, 2-ethoxybenzoic acid benzyl ester, 2-ethoxybenzoic acid phenethyl ester, 2-n-butoxy methyl benzoate, 2-n-butoxy ethyl benzoate, 2-n-butoxy Propyl benzoate, the positive fourth oxybenzoic acid of 2-isopropyl ester, the positive butyl ester of 2-n-butoxy phenylformic acid, 2-n-butoxy isobutyl benzoate, 2-n-butoxy Pentyl benzoate, the just own ester of 2-n-butoxy phenylformic acid, 2-n-butoxy peruscabin and 2-n-butoxy phenylethyl benzoate.
According to the present invention, in formula I, LB
3be preferably the hydroxybenzoate based compound shown in the hydroxy-benzoic acid based compound shown in formula IV or formula IV,
In formula IV, R
1for hydrogen, C
1-C
20straight or branched alkyl, C
3-C
20replacement or unsubstituted cycloalkyl, C
6-C
20replacement or unsubstituted aryl and C
7-C
20replacement or unsubstituted aralkyl in one;
R
2, R
3, R
4and R
5hydrogen, halogen, nitro, C respectively do for oneself
1-C
20straight or branched alkyl, C
3-C
20unsubstituted cycloalkyl, the C of replacement
6-C
20replacement or unsubstituted aryl and C
7-C
20replacement or unsubstituted aralkyl in one; Or, R
2, R
3, R
4and R
5in two or more mutual bondings, to form ring.
Preferably, in formula IV, R
1for hydrogen, C
1-C
6straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
R
2, R
3, R
4and R
5hydrogen, C respectively do for oneself
1-C
8straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one.
More preferably, in formula IV, R
1for the one in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and styroyl;
R
2, R
3, R
4and R
5the one of respectively doing for oneself in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and tolyl.
According to the present invention, at LB
3during for hydroxybenzoate based compound shown in the hydroxy-benzoic acid based compound shown in formula IV or formula IV, LB
3the more preferably one in 4-HBA based compound, 4-HBA ester based compound, 2 hydroxybenzoic acid based compound and 2 hydroxybenzoic acid ester based compound; The more preferably one in 2 hydroxybenzoic acid based compound and 2 hydroxybenzoic acid ester based compound.
In the present invention, LB
3specific examples can for but be not limited to: 2 hydroxybenzoic acid methyl esters, 2 hydroxybenzoic acid ethyl ester, 2 hydroxybenzoic acid n-propyl, 2 hydroxybenzoic acid isopropyl ester, the positive butyl ester of 2 hydroxybenzoic acid, 2 hydroxybenzoic acid isobutyl ester, 2 hydroxybenzoic acid n-pentyl ester, the just own ester of 2 hydroxybenzoic acid, 2 hydroxybenzoic acid benzyl ester, 2 hydroxybenzoic acid phenethyl ester, 2-hydroxy-3-methyl methyl benzoate, 2-hydroxy-4-methyl methyl benzoate, 2-hydroxy-5-methyl yl benzoic acid methyl esters, 2-hydroxyl-3-ethyl benzoate methyl esters, 2-hydroxyl-4-ethyl benzoate methyl esters, 2-hydroxyl-5-ethyl benzoate methyl esters, 2-hydroxy-3-methyl ethyl benzoate, 2-hydroxy-4-methyl ethyl benzoate, 2-hydroxy-5-methyl yl benzoic acid ethyl ester, 2-hydroxyl-3-ethylamino benzonitrile acetoacetic ester, 2-hydroxyl-4-ethylamino benzonitrile acetoacetic ester, 2-hydroxyl-5-ethylamino benzonitrile acetoacetic ester, 2-hydroxy-3-methyl Propyl benzoate, 2-hydroxy-4-methyl Propyl benzoate, 2-hydroxy-5-methyl yl benzoic acid n-propyl, 2-hydroxyl-3-ethyl benzoate n-propyl, 2-hydroxyl-4-ethyl benzoate n-propyl, 2-hydroxyl-5-ethyl benzoate n-propyl, 2-hydroxy-3-methyl isopropyl benzoate, 2-hydroxy-4-methyl isopropyl benzoate, 2-hydroxy-5-methyl yl benzoic acid isopropyl ester, 2-hydroxyl-3-ethylamino benzonitrile isopropyl propionate, 2-hydroxyl-4-ethylamino benzonitrile isopropyl propionate, 2-hydroxyl-5-ethylamino benzonitrile isopropyl propionate, 2-hydroxy-3-methyl isobutyl benzoate, 2-hydroxy-4-methyl isobutyl benzoate, 2-hydroxy-5-methyl yl benzoic acid isobutyl ester, 2-hydroxyl-3-ethyl benzoate isobutyl ester, 2-hydroxyl-4-ethyl benzoate isobutyl ester, 2-hydroxyl-5-ethyl benzoate isobutyl ester, 2-hydroxyl-3-n-propylbenzene ethyl formate, 2-hydroxyl-4-n-propylbenzene ethyl formate, 2-hydroxyl-5-n-propylbenzene ethyl formate, 2-hydroxyl-4-isopropyl acid ethyl ester, 2-hydroxyl-4-isobutyl-benzene ethyl formate, 2-hydroxyl-4-p t butylbenzoic acid ethyl ester, 2-hydroxyl-4-n-amylbenzene ethyl formate, 2-hydroxyl-4-isoamylbenzene ethyl formate and 2-hydroxyl-4-cyclopentyl ethyl benzoate.
According to the present invention, in formula I, m can be 1-5, is preferably 2-3.5, more preferably 2.4-3.5; N can be 0.005-2, is preferably 0.01-0.8, more preferably 0.03-0.6; K can be 0.0005-0.3, is preferably 0.001-0.1, more preferably 0.003-0.07; P can be 0.0005-0.3, is preferably 0.001-0.1, more preferably 0.003-0.07.
According to one of the present invention preferred embodiment, in formula I, X
1be chlorine with Y;
LB
1for the compound shown in formula II, in formula II, X
2for-OH, R
7for methyl, C
3-C
10straight or branched alkyl or the C being replaced by hydroxyl
1-C
10straight or branched alkyl;
LB
2for the 2-alkoxybenzoic acid ester based compound shown in formula V,
In formula V, R
1and R
6the one of respectively doing for oneself in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and styroyl; R
2, R
3, R
4and R
5the one of respectively doing for oneself in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and tolyl;
LB
3for the 2 hydroxybenzoic acid ester based compound shown in formula VI,
In formula VI, R
1for the one in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and styroyl; R
2, R
3, R
4and R
5the one of respectively doing for oneself in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and tolyl;
M is 2.4-3.5, and n is 0.03-0.6, and k is 0.003-0.07, and p is 0.003-0.07.
Spherical adduct of magnesium halides according to the present invention can also contain water, described water come from synthesis material and reaction medium with minor amount of water.
Can adopt following methods to prepare according to the adduct of magnesium halides of the catalyst component for olefinic polymerization of the present invention:
(1) by MgX
1y and ethanol, LB
1, LB
2and LB
3mix, and by the mixture heating obtaining, to obtain liquid adduct of magnesium halides; Or
By MgX
1y and ethanol, under hydrolysising condition, can form LB
1material, hydrolysis and/or alcoholysis conditions under can form LB
2material and hydrolysis and/or alcoholysis conditions under can form LB
3material mix, and by the mixture heating obtaining, to obtain liquid adduct of magnesium halides;
(2) under inert liquid medium exists, by the adduct of magnesium halides emulsification of described liquid state, and emulsification product quenching is shaped, obtain spherical adduct of magnesium halides particle.
In the present invention, the preparation method of described adduct of magnesium halides comprises the adduct of magnesium halides that preparation is liquid, and this liquid adduct of magnesium halides is shaped, thereby obtains spherical adduct of magnesium halides.Can adopt various conventional methods to prepare the adduct of magnesium halides of described liquid state according to the present invention.
In one embodiment of the invention, the method for preparing liquid adduct of magnesium halides comprises: by MgX
1y and ethanol, LB
1, LB
2and LB
3mix, and by the mixture heating obtaining, to obtain described liquid adduct of magnesium halides.
According to the preparation method of adduct of magnesium halides of the present invention, MgX
1y, LB
1, LB
2and LB
3identical with definition above, do not repeat them here.
According to the preparation method of adduct of magnesium halides of the present invention, MgX
1y, ethanol, LB
1, LB
2and LB
3consumption can carry out appropriate selection according to the composition of adduct of magnesium halides of expection, as long as MgX
1y, ethanol, LB
1, LB
2and LB
3consumption can make the composition of the adduct of magnesium halides finally obtaining meet the demands.Usually, the MgX in magnesium with respect to 1 mole
1y, the amount of ethanol can be 1-5.5 mole, LB
1amount can be 0.005-2.3 mole, LB
2amount can be 0.0005-0.32 mole, LB
3amount can be 0.0005-0.32 mole; Preferably, the MgX in magnesium with respect to 1 mole
1y, the amount of ethanol is 2-3.7 mole, LB
1amount be 0.01-0.85 mole, LB
2amount be 0.001-0.12 mole, LB
3amount be 0.001-0.12 mole; More preferably, the MgX in magnesium with respect to 1 mole
1y, the amount of ethanol is 2.4-3.7 mole, LB
1amount be 0.03-0.65 mole, LB
2amount be 0.003-0.075 mole, LB
3amount be 0.003-0.075 mole.
According to the preparation method of adduct of magnesium halides of the present invention, for by MgX
1y and ethanol, LB
1, LB
2and LB
3blend heated condition be not particularly limited, as long as the condition of described heating makes MgX
1y can with ethanol, LB
1, LB
2and LB
3react, thereby form liquid adduct of magnesium halides.Usually, the condition of described heating can comprise: temperature can be 80-140 ℃, and the time can be 0.5-4 hour.
In another embodiment of the invention, the method for preparing liquid adduct of magnesium halides comprises: by MgX
1y and ethanol, under hydrolysising condition, can form LB
1material, hydrolysis and/or alcoholysis conditions under can form LB
2material and hydrolysis and/or alcoholysis conditions under can form LB
3material mix, and by the mixture heating obtaining, to obtain liquid adduct of magnesium halides.
In this embodiment, MgX
1y, ethanol, under hydrolysising condition, can form LB
1material, hydrolysis and/or alcoholysis conditions under can form LB
2material and hydrolysis and/or alcoholysis conditions under can form LB
3amount of substance so that expection adduct of magnesium halides in, MgX
1y, ethanol, LB
1, LB
2and LB
3amount meet the demands and be as the criterion.Usually, the MgX in magnesium with respect to 1 mole
1y, the amount of ethanol is 1-5.5 mole, describedly under hydrolysising condition, can form LB
1amount of substance be 0.0025-1.2 mole, described hydrolysis and/or alcoholysis conditions under can form LB
2amount of substance be 0.0005-0.32 mole, described hydrolysis and/or alcoholysis conditions under can form LB
3amount of substance be 0.0005-0.32 mole; Preferably, the MgX in magnesium with respect to 1 mole
1y, the amount of ethanol is 2-3.7 mole, describedly under hydrolysising condition, can form LB
1amount of substance be 0.005-0.42 mole, described hydrolysis and/or alcoholysis conditions under can form LB
2amount of substance be 0.001-0.12 mole, described hydrolysis and/or alcoholysis conditions under can form LB
3amount of substance be 0.001-0.12 mole; More preferably, the MgX in magnesium with respect to 1 mole
1y, the amount of ethanol is 2.4-3.7 mole, describedly under hydrolysising condition, can form LB
1amount of substance be 0.015-0.32 mole, described hydrolysis and/or alcoholysis conditions under can form LB
2amount of substance be 0.003-0.075 mole, described hydrolysis and/or alcoholysis conditions under can form LB
3amount of substance be 0.003-0.075 mole.
According to the preparation method of adduct of magnesium halides of the present invention, describedly under hydrolysising condition, can form LB
1material can be known to the skilled person variously can form LB by hydrolysis reaction
1material.For example: at LB
1for R
7when OH, describedly under hydrolysising condition, can form LB
1material can be the compound shown in formula VII,
In formula VII, R
7for methyl, C
3-C
20alkyl or the C being replaced by heteroatom group
1-C
20alkyl; R
aand R
bhydrogen, C respectively do for oneself
1-C
10straight or branched alkyl, C
3-C
10replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one; Or, R
aand R
bbonding mutually, to form ring.
Preferably, in formula VII, R
7for methyl, C
3-C
10alkyl, or quilt-NH
2,-NHR
7' and-C of one or more replacements in OH
1-C
10alkyl; R
7' be C
1-C
5straight or branched alkyl; R
aand R
bhydrogen, C respectively do for oneself
1-C
6straight or branched alkyl and C
3-C
6replacement or unsubstituted cycloalkyl in one.
More preferably, in formula VII, R
7for methyl, C
3-C
10straight or branched alkyl, C
6-C
10replacement or unsubstituted aryl or quilt-NH
2and/or-OH replace C
1-C
10straight or branched alkyl; R
aand R
bhydrogen and C respectively do for oneself
1-C
6straight or branched alkyl in one.
Further preferably, in formula VII, R
7for the one in methyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, n-hexyl, n-octyl, 2-ethylhexyl, 2-hydroxyethyl, 3-hydroxypropyl and phenyl; R
aand R
bthe one of respectively doing for oneself in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and isobutyl-.
According to the preparation method of adduct of magnesium halides of the present invention, describedly under hydrolysising condition, can form LB
1material specific examples can for but be not limited to: 2,2-dimethoxypropane, 2,2-dimethoxy normal butane, 2,2-dimethoxy Skellysolve A, 3,3-dimethoxy Skellysolve A, 2,2-(2-hydroxy ethoxy) propane and 2,2-phenoxypropane.
According to the preparation method of adduct of magnesium halides of the present invention, described hydrolysis and/or alcoholysis conditions under can form LB
2material can be known to the skilled person various can by hydrolysis and/or alcoholysis reaction form LB
2material.For example: at LB
2during for alkoxybenzoic acid ester based compound shown in the alkoxybenzoic acid based compound shown in formula III or formula III, describedly under hydrolysis and/or alcoholysis conditions, can form LB
2material can be the alkoxy benzene formyl chloride based compound shown in formula VIII,
In formula VIII, R
2, R
3, R
4and R
5hydrogen, halogen, nitro, C respectively do for oneself
1-C
20straight or branched alkyl, C
3-C
20replacement or unsubstituted cycloalkyl, C
6-C
20replacement or unsubstituted aryl and C
7-C
20replacement or unsubstituted aralkyl in one; Or, R
2, R
3, R
4and R
5in two or more mutual bondings, to form ring;
R
6for C
1-C
20straight or branched alkyl, C
3-C
20replacement or unsubstituted cycloalkyl, C
6-C
20replacement or unsubstituted aryl and C
7-C
20replacement or unsubstituted aralkyl in one.
Preferably, in formula VIII, R
2, R
3, R
4and R
5hydrogen, C respectively do for oneself
1-C
8straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
R
6for C
1-C
6straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one.
More preferably, in formula VIII, R
2, R
3, R
4and R
5the one of respectively doing for oneself in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and tolyl;
R
6for the one in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and styroyl.
According to the preparation method of adduct of magnesium halides of the present invention, described hydrolysis and/or alcoholysis conditions under can form LB
2material while being the alkoxy benzene formyl chloride based compound shown in formula VIII, describedly under hydrolysis and/or alcoholysis conditions, can form LB
2the more preferably one in 4-alkoxy benzene formyl chloride based compound and 2-alkoxy benzene formyl chloride based compound of material; More preferably 2-alkoxy benzene formyl chloride based compound.
According to the preparation method of adduct of magnesium halides of the present invention, described hydrolysis and/or alcoholysis conditions under can form LB
3material can be known to the skilled person various can hydrolysis and/or alcoholysis conditions under can form LB
3material.For example: at LB
3during for hydroxybenzoate based compound shown in the hydroxy-benzoic acid based compound shown in formula IV or formula IV, describedly under hydrolysis and/or alcoholysis conditions, can form LB
3material can be the (2-hydroxybenzoyl) based compound shown in the alkoxy benzene formyl based compound shown in formula VIIII or formula VIIII,
In formula VIIII, R
1' be hydrogen, hydroxyl, halogen, C
1-C
20straight or branched alkoxyl group, C
3-C
20unsubstituted cycloalkyloxy, the C of replacement
6-C
20replacement or unsubstituted aryloxy and C
7-C
20replacement or unsubstituted aralkoxy in one;
R
2, R
3, R
4and R
5hydrogen, halogen, nitro, C respectively do for oneself
1-C
20straight or branched alkyl, C
3-C
20unsubstituted cycloalkyl, the C of replacement
6-C
20replacement or unsubstituted aryl and C
7-C
20replacement or unsubstituted aralkyl in one; Or, R
2, R
3, R
4and R
5in two or more mutual bondings, to form ring;
R
6for hydrogen, C
1-C
20straight or branched alkyl, C
3-C
20replacement or unsubstituted cycloalkyl, C
6-C
20replacement or unsubstituted aryl and C
7-C
20replacement or unsubstituted aralkyl in one.
Preferably, in formula VIIII, R
1' be hydrogen, hydroxyl, halogen, C
1-C
6straight or branched alkoxyl group, C
3-C
6unsubstituted cycloalkyloxy, the C of replacement
6-C
10replacement or unsubstituted aryloxy and C
7-C
10replacement or unsubstituted aralkoxy in one;
R
2, R
3, R
4and R
5hydrogen, C respectively do for oneself
1-C
8straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
R
6for hydrogen, C
1-C
6straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one.
More preferably, in formula VIIII, R
1' be the one in hydrogen, hydroxyl, chlorine, bromine, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, positive hexyloxy, benzyloxy and benzene oxyethyl group;
R
2, R
3, R
4and R
5the one of respectively doing for oneself in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and tolyl;
R
6for the one in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and styroyl.
According to the preparation method of adduct of magnesium halides of the present invention, described hydrolysis and/or alcoholysis conditions under can form LB
3material while being the (2-hydroxybenzoyl) based compound shown in the alkoxy benzene formyl based compound shown in VIIII or VIIII, describedly under hydrolysis and/or alcoholysis conditions, can form LB
3the more preferably one in 4-alkoxy benzene formyl based compound, 2-alkoxy benzene formyl based compound, 4-(2-hydroxybenzoyl) based compound and 2-(2-hydroxybenzoyl) based compound of material; The more preferably one in 2-alkoxy benzene formyl based compound and 2-(2-hydroxybenzoyl) based compound.
According to the preparation method of adduct of magnesium halides of the present invention, described hydrolysis and/or alcoholysis conditions under can form LB
3material and described hydrolysis and/or alcoholysis conditions under can form LB
2material can be identical, can be also different, be preferably identical.
According to the preparation method of adduct of magnesium halides of the present invention, term " hydrolysis " refer to utilize water by material decomposition to form the process of novel substance, described hydrolysis can be carried out well known to a person skilled in the art under condition, for example: the temperature of described hydrolysis can be 60-150 ℃, the time can be 0.5-4 hour.
According to the preparation method of adduct of magnesium halides of the present invention, the required water of the reaction that is hydrolyzed can be the water in various sources.Due to MgX
1y, ethanol, under hydrolysising condition, can form LB
1material, hydrolysis and/or alcoholysis conditions under can form LB
2material and hydrolysis and/or alcoholysis conditions under can form LB
3material all may be with water, particularly MgX
1y and ethanol, usually, for anhydrous MgX
1y, its water-content is 0.1-1.5wt%; Water-content in analytically pure dehydrated alcohol is 20-600ppm.The present inventor finds in practice process, at anhydrous MgX
1the water-content of Y and the water-content of dehydrated alcohol respectively within above-mentioned scope time, can guarantee that hydrolysis reaction carries out smoothly.Therefore described water can be for coming from MgX
1water in Y and ethanol.
According to the preparation method of adduct of magnesium halides of the present invention, term " alcoholysis " refer to utilize alcohol by material decomposition to form the process of new material, described alcoholysis can be carried out well known to a person skilled in the art under condition, for example: the temperature of described alcoholysis can be 60-150 ℃, the time can be 0.5-4 hour.
According to the preparation method of adduct of magnesium halides of the present invention, carrying out alcoholysis reaction alcohol used can be the alcohol in various sources.Because the preparation method of the adduct of magnesium halides according to the present invention need to add ethanol, the alcohol that therefore carries out alcoholysis reaction is preferably ethanol.
According to the preparation method of adduct of magnesium halides of the present invention, for by MgX
1y and ethanol, under hydrolysising condition, can form LB
1material, hydrolysis and/or alcoholysis conditions under can form LB
2material and hydrolysis and/or alcoholysis conditions under can form LB
3the mixture heating of material, be not particularly limited with the condition of reacting and form liquid adduct of magnesium halides, as long as the condition of described heating is enough to form liquid adduct of magnesium halides.Usually, the condition of described heating can comprise: temperature is 80-140 ℃, and the reaction times is 0.5-4 hour.
Further be included under inert liquid medium exists according to the preparation method of adduct of magnesium halides of the present invention, by described be liquid adduct of magnesium halides emulsification, and by emulsification product quenching shaping, obtain spherical adduct of magnesium halides particle.
Can not there is not chemically interactive liquid medium with adduct of magnesium halides for conventional various in this area in described inert liquid medium, for example: silicone oil and/or hydrocarbon system solvent.Particularly, described inert liquid medium can be one or more in kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
According to the preparation method of adduct of magnesium halides of the present invention, the consumption of described inert liquid medium can be according to MgX
1the concrete consumption of Y is selected.Usually, the MgX in magnesium with respect to 1 mole
1y, the consumption of inert liquid medium is 0.2-13L; Preferably, the MgX in magnesium with respect to 1 mole
1y, the consumption of inert liquid medium is 0.6-6.5L.
According to the preparation method of adduct of magnesium halides of the present invention, described liquid adduct of magnesium halides can be mixed with inert liquid medium, then by the emulsifying mixture obtaining, thereby realize the adduct of magnesium halides emulsification of described liquid state.
According to the preparation method of adduct of magnesium halides of the present invention, can also using described part inert liquid medium as preparation described liquid adduct of magnesium halides reaction medium (, by described part inert liquid medium and MgX
1y, ethanol, LB
1, LB
2and LB
3mix, or by described part inert liquid medium and MgX
1y, ethanol, under hydrolysising condition, can form LB
1material, hydrolysis and/or alcoholysis conditions under can form LB
2material and hydrolysis and/or alcoholysis conditions under can form LB
3material mix), thereby obtain the mixed solution that contains liquid adduct of magnesium halides, then this mixed solution is mixed to also emulsification with the inert liquid medium of remainder, and then realization is by the adduct of magnesium halides emulsification of described liquid state.
According to the preparation method of adduct of magnesium halides of the present invention, also can be using whole described inert liquid mediums as the reaction medium of preparing described liquid adduct of magnesium halides, thereby obtain the mixed solution that contains liquid adduct of magnesium halides, and by this mixed solution emulsification, and then realize the adduct of magnesium halides emulsification of described liquid state.
According to the preparation method of adduct of magnesium halides of the present invention, while needs, also optionally in described inert liquid medium, add some tensio-active agents, as smooth in glycerin fatty acid ester, lipid acid sorb, polysorbate, Soxylat A 25-7 or Pluronic F68.The consumption of described tensio-active agent can be the conventional amount used of this area, for example: with respect to the MgX in magnesium of 1 mole
1y, the consumption of described tensio-active agent can be 0.001-1 mole.
According to the preparation method of adduct of magnesium halides of the present invention, can adopt well known to a person skilled in the art the whole bag of tricks by described for liquid adduct of magnesium halides emulsification, for example: can be under inert liquid medium exists, carry out high speed shear by described for liquid adduct of magnesium halides, thus by described be liquid adduct of magnesium halides emulsification.The method of described high speed shear is known in those skilled in the art, for example: the disclosed high-speed mixing method of CN1151183C (, liquid adduct of magnesium halides being stirred with the speed of 2000-5000 rev/min in inert liquid medium); CN1267508C is disclosed to be rotated the mixture of liquid adduct of magnesium halides and inert liquid medium in hypergravity bed, and (speed of rotation can be 100-3000 rev/min) disperses; The disclosed mixture by liquid adduct of magnesium halides and silicone oil and white oil of CN1463990A is the speed output with 1500-8000 rev/min with mulser; US6020279 is disclosed will contain the emulsifying mixture of liquid adduct of magnesium halides by spray method.
According to the preparation method of adduct of magnesium halides of the present invention, can adopt the method for well known to a person skilled in the art that emulsification product quenching is shaped, thereby obtain spherical adduct of magnesium halides.For example: can by described emulsification product is transferred to method in liquid cooling medium by described emulsification product quenching to be shaped.
According to the preparation method of adduct of magnesium halides of the present invention, can not there is not chemically interactive liquid medium with adduct of magnesium halides for conventional various in this area in described liquid cooling medium.For example, described liquid cooling medium can be unreactive hydrocarbons series solvent.The specific examples of described liquid cooling medium can include but not limited to: Skellysolve A, normal hexane, normal heptane, gasoline or petrol ether.
According to the preparation method of adduct of magnesium halides of the present invention, the temperature of described liquid cooling medium with can make described emulsification product cooling and be shaped be as the criterion.Usually, the temperature of described liquid cooling medium can be-50 ℃ to 0 ℃, is preferably-40 ℃ to-20 ℃.Consumption for described heat-eliminating medium has no particular limits, as long as the consumption of described heat-eliminating medium is enough to cooling emulsification product and shaping.Particularly, the volume ratio of described heat-eliminating medium and described emulsification product is 1-15: 1, be preferably 2-9: 1.
Can also comprise that according to the preparation method of adduct of magnesium halides of the present invention the spherical adduct of magnesium halides particle obtaining being shaped through chilling washs and is dried.Can adopt the method for well known to a person skilled in the art that the spherical adduct of magnesium halides particle obtaining is washed, for example, can adopt unreactive hydrocarbons series solvent (for example: Skellysolve A, normal hexane, normal heptane, sherwood oil and gasoline) to wash the spherical adduct of magnesium halides obtaining.The present invention is not particularly limited for described dry condition, and for example: described dry temperature can be 20-70 ℃, the described dry time can be 0.5-10 hour.According to the present invention, described dry can carrying out under the condition of normal pressure or reduction pressure.
Use the adduct of magnesium halides shown in formula I according to the preparation of the catalyst component for olefinic polymerization of the present invention, the particle shape of this adduct of magnesium halides is good, between particle, there is not adhesion phenomenon, and without irregular particle, thereby make the particle form of catalyst component of the present invention good, without opposite sex material, and then the olefin polymerization catalyst system of being prepared by described catalyst component is in olefinic polyreaction, can prepare the polymkeric substance that particle shape is good.With prior art for compared with the catalyst component of olefinic polymerization, use the catalyst component of the present invention of adduct of magnesium halides shown in formula I, when for olefinic polyreaction, in fact there is the performance of improvement,, in keeping compared with high polymerization activity, demonstrate excellent hydrogen response and high stereotaxis ability, obtained hydrogen and adjusted well balanced between ability and stereotaxis ability.Therefore, the present invention is not particularly limited for kind and the consumption of the titanium compound in described catalyst component and optional internal electron donor compound, can be this area conventional various titanium compounds and internal electron donor compound.
Usually, according to the catalyst component for olefinic polymerization of the present invention, wherein said titanium compound can be three halogenated titaniums and general formula Ti (OR ')
4-mx '
mone or more in shown titanium compound, in this general formula, R ' can be C
1-C
10alkyl, X ' can be halogen, m can be the integer of 0-4.Preferably, described titanium compound is one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, chlorine three titanium butoxide, dichloro dibutoxy titanium, trichlorine one titanium butoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium and titanous chloride.More preferably, described titanium compound is titanium tetrachloride.
Can adopt method well known in the art to prepare according to the catalyst component for olefinic polymerization of the present invention, for example: can be by described adduct of magnesium halides particle is directly contacted with titanium compound, to react.Preferably, the preparation method of the described catalyst component for olefinic polymerization of preparation comprises: described adduct of magnesium halides is suspended in to the mixed solution of cold titanium compound or titanium compound and inert solvent, and (temperature of the mixture of described titanium compound or titanium compound and inert solvent can be-40 ℃ to 0 ℃, be preferably-25 ℃ to-15 ℃), then the mixture obtaining is heated to 40-130 ℃, preferably be heated to 80-130 ℃, and maintain 0.5-2 hour under said temperature, then carry out solid-liquid separation and collect solid; Then, the solid suspension obtaining, in titanium compound, and is heated to 60-130 ℃ by the mixture obtaining, preferably be heated to 80-130 ℃, and maintain 0.5-2 hour under said temperature, then carry out solid-liquid separation and collect solid, this operation can be carried out one or many, preferably carries out 2-4 time; Finally, wash the solid obtaining with inert solvent, described inert solvent is preferably aliphatic hydrocarbon or aromatic hydrocarbons, for example: normal hexane, normal heptane, octane, n-decane and toluene.
Usually, according to the needs of practical application, particularly, for the catalyst component for propylene polymerization, in order to obtain the propene polymer of high isotactic, in the preparation process of described catalyst component, can also optionally add at least one internal electron donor compound.According to the present invention, adding of described internal electron donor compound can be before adduct of magnesium halides particle reacts with titanium compound, in reaction or carry out after reaction, preferably when adduct of magnesium halides particle reacts with titanium compound, carry out.
According to the catalyst component for olefinic polymerization of the present invention, described internal electron donor compound can be the conventional various internal electron donor compounds in this area, for example: described internal electron donor compound can be one or more in ester, ether, ketone, amine and silane.Preferably, described internal electron donor compound is one or more in ester and diether type compound.
In the present invention, described ester can be one or more in monobasic aliphatic carboxylic acid esters,, polyhydric aliphatic family carboxylicesters, monobasic aromatic carboxylic acid esters, polynary aromatic carboxylic acid esters and diol ester.In the present invention, described ester is preferably polynary aromatic carboxylic acid esters.
In the present invention, term " monobasic aliphatic carboxylic acid esters, " refers to the compound being formed by esterification by monobasic aliphatic carboxylic acid and monohydroxy-alcohol.Term " polyhydric aliphatic family carboxylicesters " refers to the compound being formed by esterification by polyhydric aliphatic family carboxylic acid and monohydroxy-alcohol.Term " monobasic aromatic carboxylic acid esters " refers to the compound being formed by esterification by monobasic aromatic carboxylic acid and monohydroxy-alcohol.Term " polynary aromatic carboxylic acid esters " refers to the compound that polynary aromatic carboxylic acid and monohydroxy-alcohol form by esterification.
In the present invention, the example of described monobasic aliphatic carboxylic acid esters,, polyhydric aliphatic family carboxylicesters, monobasic aromatic carboxylic acid esters and polynary aromatic carboxylic acid esters can be benzoic ether, phthalic ester, malonic ester, succinate, glutarate, pivalate and carbonic ether; Be preferably phenylformic acid alkyl ester, O-phthalic acid alkyl ester, propanedioic acid alkyl ester, succsinic acid alkyl ester, glutaric acid alky ester, new pentane acid alkyl ester and alkyl carbonate.
Particularly, in the present invention, described monobasic aliphatic carboxylic acid esters, polyhydric aliphatic family carboxylicesters, the example of monobasic aromatic carboxylic acid esters and polynary aromatic carboxylic acid esters can be but be not limited to: ethyl benzoate, diethyl phthalate, diisobutyl phthalate, n-butyl phthalate, dimixo-octyl phthalate, dinoctyl phthalate, diethyl malonate, propanedioic acid di-n-butyl, propanedioic acid diisobutyl ester, 2,3-di-isopropyl ethyl succinate, 2,3-di-isopropyl di-iso-octyl succinate, 2,3-di-isopropyl dibutyl succinate, 2,3-di-isopropyl Succinic acid dimethylester, 2,2-dimethyl succinate diisobutyl ester, 2-Ethyl-2-Methyl di-iso-octyl succinate, 2-Ethyl-2-Methyl ethyl succinate, ethyl glutarate, pentanedioic acid di-n-butyl, pentanedioic acid diisobutyl ester, methylcarbonate, diethyl carbonate, carbonic acid diisobutyl ester, diethylene adipate, Di-n-butyl Adipate, ethyl sebacate, n-butyl sebacate, diethyl maleate, maleic acid n-butyl, naphthalene dicarboxylic acids diethyl ester, naphthalene dicarboxylic acids di-n-butyl, triethyl trimellitate, trimellitic acid tri-n-butyl, biphenyl three triethylenetetraminehexaacetic acid esters, connection benzenetricarboxylic acid tri-n-butyl, pyromellitic acid tetra-ethyl ester and the positive butyl ester of pyromellitic acid four.
In the present invention, term " diol ester " refers to the compound that dibasic alcohol and monocarboxylic acid or polycarboxylic acid form by esterification.For example, described diol ester can be the compound shown in formula X:
In formula X, R
i, R
iI, R
iII, R
iV, R
vand R
vIhydrogen, C respectively do for oneself
1-C
10replacement or unsubstituted aliphatic group, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one; Or R
i, R
iI, R
iII, R
iV, R
vand R
vIin two or more mutual bondings, to form ring; R
vIIand R
vIIIc respectively does for oneself
1-C
10straight or branched alkyl, C
3-C
20replacement or unsubstituted cycloalkyl, C
6-C
20replacement or unsubstituted aryl and C
7-C
20replacement or unsubstituted aryl aliphatic group in one.
Preferably, R
i, R
iI, R
iII, R
iV, R
vand R
vIhydrogen, C respectively do for oneself
1-C
6alkyl, the C of straight or branched
2-C
6thiazolinyl, the C of straight or branched
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one; Or, R
i, R
iI, R
iII, R
iV, R
vand R
vIin two or more mutual bondings, to form ring; R
vIIand R
vIIIc respectively does for oneself
1-C
6straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl, C
7-C
10replacement or unsubstituted aralkyl and C
7-C
10replacement or unsubstituted arylalkenyl in one.
More preferably, R
i, R
iI, R
vand R
vIin at least one be hydrogen, and R
i, R
iI, R
vand R
vIwhen different, be hydrogen.
Further preferably, R
iand R
iIin have one at least for hydrogen, and at R
iand R
iIin only have one when the hydrogen, R
iand R
iIin another group be the one in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl and halogenophenyl; R
vand R
vIin have one at least for hydrogen, and at R
vand R
vIin only have one when the hydrogen, R
vand R
vIin another group be the one in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl and halogenophenyl; R
iIIand R
iVthe one of respectively doing for oneself in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, allyl group, n-pentyl, isopentyl and n-hexyl, or R
iIIand R
iVmutually be bonded together to form and replace or unsubstituted fluorenyl; R
vIIand R
vIIIthe one of respectively doing for oneself in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, cyclopentyl, cyclohexyl, phenyl, halogenophenyl, tolyl, halogenated methyl phenyl, benzyl, styroyl and styryl.
In the present invention, the specific examples of described diol ester can be but be not limited to: 1,3-PD dibenzoate, 2-methyl isophthalic acid, ammediol dibenzoate, 2-ethyl-1,3-PD dibenzoate, 2，2-dimethyl-1，3-propanediol dibenzoate, (R)-1-phenyl-1,3-PD dibenzoate, 1,3-phenylbenzene-1,3-PD dibenzoate, 1,3-phenylbenzene-1,3-PD, two n Propanoic acid esters, 1,3-phenylbenzene-2-methyl isophthalic acid, ammediol two n Propanoic acid esters, 1,3-phenylbenzene-2-methyl isophthalic acid, ammediol diacetate esters, 1,3-phenylbenzene-2，2-dimethyl-1，3-propanediol dibenzoate, 1,3-phenylbenzene-2，2-dimethyl-1，3-propanediol, two n Propanoic acid esters, 1,3-di-t-butyl-2-ethyl-1,3-PD dibenzoate, 1,3-phenylbenzene-1,3-PD diacetate esters, 1,3-di-isopropyl-1,3-PD two (4-n-butylbenzene formic acid) ester, 1-phenyl-2-amino-1,3-propanediol dibenzoate, 1-phenyl-2-methyl isophthalic acid, 3-butyleneglycol dibenzoate, 1-phenyl-2-methyl isophthalic acid, 3-butyleneglycol two pivalates, 3-normal-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, (2S, 4S)-(+)-2,4-pentanediol dibenzoate, (2R, 4R)-(+)-2,4-pentanediol dibenzoate, 2,4-pentanediol two (Chlorodracylic acid) ester, 2,4-pentanediol two (m-chlorobenzoic acid) ester, 2,4-pentanediol two (parabromobenzoic acid) ester, 2,4-pentanediol two (o-bromobenzoic acid) ester, 2,4-pentanediol two (p-methylbenzoic acid) ester, 2,4-pentanediol two (p-tert-butyl benzoic acid) ester, 2,4-pentanediol two (aligning butylbenzoic acid) ester, 2-methyl isophthalic acid, 3-pentanediol two (Chlorodracylic acid) ester, 2-methyl isophthalic acid, 3-pentanediol two (p-methylbenzoic acid) ester, 2-normal-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 two pivalates, 2-methyl-3-cinnamoyloxy group-1-Pentyl alcohol benzoic ether, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-3-cinnamoyloxy group-1-Pentyl alcohol benzoic ether, 2-ethyl-1,3-pentanediol dibenzoate, 2-normal-butyl-1,3-pentanediol dibenzoate, 2-allyl group-1,3-pentanediol dibenzoate, 2-methyl isophthalic acid, 3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-n-propyl-1,3-pentanediol dibenzoate, 2-normal-butyl-1,3-pentanediol dibenzoate, 2,2-diη-propyl-1,3-pentanediol dibenzoate, 1,3-pentanediol two (Chlorodracylic 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-pentanediol two (p-tert-butyl benzoic acid) ester, 1,3-pentanediol two (to butylbenzoic acid) ester, 3-cinnamoyloxy group-1-Pentyl alcohol benzoic ether, 1,3-pentanediol, two laurates, 1,3-pentanediol, two n Propanoic acid esters, 2-ethyl-1,3-pentanediol dibenzoate, 2-normal-butyl-1,3-pentanediol dibenzoate, 2-allyl group-1,3-pentanediol dibenzoate, 2,2,4-trimethylammonium-1,3-pentanediol di-isopropyl manthanoate, 1-trifluoromethyl-3-methyl-2,4-pentanediol dibenzoate, 2,4-pentanediol two is to fluoro methyl benzoic acid ester, 2,4-pentanediol two (2-furancarboxylic acid) ester, 2-methyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 3-methyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 4-methyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 5-methyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 6-methyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 3-ethyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 4-ethyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 5-ethyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 6-ethyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 3-n-propyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 4-n-propyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 5-n-propyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 6-n-propyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 3-normal-butyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 4-normal-butyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 5-normal-butyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 6-normal-butyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 3,5-dimethyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 3,5-diethyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 3,5-diη-propyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 3,5-di-n-butyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 3,3-dimethyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 3,3-diethyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 3,3-diη-propyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 3,3-di-n-butyl-6-(1-nhepene) base-2,4-heptanediol dibenzoate, 3-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 5-ethyl-3,5-heptanediol dibenzoate, 3-n-propyl-3,5-heptanediol dibenzoate, 4-n-propyl-3,5-heptanediol dibenzoate, 3-normal-butyl-3,5-heptanediol dibenzoate, 2,3-dimethyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,5-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 3,5-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 4,5-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-3-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-5-ethyl-3,5-heptanediol dibenzoate, 3-methyl-3-ethyl-3,5-heptanediol dibenzoate, 3-methyl-4-ethyl-3,5-heptanediol dibenzoate, 3-methyl-5-ethyl-3,5-heptanediol dibenzoate, 4-methyl-3-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, two (benzoxy ylmethyl) fluorenes of 9,9-, two ((meta-methoxy benzoyloxy) methyl) fluorenes of 9,9-, two ((m-chloro benzoyloxy) methyl) fluorenes of 9,9-, two ((to the chlorobenzoyl oxygen base) methyl) fluorenes of 9,9-, two (cinnamoyloxy group methyl) fluorenes of 9,9-, 9-(benzoxy ylmethyl)-9-(propionyloxy ylmethyl) fluorenes, two (propionyloxy methyl) fluorenes of 9,9-, two (acryloyl-oxy ylmethyl) fluorenes of 9,9-and two (oxy acid methyl neopentyl) fluorenes of 9,9-.
CN1213080C, CN1169845C, WO 03/068828 and WO 03/068723 disclose above-mentioned diol ester compound, and its associated viscera is incorporated herein the present invention as a reference.
According to the present invention, described diether type compound can be the conventional various diether type compounds that can serve as olefin polymerization catalysis internal electron donor compound in this area.For example, described diether type compound can be 1 shown in general formula X I, 3-diether type compound:
In formula XI, R
i, R
iI, R
iII, R
iV, R
vand R
vIhydrogen, halogen, C respectively do for oneself
1-C
20straight or branched alkyl, C
3-C
20replacement or unsubstituted cycloalkyl, C
6-C
20replacement or unsubstituted aryl and C
7-C
20replacement or unsubstituted aralkyl in one, R
vIIand R
vIIIc respectively does for oneself
1-C
20straight or branched alkyl, C
3-C
20replacement or unsubstituted cycloalkyl, C
6-C
20replacement or unsubstituted aryl and C
7-C
20replacement or unsubstituted aralkyl in one.In the present invention, R
i, R
iI, R
iII, R
iV, R
vand R
vIin two or more bondings mutually, to form ring.
Preferably, in formula XI: R
i, R
iI, R
vand R
vIfor hydrogen; R
vIIand R
vIIIc respectively does for oneself
1-C
4straight or branched alkyl, more preferably methyl; R
iIIfor methyl, ethyl, n-propyl or sec.-propyl, R
iVfor the one in ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, isopentyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl and benzyl; Or, R
iIIfor hydrogen, R
iVfor the one in ethyl, normal-butyl, sec-butyl, the tertiary butyl, 2-ethylhexyl, cyclohexyl ethyl, diphenyl methyl, rubigan, 1-naphthyl and 1-decahydro naphthyl; Or, R
iIIand R
iVidentical, and be the one in ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, neo-pentyl, phenyl, benzyl, cyclohexyl and cyclopentyl; Or, R
iIIand R
iVbonding mutually, to form cyclopentadienyl, fluorenyl or indenyl.
CN1015062B and CN1121368C disclose above-mentioned diether type compound, and its disclosed associated viscera is all introduced the present invention as a reference.
According to the present invention, the consumption of the consumption of described adduct of magnesium halides, the consumption of titanium compound and internal electron donor compound can carry out appropriate selection according to the composition of the catalyst component for olefinic polymerization of expection.For example, the mol ratio of described titanium compound, internal electron donor compound and described adduct of magnesium halides can be 5-100: 0-0.5: 1; Be preferably 20-80: 0.05-0.35: 1, described titanium compound is in titanium elements, and described adduct of magnesium halides is in magnesium elements.In the present invention, the amount of titanium compound is the total amount that is included in the titanium compound using in preparation catalyst component process of the present invention.
Catalyst according to the invention component is suitable for for preparing olefin polymerization catalyst system.
The present invention further provides a kind of catalyst system for olefinic polymerization, described catalyst system comprises catalyst according to the invention component and one or more organo-aluminium compounds.
Composition and the preparation method of described catalyst component are described in detail above, do not repeat them here.
With prior art for compared with the catalyst system of olefinic polymerization, use the olefin polymerization catalyst system of the present invention of catalyst according to the invention component, when for olefinic polyreaction, in fact there is the performance of improvement,, in keeping compared with high polymerization activity, demonstrate excellent hydrogen response and high stereotaxis ability, obtained hydrogen and adjusted well balanced between ability and stereotaxis ability, and can prepare the polymkeric substance that particle shape is good.Therefore, the catalyst system for olefinic polymerization according to the present invention is all not particularly limited for kind and the consumption of organo-aluminium compound.
Described organo-aluminium compound can be the conventional various organo-aluminium compounds in this area.For example, described organo-aluminium compound can be alkylaluminium sesquichloride and general formula AlR
7r
8r
9shown in one or more in compound, in this general formula, R
7, R
8and R
9can be chlorine and C separately
1-C
8alkyl in one, and R
7, R
8and R
9in at least one be C
1-C
8alkyl.Preferably, described organo-aluminium compound is one or more in trialkyl aluminium compound, a chlorine aluminum dialkyl compound, dichloro one alkylaluminium cpd and alkylaluminium sesquichloride.More preferably, described organo-aluminium compound is triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminium, a chlorine di-n-hexyl aluminium, dichloro one aluminium triethyl, dichloro one aluminium isobutyl, dichloro one n-butylaluminum, dichloro one n-hexyl aluminium and Al
2et
3cl
3in one or more.
Usually, according to the catalyst system for olefinic polymerization of the present invention, described in the organo-aluminium compound of aluminium and can be as 1-2000 take the mol ratio of the catalyst component of titanium: 1, be preferably 20-700: 1.
For example, at alkene particularly the organic vertical structure polymerization of alpha-olefin (propylene or 1-butylene), according to the catalyst system for olefinic polymerization of the present invention can also comprise from Compound Phase as internal electron donor with or different electron donor compound as external donor compound.
Described external donor compound can be the conventional various external donor compounds in this area, for example: described external donor compound can be one or more in carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organo phosphorous compounds and silicoorganic compound.Preferably, described external electron donor is general formula R
a xr
b ysi (OR
c)
zshown silicoorganic compound, in this general formula, R
a, R
band R
cc respectively does for oneself
1-C
18alkyl or contain heteroatomic C
1-C
18alkyl; Respectively the do for oneself integer of 0-2 of x and y, the integer that z is 1-3, and x+y+z=4.More preferably, general formula R
a xr
b ysi (OR
c)
zin, R
aand R
bin at least one be selected from C
3-C
10containing or containing heteroatomic branched-chain alkyl, C
3-C
10containing or containing heteroatomic replacement or unsubstituted cycloalkyl and C
6-C
10replacement or unsubstituted aryl in one, R
cfor C
1-C
10alkyl, be preferably methyl; X is that 1, y is that 1, z is 2; Or, R
bfor C
3-C
10branched-chain alkyl or C
3-C
10cycloalkyl, and R
cfor methyl, x is that 0, y is that 1, z is 3.
In the present invention, the example of described silicoorganic compound can be but be not limited to: Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, normal-butyl cyclohexyl dimethoxy silane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane, (1, 1, the fluoro-2-propyl group of 1-tri-)-2-ethyl piperidine base dimethoxy silane, (1, 1, the fluoro-2-propyl group of 1-tri-)-methyl dimethoxysilane, cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane and tertiary hexyl Trimethoxy silane.
Usually, with respect to the organo-aluminium compound in aluminium of 1 mole, the consumption of described external donor compound can be 0.005-0.5 mole; Preferably, with respect to the organo-aluminium compound in aluminium of 1 mole, the consumption of described external donor compound is 0.01-0.4 mole.
According to the catalyst system for olefinic polymerization of the present invention, be in the situation of ester, particularly multi-carboxylate and diol ester at described internal electron donor, preferably using one or more in above-mentioned electron donor compound as external electron donor; Be ether at described internal electron donor, particularly 1 shown in formula XI, when 3-diether type compound, can not use external electron donor, and this is because the stereotaxis ability of catalyst system is enough high for the polymkeric substance for various uses.
Catalyst according to the invention system is suitable for the catalyst system as olefinic polyreaction.
The present invention also provides a kind of olefine polymerizing process, and the method is included under olefinic polymerization condition, and one or more alkene are contacted with catalyst system provided by the invention.
By using catalyst according to the invention system, can prepare the perfect polymkeric substance of particle form according to olefine polymerizing process of the present invention.Olefine polymerizing process of the present invention is not particularly limited for olefinic polymerization condition and the alkene using.
Usually, according to olefine polymerizing process of the present invention, described alkene can be general formula CH
2=CHR
13shown alkene, wherein, R
13can be hydrogen, C
1-C
12straight or branched alkyl and C
6-C
12replacement or unsubstituted aryl in one.According to olefine polymerizing process of the present invention, if desired, described alkene can also contain a small amount of diolefine.According to olefine polymerizing process of the present invention, described alkene is preferably propylene, or propylene and CH
2=CHR
13shown alkene, wherein, R
13for hydrogen and C
1-C
6straight or branched alkyl in one.
According to olefine polymerizing process of the present invention, described polymerization can be carried out according to the ordinary method of this area.For example, described polymerization can be mass polymerization, vapour phase polymerization, slurry polymerization or liquid phase body-gas phase polymerization mix.According to olefine polymerizing process of the present invention, described olefinic polymerization condition can be the normal condition of this area, and for example, polymerization temperature can be 0-150 ℃, is preferably 60-90 ℃; Polymerization pressure can be normal pressure or pressurization.
Describe the present invention in detail below in conjunction with embodiment, but be not used for limiting the present invention.
In following examples, the testing method relating to is as follows:
1, melt index (MI): measure according to the method stipulating in ASTM D1238-99.
2, polymkeric substance isotactic index (II): adopt normal heptane extraction process to measure (normal heptane boiling extracting 6 hours), concrete operations are: take the polymer samples that 2g is dry, be placed in the normal heptane extracting of seething with excitement 6 hours for Soxhlet extractor, then, residuum is dried to constant weight, and the weight (g) of gained residuum is isotactic index with 2 ratio.
3, the pattern of sample is observed by the opticmicroscope that to be purchased from the model of Nikon company be Eclipse E200.
4, adopt vapor-phase chromatography to measure ethanol, the LB in adduct of magnesium halides
1, LB
2and LB
3content, adopt chemical titration to measure the content of Mg in adduct of magnesium halides.
5, adopt the content of titanium in spectrophotometry catalyst component.
Embodiment 1
The present embodiment is used for explanation according to the catalyst component for olefinic polymerization of the present invention and catalyst system and application and olefine polymerizing process.
(1) preparation of adduct of magnesium halides
In the reactor of 500mL, add 150mL white oil, 30g Magnesium Chloride Anhydrous (being purchased the Xin Yitai factory from Fushun City), 50mL dehydrated alcohol (to be purchased from Beijing Chemical Plant, analytical pure), 4mL 2,2-Propanal dimethyl acetal (being purchased from Warner, Ningbo Chemical Co., Ltd.) and 1mL 2-methoxy benzoyl chloride (being purchased the CO.LTD from TOKYO KASEI KOGYO), be under agitation warming up to 120 ℃.After isothermal reaction 2 hours, mixture is pressed in the 300mL methyl-silicone oil (be purchased from DOW CORNING, viscosity is 300 centipoise/20 ℃) that is preheated to 120 ℃, stirs 30 minutes with the speed of 1600 revs/min, to carry out emulsification.Then, emulsification product is pressed in advance with nitrogen in the hexane of the 2L that is cooled to-30 ℃, carries out chilling shaping.Remove by filter liquid, the solid obtaining is washed 5 times with the hexane of 300mL, and in vacuum, be dried 3 hours at 35 ℃, thereby obtain spherical adduct of magnesium halides.The composition of this adduct of magnesium halides is as shown in table 1, and the particle morphology that employing observation by light microscope arrives as shown in Figure 1.
(2) preparation of catalyst component
In the glass reaction bottle of 300mL, under nitrogen protection condition, add successively 10mL hexane, 90mL titanium tetrachloride, be cooled to-20 ℃, the adduct of magnesium halides that adds 8.0g step (1) to prepare, and stir 30 minutes at-20 ℃.Then, be slowly warming up to 110 ℃, and in temperature-rise period, add 1.5mL diisobutyl phthalate.110 ℃ of isothermal reactions after 30 minutes, filtering liquid.Add 80mL titanium tetrachloride, be warming up to 120 ℃, 120 ℃ maintain 30 minutes after filtering liquid; Then, then add 80mL titanium tetrachloride, and be warming up to 120 ℃, 120 ℃ maintain 30 minutes after filtering liquid.Finally with the hexane of 60 ℃ to the solids wash 5 times (hexane consumption is 80mL/ time) obtaining; And vacuum-drying gained solids, thereby obtain spherical catalyst component.In this spherical catalyst component, the content of titanium is 2.8wt%, and the particle morphology that employing observation by light microscope arrives as shown in Figure 2.
(3) propylene polymerization A
Liquid phase bulk propylene polymerization carries out in the stainless steel autoclave of 5L.Under nitrogen protection, in reactor, add successively the hexane solution (concentration is 0.5mmol/mL) of 5mL triethyl aluminum, the hexane solution (concentration is 0.1mmol/mL) of 1mL Cyclohexyl Methyl Dimethoxysilane and spherical catalyst component prepared by 9mg step (2).Close autoclave, add 1.5L (standard volume) hydrogen and 2.3L liquid propene.Be warming up to 70 ℃, react 1 hour.Then, cooling, release, discharging, and be dried, thereby obtain polypropylene.
(4) propylene polymerization B
Adopt the method identical with (3) to carry out propylene polymerization, different, the consumption of hydrogen is 5.0L (standard volume).
Embodiment 2
The present embodiment is used for explanation according to the catalyst component for olefinic polymerization of the present invention and catalyst system and application and olefine polymerizing process.
(1) preparation of adduct of magnesium halides
Adopt the method identical with embodiment 1 to prepare spherical adduct of magnesium halides, different, the consumption of 2,2-dimethoxypropane is 9mL.The composition of this adduct of magnesium halides is as shown in table 1, and the particle morphology that employing observation by light microscope arrives as shown in Figure 3.
(2) preparation of catalyst component
Adopt the method identical with embodiment 1 to prepare spherical catalyst component, different, adduct of magnesium halides is adduct of magnesium halides prepared by embodiment 2 steps (1).In this spherical catalyst component, the content of titanium is 2.1wt%, and the particle morphology that employing observation by light microscope arrives as shown in Figure 4.
(3) propylene polymerization A
Adopt the method identical with (3) in embodiment 1 to carry out propylene polymerization, different, catalyst component is catalyst component prepared by above-mentioned steps (2).
(4) propylene polymerization B
Adopt the method identical with (4) in embodiment 1 to carry out propylene polymerization, different, catalyst component is catalyst component prepared by above-mentioned steps (2).
Comparative example 1
(1) preparation of adduct of magnesium halides
Adopt the method identical with embodiment 2 to prepare spherical adduct of magnesium halides, different, do not use 2,2-dimethoxypropane.The composition of this adduct of magnesium halides is as shown in table 1.
(2) preparation of catalyst component
Adopt the method identical with embodiment 1 to prepare spherical catalyst component, different, adduct of magnesium halides is adduct of magnesium halides prepared by comparative example 1 step (1).In this spherical catalyst component, the content of titanium is 2.4wt%.
(3) propylene polymerization A
Adopt the method identical with (3) in embodiment 1 to carry out propylene polymerization, different, catalyst component is catalyst component prepared by above-mentioned steps (2).
(4) propylene polymerization B
Adopt the method identical with (4) in embodiment 1 to carry out propylene polymerization, different, catalyst component is catalyst component prepared by above-mentioned steps (2).
Comparative example 2
(1) preparation of adduct of magnesium halides
Adopt the method identical with embodiment 2 to prepare spherical adduct of magnesium halides, different, do not use 2-methoxy benzoyl chloride.The composition of this adduct of magnesium halides is as shown in table 1, adopts observation by light microscope to the particle morphology arriving as shown in Figure 5.
(2) preparation of catalyst component
Adopt the method identical with embodiment 1 to prepare spherical catalyst component, different, adduct of magnesium halides is adduct of magnesium halides prepared by comparative example 2 steps (1).In this spherical catalyst component, the content of titanium is 2.6wt%, and the particle morphology that employing observation by light microscope arrives as shown in Figure 6.
(3) propylene polymerization A
Adopt the method identical with (3) in embodiment 1 to carry out propylene polymerization, different, catalyst component is catalyst component prepared by above-mentioned steps (2).
(4) propylene polymerization B
Adopt the method identical with (4) in embodiment 1 to carry out propylene polymerization, different, catalyst component is catalyst component prepared by above-mentioned steps (2).
Embodiment 3
The present embodiment is used for explanation according to the catalyst component for olefinic polymerization of the present invention and catalyst system and application and olefine polymerizing process.
(1) preparation of adduct of magnesium halides
In the reactor of 500mL, add 150mL white oil, 30g Magnesium Chloride Anhydrous, 50mL dehydrated alcohol, 6.0mL anhydrous methanol, 0.5mL 4-methoxybenzoic acid ethyl ester (being purchased the Chemical Co., Ltd. from A Faaisha (Tianjin)) and 0.5g 4-HBA ethyl ester (being purchased the Chemical Co., Ltd. from A Faaisha (Tianjin)), be under agitation warming up to 120 ℃.After isothermal reaction 2 hours, mixture is pressed in the 300mL methyl-silicone oil (be purchased from DOW CORNING, viscosity is 300 centipoise/20 ℃) that is preheated to 120 ℃, stirs 30 minutes with the speed of 1600 revs/min, to carry out emulsification.Then, emulsification product is pressed in advance with nitrogen in the 2L hexane that is cooled to-30 ℃, carries out chilling shaping.Remove by filter liquid, by the hexane washing of 300mL 5 times for the solid that obtains, and vacuum-drying 3 hours at 35 ℃, thereby obtain spherical adduct of magnesium halides.The composition of this adduct of magnesium halides is as shown in table 1.Adopt opticmicroscope to observe the particle morphology of the adduct of magnesium halides obtaining, find that this adduct of magnesium halides is spherical, without opposite sex material, and between particle without adhesion.
(2) preparation of catalyst component
Adopt the method identical with embodiment 1 to prepare spherical catalyst component, different, adduct of magnesium halides is adduct of magnesium halides prepared by embodiment 3 steps (1).In this spherical catalyst component, the content of titanium is 2.7wt%.Adopt opticmicroscope to observe the particle morphology of the catalyst component obtaining, find that solid particulate form is good, for spherical, without opposite sex material.
(3) propylene polymerization A
Adopt the method identical with (3) in embodiment 1 to carry out propylene polymerization, different, catalyst component is catalyst component prepared by above-mentioned steps (2).
(4) propylene polymerization B
Adopt the method identical with (4) in embodiment 1 to carry out propylene polymerization, different, catalyst component is catalyst component prepared by above-mentioned steps (2).
Comparative example 3
(1) preparation of adduct of magnesium halides
Adopt the method identical with embodiment 3 to prepare spherical adduct of magnesium halides, different, do not use methyl alcohol.The composition of this adduct of magnesium halides is as shown in table 1.
(2) preparation of catalyst component
Adopt the method identical with embodiment 1 to prepare spherical catalyst component, different, adduct of magnesium halides is adduct of magnesium halides prepared by comparative example 3 steps (1).In this spherical catalyst component, the content of titanium is 2.9wt%.
(3) propylene polymerization A
Adopt the method identical with (3) in embodiment 1 to carry out propylene polymerization, different, catalyst component is catalyst component prepared by above-mentioned steps (2).
(4) propylene polymerization B
Adopt the method identical with (4) in embodiment 1 to carry out propylene polymerization, different, catalyst component is catalyst component prepared by above-mentioned steps (2).
Embodiment 4
The present embodiment is used for explanation according to the catalyst component for olefinic polymerization of the present invention and catalyst system and application and olefine polymerizing process.
(1) preparation of adduct of magnesium halides
In the reactor of 500mL, add 150mL white oil, 30g Magnesium Chloride Anhydrous, 50mL dehydrated alcohol, 2.6mL anhydrous methanol, 0.5mL O-Anisic Acid ethyl ester (being purchased the Chemical Co., Ltd. from A Faaisha (Tianjin)) and 0.5mL 2 hydroxybenzoic acid ethyl ester (being purchased from Shanghai double happiness spices auxiliary agent company limited), be under agitation warming up to 120 ℃.After isothermal reaction 2 hours, mixture is pressed in the 300mL methyl-silicone oil (be purchased from DOW CORNING, viscosity is 300 centipoise/20 ℃) that is preheated to 120 ℃, stirs 30 minutes with the speed of 1600 revs/min, to carry out emulsification.Then, emulsification product is pressed in advance with nitrogen in the 2L hexane that is cooled to-30 ℃, carries out chilling shaping.Remove by filter liquid, by the hexane washing of 300mL 5 times for the solid that obtains, and vacuum-drying 3 hours at 35 ℃, thereby obtain spherical adduct of magnesium halides.The composition of this adduct of magnesium halides is as shown in table 1.Adopt opticmicroscope to observe the particle morphology of the adduct of magnesium halides obtaining, find that this adduct of magnesium halides is spherical, without opposite sex material, and between particle without adhesion.
(2) preparation of catalyst component
Adopt the method identical with embodiment 1 to prepare spherical catalyst component, different, adduct of magnesium halides is adduct of magnesium halides prepared by embodiment 4 steps (1).In this spherical catalyst component, the content of titanium is 2.5wt%.Adopt opticmicroscope to observe the particle morphology of the catalyst component obtaining, find that solid particulate form is good, for spherical, without opposite sex material.
(3) propylene polymerization B
Adopt the method identical with (4) in embodiment 1 to carry out propylene polymerization, different, catalyst component is catalyst component prepared by above-mentioned steps (2).
Embodiment 5
The present embodiment is used for explanation according to the catalyst component for olefinic polymerization of the present invention and catalyst system and application and olefine polymerizing process.
(1) preparation of adduct of magnesium halides
Adopt the method identical with embodiment 1 to prepare spherical adduct of magnesium halides, different, the consumption of 2,2-dimethoxypropane is 1mL, and the consumption of 2-methoxy benzoyl chloride is 0.5mL.The composition of this adduct of magnesium halides is as shown in table 1.Adopt opticmicroscope to observe the particle morphology of the adduct of magnesium halides obtaining, find that this adduct of magnesium halides is spherical, without opposite sex material, and between particle without adhesion.
(2) preparation of catalyst component
Adopt the method identical with embodiment 1 to prepare spherical catalyst component, different, adduct of magnesium halides is adduct of magnesium halides prepared by embodiment 5 steps (1).In this spherical catalyst component, the content of titanium is 3.0wt%.Adopt opticmicroscope to observe the particle morphology of the catalyst component obtaining, find that solid particulate form is good, for spherical, without opposite sex material.
(3) propylene polymerization B
Adopt the method identical with (4) in embodiment 1 to carry out propylene polymerization, different, catalyst component is catalyst component prepared by above-mentioned steps (2).
Embodiment 6
The present embodiment is used for explanation according to the catalyst component for olefinic polymerization of the present invention and catalyst system and application and olefine polymerizing process.
(1) preparation of adduct of magnesium halides
Adopt the method identical with embodiment 1 to prepare spherical adduct of magnesium halides, different, the consumption of 2,2-dimethoxypropane is 9mL, and the consumption of 2-methoxy benzoyl chloride is 5mL.The composition of this adduct of magnesium halides is as shown in table 1.Adopt opticmicroscope to observe the particle morphology of the adduct of magnesium halides obtaining, find that this adduct of magnesium halides is spherical, without opposite sex material, and between particle without adhesion.
(2) preparation of catalyst component
Adopt the method identical with embodiment 1 to prepare spherical catalyst component, different, adduct of magnesium halides is adduct of magnesium halides prepared by embodiment 6 steps (1).In this spherical catalyst component, the content of titanium is 2.4wt%.Adopt opticmicroscope to observe the particle morphology of the catalyst component obtaining, find that solid particulate form is good, for spherical, without opposite sex material.
(3) propylene polymerization B
Adopt the method identical with (4) in embodiment 1 to carry out propylene polymerization, different, catalyst component is catalyst component prepared by above-mentioned steps (2).
Embodiment 7
The present embodiment is used for explanation according to the catalyst component for olefinic polymerization of the present invention and catalyst system and application and olefine polymerizing process.
(1) preparation of adduct of magnesium halides
Adopt the method identical with embodiment 1 to prepare spherical adduct of magnesium halides, different, the consumption of ethanol is 57mL, and the consumption of 2,2-dimethoxypropane is 1mL.The composition of this adduct of magnesium halides is as shown in table 1.Adopt opticmicroscope to observe the particle morphology of the adduct of magnesium halides obtaining, find that this adduct of magnesium halides is spherical, without opposite sex material, and between particle without adhesion.
(2) preparation of catalyst component
Adopt the method identical with embodiment 1 to prepare spherical catalyst component, different, adduct of magnesium halides is adduct of magnesium halides prepared by embodiment 7 steps (1).In this spherical catalyst component, the content of titanium is 2.3wt%.Adopt opticmicroscope to observe the particle morphology of the catalyst component obtaining, find that solid particulate form is good, for spherical, without opposite sex material.
(3) propylene polymerization B
Adopt the method identical with (4) in embodiment 1 to carry out propylene polymerization, different, catalyst component is catalyst component prepared by above-mentioned steps (2).
Table 1
a: methyl alcohol;
b: O-Anisic Acid ethyl ester
c: 2 hydroxybenzoic acid ethyl ester
d: 4-methoxybenzoic acid ethyl ester
e: 4-HBA ethyl ester
Fig. 1 and Fig. 2 are respectively spherical adduct of magnesium halides prepared by embodiment 1 and the particle morphology photo of catalyst component, Fig. 3 and Fig. 4 are respectively spherical adduct of magnesium halides prepared by embodiment 2 and the particle morphology photo of catalyst component, and Fig. 5 and Fig. 6 are spherical adduct of magnesium halides that respectively prepared by comparative example 2 and the particle morphology photo of catalyst component.By Fig. 1,3 and Fig. 5 compare and can find out, not only there is abnormity material in adduct of magnesium halides prepared by comparative example 2, and particle distribution is inhomogeneous, and the particle shape of adduct of magnesium halides of the present invention is very perfect, for spherical, without abnormity material.By Fig. 2,4 and Fig. 6 compare and can find out, also there is abnormity material in the catalyst component that comparative example 2 is prepared according to its corresponding adducts, and particle distribution is inhomogeneous; And catalyst according to the invention component has good particle form, for spherical, without abnormity material.This explanation, compared with the catalyst component of being prepared by prior art polycomponent adducts, catalyst according to the invention component has the particle form of improvement.
Polymerization results when table 2 has been listed the catalyst system of being prepared by embodiment 1-7 and comparative example 1-3 for propylene polymerization.
Table 2
Embodiment 1,2 and comparative example 1, embodiment 3 are compared and can be found out with comparative example 3, when catalyst according to the invention system is used for propylene polymerization, not only demonstrates better hydrogen response, and show higher stereotaxis ability.Embodiment 2 and 3 is compared also and can be found out with comparative example 2 respectively, when catalyst according to the invention system is used for propylene polymerization, obtained the stereotaxis ability of better hydrogen response and Geng Gao, and resulting polymers particle form is good, without opposite sex material simultaneously.This shows, according to of the present invention to contain LB simultaneously
1, LB
2and LB
3the adduct of magnesium halides catalyst body that is carrier while tying up to for propylene polymerization, than by only containing LB
1or LB
2and LB
3prior art adduct of magnesium halides as the catalyst system of carrier, LB
1, LB
2and LB
3when three, exist and demonstrate good synergistic effect, make catalyst body of the present invention tie up to hydrogen response and stereotaxis ability aspect has obtained good improvement simultaneously, reached hydrogen and adjusted well balanced between ability and stereotaxis ability, over-all properties is better.
Claims (39)
1. for the catalyst component of olefinic polymerization, the reaction product that this catalyst component comprises adduct of magnesium halides, titanium compound and optional at least one internal electron donor compound, is characterized in that, described adduct of magnesium halides is suc as formula shown in I,
MgX
1Y-mEtOH-n(LB
1)-k(LB
2)-p(LB
3) （I）
In formula I, X
1for chlorine or bromine, Y is chlorine, bromine, C
1-C
14straight or branched alkyl, C
6-C
14replacement or unsubstituted aryl, C
1-C
14straight or branched alkoxyl group and C
6-C
14replacement or unsubstituted aryloxy in one;
LB
1compound for shown in formula II:
R
7X
2 （II）
In formula II, X
2for-OH, R
7for methyl, C
3-C
10straight or branched alkyl, C
6-C
10replacement or the C that replaces of unsubstituted aryl or quilt-OH
1-C
10straight or branched alkyl;
LB
2for the alkoxybenzoic acid ester based compound shown in formula III,
In formula III, R
1for C
1-C
6straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
R
2, R
3, R
4and R
5hydrogen, C respectively do for oneself
1-C
8straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
R
6for C
1-C
6straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
LB
3for the hydroxybenzoate based compound shown in formula IV,
In formula IV, R
1for C
1-C
6straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
R
2, R
3, R
4and R
5hydrogen, C respectively do for oneself
1-C
8straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
In formula I, m is 1-5; N is 0.005-2; K is 0.0005-0.3; P is 0.0005-0.3.
2. catalyst component according to claim 1, wherein, in formula I, described Y is chlorine, bromine, C
1-C
5straight or branched alkyl, C
6-C
10replacement or unsubstituted aryl, C
1-C
5straight or branched alkoxyl group and C
6-C
10replacement or unsubstituted aryloxy in one;
LB
1for the one in methyl alcohol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, ethylene glycol, 1,3-PD and phenol;
LB
2for the alkoxybenzoic acid ester based compound shown in formula III,
In formula III, R
1and R
6respectively do for oneself methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, the one in base, benzyl and styroyl just, R
2, R
3, R
4and R
5respectively do for oneself hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, the one in base, n-heptyl and tolyl just;
LB
3for the hydroxybenzoate based compound shown in formula IV,
In formula IV, R
1for methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, the one in base, benzyl and styroyl just, R
2, R
3, R
4and R
5respectively do for oneself hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, the one in base, n-heptyl and tolyl just;
M is 2-3.5; N is 0.01-0.8; K is 0.001-0.1; P is 0.001-0.1.
3. catalyst component according to claim 2, wherein, in formula I, MgX
1y is one or more in magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium.
4. catalyst component according to claim 2, wherein, LB
2for the one in 4-alkoxybenzoic acid ester based compound and 2-alkoxybenzoic acid ester based compound.
5. catalyst component according to claim 4, wherein, LB
2for 2-alkoxybenzoic acid ester based compound.
6. catalyst component according to claim 2, wherein, LB
3for the one in 4-HBA ester based compound and 2 hydroxybenzoic acid ester based compound.
7. catalyst component according to claim 6, wherein, LB
3for 2 hydroxybenzoic acid ester based compound.
8. catalyst component according to claim 1, wherein, the mol ratio of described titanium compound, internal electron donor compound and described adduct of magnesium halides is 5-100:0-0.5:1, and described titanium compound is in titanium elements, and described adduct of magnesium halides is in magnesium elements.
9. catalyst component according to claim 8, wherein, the mol ratio of described titanium compound, internal electron donor compound and described adduct of magnesium halides is 20-80:0.05-0.35:1, and described titanium compound is in titanium elements, and described adduct of magnesium halides is in magnesium elements.
10. according to the catalyst component described in any one in claim 1-9, wherein, the preparation method of described adduct of magnesium halides comprises:
(1) by MgX
1y and ethanol, LB
1, LB
2and LB
3mix, and by the mixture heating obtaining, to obtain liquid adduct of magnesium halides, with respect to the MgX in magnesium of 1 mole
1y, the amount of ethanol is 1-5.5 mole, LB
1amount be 0.005-2.3 mole, LB
2amount be 0.0005-0.32 mole, LB
3amount be 0.0005-0.32 mole; Or
By MgX
1y and ethanol, under hydrolysising condition, can form LB
1material, hydrolysis and/or alcoholysis conditions under can form LB
2material and hydrolysis and/or alcoholysis conditions under can form LB
3material mix, and by the mixture heating obtaining, to obtain liquid adduct of magnesium halides, with respect to the MgX in magnesium of 1 mole
1y, the amount of ethanol is 1-5.5 mole, describedly under hydrolysising condition, can form LB
1amount of substance be 0.0025-1.2 mole, described hydrolysis and/or alcoholysis conditions under can form LB
2amount of substance be 0.0005-0.32 mole, described hydrolysis and/or alcoholysis conditions under can form LB
3amount of substance be 0.0005-0.32 mole;
(2) under inert liquid medium exists, by the adduct of magnesium halides emulsification of described liquid state, and emulsification product quenching is shaped, obtain spherical adduct of magnesium halides particle;
MgX
1in Y, X
1for chlorine or bromine, Y is chlorine, bromine, C
1-C
14straight or branched alkyl, C
6-C
14replacement or unsubstituted aryl, C
1-C
14straight or branched alkoxyl group and C
6-C
14replacement or unsubstituted aryloxy in one;
LB
1compound for shown in formula II:
R
7X
2 （II）
In formula II, X
2for-OH, R
7for methyl, C
3-C
10straight or branched alkyl, C
6-C
10replacement or the C that replaces of unsubstituted aryl or quilt-OH
1-C
10straight or branched alkyl;
LB
2for the alkoxybenzoic acid ester based compound shown in formula III,
In formula III, R
1for C
1-C
6straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
R
2, R
3, R
4and R
5hydrogen, C respectively do for oneself
1-C
8straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
R
6for C
1-C
6straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
LB
3for the hydroxybenzoate based compound shown in formula IV,
In formula IV, R
1for C
1-C
6straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
R
2, R
3, R
4and R
5hydrogen, C respectively do for oneself
1-C
8straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one.
11. catalyst components according to claim 10 wherein, describedly can form LB under hydrolysising condition
1material be the compound shown in formula VII,
In formula VII, R
7for methyl, C
3-C
10straight or branched alkyl, C
6-C
10replacement or the C that replaces of unsubstituted aryl or quilt-OH
1-C
10straight or branched alkyl; R
aand R
bhydrogen and C respectively do for oneself
1-C
6straight or branched alkyl in one.
12. catalyst components according to claim 11 wherein, describedly can form LB under hydrolysising condition
1material be the compound shown in formula VII, in formula VII, R
7for the one in methyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, n-hexyl, n-octyl, 2-ethylhexyl, 2-hydroxyethyl, 3-hydroxypropyl and phenyl; R
aand R
bthe one of respectively doing for oneself in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and isobutyl-.
13. catalyst components according to claim 10, wherein, described hydrolysis and/or alcoholysis conditions under can form LB
2material be the alkoxy benzene formyl chloride based compound shown in formula VIII,
In formula VIII, R
2, R
3, R
4and R
5hydrogen, C respectively do for oneself
1-C
8straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
R
6for C
1-C
6straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one.
14. catalyst components according to claim 13, wherein, described hydrolysis and/or alcoholysis conditions under can form LB
2material be the alkoxy benzene formyl chloride based compound shown in formula VIII, in formula VIII, R
2, R
3, R
4and R
5respectively do for oneself hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, the one in base, n-heptyl and tolyl just;
R
6for methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, the one in base, benzyl and styroyl just.
15. catalyst components according to claim 14, wherein, described hydrolysis and/or alcoholysis conditions under can form LB
2material be the one in 4-alkoxy benzene formyl chloride based compound and 2-alkoxy benzene formyl chloride based compound.
16. catalyst components according to claim 15, wherein, described hydrolysis and/or alcoholysis conditions under can form LB
2material be 2-alkoxy benzene formyl chloride based compound.
17. catalyst components according to claim 10, wherein, described hydrolysis and/or alcoholysis conditions under can form LB
3material be the (2-hydroxybenzoyl) based compound shown in the alkoxy benzene formyl based compound shown in formula VIIII or formula VIIII,
In formula VIIII, R
1' be hydrogen, hydroxyl, halogen, C
1-C
6straight or branched alkoxyl group, C
3-C
6replacement or unsubstituted cycloalkyloxy, C
6-C
10replacement or unsubstituted aryloxy and C
7-C
10replacement or unsubstituted aralkoxy in one;
R
2, R
3, R
4and R
5hydrogen, C respectively do for oneself
1-C
8straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one;
R
6for hydrogen, C
1-C
6straight or branched alkyl, C
3-C
6replacement or unsubstituted cycloalkyl, C
6-C
10replacement or unsubstituted aryl and C
7-C
10replacement or unsubstituted aralkyl in one.
18. catalyst components according to claim 17, wherein, described hydrolysis and/or alcoholysis conditions under can form LB
3material be the (2-hydroxybenzoyl) based compound shown in the alkoxy benzene formyl based compound shown in formula VIIII or formula VIIII, in formula VIIII, R
1' be hydrogen, hydroxyl, chlorine, bromine, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, the one in oxygen base, benzyloxy and benzene oxyethyl group just;
R
2, R
3, R
4and R
5respectively do for oneself hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, the one in base, n-heptyl and tolyl just; R
6for hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, the one in base, benzyl and styroyl just.
19. catalyst components according to claim 18, wherein, described hydrolysis and/or alcoholysis conditions under can form LB
3material be the one in 4-alkoxy benzene formyl based compound, 2-alkoxy benzene formyl based compound, 4-(2-hydroxybenzoyl) based compound and 2-(2-hydroxybenzoyl) based compound.
20. catalyst components according to claim 19, wherein, described hydrolysis and/or alcoholysis conditions under can form LB
3material be the one in 2-alkoxy benzene formyl based compound and 2-(2-hydroxybenzoyl) based compound.
21. catalyst components according to claim 10, wherein, the condition of described heating comprises: temperature is 80-140 ℃, the reaction times is 0.5-4 hour.
22. catalyst components according to claim 10, wherein, described inert liquid medium is silicone oil and/or hydrocarbon system compound; With respect to the MgX in magnesium of 1 mole
1y, the consumption of inert liquid medium is 0.2-13L.
23. catalyst components according to claim 22, wherein, with respect to the MgX in magnesium of 1 mole
1y, the consumption of inert liquid medium is 0.6-6.5L.
24. according to the catalyst component described in any one in claim 1-9, and wherein, described titanium compound is three halogenated titaniums and general formula Ti (OR ')
4-mx '
mone or more in shown titanium compound, in this general formula, R ' is C
1-C
10alkyl, X ' is halogen, the integer that m is 0-4.
25. catalyst components according to claim 24, wherein, described titanium compound is one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium n-butoxide, purity titanium tetraethoxide, chlorine three titanium n-butoxide, dichloro two titanium n-butoxide, trichlorine one titanium n-butoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium and titanous chloride.
26. according to the catalyst component described in any one in claim 1-9, and wherein, described internal electron donor compound is one or more in ester, ether, ketone, amine and silane.
27. catalyst components according to claim 26, wherein, described internal electron donor compound is one or more in ester and diether type compound.
Catalyst component in 28. claim 1-27 described in any one is in the application of preparing in olefin polymerization catalyst system.
29. 1 kinds of catalyst systems for olefinic polymerization, this catalyst system comprises according to the catalyst component described in any one in claim 1-27 and one or more organo-aluminium compounds; In the described organo-aluminium compound of aluminium with take the mol ratio of the described catalyst component of titanium as 1-2000:1.
30. catalyst systems according to claim 29, wherein, in the described organo-aluminium compound of aluminium with take the mol ratio of the described catalyst component of titanium as 20-700:1.
31. catalyst systems according to claim 29, wherein, described organoaluminum is alkylaluminium sesquichloride and general formula AlR
7r
8r
9one or more in shown compound, in this general formula, R
7, R
8and R
9chlorine and C respectively do for oneself
1-C
8alkyl in one, and R
7, R
8and R
9in at least one be C
1-C
8alkyl.
32. catalyst systems according to claim 30, wherein, described organoaluminum is alkylaluminium sesquichloride and general formula AlR
7r
8r
9one or more in shown compound, in this general formula, R
7, R
8and R
9chlorine and C respectively do for oneself
1-C
8alkyl in one, and R
7, R
8and R
9in at least one be C
1-C
8alkyl.
33. according to the catalyst system described in any one in claim 29-32, and wherein, this catalyst system also comprises external donor compound; Described external donor compound with the mol ratio take the described organo-aluminium compound of aluminium as 0.005-0.5:1.
34. catalyst systems according to claim 33, described external donor compound with the mol ratio take the described organo-aluminium compound of aluminium as 0.01-0.4:1.
35. catalyst systems according to claim 33, described external donor compound is one or more in carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organo phosphorous compounds and silicoorganic compound.
36. catalyst systems according to claim 34, described external donor compound is one or more in carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organo phosphorous compounds and silicoorganic compound.
37. according to the catalyst system described in claim 35 or 36, and wherein, described external donor compound is general formula R
a xr
b ysi (OR
c)
zone or more in shown silicoorganic compound, in this general formula, R
a, R
band R
cc respectively does for oneself
1-C
18alkyl or contain heteroatomic C
1-C
18alkyl, respectively the do for oneself integer of 0-2 of x and y, the integer that z is 1-3, and x+y+z=4.
Catalyst body in 38. claim 29-37 described in any one ties up to the application in olefinic polyreaction.
39. 1 kinds of olefine polymerizing process, the method is included under olefinic polymerization condition, and one or more alkene are contacted with catalyst system described in any one in claim 29-37.
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| CN105622644B (en) * | 2014-10-28 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of adduct of magnesium halides and its application |
| CN105622793B (en) * | 2014-10-28 | 2019-05-31 | 中国石油化工股份有限公司 | For the catalytic component and catalyst system of olefinic polymerization and its application and olefine polymerizing process |
| CN105541877B (en) * | 2014-10-28 | 2019-03-22 | 中国石油化工股份有限公司 | Adduct of magnesium halides and application and the catalytic component for olefinic polymerization and catalyst system and application and olefine polymerizing process |
| CN105622794B (en) * | 2014-10-28 | 2018-07-20 | 中国石油化工股份有限公司 | For the catalytic component and catalyst system of olefinic polymerization and its application and olefine polymerizing process |
| CN104829756B (en) * | 2015-05-13 | 2018-05-15 | 中国科学院化学研究所 | A kind of solid catalyst component for olefine polymerization and its preparation method and application |
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| CN106608936B (en) * | 2015-10-27 | 2019-05-31 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and its preparation method and application and catalyst and its application for olefinic polymerization |
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