CN102796210A - 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 and catalyst system and application and olefine polymerizing process that is used for olefinic polymerization.
Background technology
With titanium compound and the compound loaded Ziegler-Natta catalyst that on magnesium halide in active, prepares of electron donor is that prior art is known.Wherein, Described magnesium halide in active often adopts magnesium halide and pure adducts; It is obtained spherical catalyst after as carrier and halogenated titanium and the reaction of electron donor compound; Said spherical catalyst is when being used for alkene (particularly propylene) polymerization; Have high polymerization activity and stereotaxis ability, resulting polymers also has particle form and higher apparent density preferably.
Disclosed magnesium halide alcohol adducts is the alcohol adduct of magnesium chloride mostly, contains magnesium chloride and pure binary composition usually.Wherein, some disclosed magnesium chloride also contains a spot of water with the adducts of alcohol.For example: disclosed magnesium chloride of US4421674, US4469648, WO8707620, WO9311166, US5100849, US6020279, US4399054, EP0395383, US6127304 and US6323152 and pure adducts.This type of adducts can be extruded or the preparation of method such as high-speed stirring through spraying drying, spray cooling, high pressure.
But, in the time will being used for olefinic polymerization, in polymerization process, being easy to take place the broken phenomenon of polymer particle, thereby causing fine polymer powder more by the catalyzer that above-mentioned disclosed magnesium chloride and pure adducts prepare.In order to overcome this shortcoming; People attempt again the electron donor compound is incorporated in the preparation process of adducts of magnesium chloride and alcohol in advance; For example: CN1169840C and CN1286863C will usually be incorporated in the building-up process of magnesium chloride and the adducts of alcohol as the phthalate compound (for example: diisobutyl phthalate or n-butyl phthalate) of internal electron donor in the field of olefin polymerisation; Thereby obtain " magnesium dichloride-alcohol-phthalic ester " ball type carrier, then with this carrier and titanium tetrachloride reaction to form catalyzer.But; Said " magnesium dichloride-alcohol-phthalic ester " ball type carrier is clamminess in the preparation process easily; Be difficult to form the suitable spheroidal particle of size, and when being used for propylene polymerization by the catalyzer of this preparing carriers, polymerization activity is low and hydrogen response is poor.
In the disclosed technology of CN100491410C, C, C-two-oxyl hydrocarbon compounds are introduced in the adduct of magnesium halides.When being used for propylene polymerization by this polycomponent adduct of magnesium halides as the catalyzer of preparing carriers, its hydrogen response obtains certain raising, and fine powder content has minimizing to a certain degree in the polymkeric substance.But; In the preparation process of this adducts carrier, be prone to form abnormity material (for example: spheroid particle and/or bar shaped particle etc.); And; When under high hydrogen concentration, carrying out propylene polymerization by the catalyzer of this adducts preparing carriers; Its stereotaxis ability, the degree of isotacticity that particularly has the polymkeric substance of high fusion index awaits further to improve.
CN101486722A passes through the mode of reaction in or directly adding in the preparation process of adduct of magnesium halides; Introduce the o-alkoxyl benzoate compounds; Make with said adduct of magnesium halides to be that the catalyzer that carrier makes has good hydrogen response and higher stereotaxis ability; And its polymerization activity is higher, and the fine powder of resulting polymers is also less.But, the cooling efficiency in the time of in the preparation process of carrier, must carefully controlling the shaping of adduct of magnesium halides chilling, otherwise cause the inter-adhesive of carrier particle easily; And hydrogen response and the balance between the stereotaxis ability by the catalyzer of this adducts preparing carriers await further to improve.
Summary of the invention
The object of the present invention is to provide a kind of novel catalyst component that is used for olefinic polymerization and catalyst system and application thereof.There is not adhesion between the particle according to the adduct of magnesium halides of the catalyst component that is used for olefinic polymerization of the present invention, do not have the abnormity material, thereby olefin polymerization catalyst components particle form of the present invention is good yet; And; The present inventor also is surprised to find that; Catalyst according to the invention component and catalyst body thereof tie up to when being used for alkene (particularly propylene) polymerization; Demonstrate excellent hydrogen response and high stereotaxis ability; Its hydrogen is transferred between ability and the stereotaxis ability and has been reached 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 that is used for olefinic polymerization, this catalyst component comprises the reaction product of adduct of magnesium halides, titanium compound and optional at least a internal electron donor compound, and wherein, said adduct of magnesium halides is suc as formula shown in the I,
MgX
1Y-mEtOH-n(LB
1)-k(LB
2)-p(LB
3) (I)
Among the formula I, X
1Be 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 a kind of; LB
1, LB
2And LB
3Respectively do for oneself carboxylic acid, aldehyde, ether, ester, ketone, silane, amine, nitrile, phenol and be different from a kind of in the alcoholic acid alcohol,
Among the 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 the application of catalyst according to the invention component in the preparation olefin polymerization catalyst system.
The present invention also provides a kind of catalyst system that is used for olefinic polymerization, and this catalyst system comprises catalyst according to the invention component and one or more organo-aluminium compounds; In the said organo-aluminium compound of aluminium with in the mol ratio of the said catalyst component of titanium is 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, and this method is included under the olefinic polymerization condition, and one or more alkene are contacted with catalyst system provided by the invention.
Particle form according to the spherical adduct of magnesium halides of the catalyst component that is used for olefinic polymerization of the present invention is good, does not have abnormity material (like spheroid material, bar shaped material etc.), and does not also have adhesion phenomenon between the particle.Thereby, use catalyst according to the invention component and catalyst system thereof, when being used for alkene (particularly propylene) polymerization, the resulting polymers particle shape is good.The present inventor also is surprised to find that; Catalyst component of the present invention and catalyst body thereof tie up to not only has high polymerization activity in the olefinic polymerization; Also demonstrate excellent hydrogen response and high stereotaxis ability, its hydrogen is transferred between ability and the stereotaxis ability and has been reached good balance.
Description of drawings
Fig. 1 is the particle morphology optical microscope photograph of the spherical adduct of magnesium halides of embodiment 1 preparation;
Fig. 2 is the particle morphology optical microscope photograph of the spherical catalyst component of embodiment 1 preparation;
Fig. 3 is the particle morphology optical microscope photograph of the spherical adduct of magnesium halides of embodiment 2 preparations;
Fig. 4 is the particle morphology optical microscope photograph of the spherical catalyst component of embodiment 2 preparations;
Fig. 5 is the particle morphology optical microscope photograph of the spherical adduct of magnesium halides of Comparative Examples 2 preparations;
Fig. 6 is the particle morphology optical microscope photograph of the spherical catalyst component of Comparative Examples 2 preparations.
Embodiment
The invention provides a kind of catalyst component that is used for olefinic polymerization, this catalyst component comprises the reaction product of adduct of magnesium halides, titanium compound and optional at least a internal electron donor compound, and wherein, said adduct of magnesium halides is suc as formula shown in the I,
MgX
1Y-mEtOH-n(LB
1)-k(LB
2)-p(LB
3) (I)
Among the formula I, X
1Be 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 a kind of; LB
1, LB
2And LB
3Be selected from Lewis base separately, for example can and be different from a kind of in the alcoholic acid alcohol for carboxylic acid, aldehyde, ether, ester, ketone, silane, amine, nitrile, phenol.
According to the present invention, among the formula I, Et representes ethyl, and EtOH representes ethanol.
Among the present invention, term " carboxylic acid " comprises aliphatic carboxylic acid and aromatic carboxylic acid, is preferably aromatic carboxylic acid.Among the present invention, term " ester " comprises aliphatic carboxylic acid esters, and aromatic carboxylic acid esters, is preferably aromatic carboxylic acid esters.Among the present invention, term " amine " comprises primary amine, secondary amine and tertiary amine.Among the present invention, term " silane " is meant SiH
4In one or more hydrogen atoms contained or do not contained heteroatomic alkyl, contain or do not contain heteroatomic alkoxyl group, contain or do not contain heteroatomic aryl, or contained or do not contain the substituted organosilane of heteroatomic aryloxy, said silane is preferably alkoxyalkyl silane or organoalkoxysilane.
Among the present invention, term " replacement " is meant that the hydrogen atom on carbon or the Siliciumatom is substituted base and replaces.
According to the present invention, among the 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 a kind of.Among the present invention, among the formula I, MgX
1Y can be a kind of halogenated magnesium compound, also can be the mixture of multiple halogenated magnesium compound.More preferably, among the formula I, MgX
1Y is one or more in magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and the chlorination n-butoxy magnesium.From the angle of being easy to get property of raw material, among the formula I, MgX
1Y further is preferably magnesium dichloride.
According to the present invention, among the formula I, LB
1Be preferably the compound shown in the formula II:
R
7X
2 (II)
Among the formula II, X
2For-NH
2,-NHR
7' and-a kind of among the OH, R
7' be C
1-C
20Alkyl, R
7Be C
1-C
20Alkyl, or by the substituted C of heteroatom group
1-C
20Alkyl, and at X
2During for-OH, R
7It is not ethyl.
Preferably, among the formula II, X
2For-OH; R
7Be methyl, C
3-C
10Alkyl, perhaps by-NH
2,-NHR
7' and-one or more substituted C among the OH
1-C
10Alkyl; R
7' be C
1-C
5The straight or branched alkyl.
More preferably, among the formula II, X
2For-OH, R
7Be methyl, C
3-C
10Straight or branched alkyl, C
6-C
10Replacement or unsubstituted aryl, or quilt-NH
2And/or-the substituted C of OH
1-C
10The straight or branched alkyl.
Among 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, terepthaloyl moietie, 1, ammediol and phenol.
Among the present invention, term " alkyl " is meant that hydrocarbon molecule loses the group that forms behind the hydrogen atom, and for example: said " 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, among the formula I, LB
2Be preferably the alkoxybenzoic acid ester based compound shown in alkoxybenzoic acid based compound shown in the formula III or the formula III,
In the formula III, R
1Be 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 a kind of;
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 a kind of; Perhaps, R
2, R
3, R
4And R
5In two or more mutual bondings, to form ring;
R
6Be 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 a kind of.
Preferably, in the formula III, R
1Be 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 a kind of;
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 a kind of;
R
6Be 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 a kind of.
More preferably, in the formula III, R
1And R
6A kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and the styroyl respectively does for oneself;
R
2, R
3, R
4And R
5A kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and the aminomethyl phenyl respectively does for oneself.
According to the present invention, at LB
2During for the alkoxybenzoic acid ester based compound shown in alkoxybenzoic acid based compound shown in the formula III or the formula III, LB
2A kind of in 4-alkoxybenzoic acid based compound, 4-alkoxybenzoic acid ester based compound, 2-alkoxybenzoic acid based compound and the 2-alkoxybenzoic acid ester based compound more preferably; Further be preferably a kind of in 2-alkoxybenzoic acid based compound and the 2-alkoxybenzoic acid ester based compound.
Among the present invention, LB
2Specific examples can for but be not limited to: the O-Anisic Acid methyl esters; The O-Anisic Acid ethyl ester; The O-Anisic Acid n-propyl; 2-methoxy benzoic acid isopropyl ester; The positive butyl ester of O-Anisic Acid; The O-Anisic Acid isobutyl ester; The O-Anisic Acid n-pentyl ester; The just own ester of O-Anisic Acid; O-Anisic Acid benzyl ester; The 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; The 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, among the formula I, LB
3Be preferably the hydroxybenzoate based compound shown in hydroxy-benzoic acid based compound shown in the formula IV or the formula IV,
Among the formula IV, R
1Be 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 a kind of;
R
2, R
3, R
4And R
5Hydrogen, halogen, nitro, C respectively do for oneself
1-C
20Straight or branched alkyl, C
3-C
20Substituted unsubstituted cycloalkyl, C
6-C
20Replacement or unsubstituted aryl and C
7-C
20Replacement or unsubstituted aralkyl in a kind of; Perhaps, R
2, R
3, R
4And R
5In two or more mutual bondings, to form ring.
Preferably, among the formula IV, R
1Be 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 a kind of;
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 a kind of.
More preferably, among the formula IV, R
1A kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and the styroyl;
R
2, R
3, R
4And R
5A kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and the tolyl respectively does for oneself.
According to the present invention, at LB
3During for the hydroxybenzoate based compound shown in hydroxy-benzoic acid based compound shown in the formula IV or the formula IV, LB
3A kind of in 4-hydroxy-benzoic acid based compound, 4-hydroxybenzoate based compound, 2 hydroxybenzoic acid based compound and the 2 hydroxybenzoic acid ester based compound more preferably; Further be preferably a kind of in 2 hydroxybenzoic acid based compound and the 2 hydroxybenzoic acid ester based compound.
Among the present invention, LB
3Specific examples can for but be not limited to: the 2 hydroxybenzoic acid methyl esters; The 2 hydroxybenzoic acid ethyl ester; The 2 hydroxybenzoic acid n-propyl; The 2 hydroxybenzoic acid isopropyl ester; The positive butyl ester of 2 hydroxybenzoic acid; The 2 hydroxybenzoic acid isobutyl ester; The 2 hydroxybenzoic acid n-pentyl ester; The just own ester of 2 hydroxybenzoic acid; 2 hydroxybenzoic acid benzyl ester; The 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, among the 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 of the present invention preferred embodiment a kind of, among the formula I, X
1Be chlorine with Y;
LB
1Be the compound shown in the formula II, among the formula II, X
2For-OH, R
7Be methyl, C
3-C
10The straight or branched alkyl, or by the substituted C of hydroxyl
1-C
10The straight or branched alkyl;
LB
2Be the 2-alkoxybenzoic acid ester based compound shown in the formula V,
Among the formula V, R
1And R
6A kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and the styroyl respectively does for oneself; R
2, R
3, R
4And R
5A kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and the tolyl respectively does for oneself;
LB
3Be the 2 hydroxybenzoic acid ester based compound shown in the formula VI,
Among the formula VI, R
1A kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and the styroyl; R
2, R
3, R
4And R
5A kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and the tolyl respectively does for oneself;
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, said water come from synthesis material and reaction medium with minor amount of water.
The adduct of magnesium halides that is used for the catalyst component of olefinic polymerization according to the present invention can adopt following method to prepare:
(1) with MgX
1Y and ethanol, LB
1, LB
2And LB
3Mix, and with the mixture heating up that obtains, to obtain liquid adduct of magnesium halides; Perhaps
With MgX
1Y and ethanol, under hydrolysising condition, can form LB
1Material, under hydrolysis and/or alcoholysis conditions, can form LB
2Material and under hydrolysis and/or alcoholysis conditions, can form LB
3Material mix, and with the mixture heating up that obtains, to obtain liquid adduct of magnesium halides;
(2) in the presence of inert liquid medium,, and, obtain spherical adduct of magnesium halides particle with the shaping of emulsification product quenching with the adduct of magnesium halides emulsification of said liquid state.
Among the present invention, the preparation method of said adduct of magnesium halides comprises the adduct of magnesium halides that preparation is liquid, and adduct of magnesium halides that should liquid state is shaped, thereby obtains spherical adduct of magnesium halides.Can adopt various methods commonly used to prepare the adduct of magnesium halides of said liquid state according to the present invention.
In one embodiment of the invention, the method for preparing liquid adduct of magnesium halides comprises: with MgX
1Y and ethanol, LB
1, LB
2And LB
3Mix, and with the mixture heating up that obtains, to obtain said 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 the definition of preamble, repeat no more at this.
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 that finally obtains meet the demands to get final product.Usually, the MgX with respect to 1 mole in magnesium
1Y, the alcoholic acid amount 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 the 0.0005-0.32 mole; Preferably, the MgX with respect to 1 mole in magnesium
1Y, the alcoholic acid amount is the 2-3.7 mole, LB
1Amount be the 0.01-0.85 mole, LB
2Amount be the 0.001-0.12 mole, LB
3Amount be the 0.001-0.12 mole; More preferably, the MgX with respect to 1 mole in magnesium
1Y, the alcoholic acid amount is the 2.4-3.7 mole, LB
1Amount be the 0.03-0.65 mole, LB
2Amount be the 0.003-0.075 mole, LB
3Amount be the 0.003-0.075 mole.
According to the preparation method of adduct of magnesium halides of the present invention, for MgX
1Y and ethanol, LB
1, LB
2And LB
3Not special qualification of blend heated condition, as long as the condition of said heating makes MgX
1Y can with ethanol, LB
1, LB
2And LB
3React, get final product thereby form liquid adduct of magnesium halides.Usually, the condition of said 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: with MgX
1Y and ethanol, under hydrolysising condition, can form LB
1Material, under hydrolysis and/or alcoholysis conditions, can form LB
2Material and under hydrolysis and/or alcoholysis conditions, can form LB
3Material mix, and with the mixture heating up that obtains, to obtain liquid adduct of magnesium halides.
In this embodiment, MgX
1Y, ethanol, under hydrolysising condition, can form LB
1Material, under hydrolysis and/or alcoholysis conditions, can form LB
2Material and under hydrolysis and/or alcoholysis conditions, can form LB
3Amount of substance so that the 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 with respect to 1 mole in magnesium
1Y, the alcoholic acid amount is the 1-5.5 mole, saidly under hydrolysising condition, can form LB
1Amount of substance be the 0.0025-1.2 mole, saidly under hydrolysis and/or alcoholysis conditions, can form LB
2Amount of substance be the 0.0005-0.32 mole, saidly under hydrolysis and/or alcoholysis conditions, can form LB
3Amount of substance be the 0.0005-0.32 mole; Preferably, the MgX with respect to 1 mole in magnesium
1Y, the alcoholic acid amount is the 2-3.7 mole, saidly under hydrolysising condition, can form LB
1Amount of substance be the 0.005-0.42 mole, saidly under hydrolysis and/or alcoholysis conditions, can form LB
2Amount of substance be the 0.001-0.12 mole, saidly under hydrolysis and/or alcoholysis conditions, can form LB
3Amount of substance be the 0.001-0.12 mole; More preferably, the MgX with respect to 1 mole in magnesium
1Y, the alcoholic acid amount is the 2.4-3.7 mole, saidly under hydrolysising condition, can form LB
1Amount of substance be the 0.015-0.32 mole, saidly under hydrolysis and/or alcoholysis conditions, can form LB
2Amount of substance be the 0.003-0.075 mole, saidly under hydrolysis and/or alcoholysis conditions, can form LB
3Amount of substance be the 0.003-0.075 mole.
According to the preparation method of adduct of magnesium halides of the present invention, saidly under hydrolysising condition, can form LB
1Material can variously can form LB for well known to a person skilled in the art through hydrolysis reaction
1Material.For example: at LB
1Be R
7During OH, saidly under hydrolysising condition, can form LB
1Material can be the compound shown in the formula VII,
Among the formula VII, R
7Be methyl, C
3-C
20Alkyl, or by the substituted C of 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 a kind of; Perhaps, R
aAnd R
bBonding encircles to form each other.
Preferably, among the formula VII, R
7Be methyl, C
3-C
10Alkyl, perhaps by-NH
2,-NHR
7' and-one or more substituted C among the OH
1-C
10Alkyl; R
7' be C
1-C
5The straight 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 a kind of.
More preferably, among the formula VII, R
7Be methyl, C
3-C
10Straight or branched alkyl, C
6-C
10Replacement or unsubstituted aryl, or quilt-NH
2And/or-the substituted C of OH
1-C
10The straight or branched alkyl; R
aAnd R
bHydrogen and C respectively do for oneself
1-C
6The straight or branched alkyl in a kind of.
Further preferably, among the formula VII, R
7A kind of in methyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, n-hexyl, n-octyl, 2-ethylhexyl, 2-hydroxyethyl, 3-hydroxypropyl and the phenyl; R
aAnd R
bA kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and the isobutyl-respectively does for oneself.
According to the preparation method of adduct of magnesium halides of the present invention, saidly under hydrolysising condition, can form LB
1Material specific examples can for but be not limited to: 2,2-Propanal dimethyl acetal, 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, saidly under hydrolysis and/or alcoholysis conditions, can form LB
2Material can variously can form LB for well known to a person skilled in the art through hydrolysis and/or alcoholysis reaction
2Material.For example: at LB
2During for the alkoxybenzoic acid ester based compound shown in alkoxybenzoic acid based compound shown in the formula III or the formula III, saidly under hydrolysis and/or alcoholysis conditions, can form LB
2Material can be the alkoxy benzene formyl chloride based compound shown in the formula VIII,
Among the 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 a kind of; Perhaps, R
2, R
3, R
4And R
5In two or more mutual bondings, to form ring;
R
6Be 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 a kind of.
Preferably, among the 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 a kind of;
R
6Be 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 a kind of.
More preferably, among the formula VIII, R
2, R
3, R
4And R
5A kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and the tolyl respectively does for oneself;
R
6A kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and the styroyl.
According to the preparation method of adduct of magnesium halides of the present invention, saidly under hydrolysis and/or alcoholysis conditions, can form LB
2Material when being the alkoxy benzene formyl chloride based compound shown in the formula VIII, saidly under hydrolysis and/or alcoholysis conditions, can form LB
2Material a kind of in 4-alkoxy benzene formyl chloride based compound and the 2-alkoxy benzene formyl chloride based compound more preferably; Further be preferably 2-alkoxy benzene formyl chloride based compound.
According to the preparation method of adduct of magnesium halides of the present invention, saidly under hydrolysis and/or alcoholysis conditions, can form LB
3Material can variously can under hydrolysis and/or alcoholysis conditions, can form LB for well known to a person skilled in the art
3Material.For example: at LB
3During for the hydroxybenzoate based compound shown in hydroxy-benzoic acid based compound shown in the formula IV or the formula IV, saidly under hydrolysis and/or alcoholysis conditions, can form LB
3Material can be the (2-hydroxybenzoyl) based compound shown in alkoxy benzene formyl based compound shown in the formula VIIII or the formula VIIII,
Among the formula VIIII, R
1' be hydrogen, hydroxyl, halogen, C
1-C
20Straight or branched alkoxyl group, C
3-C
20Substituted unsubstituted cycloalkyloxy, C
6-C
20Replacement or unsubstituted aryloxy and C
7-C
20Replacement or unsubstituted aralkoxy in a kind of;
R
2, R
3, R
4And R
5Hydrogen, halogen, nitro, C respectively do for oneself
1-C
20Straight or branched alkyl, C
3-C
20Substituted unsubstituted cycloalkyl, C
6-C
20Replacement or unsubstituted aryl and C
7-C
20Replacement or unsubstituted aralkyl in a kind of; Perhaps, R
2, R
3, R
4And R
5In two or more mutual bondings, to form ring;
R
6Be 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 a kind of.
Preferably, among the formula VIIII, R
1' be hydrogen, hydroxyl, halogen, C
1-C
6Straight or branched alkoxyl group, C
3-C
6Substituted unsubstituted cycloalkyloxy, C
6-C
10Replacement or unsubstituted aryloxy and C
7-C
10Replacement or unsubstituted aralkoxy in a kind of;
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 a kind of;
R
6Be 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 a kind of.
More preferably, among the formula VIIII, R
1' be a kind of in hydrogen, hydroxyl, chlorine, bromine, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, positive hexyloxy, benzyloxy and the benzene oxyethyl group;
R
2, R
3, R
4And R
5A kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and the tolyl respectively does for oneself;
R
6A kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and the styroyl.
According to the preparation method of adduct of magnesium halides of the present invention, saidly under hydrolysis and/or alcoholysis conditions, can form LB
3Material when being the (2-hydroxybenzoyl) based compound shown in alkoxy benzene formyl based compound shown in the VIIII or the VIIII, saidly under hydrolysis and/or alcoholysis conditions, can form LB
3Material a kind of in 4-alkoxy benzene formyl based compound, 2-alkoxy benzene formyl based compound, 4-(2-hydroxybenzoyl) based compound and the 2-(2-hydroxybenzoyl) based compound more preferably; Further be preferably a kind of in 2-alkoxy benzene formyl based compound and the 2-(2-hydroxybenzoyl) based compound.
According to the preparation method of adduct of magnesium halides of the present invention, saidly under hydrolysis and/or alcoholysis conditions, can form LB
3Material and saidly under hydrolysis and/or alcoholysis conditions, can form LB
2Material can also can be difference for identical, be preferably identical.
Preparing method according to adduct of magnesium halides of the present invention; Term " hydrolysis " is meant and utilizes water with the process of material decomposition with the formation novel substance; Said hydrolysis can be carried out well known to a person skilled in the art under the condition; For example: the temperature of said hydrolysis can be 60-150 ℃, and 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 reaction that is hydrolyzed can be the water in various sources.Because MgX
1Y, ethanol, under hydrolysising condition, can form LB
1Material, under hydrolysis and/or alcoholysis conditions, can form LB
2Material and under hydrolysis and/or alcoholysis conditions, can form LB
3Material all possibly have water, particularly MgX
1Y and ethanol, usually, for anhydrous MgX
1Y, its water-content are 0.1-1.5wt%; Water-content in the analytically pure dehydrated alcohol is 20-600ppm.The present inventor finds in practice process, at anhydrous MgX
1When the water-content of Y and the water-content of dehydrated alcohol are within the above-mentioned scope respectively, can guarantee that hydrolysis reaction carries out smoothly.Therefore said water can be for coming from MgX
1Water in Y and the ethanol.
Preparing method according to adduct of magnesium halides of the present invention; Term " alcoholysis " be meant utilize alcohol with material decomposition to form the process of new material; Said alcoholysis can be carried out well known to a person skilled in the art under the condition; For example: the temperature of said alcoholysis can be 60-150 ℃, and the time can be 0.5-4 hour.
According to the preparation method of adduct of magnesium halides of the present invention, carry out the used alcohol of alcoholysis reaction and can be the alcohol in various sources.Because preparing method's needs of adduct of magnesium halides add ethanol according to the present invention, 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 MgX
1Y and ethanol, under hydrolysising condition, can form LB
1Material, under hydrolysis and/or alcoholysis conditions, can form LB
2Material and under hydrolysis and/or alcoholysis conditions, can form LB
3The mixture heating up of material, to react and to form not special qualification of condition of liquid adduct of magnesium halides, as long as the condition of said heating is enough to form liquid adduct of magnesium halides.Usually, the condition of said heating can comprise: temperature is 80-140 ℃, and the reaction times is 0.5-4 hour.
Further be included in inert liquid medium based on the preparation method of adduct of magnesium halides of the present invention and exist down, with said be liquid adduct of magnesium halides emulsification, and, obtain spherical adduct of magnesium halides particle with the shaping of emulsification product quenching.
Chemically interactive liquid medium can not take place with adduct of magnesium halides for commonly used various in this area in said inert liquid medium, for example: silicone oil and/or hydrocarbon system solvent.Particularly, said inert liquid medium can be in kerosene, Yellow Protopet 2A, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, methylethyl silicone oil, phenyl silicone oil and the methyl phenyl silicone oil one or more.
According to the preparation method of adduct of magnesium halides of the present invention, the consumption of said inert liquid medium can be according to MgX
1The concrete consumption of Y is selected.Usually, the MgX with respect to 1 mole in magnesium
1Y, the consumption of inert liquid medium are 0.2-13L; Preferably, the MgX with respect to 1 mole in magnesium
1Y, the consumption of inert liquid medium are 0.6-6.5L.
According to the preparation method of adduct of magnesium halides of the present invention, said liquid adduct of magnesium halides can be mixed with inert liquid medium, then with the emulsifying mixture that obtains, thereby realize adduct of magnesium halides emulsification with said liquid state.
According to the preparation method of adduct of magnesium halides of the present invention, can also with the said inert liquid medium of part as the preparation said liquid adduct of magnesium halides reaction medium (that is, with said inert liquid medium of part and MgX
1Y, ethanol, LB
1, LB
2And LB
3Mix, perhaps with said inert liquid medium of part and MgX
1Y, ethanol, under hydrolysising condition, can form LB
1Material, under hydrolysis and/or alcoholysis conditions, can form LB
2Material and under hydrolysis and/or alcoholysis conditions, can form LB
3Material mix), thereby obtain containing the mixed solution of liquid adduct of magnesium halides, then this mixed solution is mixed also emulsification with the inert liquid medium of remainder, and then realization is with the adduct of magnesium halides emulsification of said liquid state.
Preparing method according to adduct of magnesium halides of the present invention; Also can be with the reaction medium of whole said inert liquid mediums as the said liquid adduct of magnesium halides of preparation; Thereby obtain containing the mixed solution of liquid adduct of magnesium halides; And with this mixed solution emulsification, and then realize adduct of magnesium halides emulsification with said liquid state.
Preparing method according to adduct of magnesium halides of the present invention; When needing; Also can be randomly in said inert liquid medium, add some tensio-active agents,, polysorbate smooth, Soxylat A 25-7 or polyoxyethylene-polyoxypropylene multipolymer like glycerin fatty acid ester, lipid acid sorb.Said amount of surfactant can be the conventional amount used of this area, for example: with respect to 1 mole the MgX in magnesium
1Y, said amount of surfactant can be the 0.001-1 mole.
Preparing method according to adduct of magnesium halides of the present invention; Can adopt and well known to a person skilled in the art that the whole bag of tricks is with said adduct of magnesium halides emulsification for liquid state; For example: can be in the presence of inert liquid medium; With said for liquid adduct of magnesium halides carries out high speed shear, thereby will saidly be the adduct of magnesium halides emulsification of liquid state.The method of said high speed shear is known in those skilled in the art, for example: the disclosed high-speed mixing method of CN1151183C (that is, liquid adduct of magnesium halides speed with 2000-5000 rev/min in inert liquid medium being stirred); The disclosed mixture with liquid adduct of magnesium halides and inert liquid medium of CN1267508C is rotated (speed of rotation can be 100-3000 rev/min) in the hypergravity bed disperses; The disclosed mixture with liquid adduct of magnesium halides and silicone oil and white oil of CN1463990A is exported with 1500-8000 rev/min speed with mulser; The disclosed emulsifying mixture that will contain liquid adduct of magnesium halides through spray method of US6020279.
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 the emulsification product quenching is shaped, thereby obtain spherical adduct of magnesium halides.For example: can through said emulsification product is transferred to method in the liquid cooling medium with said emulsification product quenching to be shaped.
According to the preparation method of adduct of magnesium halides of the present invention, chemically interactive liquid medium can not take place with adduct of magnesium halides for commonly used various in this area in said liquid cooling medium.For example, said liquid cooling medium can be the unreactive hydrocarbons series solvent.The specific examples of said 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 said liquid cooling medium is as the criterion can make said emulsification product cooling and to be shaped.Usually, the temperature of said liquid cooling medium can be-50 ℃ to 0 ℃, is preferably-40 ℃ to-20 ℃.Consumption for said heat-eliminating medium has no particular limits, as long as the consumption of said heat-eliminating medium is enough to the cooling of emulsification product and is shaped.Particularly, the volume ratio of said heat-eliminating medium and said emulsification product is 1-15: 1, be preferably 2-9: 1.
Preparation method based on adduct of magnesium halides of the present invention can also comprise the spherical adduct of magnesium halides particle washing that will be shaped through chilling and obtain and carry out drying.The spherical adduct of magnesium halides particle that can adopt the method for well known to a person skilled in the art to obtain washs, and for example can adopt unreactive hydrocarbons series solvent (for example: Skellysolve A, normal hexane, normal heptane, sherwood oil and gasoline) that the spherical adduct of magnesium halides that obtains is washed.The present invention does not limit for said exsiccant condition is special, and for example: said exsiccant temperature can be 20-70 ℃, and the said exsiccant time can be 0.5-10 hour.Based on the present invention, said drying can be carried out under the condition of normal pressure or reduction pressure.
The adduct of magnesium halides shown in the formula I is used in the preparation that is used for the catalyst component of olefinic polymerization according to the present invention; The particle shape of this adduct of magnesium halides is good; There is not adhesion phenomenon between the particle; And there is not special-shaped particle; Thereby make that the particle form of catalyst component according to the invention is good; Do not have opposite sex material, so by the olefin polymerization catalyst system of said catalyst component preparation in olefinic polyreaction, can prepare the good polymkeric substance of particle shape.Compare with the catalyst component that is used for olefinic polymerization of prior art; Used the catalyst component of the present invention of adduct of magnesium halides shown in the formula I; The performance that when being used for olefinic polyreaction, in fact has improvement; Promptly; When keeping than high polymerization activity; Demonstrate excellent hydrogen response and high stereotaxis ability, obtained hydrogen and transferred the well balanced between ability and the stereotaxis ability.Therefore, the present invention is for the kind of titanium compound in the said catalyst component and optional internal electron donor compound and consumption is not special limits, and can be this area various titanium compounds and internal electron donor compound commonly used.
Usually, according to the catalyst component that is used for olefinic polymerization of the present invention, wherein said titanium compound can be three halogenated titaniums and general formula Ti (OR ')
4-mX '
mIn the shown titanium compound one or more, in this general formula, R ' can be C
1-C
10Alkyl, X ' can be halogen, m can be the integer of 0-4.Preferably, said titanium compound is one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine three titanium butoxide, dichloro dibutoxy titanium, trichlorine one titanium butoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium and the titanous chloride.More preferably, said titanium compound is a titanium tetrachloride.
The catalyst component that is used for olefinic polymerization according to the present invention can adopt method well known in the art to prepare, for example: can be through said adduct of magnesium halides particle is directly contacted with titanium compound, to react.Preferably; Preparing the said preparation method who is used for the catalyst component of olefinic polymerization comprises: said adduct of magnesium halides is suspended in the mixed solution of cold titanium compound or titanium compound and inert solvent, and (temperature of the mixture of said titanium compound or titanium compound and inert solvent can be-40 ℃ to 0 ℃; Be preferably-25 ℃ to-15 ℃); Then with the mixture heating up that obtains to 40-130 ℃; Preferably be heated to 80-130 ℃; And under said temperature, kept 0.5-2 hour, carry out solid-liquid separation then and collect solid; Then, with the solid suspension that obtains in titanium compound, and with the mixture heating up that obtains to 60-130 ℃; Preferably be heated to 80-130 ℃, and under said temperature, kept 0.5-2 hour, carry out solid-liquid separation then and collect solid; This operation can be carried out one or many, preferably carries out 2-4 time; At last, with the solid that the inert solvent washing obtains, said inert solvent is preferably aliphatic hydrocarbon or aromatic hydrocarbons, for example: normal hexane, normal heptane, octane, n-decane and toluene.
Usually; Needs according to practical application; Particularly,, in the preparation process of said catalyst component, can also randomly add at least a internal electron donor compound in order to obtain high normal propene polymer for the catalyst component that is used for propylene polymerization.Based on the present invention, the adding of said internal electron donor compound can be before the reaction of adduct of magnesium halides particle and titanium compound, in the reaction or carry out after the reaction, preferably when adduct of magnesium halides particle and titanium compound react, carries out.
According to the catalyst component that is used for olefinic polymerization of the present invention; Said internal electron donor compound can be the various internal electron donor compounds that this area is commonly used, and for example: said internal electron donor compound can be in ester, ether, ketone, amine and the silane one or more.Preferably, said internal electron donor compound is one or more in ester and the diether type compound.
Among the present invention, said ester can be in monobasic aliphatic carboxylic acid esters,, polyhydric aliphatic family carboxylicesters, monobasic aromatic carboxylic acid esters, polynary aromatic carboxylic acid esters and the diol ester one or more.Among the present invention, said ester is preferably polynary aromatic carboxylic acid esters.
Among the present invention, term " monobasic aliphatic carboxylic acid esters, " is meant the compound that is formed through esterification by monobasic aliphatic carboxylic acid and monohydroxy-alcohol.Term " polyhydric aliphatic family carboxylicesters " is meant the compound that is formed through esterification by polyhydric aliphatic family carboxylic acid and monohydroxy-alcohol.Term " monobasic aromatic carboxylic acid esters " is meant the compound that is formed through esterification by monobasic aromatic carboxylic acid and monohydroxy-alcohol.Term " polynary aromatic carboxylic acid esters " is meant the compound that polynary aromatic carboxylic acid and monohydroxy-alcohol form through esterification.
Among the present invention, the instance of said 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; Among the present invention; Said monobasic aliphatic carboxylic acid esters; Polyhydric aliphatic family carboxylicesters; The instance of monobasic aromatic carboxylic acid esters and polynary aromatic carboxylic acid esters can for but be not limited to: ethyl benzoate; Diethyl phthalate; Diisobutyl phthalate; N-butyl phthalate; Dimixo-octyl phthalate; Dinoctyl phthalate; Diethyl malonate; The propanedioic acid di-n-butyl; The 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-methylsuccinic acid diisobutyl ester; 2-ethyl-2-methylsuccinic acid diethyl ester; Ethyl glutarate; The pentanedioic acid di-n-butyl; The pentanedioic acid diisobutyl ester; Methylcarbonate; Diethyl carbonate; The carbonic acid diisobutyl ester; Diethylene adipate; Di-n-butyl Adipate; Ethyl sebacate; N-butyl sebacate; Diethyl maleate; Maleic acid n-butyl; The naphthalene dicarboxylic acids diethyl ester; The naphthalene dicarboxylic acids di-n-butyl; Triethyl trimellitate; The trimellitic acid tri-n-butyl; Biphenyl three triethylenetetraminehexaacetic acid esters; Join the benzenetricarboxylic acid tri-n-butyl; Pyromellitic acid tetra-ethyl ester and pyromellitic acid four positive butyl esters.
Among the present invention, term " diol ester " is meant the compound that dibasic alcohol and monocarboxylic acid or polycarboxylic acid form through esterification.For example, said diol ester can be the compound shown in the formula X:
Among the 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 a kind of; Perhaps 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 a kind of.
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 a kind of; Perhaps, 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 a kind of.
More preferably, R
I, R
II, R
VAnd R
VIIn at least one be hydrogen, and R
I, R
II, R
VAnd R
VIBe not hydrogen simultaneously.
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 a kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl and the 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 a kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl and the halogenophenyl; R
IIIAnd R
IVA kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, allyl group, n-pentyl, isopentyl and the n-hexyl, perhaps R respectively do for oneself
IIIAnd R
IVBe bonded together each other to form and replace or unsubstituted fluorenyl; R
VIIAnd R
VIIIA kind of 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 the styryl respectively does for oneself.
Among the present invention, the specific examples of said diol ester can for but be not limited to: 1, the ammediol dibenzoate; The 2-methyl isophthalic acid; The ammediol dibenzoate; 2-ethyl-1, the ammediol dibenzoate; 2,2-dimethyl-1; The ammediol dibenzoate; (R)-and 1-phenyl-1, the ammediol dibenzoate; 1,3-phenylbenzene-1; The ammediol dibenzoate; 1,3-phenylbenzene-1, ammediol 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; The ammediol diacetate esters; 1,3-phenylbenzene-2,2-dimethyl-1; The ammediol dibenzoate; 1,3-phenylbenzene-2,2-dimethyl-1; Ammediol two n Propanoic acid esters; 1,3-di-t-butyl-2-ethyl-1, ammediol dibenzoate; 1; 3-phenylbenzene-1, the ammediol diacetate esters; 1,3-di-isopropyl-1; Ammediol two (4-n-butylbenzene formic acid) ester; 1-phenyl-2-amino-1, the ammediol 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; The 2-methyl isophthalic acid, 3-pentanediol two (Chlorodracylic acid) ester; The 2-methyl isophthalic acid, 3-pentanediol two (p-methylbenzoic acid) ester; 2-normal-butyl-1; 3-pentanediol two (p-methylbenzoic acid) ester; The 2-methyl isophthalic acid; 3-pentanediol two (p-tert-butyl benzoic acid) ester; The 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; The 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-di-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, two pairs of fluoro methyl benzoic acid esters of 4-pentanediol; 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-di-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-di-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; 9, two (benzoyloxy methyl) 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-(benzoyloxy methyl)-9-(propionyloxy ylmethyl) fluorenes; 9, two (propionyloxy methyl) fluorenes of 9-; 9; Two (acryloyl-oxy ylmethyl) fluorenes and 9 of 9-, two (oxy acid methyl neopentyl) fluorenes of 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, said diether type compound can be as the diether type compound of olefin polymerization catalysis internal electron donor compound for commonly used various in this area.For example, said diether type compound can be 1 shown in the general formula X I, 3-diether type compound:
Among the 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 a kind of, 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 a kind of.Among the present invention, R
I, R
II, R
III, R
IV, R
VAnd R
VIIn two or more bondings each other, to form ring.
Preferably, among the formula XI: R
I, R
II, R
VAnd R
VIBe hydrogen; R
VIIAnd R
VIIIC respectively does for oneself
1-C
4The straight or branched alkyl, methyl more preferably; R
IIIBe methyl, ethyl, n-propyl or sec.-propyl, R
IVA kind of in ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, isopentyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl and the benzyl; Perhaps, R
IIIBe hydrogen, R
IVA kind of in ethyl, normal-butyl, sec-butyl, the tertiary butyl, 2-ethylhexyl, cyclohexyl ethyl, diphenyl methyl, rubigan, 1-naphthyl and the 1-decahydro naphthyl; Perhaps, R
IIIAnd R
IVIdentical, and be a kind of in ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, neo-pentyl, phenyl, benzyl, cyclohexyl and the cyclopentyl; Perhaps, R
IIIAnd R
IVMutual bonding is 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 said 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 that is used for olefinic polymerization of expecting.For example, the mol ratio of said titanium compound, internal electron donor compound and said adduct of magnesium halides can be 5-100: 0-0.5: 1; Be preferably 20-80: 0.05-0.35: 1, said titanium compound is in titanium elements, and said adduct of magnesium halides is in magnesium elements.Among the present invention, the amount of titanium compound is the total amount that is included in the titanium compound that uses in the preparation catalyst component process of the present invention.
The catalyst according to the invention component is suitable for being used for preparing olefin polymerization catalyst system.
The present invention further provides a kind of catalyst system that is used for olefinic polymerization, and said catalyst system comprises catalyst according to the invention component and one or more organo-aluminium compounds.
The composition of said catalyst component and preparation method have carried out detailed description at preamble, repeat no more at this.
Compare with the catalyst system that is used for olefinic polymerization of prior art; Used the olefin polymerization catalyst system of the present invention of catalyst according to the invention component; The performance that when being used for olefinic polyreaction, in fact has improvement; Promptly; When keeping than high polymerization activity; Demonstrate excellent hydrogen response and high stereotaxis ability, obtained hydrogen and transferred the well balanced between ability and the stereotaxis ability, and can prepare the good polymkeric substance of particle shape.Therefore, the catalyst system that is used for olefinic polymerization according to the present invention all limits less than special for the kind and the consumption of organo-aluminium compound.
Said organo-aluminium compound can be this area various organo-aluminium compounds commonly used.For example, said organo-aluminium compound can be alkylaluminium sesquichloride and general formula AlR
7R
8R
9Shown in the compound one or more, in this general formula, R
7, R
8And R
9Can be chlorine and C separately
1-C
8Alkyl in a kind of, and R
7, R
8And R
9In at least one be C
1-C
8Alkyl.Preferably, said organo-aluminium compound is one or more in trialkyl aluminium compound, a chlorine aluminum dialkyl compound, dichloro one alkylaluminium cpd and the alkylaluminium sesquichloride.More preferably, said 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 that is used for olefinic polymerization of the present invention, said in aluminium organo-aluminium compound and can be 1-2000 in the mol ratio of the catalyst component of titanium: 1, be preferably 20-700: 1.
At alkene particularly under the organic upright structure polymeric situation of alpha-olefin (for example propylene or 1-butylene), the catalyst system that is used for olefinic polymerization according to the present invention can also comprise with as the identical or different electron donor compound of the compound of internal electron donor as the external electron donor compound.
Said external electron donor compound can be the various external electron donor compounds that this area is commonly used, and for example: said external electron donor compound can be in carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organo phosphorous compounds and the silicoorganic compound one or more.Preferably, said external electron donor is a 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, z is the integer of 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
10Contain or do not contain heteroatomic branched-chain alkyl, C
3-C
10Contain or do not contain heteroatomic replacement or unsubstituted cycloalkyl and C
6-C
10Replacement or unsubstituted aryl in a kind of, R
cBe C
1-C
10Alkyl, be preferably methyl; X is 1, and y is 1, and z is 2; Perhaps, R
bBe C
3-C
10Branched-chain alkyl or C
3-C
10Cycloalkyl, and R
cBe methyl, x is 0, and y is 1, and z is 3.
Among the present invention; The instance of said silicoorganic compound can for but be not limited to: cyclohexyl methyl dimethoxy silane; 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; 1-three fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silane; (1; 1,1-three fluoro-2-propyl group)-methyl dimethoxysilane; Cyclohexyl trimethoxy silane; Tert-butyl trimethoxy silane and uncle's hexyl Trimethoxy silane.
Usually, with respect to 1 mole the organo-aluminium compound in aluminium, the consumption of said external electron donor compound can be the 0.005-0.5 mole; Preferably, with respect to 1 mole the organo-aluminium compound in aluminium, the consumption of said external electron donor compound is the 0.01-0.4 mole.
According to the catalyst system that is used for olefinic polymerization of the present invention, be under the situation of ester, particularly multi-carboxylate and diol ester at said internal electron donor, preferably with in the above-mentioned electron donor compound one or more as external electron donor; At said internal electron donor is ether, and particularly 1 shown in the formula XI during 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 that is used for various uses.
The 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 this method is included under the olefinic polymerization condition, and one or more alkene are contacted with catalyst system provided by the invention.
Through using the 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 for olefinic polymerization condition and the not special qualification of employed alkene.
Usually, according to olefine polymerizing process of the present invention, said 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 a kind of.According to olefine polymerizing process of the present invention, in case of necessity, said alkene can also contain a spot of diolefine.According to olefine polymerizing process of the present invention, said alkene is preferably propylene, perhaps propylene and CH
2=CHR
13Shown alkene, wherein, R
13Be hydrogen and C
1-C
6The straight or branched alkyl in a kind of.
According to olefine polymerizing process of the present invention, said polymerization can be carried out according to the ordinary method of this area.For example, said 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, said 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 that relates to is following:
1, melt index (MI): measure according to the method for stipulating among the ASTM D1238-99.
2, polymkeric substance isotactic index (II): adopt the normal heptane extraction process to measure (normal heptane boiling extracting 6 hours); Concrete operations are: take by weighing 2g exsiccant polymer samples; Place Soxhlet extractor with ebullient normal heptane extracting 6 hours; Then; Residuum is dried to constant weight, and the weight of gained residuum (g) is isotactic index with 2 ratio.
3, the pattern of sample is that the opticmicroscope of Eclipse E200 is observed through being purchased model from Nikon company.
4, adopt vapor-phase chromatography to measure ethanol, LB in the adduct of magnesium halides
1, LB
2And LB
3Content, adopt chemical titration to measure the content of Mg in the adduct of magnesium halides.
5, adopt the content of titanium in the spectrophotometry catalyst component.
Embodiment 1
Present embodiment is used for illustrating catalyst component and catalyst system and application and the olefine polymerizing process that is used for olefinic polymerization according to of the present invention.
(1) preparation of adduct of magnesium halides
In the reaction kettle of 500mL; Adding 150mL white oil, 30g Magnesium Chloride Anhydrous (being purchased the prosperous Yi Taichang from the Fushun City), 50mL dehydrated alcohol (are purchased from the Beijing Chemical Plant; Analytical pure), 4mL 2; 2-Propanal dimethyl acetal (being purchased the chemical industry company limited from the Warner, Ningbo) and 1mL 2-methoxy benzoyl chloride (being purchased the CO.LTD from TOKYO KASEI KOGYO) under agitation are warming up to 120 ℃.After the isothermal reaction 2 hours, mixture is pressed in the 300mL methyl-silicone oil that is preheated to 120 ℃ (be purchased from DOW CORNING, viscosity is 300 centipoises/20 ℃), stirred 30 minutes with 1600 rev/mins speed, to carry out emulsification.Then, the emulsification product is pressed in advance with nitrogen in the hexane of the 2L that is cooled to-30 ℃, carries out chilling and be shaped.Remove by filter liquid, with the solid that obtains with the hexane wash of 300mL 5 times, and in 35 ℃ of following vacuum dry 3 hours, thus 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 the employing observation by light microscope arrives as shown in Figure 1.
(2) preparation of catalyst component
In the glass reaction bottle of 300mL, under the nitrogen protection condition, add 10mL hexane, 90mL titanium tetrachloride successively, be cooled to-20 ℃, add the adduct of magnesium halides of 8.0g step (1) preparation, and stirred 30 minutes at-20 ℃.Then, slowly be warming up to 110 ℃, and in temperature-rise period, add the 1.5mL diisobutyl phthalate.110 ℃ of isothermal reactions after 30 minutes, filtering liquid.Add the 80mL titanium tetrachloride, be warming up to 120 ℃, 120 ℃ keep 30 minutes after filtering liquid; Then, add the 80mL titanium tetrachloride again, and be warming up to 120 ℃, 120 ℃ keep 30 minutes after filtering liquid.At last with 60 ℃ the solids wash 5 time (hexane consumption be 80mL/ time) of hexane to obtaining; And vacuum-drying gained solids, thereby obtain the spherical catalyst component.The content of titanium is 2.8wt% in this spherical catalyst component, and the particle morphology that the 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 reaction kettle, add the hexane solution (concentration is 0.5mmol/mL) of 5mL triethyl aluminum, the hexane solution (concentration is 0.1mmol/mL) of 1mL cyclohexyl methyl dimethoxy silane and the spherical catalyst component of 9mg step (2) preparation successively.Close autoclave, add 1.5L (standard volume) hydrogen and 2.3L liquid propene.Be warming up to 70 ℃, reacted 1 hour.Then, cooling, release, discharging, and carry out drying, thus obtain polypropylene.
(4) propylene polymerization B
Adopt the method identical with (3) to carry out propylene polymerization, different is that the consumption of hydrogen is 5.0L (standard volume).
Embodiment 2
Present embodiment is used for illustrating catalyst component and catalyst system and application and the olefine polymerizing process that is used for olefinic polymerization according to of the present invention.
(1) preparation of adduct of magnesium halides
Adopt to prepare spherical adduct of magnesium halides with embodiment 1 identical method, different is, 2, and the consumption of 2-Propanal dimethyl acetal is 9mL.The composition of this adduct of magnesium halides is as shown in table 1, and the particle morphology that the employing observation by light microscope arrives as shown in Figure 3.
(2) preparation of catalyst component
Adopt to prepare the spherical catalyst component with embodiment 1 identical method, different is that adduct of magnesium halides is the adduct of magnesium halides of embodiment 2 steps (1) preparation.The content of titanium is 2.1wt% in this spherical catalyst component, and the particle morphology that the employing observation by light microscope arrives as shown in Figure 4.
(3) propylene polymerization A
Employing is carried out propylene polymerization with (3) the identical method among the embodiment 1, and different is that catalyst component is the catalyst component of above-mentioned steps (2) preparation.
(4) propylene polymerization B
Employing is carried out propylene polymerization with (4) the identical method among the embodiment 1, and different is that catalyst component is the catalyst component of above-mentioned steps (2) preparation.
Comparative Examples 1
(1) preparation of adduct of magnesium halides
Adopt to prepare spherical adduct of magnesium halides with embodiment 2 identical methods, different is not use 2, the 2-Propanal dimethyl acetal.The composition of this adduct of magnesium halides is as shown in table 1.
(2) preparation of catalyst component
Adopt to prepare the spherical catalyst component with embodiment 1 identical method, different is that adduct of magnesium halides is the adduct of magnesium halides of Comparative Examples 1 step (1) preparation.The content of titanium is 2.4wt% in this spherical catalyst component.
(3) propylene polymerization A
Employing is carried out propylene polymerization with (3) the identical method among the embodiment 1, and different is that catalyst component is the catalyst component of above-mentioned steps (2) preparation.
(4) propylene polymerization B
Employing is carried out propylene polymerization with (4) the identical method among the embodiment 1, and different is that catalyst component is the catalyst component of above-mentioned steps (2) preparation.
Comparative Examples 2
(1) preparation of adduct of magnesium halides
Adopt to prepare spherical adduct of magnesium halides with embodiment 2 identical methods, different is not use the 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 that arrives as shown in Figure 5.
(2) preparation of catalyst component
Adopt to prepare the spherical catalyst component with embodiment 1 identical method, different is that adduct of magnesium halides is the adduct of magnesium halides of Comparative Examples 2 steps (1) preparation.The content of titanium is 2.6wt% in this spherical catalyst component, and the particle morphology that the employing observation by light microscope arrives as shown in Figure 6.
(3) propylene polymerization A
Employing is carried out propylene polymerization with (3) the identical method among the embodiment 1, and different is that catalyst component is the catalyst component of above-mentioned steps (2) preparation.
(4) propylene polymerization B
Employing is carried out propylene polymerization with (4) the identical method among the embodiment 1, and different is that catalyst component is the catalyst component of above-mentioned steps (2) preparation.
Embodiment 3
Present embodiment is used for illustrating catalyst component and catalyst system and application and the olefine polymerizing process that is used for olefinic polymerization according to of the present invention.
(1) preparation of adduct of magnesium halides
In the reaction kettle 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 chemical company limited) and 0.5g 4-nipagin A (being purchased chemical company limited), under agitation be warming up to 120 ℃ from A Faaisha (Tianjin) from A Faaisha (Tianjin).After the isothermal reaction 2 hours, mixture is pressed in the 300mL methyl-silicone oil that is preheated to 120 ℃ (be purchased from DOW CORNING, viscosity is 300 centipoises/20 ℃), stirred 30 minutes with 1600 rev/mins speed, to carry out emulsification.Then, the emulsification product is pressed in advance with nitrogen in the 2L hexane that is cooled to-30 ℃, carries out chilling and be shaped.Remove by filter liquid, the solid that obtains with the hexane wash of 300mL 5 times, and 35 ℃ of following vacuum-dryings 3 hours, thereby is obtained spherical adduct of magnesium halides.The composition of this adduct of magnesium halides is as shown in table 1.Adopt opticmicroscope that the particle morphology of the adduct of magnesium halides that obtains is observed, find that this adduct of magnesium halides for spherical, do not have opposite sex material, and do not have adhesion between the particle.
(2) preparation of catalyst component
Adopt to prepare the spherical catalyst component with embodiment 1 identical method, different is that adduct of magnesium halides is the adduct of magnesium halides of embodiment 3 steps (1) preparation.The content of titanium is 2.7wt% in this spherical catalyst component.Adopt opticmicroscope that the particle morphology of the catalyst component that obtains is observed, find that the solid particulate form is good, be sphere, do not have opposite sex material.
(3) propylene polymerization A
Employing is carried out propylene polymerization with (3) the identical method among the embodiment 1, and different is that catalyst component is the catalyst component of above-mentioned steps (2) preparation.
(4) propylene polymerization B
Employing is carried out propylene polymerization with (4) the identical method among the embodiment 1, and different is that catalyst component is the catalyst component of above-mentioned steps (2) preparation.
Comparative Examples 3
(1) preparation of adduct of magnesium halides
Adopt to prepare spherical adduct of magnesium halides with embodiment 3 identical methods, different is not use methyl alcohol.The composition of this adduct of magnesium halides is as shown in table 1.
(2) preparation of catalyst component
Adopt to prepare the spherical catalyst component with embodiment 1 identical method, different is that adduct of magnesium halides is the adduct of magnesium halides of Comparative Examples 3 steps (1) preparation.The content of titanium is 2.9wt% in this spherical catalyst component.
(3) propylene polymerization A
Employing is carried out propylene polymerization with (3) the identical method among the embodiment 1, and different is that catalyst component is the catalyst component of above-mentioned steps (2) preparation.
(4) propylene polymerization B
Employing is carried out propylene polymerization with (4) the identical method among the embodiment 1, and different is that catalyst component is the catalyst component of above-mentioned steps (2) preparation.
Embodiment 4
Present embodiment is used for illustrating catalyst component and catalyst system and application and the olefine polymerizing process that is used for olefinic polymerization according to of the present invention.
(1) preparation of adduct of magnesium halides
In the reaction kettle 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 chemical company limited) and 0.5mL 2 hydroxybenzoic acid ethyl ester (being purchased double happiness spices auxiliary agent company limited), under agitation be warming up to 120 ℃ from Shanghai from A Faaisha (Tianjin).After the isothermal reaction 2 hours, mixture is pressed in the 300mL methyl-silicone oil that is preheated to 120 ℃ (be purchased from DOW CORNING, viscosity is 300 centipoises/20 ℃), stirred 30 minutes with 1600 rev/mins speed, to carry out emulsification.Then, the emulsification product is pressed in advance with nitrogen in the 2L hexane that is cooled to-30 ℃, carries out chilling and be shaped.Remove by filter liquid, the solid that obtains with the hexane wash of 300mL 5 times, and 35 ℃ of following vacuum-dryings 3 hours, thereby is obtained spherical adduct of magnesium halides.The composition of this adduct of magnesium halides is as shown in table 1.Adopt opticmicroscope that the particle morphology of the adduct of magnesium halides that obtains is observed, find that this adduct of magnesium halides for spherical, do not have opposite sex material, and do not have adhesion between the particle.
(2) preparation of catalyst component
Adopt to prepare the spherical catalyst component with embodiment 1 identical method, different is that adduct of magnesium halides is the adduct of magnesium halides of embodiment 4 steps (1) preparation.The content of titanium is 2.5wt% in this spherical catalyst component.Adopt opticmicroscope that the particle morphology of the catalyst component that obtains is observed, find that the solid particulate form is good, be sphere, do not have opposite sex material.
(3) propylene polymerization B
Employing is carried out propylene polymerization with (4) the identical method among the embodiment 1, and different is that catalyst component is the catalyst component of above-mentioned steps (2) preparation.
Embodiment 5
Present embodiment is used for illustrating catalyst component and catalyst system and application and the olefine polymerizing process that is used for olefinic polymerization according to of the present invention.
(1) preparation of adduct of magnesium halides
Adopt to prepare spherical adduct of magnesium halides with embodiment 1 identical method, different is, 2, and the consumption of 2-Propanal dimethyl acetal is 1mL, 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 that the particle morphology of the adduct of magnesium halides that obtains is observed, find that this adduct of magnesium halides for spherical, do not have opposite sex material, and do not have adhesion between the particle.
(2) preparation of catalyst component
Adopt to prepare the spherical catalyst component with embodiment 1 identical method, different is that adduct of magnesium halides is the adduct of magnesium halides of embodiment 5 steps (1) preparation.The content of titanium is 3.0wt% in this spherical catalyst component.Adopt opticmicroscope that the particle morphology of the catalyst component that obtains is observed, find that the solid particulate form is good, be sphere, do not have opposite sex material.
(3) propylene polymerization B
Employing is carried out propylene polymerization with (4) the identical method among the embodiment 1, and different is that catalyst component is the catalyst component of above-mentioned steps (2) preparation.
Embodiment 6
Present embodiment is used for illustrating catalyst component and catalyst system and application and the olefine polymerizing process that is used for olefinic polymerization according to of the present invention.
(1) preparation of adduct of magnesium halides
Adopt to prepare spherical adduct of magnesium halides with embodiment 1 identical method, different is, 2, and the consumption of 2-Propanal dimethyl acetal is 9mL, 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 that the particle morphology of the adduct of magnesium halides that obtains is observed, find that this adduct of magnesium halides for spherical, do not have opposite sex material, and do not have adhesion between the particle.
(2) preparation of catalyst component
Adopt to prepare the spherical catalyst component with embodiment 1 identical method, different is that adduct of magnesium halides is the adduct of magnesium halides of embodiment 6 steps (1) preparation.The content of titanium is 2.4wt% in this spherical catalyst component.Adopt opticmicroscope that the particle morphology of the catalyst component that obtains is observed, find that the solid particulate form is good, be sphere, do not have opposite sex material.
(3) propylene polymerization B
Employing is carried out propylene polymerization with (4) the identical method among the embodiment 1, and different is that catalyst component is the catalyst component of above-mentioned steps (2) preparation.
Embodiment 7
Present embodiment is used for illustrating catalyst component and catalyst system and application and the olefine polymerizing process that is used for olefinic polymerization according to of the present invention.
(1) preparation of adduct of magnesium halides
Adopt to prepare spherical adduct of magnesium halides with embodiment 1 identical method, different is, consumption of ethanol is 57mL, 2, and the consumption of 2-Propanal dimethyl acetal is 1mL.The composition of this adduct of magnesium halides is as shown in table 1.Adopt opticmicroscope that the particle morphology of the adduct of magnesium halides that obtains is observed, find that this adduct of magnesium halides for spherical, do not have opposite sex material, and do not have adhesion between the particle.
(2) preparation of catalyst component
Adopt to prepare the spherical catalyst component with embodiment 1 identical method, different is that adduct of magnesium halides is the adduct of magnesium halides of embodiment 7 steps (1) preparation.The content of titanium is 2.3wt% in this spherical catalyst component.Adopt opticmicroscope that the particle morphology of the catalyst component that obtains is observed, find that the solid particulate form is good, be sphere, do not have opposite sex material.
(3) propylene polymerization B
Employing is carried out propylene polymerization with (4) the identical method among the embodiment 1, and different is that catalyst component is the catalyst component of above-mentioned steps (2) preparation.
Table 1
a: methyl alcohol;
b: the O-Anisic Acid ethyl ester
c: the 2 hydroxybenzoic acid ethyl ester
d: 4-methoxybenzoic acid ethyl ester
e: the 4-nipagin A
Fig. 1 and Fig. 2 are respectively the spherical adduct of magnesium halides of embodiment 1 preparation and the particle morphology photo of catalyst component; Fig. 3 and Fig. 4 are respectively the spherical adduct of magnesium halides of embodiment 2 preparations and the particle morphology photo of catalyst component, and Fig. 5 and Fig. 6 are the spherical adduct of magnesium halides of Comparative Examples 2 preparations respectively and the particle morphology photo of catalyst component.With Fig. 1,3 and Fig. 5 compare and can find out, not only there is the abnormity material in the adduct of magnesium halides of Comparative Examples 2 preparation, and particle distribution is inhomogeneous, and the particle shape of adduct of magnesium halides of the present invention is very perfect, is sphere, does not have the abnormity material.With Fig. 2,4 and Fig. 6 compare and can find out, also there is the abnormity material in Comparative Examples 2 according to the catalyst component of its corresponding adducts preparation, and particle distribution is inhomogeneous; And the catalyst according to the invention component has good particle form, is sphere, does not have the abnormity material.This explanation is compared with the catalyst component that is prepared by prior art polycomponent adducts, and the catalyst according to the invention component has the particle form of improvement.
Polymerization results when table 2 has been listed catalyst system by embodiment 1-7 and Comparative Examples 1-3 preparation and is used for propylene polymerization.
Table 2
Embodiment 1,2 and Comparative Examples 1, embodiment 3 are compared and can find out with Comparative Examples 3, when the catalyst according to the invention system is used for propylene polymerization, not only demonstrate better hydrogen response, and show higher stereotaxis ability.Embodiment 2 and 3 is compared also and can find out with Comparative Examples 2 respectively; When the catalyst according to the invention system is used for propylene polymerization; Obtained the stereotaxis ability of better hydrogen response and Geng Gao simultaneously, and the resulting polymers particle form is good, does not have opposite sex material.This shows, according to of the present invention to contain LB simultaneously
1, LB
2And LB
3Adduct of magnesium halides be that the catalyst body of carrier ties up to when being used for propylene polymerization, than by only containing LB
1Or LB
2And LB
3The prior art adduct of magnesium halides as the catalyst system of carrier, LB
1, LB
2And LB
3Exist in the time of the three and demonstrate good synergistic; Make catalyst body of the present invention tie up to hydrogen response and the stereotaxis ability to has obtained good improvement simultaneously; Reached hydrogen and transferred the well balanced between ability and the stereotaxis ability, over-all properties is better.
Claims (25)
1. catalyst component that is used for olefinic polymerization, this catalyst component comprise the reaction product of adduct of magnesium halides, titanium compound and optional at least a internal electron donor compound, it is characterized in that, said adduct of magnesium halides is suc as formula shown in the I,
MgX
1Y-mEtOH-n(LB
1)-k(LB
2)-p(LB
3) (I)
Among the formula I, X
1Be 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 a kind of; LB
1, LB
2And LB
3Respectively do for oneself carboxylic acid, aldehyde, ether, ester, ketone, silane, amine, nitrile, phenol and be different from a kind of in the alcoholic acid alcohol,
Among the 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.
2. catalyst component according to claim 1, wherein, the mol ratio of said titanium compound, internal electron donor compound and said adduct of magnesium halides is 5-100: 0-0.5: 1; Be preferably 20-80: 0.05-0.35: 1, said titanium compound is in titanium elements, and said adduct of magnesium halides is in magnesium elements.
3. catalyst component according to claim 1, wherein, among the formula I, said 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 a kind of; Preferably, among the formula I, MgX
1Y is one or more in magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and the chlorination n-butoxy magnesium.
4. catalyst component according to claim 1, wherein, among the formula I, LB
1Be the compound shown in the formula II:
R
7X
2 (II)
Among the formula II, X
2For-NH
2,-NHR
7' and-a kind of among the OH, R
7' be C
1-C
20Alkyl, R
7Be C
1-C
20Alkyl, or by the substituted C of heteroatom group
1-C
20Alkyl, and at X
2During for-OH, R
7It is not ethyl;
Preferably, among the formula II, X
2For-OH; R
7Be methyl, C
3-C
10Alkyl, perhaps by-NH
2,-NHR
7' and-one or more substituted C among the OH
1-C
10Alkyl; R
7' be C
1-C
5The straight or branched alkyl;
More preferably, among the formula II, X
2For-OH, R
7Be methyl, C
3-C
10Straight or branched alkyl, C
6-C
10Replacement or unsubstituted aryl, or quilt-NH
2And/or-the substituted C of OH
1-C
10The straight or branched alkyl;
Further preferably, LB
1Be methyl alcohol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, terepthaloyl moietie, 1, a kind of in ammediol and the phenol.
5. catalyst component according to claim 1, wherein, among the formula I, LB
2Be the alkoxybenzoic acid ester based compound shown in alkoxybenzoic acid based compound shown in the formula III or the formula III,
In the formula III, R
1Be 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 a kind of;
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 not substituted cycloalkyl, C
6-C
20Replacement or unsubstituted aryl and C
7-C
20Replacement or unsubstituted aralkyl in a kind of; Perhaps, R
2, R
3, R
4And R
5In two or more mutual bondings, to form ring;
R
6Be 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 a kind of;
Preferably, in the formula III, R
1Be 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 a kind of;
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 a kind of;
R
6Be 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 a kind of;
More preferably, in the formula III, R
1And R
6A kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and the styroyl respectively does for oneself;
R
2, R
3, R
4And R
5A kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and the tolyl respectively does for oneself.
6. catalyst component according to claim 5, wherein, LB
2A kind of in 4-alkoxybenzoic acid based compound, 4-alkoxybenzoic acid ester based compound, 2-alkoxybenzoic acid based compound and the 2-alkoxybenzoic acid ester based compound; Preferably, LB
2A kind of in 2-alkoxybenzoic acid based compound and the 2-alkoxybenzoic acid ester based compound.
7. catalyst component according to claim 1, wherein, among the formula I, LB
3Be the hydroxybenzoate based compound shown in hydroxy-benzoic acid based compound shown in the formula IV or the formula IV,
Among the formula IV, R
1Be 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 a kind of;
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 a kind of; Perhaps, R
2, R
3, R
4And R
5In two or more mutual bondings, to form ring;
Preferably, among the formula IV, R
1Be 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 a kind of;
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 a kind of;
More preferably, among the formula IV, R
1A kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and the styroyl;
R
2, R
3, R
4And R
5A kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and the tolyl respectively does for oneself.
8. catalyst component according to claim 7, wherein, LB
3A kind of in 4-hydroxy-benzoic acid based compound, 4-hydroxybenzoate based compound, 2 hydroxybenzoic acid based compound and the 2 hydroxybenzoic acid ester based compound; Preferably, LB
3A kind of in 2 hydroxybenzoic acid based compound and the 2 hydroxybenzoic acid ester based compound.
9. according to any described catalyst component among the claim 1-8, wherein, the preparation method of said adduct of magnesium halides comprises:
(1) with MgX
1Y and ethanol, LB
1, LB
2And LB
3Mix, and with the mixture heating up that obtains, to obtain liquid adduct of magnesium halides, with respect to 1 mole the MgX in magnesium
1Y, the alcoholic acid amount is the 1-5.5 mole, LB
1Amount be the 0.005-2.3 mole, LB
2Amount be the 0.0005-0.32 mole, LB
3Amount be the 0.0005-0.32 mole; Perhaps
With MgX
1Y and ethanol, under hydrolysising condition, can form LB
1Material, under hydrolysis and/or alcoholysis conditions, can form LB
2Material and under hydrolysis and/or alcoholysis conditions, can form LB
3Material mix, and with the mixture heating up that obtains, to obtain liquid adduct of magnesium halides, with respect to 1 mole MgX in magnesium
1Y, the alcoholic acid amount is the 1-5.5 mole, saidly under hydrolysising condition, can form LB
1Amount of substance be the 0.0025-1.2 mole, saidly under hydrolysis and/or alcoholysis conditions, can form LB
2Amount of substance be the 0.0005-0.32 mole, saidly under hydrolysis and/or alcoholysis conditions, can form LB
3Amount of substance be the 0.0005-0.32 mole;
(2) in the presence of inert liquid medium,, and, obtain spherical adduct of magnesium halides particle with the shaping of emulsification product quenching with the adduct of magnesium halides emulsification of said liquid state;
MgX
1Among the Y, X
1Be 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 a kind of;
LB
1, LB
2And LB
3Respectively do for oneself carboxylic acid, aldehyde, ether, ester, ketone, silane, amine, nitrile, phenol and be different from a kind of in the alcoholic acid alcohol.
10. catalyst component according to claim 9, wherein, LB
1Be R
7OH saidly can form LB under hydrolysising condition
1Material be the compound shown in the formula VII,
Among the formula VII, R
7Be methyl, C
3-C
20Alkyl, or by the substituted C of 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 a kind of; Perhaps, R
aAnd R
bBonding encircles to form each other;
Preferably, among the formula VII, R
7Be methyl, C
3-C
10Alkyl, perhaps by-NH
2,-NHR
7' and-one or more substituted C among the OH
1-C
10Alkyl; R
7' be C
1-C
5The straight 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 a kind of;
More preferably, among the formula VII, R
7Be methyl, C
3-C
10Straight or branched alkyl, C
6-C
10Replacement or unsubstituted aryl, or quilt-NH
2And/or-the substituted C of OH
1-C
10The straight or branched alkyl; R
aAnd R
bHydrogen and C respectively do for oneself
1-C
6The straight or branched alkyl in a kind of;
Further preferably, among the formula VII, R
7A kind of in methyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, n-hexyl, n-octyl, 2-ethylhexyl, 2-hydroxyethyl, 3-hydroxypropyl and the phenyl; R
aAnd R
bA kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and the isobutyl-respectively does for oneself.
11. catalyst component according to claim 9, wherein, LB
2Be the alkoxybenzoic acid ester based compound shown in alkoxybenzoic acid based compound shown in the formula III or the formula III, saidly under hydrolysis and/or alcoholysis conditions, can form LB
2Material be the alkoxy benzene formyl chloride based compound shown in the formula VIII,
Among the 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 a kind of; Perhaps, R
2, R
3, R
4And R
5In two or more mutual bondings, to form ring;
R
6Be 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 a kind of;
Preferably, among the 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 a kind of;
R
6Be 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 a kind of;
More preferably, among the formula VIII, R
2, R
3, R
4And R
5A kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and the tolyl respectively does for oneself;
R
6A kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and the styroyl.
12. catalyst component according to claim 11 wherein, saidly can form LB under hydrolysis and/or alcoholysis conditions
2Material be a kind of in 4-alkoxy benzene formyl chloride based compound and the 2-alkoxy benzene formyl chloride based compound; Preferably, LB
2Be 2-alkoxy benzene formyl chloride based compound.
13. catalyst component according to claim 9, wherein, LB
3Be the hydroxybenzoate based compound shown in hydroxy-benzoic acid based compound shown in the formula IV or the formula IV, saidly under hydrolysis and/or alcoholysis conditions, can form LB
3Material be the (2-hydroxybenzoyl) based compound shown in alkoxy benzene formyl based compound shown in the formula VIIII or the formula VIIII,
Among the formula VIIII, R
1' be hydrogen, hydroxyl, halogen, C
1-C
20Straight or branched alkoxyl group, C
3-C
20Replacement or unsubstituted cycloalkyloxy, C
6-C
20Replacement or unsubstituted aryloxy and C
7-C
20Replacement or unsubstituted aralkoxy in a kind of;
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 a kind of; Perhaps, R
2, R
3, R
4And R
5In two or more mutual bondings, to form ring;
R
6Be 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 a kind of;
Preferably, among the formula VIIII, R
1' be hydrogen, hydroxyl, halogen, C
1-C
6Straight or branched alkoxyl group, C
3-C
6Substituted unsubstituted cycloalkyloxy, C
6-C
10Replacement or unsubstituted aryloxy and C
7-C
10Replacement or unsubstituted aralkoxy in a kind of;
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 a kind of;
R
6Be 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 a kind of;
More preferably, among the formula VIIII, R
1' be a kind of in hydrogen, hydroxyl, chlorine, bromine, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, positive hexyloxy, benzyloxy and the benzene oxyethyl group;
R
2, R
3, R
4And R
5A kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and the tolyl respectively does for oneself; R
6A kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl and the styroyl.
14. catalyst component according to claim 13 wherein, saidly can form LB under hydrolysis and/or alcoholysis conditions
3Material be a kind of in 4-alkoxy benzene formyl based compound, 2-alkoxy benzene formyl based compound, 4-(2-hydroxybenzoyl) based compound and the 2-(2-hydroxybenzoyl) based compound; Preferably, saidly under hydrolysis and/or alcoholysis conditions, can form LB
3Material be a kind of in 2-alkoxy benzene formyl based compound and the 2-(2-hydroxybenzoyl) based compound.
15. catalyst component according to claim 9, wherein, the condition of said heating comprises: temperature is 80-140 ℃, and the reaction times is 0.5-4 hour.
16. catalyst component according to claim 9, wherein, said inert liquid medium is silicone oil and/or hydrocarbon system compound; MgX with respect to 1 mole in magnesium
1Y, the consumption of inert liquid medium is 0.2-13L, is preferably 0.6-6.5L.
17. catalyst component according to claim 1 and 2, wherein, said titanium compound is three halogenated titaniums and general formula Ti (OR ')
4-mX '
mIn the shown titanium compound one or more, R ' is C in this general formula
1-C
10Alkyl, X ' is a halogen, m is the integer of 0-4; Preferably, said titanium compound is one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium n-butoxide, purity titanium tetraethoxide, a 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 the titanous chloride.
18. catalyst component according to claim 1 and 2, wherein, said internal electron donor compound is one or more in ester, ether, ketone, amine and the silane; Preferably, said internal electron donor compound is one or more in ester and the diether type compound.
19. the application of any described catalyst component in the preparation olefin polymerization catalyst system among the claim 1-18.
20. a catalyst system that is used for olefinic polymerization, this catalyst system comprise according to any described catalyst component and one or more organo-aluminium compounds among the claim 1-18; In the said organo-aluminium compound of aluminium with in the mol ratio of the said catalyst component of titanium is 1-2000: 1, be preferably 20-700: 1.
21. catalyst system according to claim 20, wherein, said organoaluminum is alkylaluminium sesquichloride and general formula AlR
7R
8R
9In the shown compound one or more, in this general formula, R
7, R
8And R
9Chlorine and C respectively do for oneself
1-C
8Alkyl in a kind of, and R
7, R
8And R
9In at least one be C
1-C
8Alkyl.
22. according to claim 20 or 21 described catalyst systems, wherein, this catalyst system also comprises the external electron donor compound; Said external electron donor compound is 0.005-0.5 with mol ratio in the said organo-aluminium compound of aluminium: 1, be preferably 0.01-0.4: 1.
23. catalyst system according to claim 22, said external electron donor compound are one or more in carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organo phosphorous compounds and the silicoorganic compound; Preferably, said external electron donor compound is a general formula R
a xR
b ySi (OR
c)
zIn the shown silicoorganic compound one or more, 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, z is the integer of 1-3, and x+y+z=4.
24. any described catalyst body ties up to the application in the olefinic polyreaction among the claim 20-23.
25. an olefine polymerizing process, this method are included under the olefinic polymerization condition, and any said catalyst system among one or more alkene and the claim 20-23 is contacted.
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