CN105622423A - Magnesium halide adduct, and preparation method and application thereof - Google Patents
Magnesium halide adduct, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a magnesium halide adduct used for olefin polymerization, and a preparation method and an application thereof. The magnesium halide adduct is MgX<1>Y-mR<1>OH-n(LB1)-k(LB2)-p(LB3). LB1 is an alkoxy benzoate series compound represented by formula II, LB2 is a hydroxyl benzoate series compound represented by formula III, and LB3 is R<6>OH. A catalyst prepared through a reaction of the magnesium halide adduct, a titanium compound and an optional electron donor has good stereospecificity and high polymerization activity in olefin polymerization, and especially propylene polymerization, and has high industrial application values. The magnesium halide adduct has a good granular form and no special-shaped materials (such as spheroidic materials and bar-shaped materials), and the particles have no adhesion phenomenon.
Description
Technical field
The present invention relates to a kind of adduct of magnesium halides and its preparation method and application.
Background technology
Magnesium halide alcohol adducts and its as carrier olefin polymerization catalysis prepare in application be known in the field. This adduct obtains catalyst after reacting with halogenated titanium and electron donor compound, the catalyst obtained is used for alkene (particularly propylene) when being polymerized, having higher polymerization activity and stereotaxis ability, resulting polymers also has good particle shape and higher apparent density.
Published magnesium halide alcohol adducts is the alcohol adduct of magnesium chloride mostly, generally includes magnesium chloride and alcohol binary composition. Wherein, some published magnesium chloride and the adduct of alcohol are possibly together with a small amount of water. Such as: the adduct of the magnesium chloride disclosed in US4421674, US4469648, WO8707620, WO9311166, US5100849, US6020279, US4399054, EP0395383, US6127304 and US6323152 and alcohol. This type of adduct can be prepared by methods such as spray drying, spray cooling, high pressure extrusion or high-speed stirred.
But, when the catalyst prepared by the adduct of above-mentioned published magnesium chloride Yu alcohol is used for olefinic polymerization, it is easy to the phenomenon occurring polymer particle broken in the course of the polymerization process, thus causing fine polymer powder more. In order to overcome this shortcoming, research worker attempts again being incorporated in advance by electron donor compound in the preparation process of the adduct of magnesium chloride and alcohol.
The phthalate compound (such as: diisobutyl phthalate or n-butyl phthalate) being typically used as internal electron donor in field of olefin polymerisation is incorporated in the building-up process of the adduct of magnesium chloride and alcohol by CN1169840C and CN1286863C, thus obtaining " magnesium dichloride-alcohol-phthalic acid ester " ball type carrier, then by this carrier and titanium tetrachloride reaction to form catalyst. But, described " magnesium dichloride-alcohol-phthalic acid ester " ball type carrier is easily tacky in preparation process, be difficult to be formed the spheroidal particle that size is suitable, and the catalyst prepared by this carrier for propylene polymerization time, polymerization activity is low and hydrogen response is poor.
In technology disclosed in CN100491410C, C, C-bis-oxyl hydrocarbon compound is introduced in adduct of magnesium halides. When the catalyst prepared as carrier by this multicomponent adduct of magnesium halides is for propylene polymerization, its hydrogen response obtains certain raising, and in polymer, fine powder content has a degree of minimizing. But, the preparation process of this adduct carrier is easily formed abnormity material (such as: oblate spheroid particle and/or bar shaped particle etc.), and, when the catalyst prepared by this adduct carrier carries out propylene polymerization under high hydrogen concentration, its stereotaxis ability, the isotacticity particularly with the polymer of high fusion index needs to improve further.
CN101486722B discloses a kind of adduct of magnesium halides comprising alcohol and o-alkoxyl benzoate compounds, having good hydrogen response and higher stereotaxis ability with the catalyst that described adduct of magnesium halides prepares for carrier, the catalyst that the adduct that the balance between hydrogen response and stereotaxis ability obtains than prior art prepares improves. These adducts are obtained by specific preparation method, including such as passing through reaction in-situ or the mode being directly added into, introduce o-alkoxyl benzoate compounds in the preparation process of adduct of magnesium halides. In method disclosed in CN101486722B, described o-alkoxyl benzoate compounds can derive from the alcoholysis reaction of o-alkoxyl Benzenecarbonyl chloride., in order to avoid the alkoxyl in o-alkoxyl Benzenecarbonyl chloride. is hydrolyzed, need the raw material used is carried out strict anhydrous process, by weight, the condition of described anhydrous process is generally the water content making magnesium halide lower than 0.2%, and the water content of alcohol is lower than 100ppm.
CN102796131A discloses a kind of such as formula M gXY-mR (OH)rThe adduct of magnesium halides of-nE, wherein X is chlorine or bromine, and Y is chlorine, bromine, C1-C14Straight or branched alkyl, C6-C14Substituted or unsubstituted aryl, C1-C14Straight or branched alkoxyl and C6-C14Substituted or unsubstituted aryloxy group in one, R is C1-C20Alkyl, r is the integer of more than 1, E is hydroxybenzoic acids or hydroxy benzoic acid ester type compound, m is 1-5, n is 0.001-0.5, described adduct of magnesium halides and halogenated titanium and optional internal electron donor react the catalyst of preparation when for propylene polymerization, and the hydrogen response of catalyst obtains further improvement.
CN102796127A discloses a kind of such as MgXY-mEtOH-n (LB1)-k(LB2)-p(LB3) shown in Spherical magnesium halide adduct, wherein, X is chlorine or bromine, and Y is chlorine, bromine, C1-C14Straight or branched alkyl, C6-C14Substituted or unsubstituted aryl, C1-C14Straight or branched alkoxyl and C6-C14Substituted or unsubstituted aryloxy group in one; LB1��LB2And LB3One in being respectively carboxylic acid, aldehyde, ether, ester, silane, amine, nitrile, phenol and being different from the alcohol of ethanol, m is 1-5, n be 0.005-2, k be 0.0005-0.3, p is 0.0005-0.3, by being directly added in magnesium halide and ethanol or reaction in-situ generates LB1��LB2And LB3Mode prepare described adduct of magnesium halides. Being reacted the catalyst of preparation when for propylene polymerization by these adducts and titanium compound and optional electron donor, the balance between hydrogen response and the stereotaxis ability of catalyst is further improved. But, this adduct of magnesium halides the catalyst prepared is when being polymerized for catalyzed alkene (particularly propylene), and polymerization activity needs to improve further.
Summary of the invention
It is an object of the invention to provide a kind of adduct of magnesium halides and preparation method thereof, this adduct of magnesium halides the catalyst prepared is when being polymerized for alkene (particularly propylene), it is shown that high polymerization activity.
The invention provides a kind of adduct of magnesium halides, this adduct of magnesium halides shown in formula I,
MgX1Y-mR1OH-n(LB1)-k(LB2)-p(LB3) (Formulas I)
Wherein, X1For chlorine or bromine, Y is chlorine, bromine, C1-C14Straight or branched alkyl, C6-C14Aryl, C1-C14Straight or branched alkoxyl and C6-C14Aryloxy group in one;
LB1For the oxyl benzoate based compound shown in Formula II,
LB2For the hydroxybenzoate based compound shown in formula III,
LB3For the alcohol shown in Formulas I V and/or phenol,
R6OH (Formulas I V)
R1For C1-C12Straight or branched alkyl, C3-C10Cycloalkyl and C7-C10Aralkyl in one;
R2��R3��R4And R5It is respectively hydrogen, halogen, nitro, C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C7-C20Aralkyl in one; Or, R2��R3��R4And R5In two or more be mutually bonded, to form ring;
R6With R1Differ, for C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C7-C20Aralkyl in one;
M, n, k and p in mol, meet the following conditions respectively:
M is 1-5,
0.001��n+k��0.3,
0.2��k/n��20,
P��k, and
0.0005��p < 0.05.
The preparation method that present invention also offers a kind of described adduct of magnesium halides, the method includes:
(1) by moisture MgX1Y and R1OH and the mixing of oxyl benzoyl based compound, and the mixture heating that will obtain, obtain the adduct of magnesium halides of liquid, relative to 1 mole of MgX in magnesium1Y, R1The amount of OH is 1-5.5 mole, and the amount of oxyl benzoyl based compound is 0.001-0.32 mole, moisture MgX1In Y, the amount of water is 0.011-0.081 mole; Or
By anhydrous MgX1Y and R1OH, oxyl benzoyl based compound and water mixing, and the mixture heating that will obtain, obtain the adduct of magnesium halides of liquid, relative to 1 mole of MgX in magnesium1Y, R1The amount of OH is 1-5.5 mole, and the amount of oxyl benzoyl based compound is 0.001-0.32 mole, and the amount of water is 0.011-0.081 mole;
Wherein, X1And R1Definition identical with the definition in Formulas I,
Described oxyl benzoyl based compound is such as shown in Formula VII,
In Formula VII, X2For the one in halogen atom, it is preferred to chlorine, R2��R3��R4��R5And R6Definition identical with the definition in Formula II and formula III;
(2) in the presence of inert liquid medium, by the adduct of magnesium halides emulsifying of described liquid, and it is dried after the shaping of emulsification product chilling, obtains adduct of magnesium halides granule.
Invention further provides the application in preparing olefin polymerization catalysis of the described adduct of magnesium halides.
Adduct of magnesium halides according to the present invention and titanium compound and optional electron donor are reacted the catalyst of preparation when as the catalyst of olefinic polymerization, particularly propylene polymerization, not only stereotaxis ability is good, and demonstrate higher polymerization activity, there is higher industrial application value.
The particle shape of the adduct of magnesium halides according to the present invention is good, without abnormity material (such as oblate spheroid material, bar material etc.), and also without adhesion phenomenon between particle.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below.
Fig. 1 is the optical microscope photograph of the adduct of magnesium halides of the embodiment of the present invention 1 preparation.
Detailed description of the invention
The invention provides a kind of adduct of magnesium halides, this adduct of magnesium halides shown in formula I,
MgX1Y-mR1OH-n(LB1)-k(LB2)-p(LB3) (Formulas I).
The MgX of Formulas I1In Y, X1For chlorine or bromine, Y is chlorine, bromine, C1-C14Straight or branched alkyl, C6-C14Aryl, C1-C14Straight or branched alkoxyl and C6-C14Aryloxy group in one.
Preferably, the MgX of Formulas I1In Y, Y is chlorine, bromine, C1-C5Straight or branched alkyl, C6-C10Aryl, C1-C5Straight or branched alkoxyl and C6-C10Aryloxy group in one.
In Formulas I, MgX1Y can be a kind of magnesium-containing compound, it is also possible to for the mixture of two or more magnesium-containing compounds.
Specifically, in Formulas I, MgX1The instantiation of Y can include but not limited to one or more in magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium. From the angle that raw material is ready availability, in Formulas I, MgX1Y is preferably magnesium dichloride.
The R of Formulas I1In OH, R1For C1-C12Straight or branched alkyl, C3-C10Cycloalkyl and C7-C10Aralkyl in one. Preferably, R1For C1-C6Straight or branched alkyl. It is highly preferred that R1For the one in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group and n-hexyl.
R1The instantiation of OH can include but not limited to: methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol, isoamyl alcohol, hexanol, n-octyl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol, 1,3-propylene glycol and phenyl methanol.
In Formulas I, LB1For the oxyl benzoate based compound shown in Formula II,
In Formula II, R1Definition with described previously identical, no longer describe in detail herein.
In Formula II, R2��R3��R4And R5It is respectively hydrogen, halogen, nitro, C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C7-C20Aralkyl in one, or, R2��R3��R4And R5In two or more be mutually bonded, to form ring.
Preferably, R2��R3��R4And R5It is respectively hydrogen, C1-C8Straight or branched alkyl, C3-C6Cycloalkyl, C6-C10Aryl and C7-C10Aralkyl in one.
It is highly preferred that R2��R3��R4And R5It is respectively the one in hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, cyclopenta, just base, n-heptyl and tolyl.
In Formula II, R6With R1Differ, for C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C7-C20Aralkyl in one.
Preferably, R6For C1-C6Straight or branched alkyl, C3-C6Cycloalkyl, C6-C10Aryl and C7-C10Aralkyl in one.
It is highly preferred that R6For the one in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, just base, benzyl and phenethyl.
In the present invention, as LB1Oxyl benzoate based compound be preferably 4-alkoxybenzoic acid ester based compound and/or 2-alkoxybenzoic acid ester based compound, more preferably 2-alkoxybenzoic acid ester based compound.
In the present invention, as LB1The instantiation of oxyl benzoate based compound can include but not limited to: 2-methoxybenzoic acid methyl ester, 2-methoxybenzoic acid ethyl ester, 2-methoxybenzoic acid n-propyl, 2-methoxybenzoic acid isopropyl ester, the positive butyl ester of 2-methoxybenzoic acid, 2-methoxybenzoic acid isobutyl ester, 2-methoxybenzoic acid n-pentyl ester, the just own ester of 2-methoxybenzoic acid, 2-methoxybenzoic acid benzyl ester, 2-methoxybenzoic 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 ester, 2-methoxyl group-4-ethyl benzoate methyl ester, 2-methoxyl group-5-ethyl benzoate methyl ester, 2-methoxyl group-3-methylbenzoic acid ethyl ester, 2-methoxyl group-4-methylbenzoic acid ethyl ester, 2-methoxyl group-5-methylbenzoic 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-ar-Toluic acid n-propyl, 2-methoxyl group-4-ar-Toluic acid n-propyl, 2-methoxyl group-5-ar-Toluic 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-ar-Toluic acid isopropyl ester, 2-methoxyl group-4-ar-Toluic acid isopropyl ester, 2-methoxyl group-5-ar-Toluic 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-ar-Toluic acid isobutyl ester, 2-methoxyl group-4-ar-Toluic acid isobutyl ester, 2-methoxyl group-5-ar-Toluic 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-n-propylbenzene Ethyl formate, 2-methoxyl group-4-n-propylbenzene Ethyl formate, 2-methoxyl group-5-n-propylbenzene Ethyl formate, 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-isoamyl benzene Ethyl formate, 2-methoxyl group-4-cyclopentylbenzoic acid ethyl ester, 2-ethoxy-benzoic acid methyl ester, 2-ethyl p-ethoxybenzoate, 2-ethoxybenzoic acid n-propyl, 2-ethoxy benzonitrile isopropyl propionate, 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 essence of Niobe, 2-n-butoxy ethyl benzoate, 2-n-butoxy n-Propyl benzoate, the positive fourth oxybenzoic acid isopropyl ester of 2-, 2-n-butoxy n-butylbenzoate, 2-n-butoxy isobutyl benzoate, 2-n-butoxy Pentyl benzoate, the just own ester of 2-n-butoxy benzoic acid, 2-n-butoxy benzyl benzoate and 2-n-butoxy phenylethyl benzoate.
In Formulas I, LB2For the hydroxybenzoate based compound shown in formula III,
In formula III, R1Definition with described previously identical, no longer describe in detail herein; R2��R3��R4And R5Definition with described previously identical, no longer describe in detail herein.
In the present invention, as LB2Hydroxybenzoate based compound be preferably 4-HBA ester based compound and/or 2 hydroxybenzoic acid ester based compound, more preferably 2 hydroxybenzoic acid ester based compound.
In the present invention, as LB2The instantiation of hydroxybenzoate based compound can include but not limited to: 2 hydroxybenzoic acid methyl ester, 2 hydroxybenzoic acid ethyl ester, 2 hydroxybenzoic acid n-propyl, 2 hydroxybenzoic acid isopropyl ester, the positive butyl ester of 2 hydroxybenzoic acid, 2 hydroxybenzoic acid isobutyl ester, 2 hydroxybenzoic acid n-pentyl ester, the just own ester of 2 hydroxybenzoic acid, 2 hydroxybenzoic acid benzyl ester, 2 hydroxybenzoic acid phenethyl ester, 2-hydroxy-3-methyl essence of Niobe, 2-hydroxy-4-methyl essence of Niobe, 2-hydroxy-5-methyl yl benzoic acid methyl ester, 2-hydroxyl-3-ethyl benzoate methyl ester, 2-hydroxyl-4-ethyl benzoate methyl ester, 2-hydroxyl-5-ethyl benzoate methyl ester, 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 n-Propyl benzoate, 2-hydroxy-4-methyl n-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-isoamyl benzene Ethyl formate and 2-hydroxyl-4-cyclopentylbenzoic acid ethyl ester.
In Formulas I, LB3For the alcohol shown in IV and/or phenol,
R6OH (Formulas I V)
In Formulas I V, R6Definition with described previously identical, no longer describe in detail herein.
In the present invention, as LB3R6The instantiation of OH can include but not limited to: methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexanol, 2-Ethylhexyl Alcohol, phenol and phenylethanol.
In Formulas I, m, n, k and p in mol, meet the following conditions respectively:
M is 1-5,
0.001��n+k��0.3,
0.2��k/n��20,
P��k, and
0.0005��p < 0.05.
Preferably, m, n, k and p in mol, meet the following conditions respectively:
M is 2-3.5,
0.005��n+k��0.15,
0.5��k/n��10,
P��k, and
0.001��p��0.04��
It is highly preferred that m, n, k and p are in mol, meet the following conditions respectively:
M is 2.4-3.5,
0.015��n+k��0.1,
1��k/n��6,
P��k, and
0.005��p��0.04��
Adduct of magnesium halides according to the present invention can also contain water, described water comes from synthesis material and reaction medium is with minor amount of water and/or in prepared by adduct with water that separately component is added.
The present invention one preferred embodiment in, in Formulas I, X1It is chlorine with Y; R1For the one in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group and n-hexyl;
LB1For the 2-alkoxybenzoic acid ester shown in Formula V,
In Formula V, R1For the one in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group and n-hexyl; R2��R3��R4And R5It is respectively the one in hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, cyclopenta, just base, n-heptyl and tolyl; R6For the one in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, just base, benzyl and phenethyl;
LB2For the 2 hydroxybenzoic acid ester shown in Formula IV,
In Formula IV, R1For methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group and the one in base just; R2��R3��R4And R5It is respectively the one in hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, cyclopenta, just base, n-heptyl and tolyl;
LB3For general formula R6Compound shown in OH, R6For the one in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, just base, benzyl and phenethyl;
M, n, k and p in mol, meet the following conditions respectively:
M is 2.4-3.5,
0.015��n+k��0.1,
1��k/n��6,
P��k, and
0.005��p��0.04��
Adduct of magnesium halides according to the present invention is prepared preferably by one of following two mode.
In the first embodiment, the method preparing described adduct of magnesium halides includes:
(1) by anhydrous MgX1Y and R1OH, oxyl benzoyl based compound and water mixing, and the mixture heating that will obtain, obtain the adduct of magnesium halides of liquid, relative to 1 mole of MgX in magnesium1Y, R1The amount of OH is 1-5.5 mole, it is preferred to 2-3.7 mole, more preferably 2.4-3.7 mole; The amount of oxyl benzoyl based compound is 0.001-0.32 mole, it is preferred to 0.005-0.17 mole, more preferably 0.015-0.12 mole; The amount of water is 0.011-0.081 mole, it is preferred to 0.016-0.053 mole, more preferably 0.021-0.045 mole;
(2) in the presence of inert liquid medium, by the adduct of magnesium halides emulsifying of described liquid, and it is dried after the shaping of emulsification product chilling, obtains adduct of magnesium halides granule.
In the second embodiment, the method preparing described adduct of magnesium halides includes:
(1) by moisture MgX1Y and R1OH and the mixing of oxyl benzoyl based compound, and the mixture heating that will obtain, obtain the adduct of magnesium halides of liquid, relative to 1 mole of MgX in magnesium1Y, R1The amount of OH is 1-5.5 mole, it is preferred to 2-3.7 mole, more preferably 2.4-3.7 mole; The amount of oxyl benzoyl based compound is 0.001-0.32 mole, it is preferred to 0.005-0.17 mole, more preferably 0.015-0.12 mole; Moisture MgX1In Y, the amount of water is 0.011-0.081 mole, it is preferred to 0.016-0.053 mole, more preferably 0.021-0.045 mole;
(2) in the presence of inert liquid medium, by the adduct of magnesium halides emulsifying of described liquid, and it is dried after the shaping of emulsification product chilling, obtains adduct of magnesium halides granule.
In the present invention, by weight, anhydrous MgX1Water content in Y is lower than 0.2%, and described water content adopts Karl-Fischer method to measure. Can pass through to control MgX1The drying condition of Y and/or by MgX1Y contacts with the material of activity that water is responded, thus adjusting MgX1Water content in Y. The material of described activity that water is responded can be HCl air-flow.
In above two embodiment, except MgX1All the other raw materials outside Y carry out anhydrous process before use, with by the moisture Control in raw materials used in the scope not affecting result of the test. Usually, R1The water content of OH is lower than 100ppm (by weight), and the water content of oxyl benzoyl based compound is lower than 10ppm (by weight), and the water content of inert liquid medium is lower than 50ppm (by weight). Controlling or reducing the method for water content in solid material or liquid material is well-known in the art, such as: can be undertaken liquid material distilling and/or contacting with water absorbing agent (such as molecular sieve), high-purity inert gas can be continually fed into, such as High Purity Nitrogen air-flow in the solid material of heating or liquid material.
In above two embodiment, oxyl benzoyl based compound is such as shown in Formula VII,
In Formula VII, X2For the one in halogen atom, it is preferred to chlorine; R2��R3��R4��R5And R6Identical with described previously, no longer describe in detail herein.
Described oxyl benzoyl based compound is preferably 4-oxyl benzoyl based compound and/or 2-oxyl benzoyl based compound, more preferably 2-oxyl benzoyl based compound.
In the present invention, the instantiation of described oxyl benzoyl based compound can include but not limited to: 2-methoxy benzoyl chloride, 2-methoxyl group-3-methyl benzoyl chloride, 2-methoxyl group-4-methyl benzoyl chloride, 2-methoxyl group-5-methyl benzoyl chloride, 2-methoxyl group-3-ethylamino benzonitrile acyl chlorides, 2-methoxyl group-4-ethylamino benzonitrile acyl chlorides, 2-methoxyl group-5-ethylamino benzonitrile acyl chlorides, 2-methoxyl group-3-n-propylbenzene formyl chloride, 2-methoxyl group-4-n-propylbenzene formyl chloride, 2-methoxyl group-5-n-propylbenzene formyl chloride, 2-methoxyl group-4-diisopropylbenzoyl peroxide chlorine, 2-methoxyl group-4-isobutyl-benzene formyl chloride, 2-methoxyl group-4-tert-butyl benzoyl chloride, 2-methoxyl group-4-pentylbenzoyl chloride, 2-methoxyl group-4-isoamyl benzene formyl chloride, 2-methoxyl group-4-cyclopenta Benzenecarbonyl chloride., 2-ethoxy benzoyl chloride and 2-n-butoxy Benzenecarbonyl chloride..
Described inert liquid medium can be commonly used in the art various with adduct of magnesium halides, chemically interactive liquid medium does not occur, for instance: silicone oil and/or hydrocarbon system solvent. Specifically, described inert liquid medium can be one or more in kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
The consumption of described inert liquid medium can according to MgX1The concrete consumption of Y selects. Usually, relative to 1 mole of MgX in magnesium1Y, the consumption of inert liquid medium is 0.2-13L; Preferably, relative to 1 mole of MgX in magnesium1Y, the consumption of inert liquid medium is 0.6-6.5L.
The adduct of magnesium halides of described liquid can be mixed with inert liquid medium, and the emulsifying mixture that will obtain, thus realizing the adduct of magnesium halides emulsifying of described liquid.
Can also using described for the part inert liquid medium reaction medium as the adduct of magnesium halides preparing described liquid, thus obtaining the mixed liquor of the adduct of magnesium halides containing liquid, then this mixed liquor is mixed with remainder inert liquid medium and emulsifying, and then realize the adduct of magnesium halides emulsifying of described liquid.
Can also using whole described inert liquid mediums reaction medium as the adduct of magnesium halides preparing described liquid, thus obtaining the mixed liquor of the adduct of magnesium halides containing liquid, by this mixed liquor emulsifying, and then realize the adduct of magnesium halides emulsifying of described liquid.
When needing, it is possible to optionally add some surfactants in described inert liquid medium, as smooth in fatty glyceride, fatty acid Pyrusussuriensis, Polysorbate, polyoxyethylene ether or Pluronic F68. The consumption of described surfactant can be the conventional amount used of this area, for instance: relative to 1 mole of MgX in magnesium1Y, the consumption of described surfactant can be 0.001-1 mole.
Can adopt and well known to a person skilled in the art that various method is by the adduct of magnesium halides emulsifying of liquid, for instance: in the presence of inert liquid medium, the adduct of magnesium halides of liquid can be carried out high speed shear, thus by the adduct of magnesium halides emulsifying of liquid. The method of described high speed shear is known in those skilled in the art, for instance: the adduct of magnesium halides of liquid speed with 2000-5000 rev/min in inert liquid medium (that is, is stirred) by high-speed mixing method disclosed in CN1151183C; CN1267508C is disclosed rotates (speed of rotation can be 100-3000 rev/min) dispersion by the mixture of the adduct of magnesium halides of liquid Yu inert liquid medium in hypergravity bed; The disclosed mixture by the adduct of magnesium halides of liquid with silicone oil and white oil of CN1463990A exports with the speed of 1500-8000 rev/min in mulser; The disclosed nebulization of passing through of US6020279 is by the emulsifying mixture of the adduct of magnesium halides containing liquid.
The method of well known to a person skilled in the art can be adopted to be shaped by emulsification product chilling, thus obtaining Spherical magnesium halide adduct. Such as: can by described emulsification product being transferred to method in liquid cooling medium by described emulsification product chilling to shape.
Described liquid cooling medium can be commonly used in the art various with adduct of magnesium halides, chemically interactive liquid medium does not occur. Such as, described liquid cooling medium can be unreactive hydrocarbons series solvent. The instantiation of described liquid cooling medium can include but not limited to: pentane, normal hexane, normal heptane, gasoline or petrol ether.
In the present invention, described liquid cooling medium carries out anhydrous process before use, with by the moisture Control in liquid cooling medium used in the scope not affecting result of the test. Usually, the water content of described liquid cooling medium is controlled as not higher than 5ppm (by weight). Controlling or reducing the method for water content in described liquid cooling medium is well-known in the art, such as: can be undertaken liquid material distilling and/or contacting with water absorbing agent (such as molecular sieve), high-purity inert gas can be continually fed into, such as High Purity Nitrogen air-flow in the liquid material of heating.
The temperature of described liquid cooling medium is as the criterion so that described emulsification product can be made to cool down and shape. Usually, the temperature of described liquid cooling medium can be-50 DEG C to 0 DEG C, it is preferred to-40 DEG C to-20 DEG C. Consumption for described cooling medium has no particular limits, as long as the consumption of described cooling medium is enough to be cooled down by emulsification product and shape. Specifically, described cooling medium is 1-15:1 with the volume ratio of described emulsification product, it is preferred to 2-9:1.
The adduct of magnesium halides granule shaped through chilling and obtain can carry out washing and drying. The method of well known to a person skilled in the art can be adopted to be washed by the adduct of magnesium halides obtained, for instance can adopt unreactive hydrocarbons series solvent (such as: pentane, normal hexane, normal heptane, petroleum ether and gasoline) that the adduct of magnesium halides obtained is washed. Described dry temperature can be not higher than 35 DEG C, it is preferred to 25-30 DEG C; The described dry time can be 0.5-3 hour, it is preferable that 1-2h. Described drying can carry out when normal pressure or reduction pressure.
Not by the restriction of any specific theory, with MgX1Y is MgCl2, R1OH is ethanol, and oxyl benzoyl compound is 2-methoxy benzoyl chloride is example, experiences the following reaction mechanism mechanism of reaction, thus obtaining the adduct of magnesium halides of the present invention.
The adduct of magnesium halides of the present invention contacts the catalyst formed and demonstrates higher catalysis activity in olefin polymerization with titanium compound and optional Donor compound. Thus, present invention also offers the application in preparing olefin polymerization catalysis of the described adduct of magnesium halides.
Describe the present invention in detail below in conjunction with embodiment, but be not so limited the scope of the present invention.
In following example and comparative example, the method for testing related to is as follows.
1, melt index (MI): measure according to the method for regulation in ASTMD1238-99.
2, polymer isotactic index (II): adopt normal heptane extraction process to measure (normal heptane boiling extracting 6 hours), concrete operations are: weigh the 2g polymer samples dried, it is placed in Soxhlet extractor with the normal heptane extracting seethed with excitement 6 hours, then, residue is dried to constant weight, and the weight (g) of gained residue and the ratio of 2 are isotactic index.
3, means of differential scanning calorimetry (DSC): adopt and carry out with the scanning speed of 5 DEG C/min within the scope of 5-220 DEG C purchased from the differential scanning calorimeter that model is DSC7 of PerkinElmer company. In order to avoid sample generation hydration, use in glove box equipped with sample, volume be the aluminium glue capsule of 40 �� l.
4, X-ray powder diffraction spectrum (XRD): adopting the D8Advance type high power purchased from BrukerAXS company of Germany to turn target X-ray diffractometer, the test condition of this instrument is: Cu target (wavelength), pipe pressure 40kV, pipe flow 300mA, slit system DS=SS=1mm, receive slit 0.2mm, monochromator is graphite monochromator, and scintillation counter counts, scanning speed 3 �� (2 ��) min-1, sweep limits (2 ��) 5-15 ��. Analyzed sample is sealed in 50 microns of thickness, in glove box in the polyethylene plastic bag of operation.
Embodiment 1-5 is used for the present invention is described.
Embodiment 1
(1) in the reactor of 500mL, add 150mL white oil (commercially available from Guangzhou Ming En petrochemical industry company limited, by weight, water content is lower than 50ppm), 30g contain the magnesium chloride (commercially available from Xin Yitai factory of Fushun City) of 0.44wt% moisture, 50mL dehydrated alcohol (commercially available from Beijing Chemical Plant, by weight, water content is lower than 100ppm) and 1mL2-methoxy benzoyl chloride (commercially available from TOKYOKASEIKOGYOCO.LTD), under agitation it is warming up to 120 DEG C. After isothermal reaction 2 hours, mixture press-in is preheated to the 300mL methyl-silicone oil of 120 DEG C, and (commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, by weight, water content is lower than 50ppm) in, stir 30 minutes with the speed of 1600 revs/min, to carry out emulsifying. Then, the press-in of emulsification product nitrogen is cooled in the 2L hexane (by weight, water content is lower than 5ppm) of-30 DEG C in advance, carries out chilling shaping. It is filtered to remove liquid, the hexane of solid 300mL obtained is washed 5 times, and at 30 DEG C vacuum drying 1.5 hours, thus obtaining the Spherical magnesium halide adduct according to the present invention, its composition is listed in Table 1, adopts the particle morphology that observation by light microscope arrives as shown in Figure 1.
This adduct of magnesium halides is carried out dsc analysis, and in the DSC figure obtained, at one melting peak of 99.5 DEG C and 110.6 DEG C each appearance, the fusion enthalpy relevant to the highest melting peak is 169.4 joule/gram.
The x-ray diffraction pattern of this adduct of magnesium halides shows, in the scope of the 2 �� angles of diffraction of 5-15 ��, display is present in 5 diffraction spectral lines under the angle of diffraction 2 �� of 6.08 �� (14), 8.82 �� (100), 8.98 �� (76), 9.72 �� (55), 11.46 �� (9); Numeric representation in bracket is relative to the intensity I/I of the strongest diffraction spectral line0��
(2) in the glass reaction bottle of 300mL, when nitrogen protection, it is sequentially added into 10mL hexane, 90mL titanium tetrachloride, is cooled to-20 DEG C, add Spherical magnesium halide adduct prepared by 8.0g step (1), and stir 30 minutes at-20 DEG C. Then, it is to slowly warm up to 110 DEG C, and in temperature-rise period, adds 1.5mL diisobutyl phthalate. After 110 DEG C of isothermal reactions 30 minutes, filter liquid. Add 80mL titanium tetrachloride, be warming up to 120 DEG C, after maintaining 30 minutes at 120 DEG C, filter liquid; Then, add 80mL titanium tetrachloride, and be warming up to 120 DEG C, after maintaining 30 minutes at 120 DEG C, filter liquid. Finally with the hexane of 60 DEG C solid 5 times (hexane consumption is 80mL/ time) of washing to obtaining, and vacuum drying gained solids, thus obtaining spherical catalyst components.
(3) in the rustless steel autoclave of 5L, under nitrogen protection, it is sequentially added into spherical catalyst components prepared by the hexane solution (concentration is 0.5mmol/mL) of 5mL triethyl aluminum, the hexane solution (concentration is 0.1mmol/mL) of 1mL Cyclohexyl Methyl Dimethoxysilane and 9mg step (2). Close autoclave, add 1.5L (normal volume) hydrogen and 2.3L liquid propene. It is warming up to 70 DEG C, reacts 2 hours. Then, cooling, release, discharging, and be dried, thus obtaining polypropylene. Calculating the polymerization activity of catalyst, measure polyacrylic isotacticity and the melt flow index of preparation, result is listed in table 2.
Comparative example 1
(1) method identical with embodiment 1 step (1) is adopted to prepare spherical magnesium chloride adduct, the difference is that, the magnesium chloride of use is anhydrous magnesium chloride, and the composition of the adduct of magnesium halides of preparation is listed in Table 1.
This adduct of magnesium halides is carried out dsc analysis, and in the DSC figure obtained, at one melting peak of 100.0 DEG C and 109.8 DEG C each appearance, the fusion enthalpy relevant to the highest melting peak is 168.5 joule/gram.
The x-ray diffraction pattern of this adduct of magnesium halides shows, in the scope of the 2 �� angles of diffraction of 5-15 ��, display is present in 4 diffraction spectral lines under the angle of diffraction 2 �� of 6.26 �� (12), 9.06 �� (100), 10.00 �� (51), 11.74 �� (12); Numeric representation in bracket is relative to the intensity I/I of the strongest diffraction spectral line0��
(2) method identical with embodiment 1 step (2) is adopted to prepare spherical catalyst components, the difference is that, use spherical magnesium chloride adduct prepared by comparative example 1 step (1).
(3) method identical with embodiment 1 step (3) is adopted to prepare polypropylene, the difference is that, use spherical catalyst components prepared by comparative example 1 step (2).
Experimental result is listed in table 2.
Comparative example 2
(1) method identical with embodiment 1 step (1) is adopted to prepare spherical magnesium chloride adduct, the difference is that, the magnesium chloride used is anhydrous magnesium chloride, and change 1mL2-methoxy benzoyl chloride (commercially available from TOKYOKASEIKOGYOCO.LTD) into 1mL2-nipagin A (commercially available from TOKYOKASEIKOGYOCO.LTD, by weight, water content is lower than 10ppm), the composition of the adduct of magnesium halides of preparation is listed in Table 1.
This adduct of magnesium halides is carried out dsc analysis, and in the DSC figure obtained, at one melting peak of 97.1 DEG C and 113.4 DEG C each appearance, the fusion enthalpy relevant to the highest melting peak is 178.3 joule/gram.
The x-ray diffraction pattern of this adduct of magnesium halides shows, in the scope of the 2 �� angles of diffraction of 5-15 ��, display is present in 5 diffraction spectral lines under the angle of diffraction 2 �� of 6.07 �� (28), 8.80 �� (67), 9.06 �� (100), 9.98 �� (43), 11.63 �� (11); Numeric representation in bracket is relative to the intensity I/I of the strongest diffraction spectral line0��
(2) method identical with embodiment 1 step (2) is adopted to prepare spherical catalyst components, the difference is that, use Spherical magnesium halide adduct prepared by comparative example 2 step (1).
(3) method identical with embodiment 1 step (3) is adopted to prepare polypropylene, the difference is that, use spherical catalyst components prepared by comparative example 2 step (2).
Experimental result is listed in table 2.
Embodiment 2
(1) method identical with embodiment 1 step (1) is adopted to prepare Spherical magnesium halide adduct, the difference is that, the magnesium chloride of use is the magnesium chloride containing 0.65wt% moisture, and the composition of the adduct of magnesium halides of preparation is listed in Table 1.
This adduct of magnesium halides is carried out dsc analysis, and in the DSC figure obtained, at one melting peak of 97.6 DEG C and 112.1 DEG C each appearance, the fusion enthalpy relevant to the highest melting peak is 177.3 joule/gram.
The x-ray diffraction pattern of this adduct of magnesium halides shows, in the scope of the 2 �� angles of diffraction of 5-15 ��, display is present in 5 diffraction spectral lines under the angle of diffraction 2 �� of 6.06 �� (14), 8.82 �� (100), 8.98 �� (50), 9.74 �� (66), 11.48 �� (11); Numeric representation in bracket is relative to the intensity I/I of the strongest diffraction spectral line0��
(2) method identical with embodiment 1 step (2) is adopted to prepare spherical catalyst components, the difference is that, use spherical magnesium chloride adduct prepared by embodiment 2 step (1).
(3) method identical with embodiment 1 step (3) is adopted to prepare polypropylene, the difference is that, use spherical catalyst components prepared by embodiment 2 step (2).
Experimental result is listed in table 2.
Comparative example 3
(1) in the reactor of 500mL, add 150mL white oil (commercially available from Guangzhou Ming En petrochemical industry company limited, by weight, water content is lower than 50ppm), 30g contains the magnesium chloride (commercially available from Xin Yitai factory of Fushun City) of 0.65wt% moisture, 50mL dehydrated alcohol is (commercially available from Beijing Chemical Plant, by weight, water content is lower than 100ppm), 1mL2-methoxy benzoyl chloride (commercially available from TOKYOKASEIKOGYOCO.LTD) and 1mL2, 2-dimethoxy propane is (commercially available from Warner, Ningbo Chemical Co., Ltd., by weight, water content is lower than 10ppm), under agitation it is warming up to 120 DEG C. after isothermal reaction 2 hours, mixture press-in is preheated to the 300mL methyl-silicone oil of 120 DEG C, and (commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, by weight, water content is lower than 50ppm) in, stir 30 minutes with the speed of 1600 revs/min, to carry out emulsifying. then, the press-in of emulsification product nitrogen is cooled in the 2L hexane (by weight, water content is lower than 5ppm) of-30 DEG C in advance, carries out chilling shaping. be filtered to remove liquid, the hexane of solid 300mL obtained washed 5 times, and at 30 DEG C vacuum drying 1.5 hours, thus obtaining Spherical magnesium halide adduct, its composition is listed in Table 1.
This adduct of magnesium halides is carried out dsc analysis, and in the DSC figure obtained, at 76.2 DEG C, 97.3 DEG C and 111.4 DEG C one melting peak of each appearance, the fusion enthalpy relevant to the highest melting peak is 170.2 joule/gram.
The x-ray diffraction pattern of this adduct of magnesium halides shows, in the scope of the 2 �� angles of diffraction of 5-15 ��, display is present in 5 diffraction spectral lines under the angle of diffraction 2 �� of 6.14 �� (17), 9.05 �� (100), 9.49 �� (63), 9.84 �� (66), 11.63 �� (10); Numeric representation in bracket is relative to the intensity I/I of the strongest diffraction spectral line0��
(2) method identical with embodiment 1 step (2) is adopted to prepare spherical catalyst components, the difference is that, use Spherical magnesium halide adduct prepared by comparative example 3 step (1).
(3) method identical with embodiment 1 step (3) is adopted to prepare polypropylene, the difference is that, use spherical catalyst components prepared by comparative example 3 step (2).
Experimental result is listed in table 2.
Embodiment 3
(1) in the reactor of 500mL, add 150mL white oil (commercially available from Guangzhou Ming En petrochemical industry company limited, by weight, water content is lower than 50ppm), 30g anhydrous magnesium chloride (commercially available from Xin Yitai factory of Fushun City), 50mL dehydrated alcohol is (commercially available from Beijing Chemical Plant, by weight, water content is lower than 100ppm), 1mL2-methoxy benzoyl chloride (commercially available from TOKYOKASEIKOGYOCO.LTD) and 0.15g water, be under agitation warming up to 120 DEG C. After isothermal reaction 2 hours, mixture press-in is preheated to the 300mL methyl-silicone oil of 120 DEG C, and (commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, by weight, water content is lower than 50ppm) in, stir 30 minutes with the speed of 1600 revs/min, to carry out emulsifying. Then, the press-in of emulsification product nitrogen is cooled in the 2L hexane (by weight, water content is lower than 5ppm) of-30 DEG C in advance, carries out chilling shaping. Be filtered to remove liquid, the hexane of solid 300mL obtained washed 5 times, and at 30 DEG C vacuum drying 1.5 hours, thus obtaining the Spherical magnesium halide adduct according to the present invention, its composition is listed in Table 1.
This adduct of magnesium halides is carried out dsc analysis, and in the DSC figure obtained, at one melting peak of 98.5 DEG C and 111.3 DEG C each appearance, the fusion enthalpy relevant to the highest melting peak is 171.4 joule/gram.
The x-ray diffraction pattern of this adduct of magnesium halides shows, in the scope of the 2 �� angles of diffraction of 5-15 ��, display is present in 5 diffraction spectral lines under the angle of diffraction 2 �� of 6.10 �� (21), 8.78 �� (100), 8.98 �� (66), 9.72 �� (61), 11.48 �� (10); Numeric representation in bracket is relative to the intensity I/I of the strongest diffraction spectral line0��
(2) method identical with embodiment 1 step (2) is adopted to prepare spherical catalyst components, the difference is that, use Spherical magnesium halide adduct prepared by embodiment 3 step (1).
(3) method identical with embodiment 1 step (3) is adopted to prepare polypropylene, the difference is that, adopt spherical catalyst components prepared by embodiment 3 step (2).
Experimental result is listed in table 2.
Embodiment 4
(1) in the reactor of 500mL, add 150mL white oil (commercially available from Guangzhou Ming En petrochemical industry company limited, by weight, water content is lower than 50ppm), 30g contain the magnesium chloride (commercially available from Xin Yitai factory of Fushun City) of 1.2wt% moisture, 54mL dehydrated alcohol (commercially available from Beijing Chemical Plant, by weight, water content is lower than 100ppm) and 3mL2-methoxy benzoyl chloride (commercially available from TOKYOKASEIKOGYOCO.LTD), under agitation it is warming up to 130 DEG C. After isothermal reaction 2 hours, mixture press-in is preheated to the 300mL methyl-silicone oil of 130 DEG C, and (commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, by weight, water content is lower than 50ppm) in, stir 30 minutes with the speed of 1600 revs/min, to carry out emulsifying. Then, the press-in of emulsification product nitrogen is cooled in the 2L hexane (by weight, water content is lower than 5ppm) of-30 DEG C in advance, carries out chilling shaping. Be filtered to remove liquid, the hexane of solid 300mL obtained washed 5 times, and at 30 DEG C vacuum drying 1.5 hours, thus obtaining the Spherical magnesium halide adduct according to the present invention, composition is listed in Table 1.
This adduct of magnesium halides is carried out dsc analysis, and in the DSC figure obtained, at one melting peak of 97.5 DEG C and 112.7 DEG C each appearance, the fusion enthalpy relevant to the highest melting peak is 178.2 joule/gram.
The x-ray diffraction pattern of this adduct of magnesium halides shows, in the scope of the 2 �� angles of diffraction of 5-15 ��, display is present in 4 diffraction spectral lines under the angle of diffraction 2 �� of 6.14 �� (15), 8.88 �� (100), 9.80 �� (52), 11.54 �� (9); Numeric representation in bracket is relative to the intensity I/I of the strongest diffraction spectral line0��
(2) method identical with embodiment 1 step (2) is adopted to prepare spherical catalyst components, the difference is that, use Spherical magnesium halide adduct prepared by embodiment 4 step (1).
(3) method identical with embodiment 1 step (3) is adopted to prepare polypropylene, the difference is that, use spherical catalyst components prepared by embodiment 4 step (2).
Experimental result is listed in table 2.
Embodiment 5
(1) in the reactor of 500mL, add 150mL white oil (commercially available from Guangzhou Ming En petrochemical industry company limited, by weight, water content is lower than 50ppm), 30g contain the magnesium chloride (commercially available from Xin Yitai factory of Fushun City) of 1.2wt% moisture, 58mL dehydrated alcohol (commercially available from Beijing Chemical Plant, by weight, water content is lower than 100ppm) and 5mL4-methoxy benzoyl chloride (commercially available from commercially available from TOKYOKASEIKOGYOCO.LTD), under agitation it is warming up to 130 DEG C. After isothermal reaction 2 hours, mixture press-in is preheated to the 300mL methyl-silicone oil of 130 DEG C, and (commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, by weight, water content is lower than 50ppm) in, stir 30 minutes with the speed of 1600 revs/min, to carry out emulsifying. Then, the press-in of emulsification product nitrogen is cooled in the 2L hexane (by weight, water content is lower than 5ppm) of-30 DEG C in advance, carries out chilling shaping. Be filtered to remove liquid, the hexane of solid 300mL obtained washed 5 times, and at 30 DEG C vacuum drying 1.5 hours, thus obtaining the Spherical magnesium halide adduct according to the present invention, its composition is listed in Table 1.
This adduct of magnesium halides is carried out dsc analysis, and in the DSC figure obtained, at one melting peak of 97.7 DEG C and 112.0 DEG C each appearance, the fusion enthalpy relevant to the highest melting peak is 178.8 joule/gram.
The x-ray diffraction pattern of this adduct of magnesium halides shows, in the scope of the 2 �� angles of diffraction of 5-15 ��, display is present in 4 diffraction spectral lines under the angle of diffraction 2 �� of 6.20 �� (15), 8.84 �� (100), 9.78 �� (53), 11.52 �� (9); Numeric representation in bracket is relative to the intensity I/I of the strongest diffraction spectral line0��
(2) method identical with embodiment 1 step (2) is adopted to prepare spherical catalyst components, the difference is that, use Spherical magnesium halide adduct prepared by embodiment 5 step (1).
(3) method identical with embodiment 1 step (3) is adopted to prepare polypropylene, the difference is that, use spherical catalyst components prepared by embodiment 5 step (2).
Experimental result is listed in table 2.
Table 1
a: 2-methoxybenzoic acid ethyl esterb: 2 hydroxybenzoic acid ethyl esterc: methanol
d: 4-methoxy ethylbenzoatee: 4-HBA ethyl ester
Table 2
From the results shown in Table 2, by the catalyst formed according to the adduct of magnesium halides of the present invention when for propylene polymerization, it is shown that higher polymerization activity, the polymer simultaneously prepared also has higher isotacticity.
Fig. 1's as a result, it was confirmed that the particle shape according to the adduct of magnesium halides of the present invention is good, exists without opposite sex material.
Claims (14)
1. an adduct of magnesium halides, this adduct of magnesium halides shown in formula I,
MgX1Y-mR1OH-n(LB1)-k(LB2)-p(LB3) (Formulas I)
Wherein, X1For chlorine or bromine, Y is chlorine, bromine, C1-C14Straight or branched alkyl, C6-C14Aryl, C1-C14Straight or branched alkoxyl and C6-C14Aryloxy group in one;
LB1For the oxyl benzoate based compound shown in Formula II,
LB2For the hydroxybenzoate based compound shown in formula III,
LB3For the alcohol shown in Formulas I V and/or phenol,
R6OH (Formulas I V)
R1For C1-C12Straight or branched alkyl, C3-C10Cycloalkyl and C7-C10Aralkyl in one;
R2��R3��R4And R5It is respectively hydrogen, halogen, nitro, C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C7-C20Aralkyl in one; Or, R2��R3��R4And R5In two or more be mutually bonded, to form ring;
R6With R1Differ, for C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C7-C20Aralkyl in one;
M, n, k and p in mol, meet the following conditions respectively:
M is 1-5,
0.001��n+k��0.3,
0.2��k/n��20,
P��k, and
0.0005��p < 0.05.
2. adduct of magnesium halides according to claim 1, wherein, Y is chlorine, bromine, C1-C5Straight or branched alkyl, C6-C10Aryl, C1-C5Straight or branched alkoxyl and C6-C10Aryloxy group in one;
Preferably, MgX1Y is one or more in magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium.
3. adduct of magnesium halides according to claim 1, wherein, R1For C1-C6Straight or branched alkyl;
Preferably, R1For the one in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group and n-hexyl.
4. the adduct of magnesium halides according to claim 1 or 3, wherein, R2��R3��R4And R5It is respectively hydrogen, C1-C8Straight or branched alkyl, C3-C6Cycloalkyl, C6-C10Aryl and C7-C10Aralkyl in one;
Preferably, R2��R3��R4And R5It is respectively the one in hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, cyclopenta, just base, n-heptyl and tolyl.
5. the adduct of magnesium halides according to any one in claim 1,3 and 4, wherein, R6For C1-C6Straight or branched alkyl, C3-C6Cycloalkyl, C6-C10Aryl and C7-C10Aralkyl in one;
Preferably, R6For the one in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, just base, benzyl and phenethyl.
6. the adduct of magnesium halides according to any one in claim 1 and 3-5, wherein, LB2For 4-alkoxybenzoic acid ester based compound and/or 2-alkoxybenzoic acid ester based compound; LB3For 4-HBA ester based compound and/or 2 hydroxybenzoic acid ester based compound.
7. adduct of magnesium halides according to claim 1, wherein, m, n, k and p in mol, meet the following conditions respectively:
M is 2-3.5,
0.005��n+k��0.15,
0.5��k/n��10,
P��k, and
0.001��p��0.04;
Preferably, m, n, k and p in mol, meet the following conditions respectively:
M is 2.4-3.5,
0.015��n+k��0.1,
1��k/n��6,
P��k, and
0.005��p��0.04��
8. a preparation method for adduct of magnesium halides described in any one in claim 1-7, the method includes:
(1) by moisture MgX1Y and R1OH and the mixing of oxyl benzoyl based compound, and the mixture heating that will obtain, obtain the adduct of magnesium halides of liquid, relative to 1 mole of MgX in magnesium1Y, R1The amount of OH is 1-5.5 mole, and the amount of oxyl benzoyl based compound is 0.001-0.32 mole, moisture MgX1In Y, the amount of water is 0.011-0.081 mole; Or
By anhydrous MgX1Y and R1OH, oxyl benzoyl based compound and water mixing, and the mixture heating that will obtain, obtain the adduct of magnesium halides of liquid, relative to 1 mole of MgX in magnesium1Y, R1The amount of OH is 1-5.5 mole, and the amount of oxyl benzoyl based compound is 0.001-0.32 mole, and the amount of water is 0.011-0.081 mole;
Wherein, X1And R1Definition identical with the definition in Formulas I,
Described oxyl benzoyl based compound is such as shown in Formula VII,
In Formula VII, X2For the one in halogen atom, it is preferred to chlorine, R2��R3��R4��R5And R6Definition identical with the definition in Formula II and formula III;
(2) in the presence of inert liquid medium, by the adduct of magnesium halides emulsifying of described liquid, and it is dried after the shaping of emulsification product chilling, obtains adduct of magnesium halides granule.
9. method according to claim 8, wherein, relative to 1 mole of MgX in magnesium1Y, R1The amount of OH is 2-3.7 mole, it is preferred to 2.4-3.7 mole; The amount of oxyl benzoyl based compound is 0.005-0.17 mole, it is preferred to 0.015-0.12 mole; Moisture MgX1In Y, the amount of water is 0.016-0.053 mole, it is preferred to 0.021-0.045 mole; Or
Relative to 1 mole of MgX in magnesium1Y, R1The amount of OH is 2-3.7 mole, it is preferred to 2.4-3.7 mole; The amount of oxyl benzoyl based compound is 0.005-0.17 mole, it is preferred to 0.015-0.12 mole; The amount of water is 0.016-0.053 mole, it is preferred to 0.021-0.045 mole.
10. method according to claim 8 or claim 9, wherein, described oxyl benzoyl based compound is 4-alkoxy benzene formyl based compound and/or 2-alkoxy benzene formyl based compound.
11. method according to claim 8, wherein, the condition of described heating includes: temperature is 80-140 DEG C, and the time is 0.5-4 hour.
12. method according to claim 8, wherein, described inert liquid medium is silicone oil and/or hydrocarbon system solvent; Relative to 1 mole in the MgX of magnesium1Y, the consumption of described inert liquid medium is 0.2-13L, it is preferred to 0.6-6.5L.
13. method according to claim 8, wherein, described dry condition includes: temperature is for not higher than 35 DEG C, it is preferred to 25-30 DEG C; Time is 0.5-3 hour, it is preferred to 1-2 hour.
14. adduct of magnesium halides described in any one application in preparing olefin polymerization catalysis in claim 1-7.
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| CN101724101A (en) * | 2008-10-24 | 2010-06-09 | 中国石油化工股份有限公司 | Catalyzer component for olefin polymerization and catalyzer thereof |
| CN102234338A (en) * | 2010-04-22 | 2011-11-09 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst comprising same |
| US20120184694A1 (en) * | 2009-07-15 | 2012-07-19 | Xianzhi Xia | Spherical magnesium halide adduct, a catalyst component and a catalyst for olefin polymerization prepared therefrom |
| CN102796127A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Spherical magnesium halide adduct and preparation method and application thereof |
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| US20120184694A1 (en) * | 2009-07-15 | 2012-07-19 | Xianzhi Xia | Spherical magnesium halide adduct, a catalyst component and a catalyst for olefin polymerization prepared therefrom |
| CN102234338A (en) * | 2010-04-22 | 2011-11-09 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst comprising same |
| CN102796127A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Spherical magnesium halide adduct and preparation method and application thereof |
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