CN105622423B - A kind of adduct of magnesium halides and its preparation method and application - Google Patents
A kind of adduct of magnesium halides and its preparation method and application Download PDFInfo
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Abstract
The adduct of magnesium halides and its preparation method and application that the invention discloses a kind of for olefinic polymerization, the adduct of magnesium halides are MgX1Y‑mR1OH‑n(LB1)‑k(LB2)‑p(LB3), wherein LB1For oxyl benzoic ether based compound, LB shown in Formula II2For hydroxybenzoate based compound shown in formula III, LB3For R6OH.The adduct of magnesium halides is reacted to the catalyst of preparation with titanium compound and optional electron donor when being used as the catalyst of olefinic polymerization, particularly propylene polymerization, not only stereotaxis ability is good, and show higher polymerization activity, industrial application value with higher.The particle shape of the adduct of magnesium halides is good, no abnormity material (such as oblate spheroid material, bar material), and also without adhesion phenomenon between particle.
Description
Technical field
The present invention relates to a kind of adduct of magnesium halides and its preparation method and application.
Background technique
The application of magnesium halide alcohol adducts as well as carrier in olefin polymerization catalysis preparation is this field institute
It is well known.The adduct obtains catalyst after reacting with halogenated titanium and electron donor compound, and obtained catalyst is used for
When alkene (especially propylene) polymerize, polymerization activity and stereotaxis ability with higher, resulting polymers also have preferably
Particle shape and higher apparent density.
Published magnesium halide alcohol adducts are the alcohol adduct of magnesium chloride mostly, generally include magnesium chloride and alcohol binary group
Point.Wherein, the adduct of some published magnesium chlorides and alcohol also contains a small amount of water.Such as: US4421674,
US4469648、WO8707620、WO9311166、US5100849、US6020279、US4399054、EP0395383、
The adduct of magnesium chloride disclosed in US6127304 and US6323152 and alcohol.Such adduct can be by being spray-dried, spraying
Mist cooling, high pressure squeeze out or the methods of high-speed stirred preparation.
But when the catalyst prepared by the adduct of above-mentioned published magnesium chloride and alcohol is used for olefinic polymerization,
It is easy in the course of the polymerization process there is a phenomenon where polymer particle is broken, to cause fine polymer powder more.In order to overcome this
One disadvantage, researcher attempt the preparation process that electron donor compound is introduced into the adduct of magnesium chloride and alcohol in advance again
In.
CN1169840C and CN1286863C will be typically used as the phthalic acid of internal electron donor in field of olefin polymerisation
Ester type compound (such as: diisobutyl phthalate or n-butyl phthalate) it is introduced into the adduction of magnesium chloride and alcohol
In the synthesis process of object, so that " magnesium dichloride-alcohol-phthalic acid ester " ball type carrier is obtained, then by the carrier and four chlorinations
Titanium is reacted to form catalyst.But " magnesium dichloride-alcohol-phthalic acid ester " ball type carrier is easy during the preparation process
It is tacky, it is difficult to when forming the suitable spheric granules of particle size, and being used for propylene polymerization by catalyst prepared by the carrier, to gather
It is poor to close active low and hydrogen response.
In technology disclosed in CN100491410C, bis- oxyl hydrocarbon compound of C, C- is introduced in adduct of magnesium halides
In.When being used for propylene polymerization as catalyst prepared by carrier by the multicomponent adduct of magnesium halides, hydrogen response is obtained
Certain raising, fine powder content has a degree of reduction in polymer.But in the preparation process of the adduct carrier easily
Formation abnormity material (such as: oblate spheroid particle and/or bar shaped particle etc.), also, existed by catalyst prepared by the adduct carrier
When carrying out propylene polymerization under high hydrogen concentration, stereotaxis ability, the especially isotacticity of the polymer with high fusion index
It needs to be further increased.
CN101486722B discloses a kind of adduct of magnesium halides comprising pure and mild o-alkoxyl benzoate compounds,
There is good hydrogen response and higher stereotaxis ability by catalyst made from carrier of the adduct of magnesium halides,
Catalyst made from the adduct that balance between hydrogen response and stereotaxis ability is obtained than prior art is changed
It is kind.These adducts are obtained by specific preparation method, including such as reaction in-situ or by way of being directly added into,
O-alkoxyl benzoate compounds are introduced in the preparation process of adduct of magnesium halides.Method disclosed in CN101486722B
In, the o-alkoxyl benzoate compounds can derive from the alcoholysis reaction of o-alkoxyl chlorobenzoyl chloride, in order to avoid
Alkoxy in o-alkoxyl chlorobenzoyl chloride hydrolyzes, and needs to carry out used raw material stringent anhydrous processing, with
Poidometer, the condition of the anhydrous processing, which is generally, makes the water content of magnesium halide lower than 0.2%, the water content of alcohol be lower than
100ppm。
CN102796131A discloses a kind of such as formula M gXY-mR (OH)rThe adduct of magnesium halides of-nE, wherein X be chlorine or
Bromine, Y are chlorine, bromine, C1-C14Linear or branched alkyl group, C6-C14Substituted or unsubstituted aryl, C1-C14Linear chain or branched chain
Alkoxy and C6-C14One of substituted or unsubstituted aryloxy group, R C1-C20Alkyl, the integer that r is 1 or more, E is
Hydroxybenzoic acids or hydroxybenzoic acid esters compound, m 1-5, n 0.001-0.5, the adduct of magnesium halides
The catalyst of preparation is reacted with halogenated titanium and optional internal electron donor when for propylene polymerization, the hydrogen response of catalyst
Further improvement is obtained.
CN102796127A discloses a kind of such as MgXY-mEtOH-n (LB1)-k(LB2)-p(LB3) shown in spherical shape halogenation
Magnesium adduct, wherein X is chlorine or bromine, and Y is chlorine, bromine, C1-C14Linear or branched alkyl group, C6-C14It is substituted or unsubstituted
Aryl, C1-C14Straight or branched alkoxyl and C6-C14One of substituted or unsubstituted aryloxy group；LB1、LB2And LB3
Respectively carboxylic acid, aldehyde, ether, ester, silane, amine, nitrile, phenol and different from one of alcohol of ethyl alcohol, m 1-5, n 0.005-2, k
For 0.0005-0.3, p 0.0005-0.3, by being directly added into magnesium halide and ethyl alcohol or reaction in-situ generates LB1、LB2With
LB3Mode prepare the adduct of magnesium halides.Preparation is reacted with titanium compound and optional electron donor by these adducts
Catalyst be used for propylene polymerization when, the balance between the hydrogen response and stereotaxis ability of catalyst is obtained into one
The improvement of step.But the catalyst prepared by the adduct of magnesium halides gathers when for catalyzed alkene (especially propylene) polymerization
Activity is closed to need to be further increased.
Summary of the invention
The purpose of the present invention is to provide a kind of adduct of magnesium halides and preparation method thereof, are prepared by the adduct of magnesium halides
Catalyst for alkene (especially propylene) polymerization when, show high polymerization activity.
The present invention provides a kind of adduct of magnesium halides, and the adduct of magnesium halides is shown in formula I,
MgX1Y-mR1OH-n(LB1)-k(LB2)-p(LB3) (Formulas I)
Wherein, X1For chlorine or bromine, Y is chlorine, bromine, C1-C14Linear or branched alkyl group, C6-C14Aryl, C1-C14It is straight
Chain or branched alkoxy and C6-C14One of aryloxy group；
LB1For oxyl benzoic ether based compound shown in Formula II,
LB2For hydroxybenzoate based compound shown in formula III,
LB3For alcohol shown in formula IV and/or phenol,
R6OH (formula IV)
R1For C1-C12Linear or branched alkyl group, C3-C10Naphthenic base and C7-C10One of aralkyl；
R2、R3、R4And R5Respectively hydrogen, halogen, nitro, C1-C20Linear or branched alkyl group, C3-C20Naphthenic base, C6-
C20Aryl and C7-C20One of aralkyl；Alternatively, R2、R3、R4And R5In two or more be mutually bonded, with
Form ring；
R6With R1It is not identical, it is C1-C20Linear or branched alkyl group, C3-C20Naphthenic base, C6-C20Aryl and C7-C20
One of aralkyl；
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 present invention also provides a kind of preparation methods of adduct of magnesium halides, this method comprises:
(1) by aqueous MgX1Y and R1OH and the mixing of oxyl benzoyl based compound, and obtained mixture is heated, it obtains
To the adduct of magnesium halides of liquid, relative to 1 mole of MgX in terms of magnesium1Y, R1The amount of OH is 1-5.5 moles, oxyl benzoyl
The amount of based compound is 0.001-0.32 moles, aqueous MgX1The amount of water is 0.011-0.081 moles in Y；Or
By anhydrous MgX1Y and R1OH, oxyl benzoyl based compound and water mixing, and obtained mixture is heated, it obtains
To the adduct of magnesium halides of liquid, relative to 1 mole of MgX in terms of magnesium1Y, R1The amount of OH is 1-5.5 moles, oxyl benzoyl
The amount of based compound is 0.001-0.32 moles, and the amount of water is 0.011-0.081 moles；
Wherein, X1And R1Definition it is identical as the definition in Formulas I,
The oxyl benzoyl based compound as shown in Formula VII,
In Formula VII, X2For one of halogen atom, preferably chlorine, R2、R3、R4、R5And R6Definition and Formula II and formula
Definition in III is identical；
(2) in the presence of inert liquid medium, the adduct of magnesium halides of the liquid is emulsified, and by emulsification product chilling
It is dried after forming, obtains adduct of magnesium halides particle.
Invention further provides the adduct of magnesium halides to prepare the application in olefin polymerization catalysis.
Adduct of magnesium halides according to the present invention is reacted to the catalysis of preparation with titanium compound and optional electron donor
When being used as the catalyst of olefinic polymerization, particularly propylene polymerization, not only stereotaxis ability is good, but also shows higher for agent
Polymerization activity, industrial application value with higher.
The particle shape of adduct of magnesium halides according to the present invention is good, no abnormity material (such as oblate spheroid material, bar material),
And also without adhesion phenomenon between particle.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is the optical microscope photograph of adduct of magnesium halides prepared by the embodiment of the present invention 1.
Specific embodiment
The present invention provides a kind of adduct of magnesium halides, and the adduct of magnesium halides is 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-C14Linear or branched alkyl group, C6-C14Aryl, C1-
C14Straight or branched alkoxyl and C6-C14One of aryloxy group.
Preferably, the MgX of Formulas I1In Y, Y is chlorine, bromine, C1-C5Linear or branched alkyl group, C6-C10Aryl, C1-C5's
Straight or branched alkoxyl and C6-C10One of aryloxy group.
In Formulas I, MgX1Y can be a kind of magnesium-containing compound, or the mixture of two or more magnesium-containing compounds.
Specifically, in Formulas I, MgX1The specific example of Y can include but is not limited to magnesium dichloride, magnesium dibromide, Benzene Chloride
One or more of oxygroup magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium.The angle ready availability from raw material goes out
It sends out, in Formulas I, MgX1Y is preferably magnesium dichloride.
The R of Formulas I1In OH, R1For C1-C12Linear or branched alkyl group, C3-C10Naphthenic base and C7-C10Aralkyl in
It is a kind of.Preferably, R1For C1-C6Linear or branched alkyl group.It is highly preferred that R1For methyl, ethyl, n-propyl, isopropyl, just
One of butyl, isobutyl group and n-hexyl.
R1The specific example of OH can include but is not limited to: methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol,
N-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol, 1,3- propylene glycol and phenyl methanol.
In Formulas I, LB1For oxyl benzoic ether based compound shown in Formula II,
In Formula II, R1Definition with it is described previously identical, and will not be described here in detail.
In Formula II, R2、R3、R4And R5Respectively hydrogen, halogen, nitro, C1-C20Linear or branched alkyl group, C3-C20Ring
Alkyl, C6-C20Aryl and C7-C20One of aralkyl, alternatively, R2、R3、R4And R5In two or more phases
Mutually bonding, to form ring.
Preferably, R2、R3、R4And R5Respectively hydrogen, C1-C8Linear or branched alkyl group, C3-C6Naphthenic base, C6-C10's
Aryl and C7-C10One of aralkyl.
It is highly preferred that R2、R3、R4And R5Respectively hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, uncle
Butyl, n-pentyl, isopentyl, cyclopenta, just one of base, n-heptyl and tolyl.
In Formula II, R6With R1It is not identical, it is C1-C20Linear or branched alkyl group, C3-C20Naphthenic base, C6-C20Aryl
And C7-C20One of aralkyl.
Preferably, R6For C1-C6Linear or branched alkyl group, C3-C6Naphthenic base, C6-C10Aryl and C7-C10Aralkyl
One of base.
It is highly preferred that R6For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, just
One of base, benzyl and phenethyl.
In the present invention, as LB1Oxyl benzoic ether based compound be preferably 4- alkoxybenzoic acid ester system chemical combination
Object and/or 2- alkoxybenzoic acid ester based compound, more preferably 2- alkoxybenzoic acid ester based compound.
In the present invention, as LB1The specific example of oxyl benzoic ether based compound can include but is not limited to: 2-
Methoxyl methyl benzoate, O-Anisic Acid ethyl ester, O-Anisic Acid n-propyl, O-Anisic Acid isopropyl
Ester, O-Anisic Acid N-butyl, O-Anisic Acid isobutyl ester, O-Anisic Acid n-pentyl ester, 2- methoxybenzene
The just own ester of formic acid, O-Anisic Acid benzyl ester, O-Anisic Acid phenethyl ester, 2- methoxyl group -3- methyl toluate,
2- methoxyl group-methyl 4 methylbenzoate, 2- methoxyl group -5- methyl toluate, 2- methoxyl group -3- ethyl benzoate first
Ester, 2- methoxyl group -4- ethyl benzoate methyl esters, 2- methoxyl group -5- ethyl benzoate methyl esters, 2- methoxyl group -3- methyl benzoic 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- methylbenzene
N-propyl formate, 2- methoxyl group -4- methyl benzoic acid n-propyl, 2- methoxyl group -5- methyl benzoic 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- methyl benzoic acid isopropyl ester, 2- methoxyl group -4- methyl benzoic acid isopropyl ester, 2- methoxyl group -5- methyl benzoic acid are different
Propyl ester, 2- methoxyl group -3- ethylamino benzonitrile isopropyl propionate, 2- methoxyl group -4- ethylamino benzonitrile isopropyl propionate, 2- methoxyl group -5- ethyl
Isopropyl benzoate, 2- methoxyl group -3- methyl benzoic acid isobutyl ester, 2- methoxyl group -4- methyl benzoic acid isobutyl ester, 2- methoxy
Base -5- methyl benzoic 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-propyl
Ethyl benzoate, 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- amyl ethyl benzoate, 2- first
Oxygroup -4- isoamyl benzene Ethyl formate, 2- methoxyl group -4- cyclopentylbenzoic acid ethyl ester, 2- ethoxy-benzoic acid methyl ester, 2- ethoxy
Yl benzoic acid ethyl ester, 2- ethoxybenzoic acid n-propyl, 2- ethoxy benzonitrile isopropyl propionate, 2- ethoxybenzoic acid N-butyl,
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, the positive fourth oxygen of 2-
The positive fourth oxybenzoic acid isopropyl ester of yl benzoic acid n-propyl, 2-, 2- n-butoxy n-butylbenzoate, 2- n-butoxy benzoic acid are different
Butyl ester, 2- n-butoxy Pentyl benzoate, the just own ester of 2- n-butoxy benzoic acid, 2- n-butoxy Ergol and 2- are just
Butoxybenzoic acid phenethyl ester.
In Formulas I, LB2For hydroxybenzoate based compound shown in formula III,
In formula III, R1Definition with it is described previously identical, and will not be described here in detail；R2、R3、R4And R5Definition and institute above
State identical, and will not be described here in detail.
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 specific example of hydroxybenzoate based compound can include but is not limited to: 2- hydroxyl
Yl benzoic acid methyl esters, 2 hydroxybenzoic acid ethyl ester, 2 hydroxybenzoic acid n-propyl, 2 hydroxybenzoic acid isopropyl ester, 2- hydroxy benzenes
The just own ester of n-buty formate, 2 hydroxybenzoic acid isobutyl ester, 2 hydroxybenzoic acid n-pentyl ester, 2 hydroxybenzoic acid, 2- hydroxy benzenes
Benzyl formate, 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
Base -5- ethyl benzoate methyl esters, 2- hydroxy-3-methyl ethyl benzoate, 2- hydroxy-4-methyl ethyl benzoate, 2- hydroxyl -5-
Methylbenzoic acid ethyl ester, 2- hydroxyl -3- ethylamino benzonitrile acetoacetic ester, 2- hydroxyl -4- ethylamino benzonitrile acetoacetic ester, 2- hydroxyl -5- ethyl
Ethyl benzoate, 2- hydroxy-3-methyl Propyl benzoate, 2- hydroxy-4-methyl Propyl benzoate, 2- hydroxy-5-methyl base
Propyl benzoate, 2- hydroxyl -3- ethyl benzoate n-propyl, 2- hydroxyl -4- ethyl benzoate n-propyl, 2- hydroxyl -5- second
Yl benzoic acid n-propyl, 2- hydroxy-3-methyl isopropyl benzoate, 2- hydroxy-4-methyl isopropyl benzoate, 2- hydroxyl -5-
Methyl 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- hydroxyl
Base -5- methyl 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 formic acid second
Ester, 2- hydroxyl -4- p t butylbenzoic acid ethyl ester, 2- hydroxyl -4- n-amylbenzene Ethyl formate, 2- hydroxyl -4- isoamyl benzene formic acid
Ethyl ester and 2- hydroxyl -4- cyclopentylbenzoic acid ethyl ester.
In Formulas I, LB3For alcohol shown in IV and/or phenol,
R6OH (formula IV)
In formula IV, R6Definition with it is described previously identical, and will not be described here in detail.
In the present invention, as LB3R6The specific example of OH can include but is not limited to: methanol, ethyl alcohol, normal propyl alcohol, isopropyl
Alcohol, n-butanol, isobutanol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, 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 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, and the water is from synthesis material and reaction medium institute
The minor amount of water of band and/or the water added in adduct preparation with separated component.
In a preferred embodiment of the invention, in Formulas I, X1It is chlorine with Y；R1For methyl, ethyl, n-propyl,
One of isopropyl, normal-butyl, isobutyl group and n-hexyl；
LB1For 2- alkoxybenzoic acid ester shown in Formula V,
In Formula V, R1For one of methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group and n-hexyl；R2、R3、
R4And R5Respectively hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, ring penta
Base, just one of base, n-heptyl and tolyl；R6For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, uncle
Butyl, n-pentyl, just one of base, benzyl and phenethyl；
LB2For 2 hydroxybenzoic acid ester shown in Formula IV,
In Formula IV, R1For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group and just one of base；R2、
R3、R4And R5Respectively hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl,
Cyclopenta, just one of base, n-heptyl and tolyl；
LB3For general formula R6Compound shown in OH, R6For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, just one of 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 preferably prepared by one of following two mode.
In the first embodiment, the method for preparing the adduct of magnesium halides includes:
(1) by anhydrous MgX1Y and R1OH, oxyl benzoyl based compound and water mixing, and obtained mixture is added
Heat obtains the adduct of magnesium halides of liquid, relative to 1 mole of MgX in terms of magnesium1Y, R1The amount of OH is 1-5.5 moles, preferably
2-3.7 moles, more preferably 2.4-3.7 moles；The amount of oxyl benzoyl based compound is 0.001-0.32 moles, preferably
0.005-0.17 moles, more preferably 0.015-0.12 moles；The amount of water is 0.011-0.081 moles, preferably 0.016-
0.053 mole, more preferably 0.021-0.045 moles；
(2) in the presence of inert liquid medium, the adduct of magnesium halides of the liquid is emulsified, and by emulsification product chilling
It is dried after forming, obtains adduct of magnesium halides particle.
In the second embodiment, the method for preparing the adduct of magnesium halides includes:
(1) by aqueous MgX1Y and R1OH and the mixing of oxyl benzoyl based compound, and obtained mixture is heated, it obtains
To the adduct of magnesium halides of liquid, relative to 1 mole of MgX in terms of magnesium1Y, R1The amount of OH is 1-5.5 moles, preferably 2-3.7
Mole, more preferably 2.4-3.7 moles；The amount of oxyl benzoyl based compound is 0.001-0.32 moles, preferably
0.005-0.17 moles, more preferably 0.015-0.12 moles；Aqueous MgX1The amount of water is 0.011-0.081 moles in Y, preferably
It is 0.016-0.053 moles, more preferably 0.021-0.045 moles；
(2) in the presence of inert liquid medium, the adduct of magnesium halides of the liquid is emulsified, and by emulsification product chilling
It is dried after forming, obtains adduct of magnesium halides particle.
In the present invention, by weight, anhydrous MgX1Water content in Y is lower than 0.2%, and the water content is taken using karr
Not method measures.It can be by controlling MgX1The drying condition of Y and/or by MgX1Y has the substance of reactivity to contact with to water,
So as to adjust MgX1Water content in Y.The substance for having reactivity to water can be HCl air-flow.
In above two embodiment, MgX is removed1Remaining raw material outside Y is carrying out anhydrous processing using preceding, by institute
It is controlled in the range of not influencing test result with the moisture in raw material.Generally, R1The water content of OH be lower than 100ppm (with
Poidometer), the water content of oxyl benzoyl based compound is lower than 10ppm (by weight), and the water of inert liquid medium contains
Amount is lower than 50ppm (by weight).Control reduces the method for water content in solid material or liquid material in the art
It is well-known, such as: liquid material can be carried out distilling and/or contacting with water absorbing agent (such as molecular sieve), it can be to adding
It is continually fed into high-purity inert gas in the solid material or liquid material of heat, such as High Purity Nitrogen air-flow.
In above two embodiment, oxyl benzoyl based compound as shown in Formula VII,
In Formula VII, X2For one of halogen atom, preferably chlorine；R2、R3、R4、R5And R6With it is described previously identical, this
Place is no longer described in detail.
The oxyl benzoyl based compound is preferably 4- oxyl benzoyl based compound and/or 2- oxyl benzene first
Acyl based compound, more preferably 2- oxyl benzoyl based compound.
In the present invention, the specific example of the oxyl benzoyl based compound be can include but is not limited to: 2- methoxyl group
Chlorobenzoyl chloride, 2- methoxyl group -3- methyl benzoyl chloride, 2- methoxyl group -4- methyl benzoyl chloride, 2- methoxyl group -5- methylbenzene first
Acyl chlorides, 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
Chlorine, 2- methoxyl group -4- diisopropylbenzoyl peroxide chlorine, 2- methoxyl group -4- isobutyl-benzene formyl chloride, 2- methoxyl group -4- tert-butyl benzene first
Acyl chlorides, 2- methoxyl group -4- pentylbenzoyl chloride, 2- methoxyl group -4- isoamyl benzene formyl chloride, 2- methoxyl group -4- cyclopenta benzene first
Acyl chlorides, 2- ethoxy benzoyl chloride and 2- n-butoxy chlorobenzoyl chloride.
Various chemical phase interaction can not occur with adduct of magnesium halides for the inert liquid medium to be commonly used in the art
Liquid medium, such as: silicone oil and/or hydrocarbon system solvent.Specifically, the inert liquid medium can for kerosene, paraffin oil,
One of vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil or
It is two or more.
The dosage of the inert liquid medium can be according to MgX1The specific dosage of Y selects.Generally, it rubs relative to 1
MgX of that in terms of magnesium1Y, the dosage of inert liquid medium are 0.2-13L；Preferably, relative to 1 mole of MgX in terms of magnesium1Y, it is lazy
Property liquid medium dosage be 0.6-6.5L.
The emulsifying mixture that the adduct of magnesium halides of the liquid can be mixed with inert liquid medium, and will be obtained,
The adduct of magnesium halides of the liquid is emulsified to realize.
Can also using the part inert liquid medium as the reaction medium for the adduct of magnesium halides for preparing the liquid,
To obtain the mixed liquor of the adduct of magnesium halides containing liquid, then the mixed liquor and remainder inert liquid medium are mixed
Merge emulsification, and then realizes and emulsify the adduct of magnesium halides of the liquid.
Can also using all inert liquid mediums as the reaction medium for the adduct of magnesium halides for preparing the liquid,
To obtain the mixed liquor of the adduct of magnesium halides containing liquid, which is emulsified, and then is realized the halogen of the liquid
Change the emulsification of magnesium adduct.
When needing, some surfactants, such as fatty acid glycerine are also optionally added into the inert liquid medium
Ester, fatty acid sorbitan, polysorbate, polyoxyethylene ether or Pluronic F68.The surfactant
Dosage can be the conventional amount used of this field, such as: relative to 1 mole of MgX in terms of magnesium1Y, the dosage of the surfactant
It can be 0.001-1 moles.
The adduct of magnesium halides of liquid can be emulsified using well known to a person skilled in the art various methods, such as: it can
In the presence of inert liquid medium, the adduct of magnesium halides of liquid is carried out high speed shear, so that the magnesium halide of liquid be added
Close object emulsification.The method of the high speed shear is known in those skilled in the art, such as: the disclosed high speed of CN1151183C
Paddling process is (that is, the adduct of magnesium halides of liquid is stirred in inert liquid medium with 2000-5000 revs/min of speed
It mixes)；CN1267508C it is disclosed by the adduct of magnesium halides of liquid and the mixture of inert liquid medium in hypergravity bed into
Row rotation (speed of rotation can be 100-3000 revs/min) dispersion；CN1463990A is disclosed to add the magnesium halide of liquid
The mixture for closing object and silicone oil and white oil is exported in mulser with 1500-8000 revs/min of speed；US6020279 is disclosed
By spray-on process by the emulsifying mixture of the adduct of magnesium halides containing liquid.
Emulsification product chilling can be shaped using well known to a person skilled in the art methods, to obtain spherical magnesium halide
Adduct.Such as: it can be anxious by the emulsification product by the way that the emulsification product is transferred to the method in liquid cooling medium
It is cold with forming.
Various chemical phase interaction can not occur with adduct of magnesium halides for the liquid cooling medium to be commonly used in the art
Liquid medium.For example, the liquid cooling medium can be unreactive hydrocarbons series solvent.The specific reality of the liquid cooling medium
Example can include but is not limited to: pentane, n-hexane, normal heptane, gasoline or petrol ether.
In the present invention, the liquid cooling medium is carrying out anhydrous processing using preceding, by liquid cooling medium used
In moisture control in the range of not influencing test result.Generally, it is by the water content control of the liquid cooling medium
Not higher than 5ppm (by weight).The method for controlling or reducing water content in the liquid cooling medium is many institutes in the art
Known, such as: liquid material can be carried out distilling and/or contacting with water absorbing agent (such as molecular sieve), it can be to the liquid of heating
High-purity inert gas is continually fed into body material, such as High Purity Nitrogen air-flow.
The temperature of the liquid cooling medium, which is subject to, can make the emulsification product cooling and shape.Generally, described
The temperature of liquid cooling medium can be -50 DEG C to 0 DEG C, preferably -40 DEG C to -20 DEG C.For the dosage of the cooling medium
It is not particularly limited, as long as the dosage of the cooling medium is enough emulsification product is cooling and shapes.Specifically, described
Cooling medium and the volume ratio of the emulsification product are 1-15:1, preferably 2-9:1.
Adduct of magnesium halides particle obtained from shaping through chilling can be washed and be dried.This field skill can be used
Method well known to art personnel washs obtained adduct of magnesium halides, for example, can using inertia hydrocarbon system solvent (such as: just
Pentane, n-hexane, normal heptane, petroleum ether and gasoline) obtained adduct of magnesium halides is washed.The temperature of the drying can
Think not higher than 35 DEG C, preferably 25-30 DEG C；The time of the drying can be 0.5-3 hours, preferably 1-2h.The drying
It can be carried out under conditions of normal pressure or reduction pressure.
It is not limited by any specific theory, with MgX1Y is MgCl2, R1OH is ethyl alcohol, oxyl benzoyl compound
For 2- methoxy benzoyl chloride, the following reaction mechanism mechanism of reaction is undergone, to obtain adduct of magnesium halides of the invention.
Adduct of magnesium halides of the invention contacts the catalyst to be formed with titanium compound and optional Donor compound and exists
Higher catalytic activity is shown in olefinic polymerization.The present invention also provides the adduct of magnesium halides to prepare alkene as a result,
Application in polymerization catalyst.
The present invention will be described in detail with reference to embodiments, but is not so limited the scope of the present invention.
In following embodiment and comparative example, the test method being related to is as follows.
1, it melt index (MI): is measured according to method specified in ASTM D1238-99.
2, polymer isotactic index (II): specific to grasp using the measurement of normal heptane extraction process (normal heptane boiling extracting 6 hours)
As: the dry polymer samples of 2g are weighed, is placed in Soxhlet extractor and is extracted 6 hours with the normal heptane of boiling, then, will be remained
Excess is dry to constant weight, and the weight (g) of gained residue and 2 ratio are isotactic index.
3, differential scanning calorimetry (DSC): using the differential scanning amount of the model DSC7 purchased from Perkin Elmer company
Hot instrument is carried out within the scope of 5-220 DEG C with 5 DEG C/min of scanning speed.In order to avoid aquation occurs for sample, in glove box
The middle aluminium glue capsule for the use of equipped with sample, volume being 40 μ l.
4, X-ray powder diffraction spectrum (XRD): using the D8Advance type high power for being purchased from Bruker AXS company, Germany
Turn target X-ray diffractometer, the test condition of the instrument are as follows: Cu target (wavelength), pipe presses 40kV, Guan Liu 300mA, slit
System DS=SS=1mm receives slit 0.2mm, and monochromator is graphite monochromator, and scintillation counter counts, and 3 ° (2 of scanning speed
θ)·min-1, 5-15 ° of scanning range (2 θ).The polyethylene that analyzed sample is sealed in 50 microns of thickness, operates in glove box
In polybag.
Embodiment 1-5 is for illustrating the present invention.
Embodiment 1
(1) in the reaction kettle of 500mL, addition 150mL white oil (it is commercially available from Guangzhou Ming En petrochemical industry Co., Ltd,
By weight, water content be lower than 50ppm), 30g contain 0.44wt% moisture magnesium chloride (being commercially available from Xin Yitai factory, Fushun City),
50mL dehydrated alcohol (being commercially available from Beijing Chemical Plant, by weight, water content is lower than 100ppm) and 1mL 2- methoxybenzene first
Acyl chlorides (is commercially available from TOKYOKASEI KOGYO CO.LTD), is warming up to 120 DEG C under stiring.After isothermal reaction 2 hours, it will mix
Close object indentation be preheated to 120 DEG C 300mL methyl-silicone oil (be commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, by weight,
Water content is lower than 50ppm) in, it is stirred 30 minutes with 1600 revs/min of speed, to be emulsified.Then, emulsification product is used
Nitrogen indentation was pre-cooled into -30 DEG C of 2L hexane (by weight, water content is lower than 5ppm), carried out chilling forming.Filtering
Liquid is removed, obtained solid is washed 5 times with the hexane of 300mL, and is dried in vacuo 1.5 hours at 30 DEG C, to obtain
Spherical magnesium halide adduct according to the present invention, composition are listed in table 1, the particle morphology observed using optical microscopy
As shown in Figure 1.
By adduct of magnesium halides progress dsc analysis, in obtained DSC figure, in 99.5 DEG C and 110.6 DEG C each appearance one
A melting peak, fusion enthalpy relevant to highest melting peak are 169.4 joule/grams.
The x-ray diffraction pattern of the adduct of magnesium halides, which shows to show in the range of 5-15 ° of the 2 θ angle of diffraction, to be present in
6.08 ° (14), 8.82 ° (100), 8.98 ° (76), 9.72 ° (55), 5 diffraction spectral lines under 11.46 ° (9) of 2 θ of the angle of diffraction；
Numerical value in bracket indicates the intensity I/I relative to most strong diffraction spectral line0。
(2) in the glass reaction bottle of 300mL, under the conditions of nitrogen protection, 10mL hexane, tetra- chlorination of 90mL are sequentially added
Titanium is cooled to -20 DEG C, the Spherical magnesium halide adduct of 8.0g step (1) preparation is added, and stir 30 minutes at -20 DEG C.So
Afterwards, 110 DEG C are to slowly warm up to, and 1.5mL diisobutyl phthalate is added in temperature-rise period.In 110 DEG C of isothermal reactions
After 30 minutes, liquid is filtered out.80mL titanium tetrachloride is added, is warming up to 120 DEG C, filters out liquid after maintaining 30 minutes at 120 DEG C；It connects
, 80mL titanium tetrachloride is added, and be warming up to 120 DEG C, filters out liquid after maintaining 30 minutes at 120 DEG C.Finally with 60 DEG C
Hexane washs obtained solid 5 times (hexane dosage is 80mL/ times), and is dried in vacuo obtained solid object, to obtain spherical shape
Catalytic component.
(3) under nitrogen protection, the hexane solution of 5mL triethyl aluminum is sequentially added into the stainless steel autoclave of 5L
The hexane solution (concentration 0.1mmol/mL) and 9mg of (concentration 0.5mmol/mL), 1mL Cyclohexyl Methyl Dimethoxysilane
The spherical catalyst components of step (2) preparation.Autoclave is closed, 1.5L (normal volume) hydrogen and 2.3L liquid propene is added.
70 DEG C are warming up to, is reacted 2 hours.Then, cool down, release, discharging, and be dried, to obtain polypropylene.Calculate catalyst
Polymerization activity, measure the polyacrylic isotacticity and melt flow index of preparation, as a result listed in table 2.
Comparative example 1
(1) spherical magnesium chloride adduct is prepared using method identical with 1 step of embodiment (1), unlike, it uses
Magnesium chloride is anhydrous magnesium chloride, and the composition of the adduct of magnesium halides of preparation is listed in table 1.
By adduct of magnesium halides progress dsc analysis, in obtained DSC figure, in 100.0 DEG C and 109.8 DEG C each appearance
One melting peak, fusion enthalpy relevant to highest melting peak are 168.5 joule/grams.
The x-ray diffraction pattern of the adduct of magnesium halides, which shows to show in the range of 5-15 ° of the 2 θ angle of diffraction, to be present in
6.26 ° (12), 9.06 ° (100), 10.00 ° (51), 4 diffraction spectral lines under 11.74 ° (12) of 2 θ of the angle of diffraction；In bracket
Numerical value indicate intensity I/I relative to most strong diffraction spectral line0。
(2) using identical method prepares spherical catalyst components with 1 step of embodiment (2), unlike, use comparison
The spherical magnesium chloride adduct of 1 step of example (1) preparation.
(3) using identical method prepares polypropylene with 1 step of embodiment (3), unlike, use 1 step of comparative example
(2) spherical catalyst components prepared.
Experimental result is listed in table 2.
Comparative example 2
(1) spherical magnesium chloride adduct is prepared using method identical with 1 step of embodiment (1), unlike, it uses
Magnesium chloride is anhydrous magnesium chloride, and 1mL 2- methoxy benzoyl chloride (being commercially available from TOKYO KASEI KOGYO CO.LTD) is changed
For 1mL 2 hydroxybenzoic acid ethyl ester (be commercially available from TOKYO KASEI KOGYO CO.LTD, by weight, water content be lower than
10ppm), the composition of the adduct of magnesium halides of preparation is listed in table 1.
By adduct of magnesium halides progress dsc analysis, in obtained DSC figure, in 97.1 DEG C and 113.4 DEG C each appearance one
A melting peak, fusion enthalpy relevant to highest melting peak are 178.3 joule/grams.
The x-ray diffraction pattern of the adduct of magnesium halides, which shows to show in the range of 5-15 ° of the 2 θ angle of diffraction, to be present in
6.07 ° (28), 8.80 ° (67), 9.06 ° (100), 9.98 ° (43), 5 diffraction spectral lines under 11.63 ° (11) of 2 θ of the angle of diffraction；
Numerical value in bracket indicates the intensity I/I relative to most strong diffraction spectral line0。
(2) using identical method prepares spherical catalyst components with 1 step of embodiment (2), unlike, use comparison
The Spherical magnesium halide adduct of 2 step of example (1) preparation.
(3) using identical method prepares polypropylene with 1 step of embodiment (3), unlike, use 2 step of comparative example
(2) spherical catalyst components prepared.
Experimental result is listed in table 2.
Embodiment 2
(1) Spherical magnesium halide adduct is prepared using method identical with 1 step of embodiment (1), unlike, it uses
Magnesium chloride is the magnesium chloride containing 0.65wt% moisture, and the composition of the adduct of magnesium halides of preparation is listed in table 1.
By adduct of magnesium halides progress dsc analysis, in obtained DSC figure, in 97.6 DEG C and 112.1 DEG C each appearance one
A melting peak, fusion enthalpy relevant to highest melting peak are 177.3 joule/grams.
The x-ray diffraction pattern of the adduct of magnesium halides, which shows to show in the range of 5-15 ° of the 2 θ angle of diffraction, to be present in
6.06 ° (14), 8.82 ° (100), 8.98 ° (50), 9.74 ° (66), 5 diffraction spectral lines under 11.48 ° (11) of 2 θ of the angle of diffraction；
Numerical value in bracket indicates the intensity I/I relative to most strong diffraction spectral line0。
(2) using identical method prepares spherical catalyst components with 1 step of embodiment (2), unlike, use implementation
The spherical magnesium chloride adduct of 2 step of example (1) preparation.
(3) using identical method prepares polypropylene with 1 step of embodiment (3), unlike, use 2 step of embodiment
(2) spherical catalyst components prepared.
Experimental result is listed in table 2.
Comparative example 3
(1) in the reaction kettle of 500mL, addition 150mL white oil (it is commercially available from Guangzhou Ming En petrochemical industry Co., Ltd,
By weight, water content be lower than 50ppm), 30g contain 0.65wt% moisture magnesium chloride (being commercially available from Xin Yitai factory, Fushun City),
50mL dehydrated alcohol (being commercially available from Beijing Chemical Plant, by weight, water content is lower than 100ppm), 1mL 2- methoxybenzoyl
(being commercially available from Ningbo Warner chemical industry has for chlorine (being commercially available from TOKYOKASEI KOGYO CO.LTD) and 1mL 2,2- dimethoxy propane
Limit company, by weight, water content are lower than 10ppm), it is warming up to 120 DEG C under stiring.After isothermal reaction 2 hours, it will mix
The 300mL methyl-silicone oil that object indentation is preheated to 120 DEG C (is commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, by weight, water
Content is lower than 50ppm) in, it is stirred 30 minutes with 1600 revs/min of speed, to be emulsified.Then, by emulsification product nitrogen
Air pressure entered to pre-cool into -30 DEG C of 2L hexane (by weight, water content is lower than 5ppm), carried out chilling forming.It crosses and filters out
Liquid is removed, obtained solid is washed 5 times with the hexane of 300mL, and is dried in vacuo 1.5 hours at 30 DEG C, to obtain ball
Shape adduct of magnesium halides, composition are listed in table 1.
By adduct of magnesium halides progress dsc analysis, in obtained DSC figure, at 76.2 DEG C, 97.3 DEG C and 111.4 DEG C
Respectively there is a melting peak, fusion enthalpy relevant to highest melting peak is 170.2 joule/grams.
The x-ray diffraction pattern of the adduct of magnesium halides, which shows to show in the range of 5-15 ° of the 2 θ angle of diffraction, to be present in
6.14 ° (17), 9.05 ° (100), 9.49 ° (63), 9.84 ° (66), 5 diffraction spectral lines under 11.63 ° (10) of 2 θ of the angle of diffraction；
Numerical value in bracket indicates the intensity I/I relative to most strong diffraction spectral line0。
(2) using identical method prepares spherical catalyst components with 1 step of embodiment (2), unlike, use comparison
The Spherical magnesium halide adduct of 3 step of example (1) preparation.
(3) using identical method prepares polypropylene with 1 step of embodiment (3), unlike, use 3 step of comparative example
(2) spherical catalyst components prepared.
Experimental result is listed in table 2.
Embodiment 3
(1) in the reaction kettle of 500mL, addition 150mL white oil (it is commercially available from Guangzhou Ming En petrochemical industry Co., Ltd,
By weight, water content is lower than 50ppm), 30g anhydrous magnesium chloride (being commercially available from Xin Yitai factory, Fushun City), 50mL dehydrated alcohol (quotient
Purchased from Beijing Chemical Plant, by weight, water content be lower than 100ppm), 1mL 2- methoxy benzoyl chloride (be commercially available from TOKYO
KASEI KOGYOCO.LTD) and 0.15g water, it is warming up to 120 DEG C under stiring.After isothermal reaction 2 hours, mixture is pressed into
It is preheated to 120 DEG C of 300mL methyl-silicone oil and (is commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, and by weight, water content is low
In 50ppm) in, it is stirred 30 minutes with 1600 revs/min of speed, to be emulsified.Then, emulsification product is pressed into nitrogen
It pre-cools into -30 DEG C of 2L hexane (by weight, water content is lower than 5ppm), carries out chilling forming.Liquid is filtered to remove,
Obtained solid is washed 5 times with the hexane of 300mL, and is dried in vacuo 1.5 hours at 30 DEG C, to obtain according to the present invention
Spherical magnesium halide adduct, composition listed in table 1.
By adduct of magnesium halides progress dsc analysis, in obtained DSC figure, in 98.5 DEG C and 111.3 DEG C each appearance one
A melting peak, fusion enthalpy relevant to highest melting peak are 171.4 joule/grams.
The x-ray diffraction pattern of the adduct of magnesium halides, which shows to show in the range of 5-15 ° of the 2 θ angle of diffraction, to be present in
6.10 ° (21), 8.78 ° (100), 8.98 ° (66), 9.72 ° (61), 5 diffraction spectral lines under 11.48 ° (10) of 2 θ of the angle of diffraction；
Numerical value in bracket indicates the intensity I/I relative to most strong diffraction spectral line0。
(2) using identical method prepares spherical catalyst components with 1 step of embodiment (2), unlike, use implementation
The Spherical magnesium halide adduct of 3 step of example (1) preparation.
(3) using identical method prepares polypropylene with 1 step of embodiment (3), unlike, using 3 step of embodiment
(2) spherical catalyst components prepared.
Experimental result is listed in table 2.
Embodiment 4
(1) in the reaction kettle of 500mL, addition 150mL white oil (it is commercially available from Guangzhou Ming En petrochemical industry Co., Ltd,
By weight, water content be lower than 50ppm), 30g contain 1.2wt% moisture magnesium chloride (being commercially available from Xin Yitai factory, Fushun City),
54mL dehydrated alcohol (being commercially available from Beijing Chemical Plant, by weight, water content is lower than 100ppm) and 3mL 2- methoxybenzene first
Acyl chlorides (is commercially available from TOKYO KASEI KOGYO CO.LTD), is warming up to 130 DEG C under stiring.After isothermal reaction 2 hours, it will mix
Close object indentation be preheated to 130 DEG C 300mL methyl-silicone oil (be commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, by weight,
Water content is lower than 50ppm) in, it is stirred 30 minutes with 1600 revs/min of speed, to be emulsified.Then, emulsification product is used
Nitrogen indentation was pre-cooled into -30 DEG C of 2L hexane (by weight, water content is lower than 5ppm), carried out chilling forming.Filtering
Liquid is removed, obtained solid is washed 5 times with the hexane of 300mL, and is dried in vacuo 1.5 hours at 30 DEG C, to obtain
Spherical magnesium halide adduct according to the present invention, composition are listed in table 1.
By adduct of magnesium halides progress dsc analysis, in obtained DSC figure, in 97.5 DEG C and 112.7 DEG C each appearance one
A melting peak, fusion enthalpy relevant to highest melting peak are 178.2 joule/grams.
The x-ray diffraction pattern of the adduct of magnesium halides, which shows to show in the range of 5-15 ° of the 2 θ angle of diffraction, to be present in
6.14 ° (15), 8.88 ° (100), 9.80 ° (52), 4 diffraction spectral lines under 11.54 ° (9) of 2 θ of the angle of diffraction；In bracket
Numerical value indicates the intensity I/I relative to most strong diffraction spectral line0。
(2) using identical method prepares spherical catalyst components with 1 step of embodiment (2), unlike, use implementation
The Spherical magnesium halide adduct of 4 step of example (1) preparation.
(3) using identical method prepares polypropylene with 1 step of embodiment (3), unlike, use 4 step of embodiment
(2) spherical catalyst components prepared.
Experimental result is listed in table 2.
Embodiment 5
(1) in the reaction kettle of 500mL, addition 150mL white oil (it is commercially available from Guangzhou Ming En petrochemical industry Co., Ltd,
By weight, water content be lower than 50ppm), 30g contain 1.2wt% moisture magnesium chloride (being commercially available from Xin Yitai factory, Fushun City),
58mL dehydrated alcohol (being commercially available from Beijing Chemical Plant, by weight, water content is lower than 100ppm) and 5mL 4- methoxybenzene first
Acyl chlorides (is commercially available from TOKYO KASEI KOGYO CO.LTD), is warming up to 130 DEG C under stiring.Isothermal reaction 2 hours
Afterwards, by mixture indentation be preheated to 130 DEG C 300mL methyl-silicone oil (be commercially available from DOW CORNING, viscosity is 300 centipoise/20 DEG C, with
Poidometer, water content are lower than 50ppm) in, it is stirred 30 minutes with 1600 revs/min of speed, to be emulsified.It then, will be newborn
Change the indentation of product nitrogen to pre-cool into -30 DEG C of 2L hexane (by weight, water content be lower than 5ppm), carry out chilling at
Shape.It is filtered to remove liquid, obtained solid is washed 5 times with the hexane of 300mL, and is dried in vacuo 1.5 hours at 30 DEG C, from
And Spherical magnesium halide adduct according to the present invention is obtained, composition is listed in table 1.
By adduct of magnesium halides progress dsc analysis, in obtained DSC figure, in 97.7 DEG C and 112.0 DEG C each appearance one
A melting peak, fusion enthalpy relevant to highest melting peak are 178.8 joule/grams.
The x-ray diffraction pattern of the adduct of magnesium halides, which shows to show in the range of 5-15 ° of the 2 θ angle of diffraction, to be present in
6.20 ° (15), 8.84 ° (100), 9.78 ° (53), 4 diffraction spectral lines under 11.52 ° (9) of 2 θ of the angle of diffraction；In bracket
Numerical value indicates the intensity I/I relative to most strong diffraction spectral line0。
(2) using identical method prepares spherical catalyst components with 1 step of embodiment (2), unlike, use implementation
The Spherical magnesium halide adduct of 5 step of example (1) preparation.
(3) using identical method prepares polypropylene with 1 step of embodiment (3), unlike, use 5 step of embodiment
(2) spherical catalyst components prepared.
Experimental result is listed in table 2.
Table 1
a: O-Anisic 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, the catalyst formed by adduct of magnesium halides according to the present invention is for propylene
The polymer for when polymerization, showing higher polymerization activity, while preparing also isotacticity with higher.
Fig. 1's as a result, it was confirmed that the particle shape of adduct of magnesium halides according to the present invention is good, and no anisotropic material exists.
Claims (8)
1. a kind of adduct of magnesium halides, the adduct of magnesium halides is shown in formula I,
MgX1Y-mR1OH-n(LB1)-k(LB2)-p(LB3) (Formulas I)
Wherein, X1For chlorine, Y is chlorine；
LB1For 4- alkoxybenzoic acid ester based compound shown in Formula II and/or 2- alkoxybenzoic acid ester based compound,
LB2For 4-HBA ester based compound shown in formula III and/or 2 hydroxybenzoic acid ester based compound,
LB3For alcohol shown in formula IV,
R6OH (formula IV)
R1For one of methyl, ethyl, n-propyl and isopropyl；
R2、R3、R4And R5Respectively hydrogen；
R6With R1It is not identical, it is one of methyl, ethyl, n-propyl and isopropyl；
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。
2. a kind of preparation method of adduct of magnesium halides described in claim 1, this method comprises:
(1) by aqueous MgX1Y and R1OH and the mixing of oxyl benzoyl based compound, and obtained mixture is heated, obtain liquid
The adduct of magnesium halides of state, relative to 1 mole of MgX in terms of magnesium1Y, R1The amount of OH is 2.4-3.7 moles, oxyl benzoyl system
The amount of compound is 0.015-0.12 moles, aqueous MgX1The amount of water is 0.021-0.045 moles in Y；Or
By anhydrous MgX1Y and R1OH, oxyl benzoyl based compound and water mixing, and obtained mixture is heated, obtain liquid
The adduct of magnesium halides of state, relative to 1 mole of MgX in terms of magnesium1Y, R1The amount of OH is 2.4-3.7 moles, oxyl benzoyl system
The amount of compound is 0.015-0.12 moles, and the amount of water is 0.021-0.045 moles；
Wherein, X1, Y and R1Definition it is identical as the definition in Formulas I,
For the oxyl benzoyl based compound as shown in Formula VII, the oxyl benzoyl based compound is 4- alkoxy benzene
Formyl based compound and/or 2- alkoxy benzene formyl based compound,
In Formula VII, X2For chlorine, R2、R3、R4And R5Definition it is identical as the definition in Formula II and formula III, R6Definition and Formula II in
Definition it is identical；
(2) in the presence of inert liquid medium, the adduct of magnesium halides of the liquid is emulsified, and emulsification product chilling is shaped
After be dried, obtain adduct of magnesium halides particle.
3. the condition of the heating includes: that temperature is 80-140 DEG C according to the method described in claim 2, wherein, the time is
0.5-4 hours.
4. according to the method described in claim 2, wherein, the inert liquid medium is silicone oil and/or hydrocarbon system solvent；Relative to
1 mole of the MgX in terms of magnesium1Y, the dosage of the inert liquid medium are 0.2-13L.
5. according to the method described in claim 4, wherein, relative to 1 mole of the MgX in terms of magnesium1Y, the inert liquid medium
Dosage be 0.6-6.5L.
6. according to the method described in claim 2, wherein, the condition of the drying includes: that temperature is not higher than 35 DEG C；Time is
0.5-3 hours.
7. according to the method described in claim 6, wherein, the condition of the drying includes: that temperature is 25-30 DEG C；Time is 1-2
Hour.
8. adduct of magnesium halides described in claim 1 is preparing the application in olefin polymerization catalysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410587751.8A CN105622423B (en) | 2014-10-28 | 2014-10-28 | A kind of adduct of magnesium halides and its preparation method and application |
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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 |
| 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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| 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 |
| 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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